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Sample records for nitrate protonation reaction

  1. Proton transfer reaction - mass spectrometry

    International Nuclear Information System (INIS)

    Cappellin, L.

    2012-01-01

    Proton transfer reaction mass spectrometry (PTR-MS) provides on-line monitoring of volatile organic compounds (VOCs) with a low detection threshold and a fast response time. Commercially available set-ups are usually based on quadrupole analysers but recently new instruments based on time-of-flight (PTR-ToF-MS) analysers have been proposed and commercialized. PTR-MS has been successfully applied to a variety of fields including environmental science, food science and technology, plant physiology and medical science. Many new challenges arise from the newly available PTR-ToF-MS instruments, ranging from mass calibration and absolute VOC concentration determination to data mining and sample classification. This thesis addresses some of these problems in a coherent framework. Moreover, relevant applications in food science and technology are presented. It includes twelve papers published in peer reviewed journals. Some of them address methodological issues regarding PTR-ToF-MS; the others contain applicative studies of PTR-ToF-MS to food science and technology. Among them, there are the first two published applications of PTR-ToF-MS in this field. (author)

  2. On correlation for proton spins in molecules of crystalized water of the lanthanum-magnesium nitrate

    International Nuclear Information System (INIS)

    Taran, Yu.V.; Shapiro, F.L.

    1974-01-01

    Effect of a single transmission of cold neutrons has been measured on a polarized proton target of a lanthanum-magnesium nitrate monocrystal. Experimental results indicate the absence of thermally equilibrium concentration of paramolecules of crystallized water of lanthanum-magnesium nitrate in case of the proton polarization about 70%

  3. Proton conduction based on intracrystalline chemical reaction

    International Nuclear Information System (INIS)

    Schuck, G.; Lechner, R.E.; Langer, K.

    2002-01-01

    Proton conductivity in M 3 H(SeO 4 ) 2 crystals (M=K, Rb, Cs) is shown to be due to a dynamic disorder in the form of an intracrystalline chemical equilibrium reaction: alternation between the association of the monomers [HSeO 4 ] 1- and [SeO 4 ] 2- resulting in the dimer [H(SeO 4 ) 2 ] 3- (H-bond formation) and the dissociation of the latter into the two monomers (H-bond breaking). By a combination of quasielastic neutron scattering and FTIR spectroscopy, reaction rates were obtained, as well as rates of proton exchange between selenate ions, leading to diffusion. The results demonstrate that this reaction plays a central role in the mechanism of proton transport in these solid-state protonic conductors. (orig.)

  4. Heterogeneous Reaction gaseous chlorine nitrate and solid sodium chloride

    Science.gov (United States)

    Timonen, Raimo S.; Chu, Liang T.; Leu, Ming-Taun

    1994-01-01

    The heterogeneous reaction of gaseous chlorine nitrate and solid sodium chloride was investigated over a temperature range of 220 - 300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer.

  5. Proton transfer reactions and dynamics in protonated water clusters.

    Science.gov (United States)

    Lao-Ngam, Charoensak; Asawakun, Prapasri; Wannarat, Sornthep; Sagarik, Kritsana

    2011-03-14

    Proton transfer reactions and dynamics were theoretically studied using the hydrogen-bond (H-bond) complexes formed from H(3)O(+) and nH(2)O, n = 1-4, as model systems. The investigations began with searching for characteristics of transferring protons in the gas phase and continuum aqueous solution using DFT method at the B3LYP/TZVP level, followed by Born-Oppenheimer molecular dynamics (BOMD) simulations at 350 K. B3LYP/TZVP calculations revealed the threshold asymmetric O-H stretching frequencies (ν(OH)*) for the proton transfers in the Zundel complex (H(5)O) in the gas phase and continuum aqueous solution at 1984 and 1881 cm(-1), respectively. BOMD simulations suggested lower threshold frequencies (ν(OH,MD)* = 1917 and 1736 cm(-1), respectively), with two characteristic ν(OH,MD) being the IR spectral signatures of the transferring protons. The low-frequency band could be associated with the "oscillatory shuttling motion" and the high-frequency band with the "structural diffusion motion". These can be regarded as the spectroscopic evidences of the formations of the shared-proton structure (O···H(+)···O) and the H(3)O(+)-H(2)O contact structure (O-H(+)···O), respectively. Since the quasi-dynamic equilibrium between the Zundel and Eigen complexes was suggested to be the rate-determining step, in order to achieve an "ideal" maximum efficiency of proton transfer, a concerted reaction pathway should be taken. The most effective interconversion between the two proton states, the shared-proton structure and the H(3)O(+)-H(2)O contact structure, can be reflected from comparable intensities of the oscillatory shuttling and structural diffusion bands. The present results iterated the previous conclusions that static proton transfer potentials cannot provide complete description of the structural diffusion process and it is essential to incorporate thermal energy fluctuations and dynamics in the model calculations.

  6. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  7. Conjugate addition–enantioselective protonation reactions

    Directory of Open Access Journals (Sweden)

    James P. Phelan

    2016-06-01

    Full Text Available The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals.

  8. Nitrate Deposition to Surface Snow at Summit, Greenland, Following the 9 November 2000 Solar Proton Event

    Science.gov (United States)

    Duderstadt, Katharine A.; Dibb, Jack E.; Schwadron, Nathan A.; Spence, Harlan E.; Jackman, Charles Herbert; Randall, Cora E.; Solomon, Stanley C.; Mills, Michael J.

    2014-01-01

    This study considers whether spurious peaks in nitrate ions in snow sampled at Summit, Greenland from August 2000 to August 2002 are related to solar proton events. After identifying tropospheric sources of nitrate on the basis of correlations with sulfate, ammonium, sodium, and calcium, we use the three-dimensional global Whole Atmosphere Community Climate Model (WACCM) to examine unaccounted for nitrate spikes. Model calculations confirm that solar proton events significantly impact HOx, NOx, and O3 levels in the mesosphere and stratosphere during the weeks and months following the major 9 November 2000 solar proton event. However, SPE-enhanced NOy calculated within the atmospheric column is too small to account for the observed nitrate ion peaks in surface snow. Instead, our WACCM results suggest that nitrate spikes not readily accounted for by measurement correlations are likely of anthropogenic origin. These results, consistent with other recent studies, imply that nitrate spikes in ice cores are not suitable proxies for individual SPEs and motivate the need to identify alternative proxies.

  9. Proton capture reactions and nuclear structure

    International Nuclear Information System (INIS)

    Kikstra, S.W.

    1989-01-01

    Experimental studies are described of the structure of 40 Ca and 42 Sc with measurements at proton-capture of (p, gamma) reactions. Where possible, an attempt has been made to interpret the results of the measurements in termsof existing models. The 40 Ca and 42 Sc nuclides were excited by bombarding 39 K and 41 Ca targets, respectively with low energy protons (E p = 0.3-3.0 MeV), that were produced by the Utrecht 3MV van de Graaff accelerator. From the measured energy and intensity of the gamma-rays created in the subsequent decay of the cuclei, information was obtained on the existence and properties of their excited states. In addition properties of two T = 3/2 levels at high excitation energy of the 9 Be nucleus were investigated. These levels were excited by the resonant absorption of gamma-rays from the 11 B(p, gamma) 12 C reaction. The results of the measurements are interpreted by a comparison to the analoque β-decay of 9 Li and to shell model calculations. The total decay energy of the superallowed O + → O + transition between the ground states of 42 Sc and 42 Ca was determined by measurements in Utrecht of the proton separation energy S p of 42 Sc and in Oak Ridge of S n of 42 Sc and 42 Ca. The results were used for verification of the conserved vector current hypothesis, which implies that the ft values of all superallowed O + → O + β-decays are the same. An attempt was made to describe properties of odd-parity states of A = 37-41 nuclei with a variant of the Warburton, Becker, Millener and Brown (WBMB) interaction.Finally a new method for the assignment of nuclear spins by a simple statistical analysis of spectroscopic information is proposed. (author). 169 refs.; 22 figs.; 24 schemes; 29 tabs

  10. Equilibrium and kinetics of nitrate removal by protonated cross ...

    African Journals Online (AJOL)

    drinie

    2001-01-01

    Jan 1, 2001 ... reverse osmosis could also remove nitrate, but their applications are actually hampered by their high cost. Chitosan is a natural product derived by desacetylation from the polysaccharide chitin. Chitin is found in the exo-skeletons of shrimp, crab and other shellfish. Thanks to its exceptional properties,.

  11. Chemical reaction of protons with antiprotonic helium

    Science.gov (United States)

    Sakimoto, Kazuhiro

    2012-07-01

    Collisions of protons p with antiprotonic helium atoms p¯He+ (bound orbital states of an antiproton p¯ and a helium ion He+) are investigated from the viewpoint of chemical reaction. The p¯He+ atoms with high orbital angular momentum quantum numbers L>40 can be abundantly produced in the capture of p¯ by metastable helium atoms He(21,3S). Since such orbital states are considered to be practically stable despite having Auger decay channels (p¯He+→p¯He2++e), atomic and molecular collision processes involving p¯He+(L>40) are experimentally measurable. In this study, adiabatic electron energies in the Born-Oppenheimer approximation are calculated for the p+p¯He+ system. The p+p¯He+ dynamical calculations of p¯ exchange (→p¯p+He+) and dissociation (→p+p¯+He+) reactions on the ground-state adiabatic potential energy surface are carried out for various high orbital states of p¯He by using a classical trajectory Monte Carlo method. The reaction cross sections and the state distributions of antiprotonic hydrogen atoms (protonium) p¯p produced in the exchange reaction are presented. If the orbital shape of p¯He+ is near circular, the exchange reaction becomes inactive at low energies because the repulsive part of the interaction plays a critical role. In the p+p¯p system, however, the low-energy p¯ exchange reaction remains active for any type of the initial p¯p orbital motion.

  12. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  13. Theoretical studies on proton transfer reaction of 3 (5)-substituted ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 1. Theoretical studies on proton transfer reaction of 3(5)-substituted pyrazoles ... Abstract. The inter and intra molecular proton transfer reactions of a series of pyrazole derivatives have been studied by using density functional theory (DFT) andMP2 methods ...

  14. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 1. Variation of kinetic isotope ... An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence ...

  15. Parallel proton transfer pathways in aqueous acid-base reactions

    NARCIS (Netherlands)

    Cox, M.J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using

  16. Comparison of dynamical aspects of nonadiabatic electron, proton, and proton-coupled electron transfer reactions

    International Nuclear Information System (INIS)

    Hatcher, Elizabeth; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2005-01-01

    The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transfer

  17. Aromatic nitrations by mixed acid. Slow liquid-liquid reaction regime

    NARCIS (Netherlands)

    Zaldivar, J.M.; Zaldivar, J.M.; Molga, E.J.; Alos, M.A.; Hernandez sanchez, F.; Hernandez, H.; Westerterp, K.R.

    1995-01-01

    Aromatic nitrations by mixed acid have been selected as a specific case of a heterogeneous liquid-liquid reaction. An extensive experimental programme has been followed using adiabatic and heat-flow calorimetry and pilot reactor experiments, supported by chemical analysis. A series of nitration

  18. Total reaction cross section calculations in proton-nucleus scattering

    International Nuclear Information System (INIS)

    Wellisch, H.P.; Axen, D.

    1996-01-01

    We have developed a general semiempirical total reaction cross section formula for proton-nucleus reactions. It is applicable for all materials with nuclear charge Z greater than 5, and all proton kinetic energies from the lowest measured energies up to ≅20 GeV. While the regime of applicability is greatly enlarged, agreement between the calculated cross sections and the experimental data is comparable to or better than all earlier published results in their regime of applicability. copyright 1996 The American Physical Society

  19. Energetic Proton Emission and Reaction Dynamics in Heavy Ion Reactions Close to the Fermi Energy

    Science.gov (United States)

    Coniglione, R.; Sapienza, P.; Migneco, E.; Agodi, C.; Alba, R.; Bellia, G.; Colonna, M.; Del Zoppo, A.; Finocchiaro, P.; Greco, V.; Loukachine, K.; Maiolino, C.; Piattelli, P.; Santonocito, D.; Ventura, P. G.; Colonna, N.; Bruno, M.; D'Agostino, M.; Fiandri, M. L.; Vannini, G.; Mastinu, P. F.; Gramegna, F.; Iori, I.; Fabbietti, L.; Moroni, A.; Margagliotti, G. V.; Milazzo, P. M.; Rui, R.; Tonetto, F.; Blumenfeld, Y.; Scarpaci, J. A.

    2001-11-01

    The energetic proton emission has been investigated in the 58Ni+58Ni at 30 MeV/u and 40Ar+ 51V at 44 MeV/u reactions. Information on the origin of the energetic protons and on basic ingredients of the BNV models such as the mean field interaction and the elementary nucleon-nucleon cross section was extracted. Extremely energetic protons were measured and their impact parameter dependence indicates the presence of cooperative processes.

  20. THE COURSE OF THE ALKALI-AGGREGATE REACTION IN THE PRESENCE OF LITHIUM NITRATE

    Directory of Open Access Journals (Sweden)

    Owsiak Z.

    2013-06-01

    Full Text Available Lithium nitrate is recognized as a chemical compound capable of inhibiting the alkali-silica aggregate reaction. The extent to which the reaction is inhibited or limited is affected by the amount of the applied lithium compound and by the kind of reactive aggregate that has been used. In the case of the polymineral aggregate this process is particularly complex, as the alkali-silicate reaction may be accompanied by other alkali-aggregate reactions, i.a. the alkali-carbonate reaction. The paper presents the results of the investigation on the effect of lithium nitrate on the course of the alkali - reactive gravel aggregate reaction. The investigation was conducted in accordance with ASTM 1260 standard. The investigation results showed that lithium nitrate, when applied in appropriate amount, inhibits the process of mortar samples expansion. The appearance of spalls in the samples modified with a lithium compound indicates the occurrence of two reaction types: alkalisilica and alkali-carbonate.

  1. Reactions of Proton Halo Nuclei in a Relativistic Optical Potential

    CERN Document Server

    Rashdan, M

    2003-01-01

    The reaction cross section, sigma sub R; of the proton halo nuclei sup 1 sup 7 Ne and sup 1 sup 2 N on Si is calculated using an optical potential derived from the solution of the Dirac-Brueckner-Bethe-Goldstone equation, starting from the one-boson-exchange potential of Bonn. The nuclear densities are generated from self-consistent Hartree-Fock calculations using the recent Skyrme interaction SKRA. It is found that the enhancement in the reaction cross section found experimentally for the sup 1 sup 7 Ne + Si system in comparison to sup 1 sup 5 O + Si, where sup 1 sup 5 O has been considered as a core of sup 1 sup 7 Ne, is mainly due to the proton halo structure of sup 1 sup 7 Ne which increases the interaction, in the surface and tail regions. Glauber model calculations did not produce this enhancement in sigma sub R for proton halo nuclei

  2. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Proton transfer; promoter modes; kinetic isotope effect. 1. Introduction. Kinetic isotope effect (KIE) is the dependence of the rate constant on the mass of the isotope of the atom in a chemical reaction. The primary kinetic isotope effect is the KIE when the bonds connecting that atom to the rest of the molecular frame are broken ...

  3. Dynamics of Anti-Proton -- Protons and Anti-Proton -- Nucleus Reactions

    CERN Document Server

    Galoyan, A; Uzhinsky, V

    2016-01-01

    A short review of simulation results of anti-proton-proton and anti-proton-nucleus interactions within the framework of Geant4 FTF (Fritiof) model is presented. The model uses the main assumptions of the Quark-Gluon-String Model or Dual Parton Model. The model assumes production and fragmentation of quark-anti-quark and diquark-anti-diquark strings in the mentioned interactions. Key ingredients of the model are cross sections of string creation processes and an usage of the LUND string fragmentation algorithm. They allow one to satisfactory describe a large set of experimental data, especially, a strange particle production, Lambda hyperons and K mesons.

  4. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  5. Redox reaction rates in shallow aquifers: Implications for nitrate transport in groundwater and streams

    Science.gov (United States)

    Tesoriero, Anthony J.

    2012-01-01

    Groundwater age and water chemistry data along flow paths from recharge areas to streams were used to evaluate the trends and transformations of agricultural chemicals. Results from this analysis indicate that median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years from 4 mg N/L in samples collected prior to 1983 to 7.5 mg N/L in samples collected since 1983. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the rate of redox reactions along flow paths and on the age distribution of nitrate discharging to supply wells and streams.

  6. Medium effects on spin observables of proton knockout reactions

    Energy Technology Data Exchange (ETDEWEB)

    Krein, G. [Instituto de Fisica Teorica (IFT), Sao Paulo, SP (Brazil); Maris, T.A.J.; Rodrigues, B.B.; Veit, E.A. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Fisica

    1994-07-01

    Medium modifications of the properties of bound nucleons and mesons are investigated by means of medium energy quasi free proton knockout reactions with polarized incident protons. The sensitivity of the spin observables of these reactions to modifications of the nucleon and meson properties is studied using the Bonn one-boson exchange model of the nucleon-nucleon interaction. A method proposed to extract the pp analysing power in medium from the (p, 2 p) asymmetries indicates a reduction of this quantity compared to its free space value. This reduction is linked to modifications of masses and coupling constants of the nucleons and mesons in the nucleus. The implications of these modifications for another spin observable to be measured in the future are discussed. (author). 39 refs, 9 figs.

  7. Influence of Exposure Conditions on the Efficacy of Lithium Nitrate in Mitigating Alkali Silica Reaction

    Science.gov (United States)

    Zapała-Sławeta, Justyna; Owsiak, Zdzisława

    2017-10-01

    Lithium nitrate is known to have the highest potential to inhibit alkali silica reaction in concrete. It is well soluble in water and does not increase the pH of concrete pore solution. The extent to which the alkali silica reaction is mitigated is affected by the amount of the applied lithium ions, exposure conditions and by the kind of reactive aggregate. It is known that some lithium compounds such as lithium carbonate or lithium fluoride, when used in insufficient amount, may increase expansion due to alkali silica reaction. This effect was not detected in the presence of lithium nitrate. The aim of this study was to determine the effect of lithium nitrate on alkali silica reaction in mortars exposed to different conditions. Expansion studies were conducted in accordance with the accelerated mortar bar test (ASTM C1260) and the standard mortar bar test (ASTM C227). It was observed that the long-term expansion results are different from the values obtained in the accelerated mortar bar test. Lithium nitrate does not reduce ASR-induced expansion when mortars are stored under conditions specified in ASTM C 227. The microstructure of the mortar samples exposed to different conditions was examined and X-ray microanalysis was performed. The microstructure and compositions of the alkali-silica reaction products varied. The amount of alkali silica gel in mortars with lithium nitrate in which the expansion was high was greater than that in the mortar bars tested by accelerated method.

  8. Fragmentation reactions of protonated peptides containing glutamine or glutamic acid.

    Science.gov (United States)

    Harrison, Alex G

    2003-02-01

    A variety of protonated dipeptides and tripeptides containing glutamic acid or glutamine were prepared by electrospray ionization or by fast atom bombardment ionization and their fragmentation pathways elucidated using metastable ion studies, energy-resolved mass spectrometry and triple-stage mass spectrometry (MS(3)) experiments. Additional mechanistic information was obtained by exchanging the labile hydrogens for deuterium. Protonated H-Gln-Gly-OH fragments by loss of NH(3) and loss of H(2)O in metastable ion fragmentation; under collision-induced dissociation (CID) conditions loss of H-Gly-OH + CO from the [MH - NH(3)](+) ion forms the base peak C(4)H(6)NO(+) (m/z 84). Protonated dipeptides with an alpha-linkage, H-Glu-Xxx-OH, are characterized by elimination of H(2)O and by elimination of H-Xxx-OH plus CO to form the glutamic acid immonium ion of m/z 102. By contrast, protonated dipeptides with a gamma-linkage, H-Glu(Xxx-OH)-OH, do not show elimination of H(2)O or formation of m/z 102 but rather show elimination of NH(3), particularly in metastable ion fragmentation, and elimination of H-Xxx-OH to form m/z 130. Both the alpha- and gamma-dipeptides show formation of [H-Xxx-OH]H(+), with this reaction channel increasing in importance as the proton affinity (PA) of H-Xxx-OH increases. The characteristic loss of H(2)O and formation of m/z 102 are observed for the protonated alpha-tripeptide H-Glu-Gly-Phe-OH whereas the protonated gamma-tripeptide H-Glu(Gly-Gly-OH)-OH shows loss of NH(3) and formation of m/z 130 as observed for dipeptides with the gamma-linkage. Both tripeptides show abundant formation of the y(2)'' ion under CID conditions, presumably because a stable anhydride neutral structure can be formed. Under metastable ion conditions protonated dipeptides of structure H-Xxx-Glu-OH show abundant elimination of H(2)O whereas those of structure H-Xxx-Gln-OH show abundant elimination of NH(3). The importance of these reaction channels is much reduced under CID

  9. Measurement of Proton-Induced Transfer Reactions with JENSA

    Science.gov (United States)

    Chatterjee, Sidharth; Chipps, Kelly; Pain, Steven; Cizewski, Jolie; Jensa Collaboration

    2017-09-01

    Reaction measurements of radioactive nuclei on light targets are important to understanding the origin of and the trends in the structure of nuclei. To efficiently measure nuclear reactions, measurements require highly localized and pure light targets and need to accommodate arrays of light charged particles, gamma rays, and recoiling heavy ions. The Jet Experiments in Nuclear Structure and Astrophysics (JENSA) jet target system was designed to facilitate high resolution, low background nuclear reaction studies. To demonstrate the capability of the JENSA system, the 20Ne(p,3He)18F reaction was studied during the commissioning phase. The radioisotope 18F is one of the galactic gamma-ray sources targeted by next-generation space-based telescopes. In addition, the 20Ne(p,3He) reaction has not been previously used for the spectroscopic study of 18F. The JENSA system gives us the opportunity to study this reaction with high resolution and low background. The measurement was performed with a proton beam from the Holifield Radioactive Ion Beam Facility tandem on a neon jet of natural isotopic abundance from JENSA. The experimental setup of JENSA and preliminary results will be discussed. Oak Ridge National Laboratory; Rutgers University Department of Physics and Astronomy.

  10. Proton-induced knockout reactions with polarized and unpolarized beams

    Science.gov (United States)

    Wakasa, T.; Ogata, K.; Noro, T.

    2017-09-01

    Proton-induced knockout reactions provide a direct means of studying the single particle or cluster structures of target nuclei. In addition, these knockout reactions are expected to play a unique role in investigations of the effects of the nuclear medium on nucleon-nucleon interactions as well as the properties of nucleons and mesons. However, due to the nature of hadron probes, these reactions can suffer significant disturbances from the nuclear surroundings and the quantitative theoretical treatment of such processes can also be challenging. In this article, we review the experimental and theoretical progress in this field, particularly focusing on the use of these reactions as a spectroscopic tool and as a way to examine the medium modification of nucleon-nucleon interactions. With regard to the former aspect, the review presents a semi-quantitative evaluation of these reactions based on existing experimental data. In terms of the latter point, we introduce a significant body of evidence that suggests, although does not conclusively prove, the existence of medium effects. In addition, this paper also provides information and comments on other related subjects.

  11. Self-triggering reaction kinetics between nitrates and aluminium powder

    Energy Technology Data Exchange (ETDEWEB)

    Demichela, Micaela [SAfeR-Centro Studi su Sicurezza Affidabilita e Rischi, Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi, 24, I 10129 Torino (Italy)], E-mail: micaela.demichela@polito.it

    2007-09-05

    During the night between the 19 and 20 September 2003, a loud explosion occurred at about 3 km from the town of Carignano that was clearly heard at a distance of some tens of kilometres. The explosion almost completely destroyed most of the laboratories of the Panzera Company that were used for the production of fireworks. The results of the research activities that were carried out using a differential scanning calorimeter (DSC) on the same raw materials that made up the pyrotechnical mixture that exploded are reported in this paper. This activity was carried out to identify the dynamics of the accident. It proved possible to verify how the event was produced because of a slow exothermic reaction which, after about 8 h, caused the self-triggering of 120 kg of finished product. The detonation can therefore be put down to a runaway reaction in the solid phase, whose primogenial causes can be attributed to a still craftsman type production system, not conformed to the rigorous controls and inspections as those required by a safety management system for major risk plants, as the Panzera Company was.

  12. Investigation of GeV proton-induced spallation reactions

    International Nuclear Information System (INIS)

    Hilscher, D.; Herbach, C.-M.; Jahnke, U.

    2003-01-01

    A reliable and precise modeling of GeV proton-induced spallation reactions is indispensable for the design of the spallation module and the target station of future accelerator driven hybrid reactors (ADS) or spallation neutron sources (ESS), in particular, to provide precise predictions for the neutron production, the radiation damage of materials (window), and the production of radioactivity ( 3 H, 7 Be etc.) in the target medium. Detailed experimental nuclear data are needed for sensitive validations and improvements of the models, whose predictive power is strongly dependent on the correct physical description of the three main stages of a spallation reaction: (i) the Intra-Nuclear-Cascade (INC) with the fast heating of the target nucleus, (ii) the de-excitation due to pre-equilibrium emission including the possibility of multi-fragmentation, and (iii) the statistical decay of thermally excited nuclei by evaporation of light particles and fission in the case of heavy nuclei. Key experimental data for this endeavour are absolute production cross sections and energy spectra for neutrons and light charged-particles (LCPs), emission of composite particles prior and post to the attainment of an equilibrated system, distribution of excitation energies deposited in the nuclei after the INC, and fission probabilities. The correlations of these quantities are particularly important to detect and identify possible deficiencies of the theoretical modeling of the various stages of a spallation reaction. Systematic measurements of such data are furthermore needed over large ranges of target nuclei and incident proton energies. Such data has been measured with the NESSI detector. An overview of new and previous results will be given. (authors)

  13. Membrane introduction proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Alexander, M.; Boscaini, E.; Maerk, T.; Lindinger, W.

    2002-01-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) is a rapidly expanding field with multiple applications in ion physics, atmospheric chemistry, food chemistry, volatile organic compounds monitoring and biology. Initial studies that combine PTR-MS and membrane introduction mass spectrometry (MIMS) were researched and outlined. First using PTR-MS, certain fundamental physical properties of a poly-dimethylsiloxane (PDMS) membrane including solubilities and diffusion coefficients were measured. Second, it was shown how the chemical selectivity of the (PDMS) can be used to extend the capabilities of the PTR-MS instrument by eliminating certain isobaric interferences and excluding water from volatile organic compounds (VOCs). Experiments with mixtures of several VOCs (toluene, benzene, acetone, propanal, methanol) are presented. (nevyjel)

  14. Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

    Energy Technology Data Exchange (ETDEWEB)

    Leleux, P. [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

    1998-06-01

    In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

  15. Closure of the condensed-phase organic-nitrate reaction unreviewed safety question at Hanford site

    International Nuclear Information System (INIS)

    COWLEY, W.L.

    1999-01-01

    A discovery Unreviewed Safety Question (USQ) was declared on the underground waste storage tanks at the Hanford Site in May 1996. The USQ was for condensed-phase organic-nitrate reactions (sometimes called organic complexant reactions) in the tanks. This paper outlines the steps taken to close the USQ, and resolve the related safety issue. Several processes were used at the Hanford Site to extract and/or process plutonium. These processes resulted in organic complexants (for chelating multivalent cations) and organic extraction solvents being sent to the underground waste storage tanks. This paper addresses the organic complexant hazard. The organic complexants are in waste matrices that include inert material, diluents, and potential oxidizers. In the presence of oxidizing material, the complexant salts can be made to react exothermically by heating to high temperatures or by applying an external ignition source of sufficient energy. The first organic complexant hazard assessments focused on determining whether a hulk runaway reaction could occur, similar to the 1957 accident at Kyshtm (a reprocessing plant in the former U.S.S.R.). Early analyses (1977 through 1994) examined organic-nitrate reaction onset temperatures and concluded that a bulk runaway reaction could not occur at the Hanford Site because tank temperatures were well below that necessary for bulk runaway. Therefore, it was believed that organic-nitrate reactions were adequately described in the then current Authorization Basis (AB). Subsequent studies examined a different accident scenario, propagation resulting from an external ignition source (e.g., lightning or welding slag) that initiates a combustion front that propagates through the organic waste. A USQ evaluation determined that localized high energy ignition sources were credible, and that point source ignition of organic complexant waste was not adequately addressed i n the then existing AB. Consequently, the USQ was declared on the

  16. Closure of the condensed-phase organic-nitrate reaction USQ at hanford

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-06-24

    A discovery Unreviewed Safety Question (USQ) was declared on the underground waste storage tanks at the Hanford Site in May 1996. The USQ was for condensed-phase organic-nitrate reactions (sometimes called organic complexant reactions) in the tanks. This paper outlines the steps taken to close the USQ, and resolve the related safety issue. Several processes were used at the Hanford Site to extract and/or process plutonium. These processes resulted in organic complexants (for chelating multivalent cations) and organic extraction solvents being sent to the underground waste storage tanks. This paper addresses the organic complexant hazard. The organic complexants are in waste matrices that include inert material, diluents, and potential oxidizers. In the presence of oxidizing material, the complexant salts can be made to react exothermically by heating to high temperatures or by applying an external ignition source of sufficient energy. The first organic complexant hazard assessments focused on determining whether a hulk runaway reaction could occur, similar to the 1957 accident at Kyshtm (a reprocessing plant in the former U.S.S.R.). Early analyses (1977 through 1994) examined organic-nitrate reaction onset temperatures and concluded that a bulk runaway reaction could not occur at the Hanford Site because tank temperatures were well below that necessary for bulk runaway. Therefore, it was believed that organic-nitrate reactions were adequately described in the then current Authorization Basis (AB). Subsequent studies examined a different accident scenario, propagation resulting from an external ignition source (e.g., lightning or welding slag) that initiates a combustion front that propagates through the organic waste. A USQ evaluation determined that localized high energy ignition sources were credible, and that point source ignition of organic complexant waste was not adequately addressed i n the then existing AB. Consequently, the USQ was declared on the

  17. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

    A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

  18. Proton exchange in acid-base complexes induced by reaction coordinates with heavy atom motions

    Energy Technology Data Exchange (ETDEWEB)

    Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca [Steacie Institute for Molecular Sciences, National Research Council of Canada, Ontario, K1A 0R6 (Canada); Taghikhani, Mahdi [Department of Chemistry, Sharif Institute of Technology, Tehran (Iran, Islamic Republic of)

    2012-06-19

    Highlights: Black-Right-Pointing-Pointer Proton exchange in acid-base complexes is studied. Black-Right-Pointing-Pointer The structures, binding energies, and normal mode vibrations are calculated. Black-Right-Pointing-Pointer Transition state structures of proton exchange mechanism are determined. Black-Right-Pointing-Pointer In the complexes studied, the reaction coordinate involves heavy atom rocking. Black-Right-Pointing-Pointer The reaction coordinate is not simply localized in the proton movements. - Abstract: We extend previous work on nitric acid-ammonia and nitric acid-alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid-strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are <400 cm{sup -1}. This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm{sup -1}. Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  19. Proton exchange in acid–base complexes induced by reaction coordinates with heavy atom motions

    International Nuclear Information System (INIS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-01-01

    Highlights: ► Proton exchange in acid–base complexes is studied. ► The structures, binding energies, and normal mode vibrations are calculated. ► Transition state structures of proton exchange mechanism are determined. ► In the complexes studied, the reaction coordinate involves heavy atom rocking. ► The reaction coordinate is not simply localized in the proton movements. - Abstract: We extend previous work on nitric acid–ammonia and nitric acid–alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid–strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are −1 . This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm −1 . Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  20. Reactions of the nitrate radical with a series og reduced organic sulfur-compounds in air

    DEFF Research Database (Denmark)

    JENSEN, NR; HJORTH, J; LOHSE, C

    1992-01-01

    A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air...... reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO3 radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH3SCH3, CH3SH......) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct. For the reaction between NO3 and R-S-S-R type compounds, evidence for an addition-decomposition reaction, as the initial steps, was obtained. R-S-, R-S(O)., and R-S(O)2. appear...

  1. The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact

    Science.gov (United States)

    Rindelaub, Joel D.; Borca, Carlos H.; Hostetler, Matthew A.; Slade, Jonathan H.; Lipton, Mark A.; Slipchenko, Lyudmila V.; Shepson, Paul B.

    2016-12-01

    The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant

  2. Recent aspects of the proton transfer reaction in H-bonded complexes

    Science.gov (United States)

    Szafran, Mirosław

    1996-07-01

    Proton transfer processes cover a very wide range of situations and time scales and they are of great interest from the viewpoint of chemical reactions in solution. These processes can occur via thermally activated crossing or tunneling. This review considers various aspects of this many-faceted field. Spectroscopic, dielectric, colligative and energetic properties and structures of various species with H-bonds are examined. Proton transfer reactions in water and organic solvents, and the contribution of various H-bonded species and ions to these processes are discussed. Among other topics, this survey includes the effects of solvent, acid-base stoichiometry, concentration, temperature and impurity on proton transfer reactions in complexes of phenols and carboxylic acids with amines, pyridines and pyridine N-oxides. The contribution of the nonstoichiometric acid-base complexes and ionic species to the reversible proton transfer mechanism is discussed.

  3. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solutions based upon mixed quantum-classical approximation. I. Proton transfer reaction in water.

    Science.gov (United States)

    Yamada, Atsushi; Kojima, Hidekazu; Okazaki, Susumu

    2014-08-28

    In order to investigate proton transfer reaction in solution, mixed quantum-classical molecular dynamics calculations have been carried out based on our previously proposed quantum equation of motion for the reacting system [A. Yamada and S. Okazaki, J. Chem. Phys. 128, 044507 (2008)]. Surface hopping method was applied to describe forces acting on the solvent classical degrees of freedom. In a series of our studies, quantum and solvent effects on the reaction dynamics in solutions have been analysed in detail. Here, we report our mixed quantum-classical molecular dynamics calculations for intramolecular proton transfer of malonaldehyde in water. Thermally activated proton transfer process, i.e., vibrational excitation in the reactant state followed by transition to the product state and vibrational relaxation in the product state, as well as tunneling reaction can be described by solving the equation of motion. Zero point energy is, of course, included, too. The quantum simulation in water has been compared with the fully classical one and the wave packet calculation in vacuum. The calculated quantum reaction rate in water was 0.70 ps(-1), which is about 2.5 times faster than that in vacuum, 0.27 ps(-1). This indicates that the solvent water accelerates the reaction. Further, the quantum calculation resulted in the reaction rate about 2 times faster than the fully classical calculation, which indicates that quantum effect enhances the reaction rate, too. Contribution from three reaction mechanisms, i.e., tunneling, thermal activation, and barrier vanishing reactions, is 33:46:21 in the mixed quantum-classical calculations. This clearly shows that the tunneling effect is important in the reaction.

  4. Monte Carlo simulation of proton boron fusion reaction for radiation therapy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sun Mi; Yoon, Do Kun; Suh, Tae Suk [Catholic University of Korea, Seoul (Korea, Republic of)

    2016-05-15

    The principle of the proton boron fusion therapy (PBFT) is based on this reaction as the radiation therapy technique. First, because three alpha particles can contribute to the death of the tumor cell by the use of one proton, high therapy efficiency can be achieved by using smaller flux than conventional proton therapy or the boron neutron capture therapy (BNCT), after the thermal neutron was captured by the labeled boron in the tumor region, an alpha particle is emitted from the capture reaction point. An alpha particle induces the death of the tumor cell by the one capture reaction. However, three alpha particles are emitted from the point of the proton boron fusion reaction. If this reaction is applied to the radiation therapy, the therapy results could be more effective in inducing the death of tumor cells using a smaller flux. In addition, the proton's energy loss during its propagation through matter is described by the Bragg-peak. After the boron-labeled compound is accumulated in the tumor region, if the portion of the proton's maximum dose (Bragg-peak) is included at the tumor region, which is the boron uptake region (BUR), a dramatic therapy effect with less damage to normal tissue can be expected. This study was performed to introduce a therapy method using the proton boron fusion reaction and verify the theoretical validity of PBFT using Monte Carlo simulations. In this study, there are two parts of the simulation to confirm the validity of PBFT. First, the variation of the Bragg-peak of the proton depending on the location of the BUR was examined. The other simulation was performed to confirm the existence of the prompt gamma ray peak of 719 keV from energy spectrum simulation. PBFT method is still at the conceptual stage, the verification of its effectiveness is required for the use of a physical approach.

  5. Contribution of Proton Capture Reactions to the Ascertained ...

    Indian Academy of Sciences (India)

    Upakul Mahanta

    2017-11-27

    Nov 27, 2017 ... Abstract. The origin of the abundance pattern and also the (anti)correlation present among the elements found .... The paper is structured as follows. ... 2003) since its proton capture life- time is quite large in the considered temperature density condition. On the other hand 13C is a stable isotope of. Table 1.

  6. Proton cycling, buffering, and reaction stoichiometry in natural waters

    NARCIS (Netherlands)

    Hofmann, A.F.; Middelburg, J.J.; Soetaert, K.; Wolf-Gladrow, D.A.; Meysman, F.J.R.

    2010-01-01

    Ongoing acidification of the global ocean necessitates a solid understanding of how biogeochemical processes are driving proton cycling and observed pH changes in natural waters. The standard way of calculating the pH evolution of an aquatic system is to specify first how biogeochemical processes

  7. Probing the structure of unstable nuclei through the recoiled proton tagged knockout reaction

    International Nuclear Information System (INIS)

    Ye, Y.; Cao, Z.; Jiang, D.

    2010-01-01

    Recoiled proton tagged knockout reaction experiments were carried-out for 8 He at 82,5 MeV/u in RIKEN and for 6 He at 65 MeV/u in Lanzhou. The very preliminary results for the distinguish of the reaction mechanism are presented and compared to the kinematics calculation. (authors)

  8. [Immediate type reactions to proton pump inhibitors using pantoprazole and omeprazole as examples].

    Science.gov (United States)

    Dohr, J; Hunzelmann, N; Brown, A

    2018-02-01

    Proton pump inhibitors (PPIs) belong to the most frequently taken drugs worldwide. Hypersensitivity to these medications is rare, but can lead to severe immediate type reactions. Especially cross-reactivity between the different PPIs can occur. In this case series, we describe 4 patients with immediate type reactions to pantoprazole and/or omeprazole.

  9. Status of experimental data of proton-induced reactions for intermediate-energy nuclear data evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Yukinobu; Kawano, Toshihiko [Kyushu Univ., Fukuoka (Japan); Yamano, Naoki; Fukahori, Tokio

    1998-11-01

    The present status of experimental data of proton-induced reactions is reviewed, with particular attention to total reaction cross section, elastic and inelastic scattering cross section, double-differential particle production cross section, isotope production cross section, and activation cross section. (author)

  10. Aprotic solvent systems provide mechanistic windows for biomolecular reactions: nucleic acid proton exchange

    International Nuclear Information System (INIS)

    McConnell, B.; Tan, A.

    1986-01-01

    Detection of general acid-base catalysis of proton transfer reactions in aqueous cytidine (or adenosine) is completely obscured by the highly reactive endocyclic protonated species of the nucleobase, whose amino proton lifetime is much shorter than that of the neutral form. In aqueous solution, protonation of the nucleobase always accompanies protonation of the buffer catalyzing exchange. However, in DMSO/water mixtures this is not the case; aqueous protonated acetate or chloroacetate can be added to cytidine in DMSO solutions without further dissociation of the buffer or significant protonation of cytidine N-3. Under these conditions general acid catalysis is observed, which involves an H-bonded complex between cytidine (N-3) and the buffer acid. Increased amino proton exchange in response to H-bond donation to C(N-3) is further suggested by increased 1 H NMR saturation-recovery rates with the formation of G-C base-pairs in DMSO and by the inverse dependence of amino proton exchange on nucleoside concentration

  11. Specific Features of Intramolecular Proton Transfer Reaction in Schiff Bases

    Directory of Open Access Journals (Sweden)

    Aleksander Koll

    2003-06-01

    Full Text Available Abstract: The differences between the intramolecular proton transfer in Mannich and Schiff bases are discussed. The tautomeric forms being in equilibrium in both types of molecules are seriously different. In Mannich bases there are in equilibrium the forms of phenols and phenolates. In Schiff bases each of tautomers is strongly influenced by resonance between zwitterionic and keto structures. Despite the common opinion that the proton transfer forms in compounds with internal π-electronic coupling are mainly keto forms it is shown in this work, that in Schiff bases the content of keto structure is slightly less than zwitterionic one. Almost equal participation of both forms leads to effective resonance between them and stabilization of intramolecular hydrogen bond in this way.

  12. Sunflower oil ozonation. Following of the reaction by proton Nuclear Magnetic Resonance

    International Nuclear Information System (INIS)

    Diaz Gomez, Maritza F.

    2005-01-01

    Previous studies have demonstrated that the technique of Proton Nuclear Magnetic Resonance can be used for the pursuit of the reaction between the ozone and the unsaturated fatty acids. It's carried out the sunflower oil ozonization to different applied dose of ozone and the index of peroxides and the concentration of aldehydes are determined. The main reaction products were identified by Proton Nuclear Magnetic Resonance Spectroscopy (NMR 1 H). The intensities of the signs were used to follow the advance of the reaction between the ozone and the sunflower oil. It is was carried out until obtaining an index of peroxides of 1 202 mmol-equiv/kg. The intensities of the signs of the olefinic protons diminish with a gradual increment in the dose of applied ozone, but without ending up disappearing completely. The ozonides of Criegee obtained to applied dose of ozone of 107,1 mg/g were approximately bigger 7,4 times that those obtained at the beginning from the reaction to applied dose of ozone of 15,3 mg/g. The aldehydes protons were observed as a sign of weak intensity in all the spectra. The signs belonging to the olenifics protons of the hydroperoxides in d = 5,55 ppm increases with the increment of the applied dose of ozone. You concludes that to higher applied dose of ozone, haggler is the advance of the ozonization reaction, what belongs together with a bigger formation of oxygenated compounds

  13. Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

    International Nuclear Information System (INIS)

    Pyartman, A.K.

    1995-01-01

    Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

  14. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    Science.gov (United States)

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

  15. SU-D-304-07: Application of Proton Boron Fusion Reaction to Radiation Therapy

    International Nuclear Information System (INIS)

    Jung, J; Yoon, D; Shin, H; Kim, M; Suh, T

    2015-01-01

    Purpose: we present the introduction of a therapy method using the proton boron fusion reaction. The purpose of this study is to verify the theoretical validity of proton boron fusion therapy using Monte Carlo simulations. Methods: After boron is accumulated in the tumor region, the emitted from outside the body proton can react with the boron in the tumor region. An increase of the proton’s maximum dose level is caused by the boron and only the tumor cell is damaged more critically. In addition, a prompt gamma ray is emitted from the proton boron reaction point. Here we show that the effectiveness of the proton boron fusion therapy (PBFT) was verified using Monte Carlo simulations. Results: We found that a dramatic increase by more than half of the proton’s maximum dose level was induced by the boron in the tumor region. This increase occurred only when the proton’s maximum dose point was located within the boron uptake region (BUR). In addition, the 719 keV prompt gamma ray peak produced by the proton boron fusion reaction was positively detected. Conclusion: This therapy method features the advantages such as the application of Bragg-peak to the therapy, the accurate targeting of tumor, improved therapy effects, and the monitoring of the therapy region during treatment

  16. Observing Proton Transfer Reactions Inside the MALDI Plume: Experimental and Theoretical Insight into MALDI Gas-Phase Reactions

    Science.gov (United States)

    Mirabelli, Mario F.; Zenobi, Renato

    2017-08-01

    We evaluated the contribution of gas-phase in-plume proton transfer reactions to the formation of protonated and deprotonated molecules in the MALDI process. A split sample holder was used to separately deposit two different samples, which avoids any mixing during sample preparation. The two samples were brought very close to each other and desorbed/ionized by the same laser pulse. By using a combination of deuterated and non-deuterated matrices, it was possible to observe exclusively in-plume proton transfer processes. The hydrogen/deuterium exchange (HDX) kinetics were evaluated by varying the delayed extraction (DE) time, allowing the desorbed ions and neutrals to interact inside the plume for a variable period of time before being extracted and detected. Quantum mechanical calculations showed that the HDX energy barriers are relatively low for such reactions, corroborating the importance of gas-phase proton transfer in the MALDI plume. The experimental results, supported by theoretical simulations, confirm that the plume is a very reactive environment, where HDX reactions could be observed from 0 ns up to 400 ns after the laser pulse. These results could be used to evaluate the relevance of previously proposed (and partially conflicting) ionization models for MALDI.

  17. Two-proton transfer reactions on even Ni and Zn isotopes

    International Nuclear Information System (INIS)

    Boucenna, A.; Kraus, L.; Linck, I.; Tsan Ung Chan

    1988-01-01

    Two-proton transfer reactions induced by 112 MeV 12 C ions on even Ni and Zn isotopes are found to be less selective than the analogous two-neutron transfer reactions induced on the same targets in a similar incident energy range. The additional collective aspects observed in the proton transfer are examined in view of a semiphenomenological model of two quasi-particles coupled to a triaxial asymmetric rotor. Tentative spin and parity assignments emerge from this comparison, from crude shell model calculations and from systematic trends

  18. Analysis of trace gases at ppb levels by proton transfer reaction mass spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Lindinger, W.; Hansel, A.

    1996-01-01

    A proton transfer reaction mass spectrometry (PTR-MS) system has been developed which allows for on-line measurements of trace gas components with concentrations as low as 1 ppb. The method is based on reactions of H 3 O + ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of medical information obtained by means of breath analysis, of environmental trace analysis, and examples in the field of food chemistry demonstrate the wide applicability of the method. (Authors)

  19. Application of the re-circulating tracer well test method to determine nitrate reaction rates in shallow unconfined aquifers.

    Science.gov (United States)

    Burbery, Lee F; Flintoft, Mark J; Close, Murray E

    2013-02-01

    Five re-circulating tracer well tests (RCTWTs) have been conducted in a variety of aquifer settings, at four sites across New Zealand. The tests constitute the first practical assessment of the two-well RCTWT methodology described by Burbery and Wang (Journal of Hydrology, 2010; 382:163-173) and were aimed at evaluating nitrate reaction rates in situ. The performance of the RCTWTs differed significantly at the different sites. The RCTWT method performed well when it was applied to determine potential nitrate reaction rates in anoxic, electro-chemically reductive, nitrate-free aquifers of volcanic lithology, on the North Island, New Zealand. Regional groundwater flow was not fast-flowing in this setting. An effective first-order nitrate reaction rate in the region of 0.09 d(-1) to 0.26 d(-1) was determined from two RCTWTs applied at one site where a reaction rate of 0.37 d(-1) had previously been estimated from a push-pull test. The RCTWT method performed poorly, however, in a fast-flowing, nitrate-impacted fluvio-glacial gravel aquifer that was examined on the South Island, New Zealand. This setting was more akin to the hypothetical physiochemical problem described by Burbery and Wang (2010). Although aerobic conditions were identified as the primary reason for failure to measure any nitrate reaction in the gravel aquifer, failure to establish significant interflow in the re-circulation cell due to the heterogeneous nature of the aquifer structure, and natural variability exhibited in nitrate contaminant levels of the ambient groundwater further contributed to the poor performance of the test. Our findings suggest that in practice, environmental conditions are more complex than assumed by the RCTWT methodology, which compromises the practicability of the method as one for determining attenuation rates in groundwater based on tracing ambient contaminant levels. Although limited, there appears to be a scope for RCTWTs to provide useful information on potential

  20. Application of the re-circulating tracer well test method to determine nitrate reaction rates in shallow unconfined aquifers

    Science.gov (United States)

    Burbery, Lee F.; Flintoft, Mark J.; Close, Murray E.

    2013-02-01

    Five re-circulating tracer well tests (RCTWTs) have been conducted in a variety of aquifer settings, at four sites across New Zealand. The tests constitute the first practical assessment of the two-well RCTWT methodology described by Burbery and Wang (Journal of Hydrology, 2010; 382:163-173) and were aimed at evaluating nitrate reaction rates in situ. The performance of the RCTWTs differed significantly at the different sites. The RCTWT method performed well when it was applied to determine potential nitrate reaction rates in anoxic, electro-chemically reductive, nitrate-free aquifers of volcanic lithology, on the North Island, New Zealand. Regional groundwater flow was not fast-flowing in this setting. An effective first-order nitrate reaction rate in the region of 0.09 d- 1 to 0.26 d- 1 was determined from two RCTWTs applied at one site where a reaction rate of 0.37 d- 1 had previously been estimated from a push-pull test. The RCTWT method performed poorly, however, in a fast-flowing, nitrate-impacted fluvio-glacial gravel aquifer that was examined on the South Island, New Zealand. This setting was more akin to the hypothetical physiochemical problem described by Burbery and Wang (2010). Although aerobic conditions were identified as the primary reason for failure to measure any nitrate reaction in the gravel aquifer, failure to establish significant interflow in the re-circulation cell due to the heterogeneous nature of the aquifer structure, and natural variability exhibited in nitrate contaminant levels of the ambient groundwater further contributed to the poor performance of the test. Our findings suggest that in practice, environmental conditions are more complex than assumed by the RCTWT methodology, which compromises the practicability of the method as one for determining attenuation rates in groundwater based on tracing ambient contaminant levels. Although limited, there appears to be a scope for RCTWTs to provide useful information on potential

  1. Quantifying in-stream nitrate reaction rates using continuously-collected water quality data

    Science.gov (United States)

    Matthew Miller; Anthony Tesoriero; Paul Capel

    2016-01-01

    High frequency in situ nitrate data from three streams of varying hydrologic condition, land use, and watershed size were used to quantify the mass loading of nitrate to streams from two sources – groundwater discharge and event flow – at a daily time step for one year. These estimated loadings were used to quantify temporally-variable in-stream nitrate processing ...

  2. Statistical properties from high resolution proton resonance reactions

    International Nuclear Information System (INIS)

    Mitchell, G.E.

    1980-01-01

    High resolution proton resonance measurements are of great value in the study of statistical and non-statistical effects involving compound nuclear resonances. First, these measurements provide valuable information on both global and local properties of widths and spacings. This information is a valuable supplement to that obtained from neutron experiments. Second, as Mahaux and Weidenmueller summarize: Isobaric analog resonances provide the best understood examples of doorway states. They are thus well suited for an experimental check of the theory. Third, the measurement of channel spin interference effects provide the most sensitive test yet for certain aspects of statistical theories, as well as providing examples of new types of intermediate structure. Examples are discussed

  3. Mechanisms of Peroxynitrite Mediated Nitration of Tyrosine

    Science.gov (United States)

    Gunaydin, Hakan; Houk, K. N.

    2009-01-01

    The mechanisms of tyrosine nitration by peroxynitrous acid or nitrosoperoxycarbonate were investigated with the CBS-QB3 method. Either the protonation of peroxynitrite, or a reaction with carbon dioxide gives a reactive peroxide intermediate. Peroxynitrous acid mediated nitration of phenol occurs via the unimolecular decomposition to give nitrogen dioxide and hydroxyl radicals. Nitrosoperoxycarbonate also undergoes unimolecular decomposition to give carbonate and nitrogen dioxide radicals. The reactions of tyrosine with the hydroxyl or carbonate radicals give a phenoxy radical intermediate. The reaction of the nitrogen dioxide with this radical intermediate followed by tautomerization gives nitrated tyrosine in both cases. According to CBS-QB3 calculations, the rate-limiting step for the nitration of phenol is the decomposition of peroxynitrous acid or of nitrosoperoxycarbonate. PMID:19374346

  4. SU-F-T-140: Assessment of the Proton Boron Fusion Reaction for Practical Radiation Therapy Applications Using MCNP6

    International Nuclear Information System (INIS)

    Adam, D; Bednarz, B

    2016-01-01

    Purpose: The proton boron fusion reaction is a reaction that describes the creation of three alpha particles as the result of the interaction of a proton incident upon a 11B target. Theoretically, the proton boron fusion reaction is a desirable reaction for radiation therapy applications in that, with the appropriate boron delivery agent, it could potentially combine the localized dose delivery protons exhibit (Bragg peak) and the local deposition of high LET alpha particles in cancerous sites. Previous efforts have shown significant dose enhancement using the proton boron fusion reaction; the overarching purpose of this work is an attempt to validate previous Monte Carlo results of the proton boron fusion reaction. Methods: The proton boron fusion reaction, 11B(p, 3α), is investigated using MCNP6 to assess the viability for potential use in radiation therapy. Simple simulations of a proton pencil beam incident upon both a water phantom and a water phantom with an axial region containing 100ppm boron were modeled using MCNP6 in order to determine the extent of the impact boron had upon the calculated energy deposition. Results: The maximum dose increase calculated was 0.026% for the incident 250 MeV proton beam scenario. The MCNP simulations performed demonstrated that the proton boron fusion reaction rate at clinically relevant boron concentrations was too small in order to have any measurable impact on the absorbed dose. Conclusion: For all MCNP6 simulations conducted, the increase of absorbed dose of a simple water phantom due to the 11B(p, 3α) reaction was found to be inconsequential. In addition, it was determined that there are no good evaluations of the 11B(p, 3α) reaction for use in MCNPX/6 and further work should be conducted in cross section evaluations in order to definitively evaluate the feasibility of the proton boron fusion reaction for use in radiation therapy applications.

  5. Measurements of acetone yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Wisthaler, A.; Lindinger, W.; Jensen, N.R.; Winterhalter, R.; Hjorth, J.

    2002-01-01

    Biogenic VOCs (Volatile Organic Compounds) are known to be emitted in large quantities from vegetation exceeding largely global emissions of anthropogenic VOCs. Monoterpenes (C 10 H 16 ) are important constituents of biogenic VOC emissions. The atmospheric oxidation of Monoterpenes appears to be a potentially relevant source of acetone in the atmosphere. Acetone is present as a significant trace gas in the whole troposphere and influences in particular the atmospheric chemistry in the upper troposphere by substantially contributing to the formation of HO x radicals and peroxyacetyl nitrate (PAN). Acetone is formed promptly, following attack by the OH-radical on the terpene, via a series of highly unstable radical intermediates, but it is also formed slowly via the degradation of stable non-radical intermediates such as pinonaldehyde and nopinone. In order to investigate the relative importance of these processes, the OH-initiated oxidation of α-pinene and β-pinene was investigated in a chamber study, where the concentrations of monoterpenes, acetone, pinonaldehyde and nopinone were monitored by proton-transfer-reaction mass spectrometry (PTR-MS). It was found that significant amounts of acetone are formed directly, whenα-pinene and β-pinene are oxidized by the OH radical, but also secondary chemistry (degradation of primary reaction products) gives a significant contribution to the formation of acetone from monoterpenes. It can be concluded that atmospheric oxidation of monoterpenes contributes a significant fraction to the global acetone source strength. (nevyjel)

  6. A simple functional form for proton-208Pb total reaction cross sections

    International Nuclear Information System (INIS)

    Majumdar, S.; Deb, P.K.; Amos, K.

    2001-01-01

    A simple functional form has been found that gives a good representation of the total reaction cross sections for the scattering from 208 Pb of protons with energies in the range 30 to 300 MeV. The ratios of the total reaction cross sections calculated under this approximations compared well (to within a few percent) to those determined from the microscopic optical model potentials

  7. Angular distributions of four proton groups from the b10(d, p)b11 reaction

    NARCIS (Netherlands)

    Endt, P.M.; Paris, C.H.; Jongerius, H.M.; Valckx, F.P.G.

    Angular distributions have been measured of four proton groups from the B10(d, p)B11 reaction corresponding to transitions to the groundstate (group (0)) and the three lowest excited states of B11 (groups (1), (2) and (3)). A thin target of natural boron was bombarded with 310 keV deuterons and

  8. Offline thermal-desorption proton-transfer-reaction mass spectrometry to study composition of organic aerosol

    NARCIS (Netherlands)

    Timkovsky, J.; Dusek, U.|info:eu-repo/dai/nl/314134166; Henzing, J. S.; Kuipers, T. L.; Röckmann, T.|info:eu-repo/dai/nl/304838233; Holzinger, R.|info:eu-repo/dai/nl/337989338

    2015-01-01

    We present a novel approach to study the organic composition of aerosol filter samples using thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) in the laboratory. The method is tested and validated based on the comparison with in situ TD-PTR-MS measurements. In general, we

  9. Promotion of a Ti-Mediated Mannich Reaction by a Proton Source.

    Science.gov (United States)

    Limanto, John; Yoshikawa, Naoki; Reamer, Robert A; Tan, Lushi; Brunskill, Andrew; Reibarkh, Mikhail

    2016-01-15

    Low temperature NMR studies revealed that a diastereoselective Mannich reaction between a phenyl oxazolidone-derived titanium enolate and an aromatic aldimine was found to occur only after introduction of a proton source. While various protic additives could be used to promote the transformation, the best results were obtained using AcOH to afford the corresponding Mannich products in high diastereoselectivities and yields.

  10. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    International Nuclear Information System (INIS)

    Janev, R.K.; Kato, T.; Wang, J.G.

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  11. Immediate and Delayed Hypersensitivity Reactions to Proton Pump Inhibitors: Evaluation and Management.

    Science.gov (United States)

    Otani, Iris M; Banerji, Aleena

    2016-03-01

    PPIs are among the most commonly administered medications in the USA and are generally well tolerated. Immediate and delayed immune-mediated hypersensitivity reactions are rare but increasingly recognized adverse effects of proton pump inhibitors (PPIs). Immediate hypersensitivity reactions can occur due to IgE-mediated hypersensitivity to PPIs and can be evaluated by immediate hypersensitivity skin testing and oral provocation challenge testing. A desensitization protocol can be used when PPI use cannot be avoided in an allergic patient. Delayed hypersensitivity reactions to PPIs have also been reported. Occupational exposures causing cutaneous reactions to PPIs are the most commonly reported delayed hypersensitivity reaction, followed by drug-induced subacute cutaneous lupus erythematosus. This review presents a summary of the clinical presentation, diagnostic evaluation, and management of immune-mediated hypersensitivity reactions to PPIs.

  12. Study on possible explosive reactions of sodium nitrate-bitumen mixtures initiated by a shock wave

    International Nuclear Information System (INIS)

    Savornin, J.; Vasseur, C.

    1986-01-01

    Potential hazards of the mixture sodium nitrate-bitumen obtained by embedding in bitumen liquid radioactive effluents concentrated by evaporation are studied in case of accidental shock wave. A theoretical evaluation based on thermodynamical data show a low probability, nevertheless different from zero. No explosion occurred in tests realized in severe conditions. In conclusion there is no risk of detonation of large quantity of bitumen-nitrates stored in 200-liter drum in radioactive waste storage [fr

  13. The Nitrite-Scavenging Properties of Catechol, Resorcinol, and Hydroquinone: A Comparative Study on Their Nitration and Nitrosation Reactions.

    Science.gov (United States)

    Lu, Yunhao; Dong, Yanzuo; Li, Xueli; He, Qiang

    2016-10-14

    The nitration and nitrosation reactions of catechol, resorcinol, and hydroquinone (0.05 mmol/L) with sodium nitrite (0.05 mmol/L) at pH 3 and 37 °C were studied by using liquid chromatography and mass spectrometry (LC-MS) and atom charge analysis, which was aimed to provide chemical insight into the nitrite-scavenging behavior of polyphenols. The 3 benzenediols showed different mechanisms to scavenge nitrite due to their differences in hydroxyl position. Catechol was nitrated with 1 NO 2 group at the hydroxyl oxygen, and resorcinol was nitrosated with 2 NO groups at the C 2 and C 4 (or C 6 ) positions of the benzene ring. Hydroquinone could scavenge nitrite through both nitration and nitrosation mechanisms. The nitrated hydroquinone had 1 NO 2 group at the hydroxyl oxygen in the molecule, while the nitrosated 1 containing 2 NO groups at the benzene ring might have 3 structure probabilities. The results may provide a structure-activity understanding on the nitrite-scavenging property of polyphenols, so as to promote their application in the food industry for the removal of possibly toxic nitrites found in many vegetables and often in processed meat products. © 2016 Institute of Food Technologists®.

  14. Multi-neutron and proton transfer reactions in deep inelastic heavy-ion collisions

    International Nuclear Information System (INIS)

    Yoshida, Satoshi; Patra, S.K.; Takigawa, Noboru

    1997-01-01

    We discuss the characteristics of multi-nucleon transfer reactions in deep-inelastic heavy-ion collisions. We calculate the number of transferred neutrons and protons based on a macroscopic approach using a Fokker-Planck equation, and compare with experimental data. We show that our macroscopic approach well reproduces the experimental data concerning the ratio of the mass to the proton numbers in the projectile-like fragment as a function of the energy loss from the relative motion. Our calculations, however, do not reproduce the recent data, where the transferred number of neutrons and protons are measured separately. The net flow of nucleons evolve even in opposite directions in the experimental data and in our transport theory. (author)

  15. Experimental determination of proton induced reaction cross sections on {sup nat}Ni near threshold energy

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, Md. Shuza [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Chakraborty, Animesh Kumer [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics; Spellerberg, Stefan; Spahn, Ingo; Qaim, Syed M. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Shariff, Md. Asad; Das, Sopan [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Rashid, Md. Abdur [Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics

    2016-08-01

    A newly developed facility at the 3 MV Tandem Accelerator at Dhaka for measurement of proton induced reaction cross sections in the energy region below 5 MeV is outlined and tests for the beam characterization are described. The results were validated by comparison with the well-known excitation function of the {sup 64}Ni(p, n){sup 64}Cu reaction. Excitation functions of the reactions {sup nat}Ni(p, x){sup 60,61}Cu, {sup nat}Ni(p, x){sup 55,57,58m+g}Co and {sup nat}Ni(p, x){sup 57}Ni were also measured from threshold to 16 MeV using the stacked-foil technique, whereby irradiations were performed with 5 MeV protons available at the Tandem Accelerator and 16.7 MeV protons at the BC 1710 cyclotron at Juelich, Germany. The radioactivity was measured using HPGe γ-ray detectors. A few results are new, the others strengthen the database. In particular, the results of the reaction {sup nat}Ni(p, x){sup 61}Cu below 3 MeV could serve as beam monitor.

  16. The proton transfer reaction in malonaldehyde derivatives: Substituent effects and quasi-aromaticity of the proton bridge

    International Nuclear Information System (INIS)

    Palusiak, Marcin; Simon, Silvia; Sola, Miquel

    2007-01-01

    The proton transfer in malonaldehyde and in some of its derivatives have been considered in order to study the interrelation between the reaction barrier and the π-delocalization in the quasi-ring. A set of simple and mostly common substituents having different properties in resonance effect according to values of substituents constants were chosen in order to simulate the influence of substitution in position 2 or in position 1 (or 3) of malonaldehyde on the quasi-aromaticity and H-bonding. The following substituents have been taken into consideration: NO, NO 2 , CN, CHO, F, H, CH 3 , OCH 3 , OH, and NH 2 . Our results show that when the substituent is attached at position 2 of the quasi-ring, the resonance effect predominates over the field/inductive effect which leads to changes in H-bonding and quasi-aromaticity of the ring motif, while in the case of 1(3) substitution the field/inductive effect is significantly more effective influencing the HB strength, and thus, the proton transfer barrier. Somehow counterintuitively, for the 1(3) substituted systems, the most stable isomer is the one having the weakest HB and lower aromaticity. The reason for this surprising behaviour is discussed

  17. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

    International Nuclear Information System (INIS)

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  18. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

    Science.gov (United States)

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  19. Protons in ceria and their roles in SOFC electrode reactions from thermodynamic and SIMS analyses

    Energy Technology Data Exchange (ETDEWEB)

    Yokokawa, H.; Horita, T.; Sakai, N.; Yamaji, K.; Brito, M.E.; Xiong, Y.-P.; Kishimoto, H. [Energy Electronics Institute, National Institute of Advanced Industrial Science and Technology AIST, Central No. 5 1-1 Higashi, 305-8565, Tsukuba, Ibaraki (Japan)

    2004-10-29

    This paper reviews our recent activities of investigations on protons and other defects in ceria and their relations to the solid oxide fuel cell (SOFC) electrode reactions. Thermodynamic analyses have revealed that the chemical potential of dopant YO{sub 1.5} is a good measure for indicating the configuration of oxide ion vacancies in ceria and zirconia; that is, the large negative value of YO{sub 1.5} chemical potential in YSZ corresponds to the next nearest neighbor position of vacancies to the dopant site, whereas in doped ceria, the nearest neighbor position is favored and it corresponds to the less-negative chemical potential. Further thermodynamic analyses based on activities for CeO{sub 1.5} and YO{sub 1.5} have revealed that protons solubility and hole conductivity are governed mainly by the activity of YO{sub 1.5}, whereas electron conductivity is well interpreted with CeO{sub 1.5} concentration calculated from the activities of CeO{sub 2} and CeO{sub 1.5}. Analysis of the oxygen isotope exchange reaction rate that is enhanced in the presence of water vapor was made based on recognition that adsorption and desorption can be taken place at different sites which are connected with hopping processes; when a reaction-related elementary process is enhanced by water vapor, such a hopping process may become the rate-limiting step; this can explain why essentially the same activation energy was obtained for the surface reaction rate and the oxide ion diffusivity. In the electrochemical reactions, effects due to water vapors have been analyzed based on the fact that protons can be migrated in ceria due to the high proton solubility. For anodes, the oxygen transfer mechanism via water vapor from the electrolyte surface or from the electrolyte/anode/gas triple-phase boundaries to nickel surface is suggested under the assumption that protons in nickel can be transferred to ceria or consumed at the three-phase boundaries. This mechanism can explain why ceria can help

  20. Analysis for mass distribution of proton-induced reactions in intermediate energy range

    CERN Document Server

    Xiao Yu Heng

    2002-01-01

    The mass and charge distribution of residual products produced in the spallation reactions needs to be studied, because it can provide useful information for the disposal of nuclear waste and residual radioactivity generated by the spallation neutron target system. In present work, the Many State Dynamical Model (MSDM) is based on the Cascade-Exciton Model (CEM). The authors use it to investigate the mass distribution of Nb, Au and Pb proton-induced reactions in energy range from 100 MeV to 3 GeV. The agreement between the MSDM simulations and the measured data is good in this energy range, and deviations mainly show up in the mass range of 90 - 150 for the high energy proton incident upon Au and Pb

  1. Study of the reaction. gamma. p. --> delta. /sup + +/. pi. /sup -/ on polarized protons

    Energy Technology Data Exchange (ETDEWEB)

    Belyaev, A.; Get' man, V.; Gorbenko, V.; Gushchin, V.; Derkach, A.; Zhebrovskii, Y.; Zayats, A.; Karnaukhov, I.; Kolesnikov, L.; Lukhanin, A.; Rubashkin, A.; Sobol' , M.; Sorokin, P.; Sporov, E.; Telegin, Y.

    1982-02-01

    We have measured for the first time the asymmetry of the cross section for the reaction ..gamma..p..--> delta../sup + +/..pi../sup -/ on polarized protons. The measurements were made at E/sub ..gamma../ = 660 MeV in the range of pion emission angles 45--120/sup 0/ c.m.s. The experimental data obtained are compared with the theoretical predictions.

  2. Experimental cross-sections for proton-induced nuclear reactions on Mo-nat

    Czech Academy of Sciences Publication Activity Database

    Červenák, Jaroslav; Lebeda, Ondřej

    2016-01-01

    Roč. 380, AUG (2016), s. 32-49 ISSN 0168-583X R&D Project s: GA MŠk(CZ) LM2011019 Institutional support: RVO:61389005 Keywords : cross-sections * excitation functions * proton-induced nuclear reactions * natural molybdenum * Mo-99 * Tc-99m * Tc96m+g * Tc-95m * thick target yields * U-120M cyclotron Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.109, year: 2016

  3. Dynamics of Reactions Involving Hydrogen Atom or Proton Transfer Symmetric Case.

    Science.gov (United States)

    1980-09-01

    rates; tunneling; atom and proton transfer. 20 ABSTRACT ( ContInuo an revese side It necoee.,y and idenlify by block moibor) / C_ -3 A method is... improve the understanding of the dynamics of the reaction and facilitate its computational treatment. If a quasi-constant of the motion does exist for a...neglect of nonadiabatic effects and (ii) use of polar coordinates to treat the dynamics. Each could be improved , e. g. , in (i) by including perturbatively

  4. Structures revealed in the neutron-proton mass spectrum in the deuteron break-up reaction

    Science.gov (United States)

    Siemiarczuk, T.; Stepaniak, J.; Zieliński, P.

    1983-09-01

    A sample of “non-spectator” events in the dp→(pn) p break-up reaction at 3.3 GeV/ c deuteron momentum is studied using films from 1 m hydrogen bubble chamber. The effective mass distribution of two nucleons from the deuteron break-up exhibits enhancements near the sum of neutron and proton masses and at Mpn = 2020 and 2130 MeV.

  5. Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

    Science.gov (United States)

    Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

    1987-01-01

    The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

  6. Measurement of activation cross sections of the proton induced nuclear reactions on palladium

    International Nuclear Information System (INIS)

    Ditroi, F.; Tarkanyi, F.; Takacs, S.; Mahunka, I.; Csikai, J.; Hermanne, A.; Uddin, M.S.; Hagiwara, M.; Baba, M.; Ido, T.

    2007-01-01

    Excitation functions of proton induced reactions on Pd are important for medical radioisotope production, for activation analysis, for development of low activation materials and other purposes. No experimental data exist in the literature for low and medium energy range protons. A detailed study of the excitation functions was performed up to 80 MeV proton energy by using the stacked foil irradiation technique and gamma-ray spectrometry. The irradiations were carried out at the external beam lines of the AVF cyclotron at the Tohoku University, Japan (80 and 70 MeV) and the CGR 560 cyclotron at the Vrije Universiteit Brussels (38, 29 and 17 MeV). The beam intensity, the incident energy and the energy degradation were controlled by a method based on flux constancy via normalization to the parallel measured excitation functions of nat Al(p,x) 22,24 Na and nat Cu(p,x) 56,58 Co, 62,65 Zn monitor reactions. Excitation functions for direct and cumulative cross sections have been measured for the production of 105mg,106m,110m Ag, 101 Pd, 101 mRh and 97 Ru radionuclei. Calculations for the excitation functions using the Alice-IPPE code were performed with a view to estimate the weight of the different contributing reactions and to check the trend and the magnitude of the obtained experimental data. (author)

  7. Field theoretical approach to proton-nucleus reactions. I - One step inelastic scattering

    International Nuclear Information System (INIS)

    Eiras, A.; Kodama, T.; Nemes, M.C.

    1988-01-01

    In this work we obtain a closed form expression to the double differential cross section for one step proton-nucleus reaction within a field theoretical framework. Energy and momentum conservation as well as nuclear structure effects are consistently taken into account within the field theoretical eikonal approximation. In our formulation the kinematics of such reaction is not dominated by the free nucleon-nucleon cross section but a new factor which we call relativistic differential cross section in a Born Approximation. (author) [pt

  8. p-process nucleosynthesis via proton-capture reactions in thermonuclear supernovae explosions

    Directory of Open Access Journals (Sweden)

    Endres Anne

    2015-01-01

    Full Text Available Model calculations within the framework of the so-called γ process show an underproduction of the p nucleus with the highest isotopic abundace 92Mo. This discrepancy can be narrowed by taking into account the alternative production site of a type Ia supernova explosion. Here, the nucleus 92Mo can be produced by a sequence of proton-capture reactions. The amount of 92Mo nuclei produced via this reaction chain is most sensitive to the reactions 90Zr(p,γ and 91Nb(p,γ. Both rates have to be investigated experimentally to study the impact of this nucleosynthesis aspect on the long-standing 92Mo-problem. We have already measured the proton-capture reaction on 90Zr using high-resolution in-beam γ-ray spectroscopy. In this contribution, we will present our preliminary results of the total cross sections as well as the partial cross sections. Furthermore, we plan to measure the 91Nb(p,γ reaction soon. Due to the radioactive target material, the 91Nb nuclei have to be produced prior to the experiment. The current status of this production will be presented in this contribution.

  9. The neutron-proton charge-exchange amplitudes measured in the dp {yields} ppn reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mchedlishvili, D.; Chiladze, D. [Tbilisi State University, High Energy Physics Institute, Tbilisi (Georgia); Forschungszentrum Juelich, Institut fuer Kernphysik and Juelich Centre for Hadron Physics, Juelich (Germany); Barsov, S.; Dzyuba, A. [Petersburg Nuclear Physics Institute, High Energy Physics Department, Gatchina (Russian Federation); Carbonell, J. [Universite Paris-Sud, IN2P3-CNRS, Institut de Physique Nucleaire, Orsay Cedex (France); Dymov, S. [JINR, Laboratory of Nuclear Problems, Dubna (Russian Federation); Universitaet Erlangen-Nuernberg, Physikalisches Institut II, Erlangen (Germany); Engels, R.; Gebel, R.; Hartmann, M.; Kacharava, A.; Kamerdzhiev, V.; Lehrach, A.; Lorentz, B.; Maier, R.; Ohm, H.; Prasuhn, D.; Rathmann, F.; Serdyuk, V.; Seyfarth, H.; Stein, H.J.; Stockhorst, H.; Stroeher, H. [Forschungszentrum Juelich, Institut fuer Kernphysik and Juelich Centre for Hadron Physics, Juelich (Germany); Glagolev, V. [JINR, Laboratory of High Energies, Dubna (Russian Federation); Grigoryev, K.; Mikirtychyants, M.; Mikirtychyants, S.; Valdau, Yu. [Forschungszentrum Juelich, Institut fuer Kernphysik and Juelich Centre for Hadron Physics, Juelich (Germany); Petersburg Nuclear Physics Institute, High Energy Physics Department, Gatchina (Russian Federation); Goslawski, P.; Khoukaz, A.; Mielke, M.; Papenbrock, M. [Universitaet Muenster, Institut fuer Kernphysik, Muenster (Germany); Keshelashvili, I. [Tbilisi State University, High Energy Physics Institute, Tbilisi (Georgia); University of Basel, Department of Physics, Basel (Switzerland); Komarov, V.; Kulikov, A. [JINR, Laboratory of Nuclear Problems, Dubna (Russian Federation); Kulessa, P. [H. Niewodniczanski Institute of Nuclear Physics PAN, Krakow (Poland); Lomidze, N.; Nioradze, M.; Tabidze, M. [Tbilisi State University, High Energy Physics Institute, Tbilisi (Georgia); Macharashvili, G. [Tbilisi State University, High Energy Physics Institute, Tbilisi (Georgia); JINR, Laboratory of Nuclear Problems, Dubna (Russian Federation); Merzliakov, S. [Forschungszentrum Juelich, Institut fuer Kernphysik and Juelich Centre for Hadron Physics, Juelich (Germany); JINR, Laboratory of Nuclear Problems, Dubna (Russian Federation); Steffens, E. [Universitaet Erlangen-Nuernberg, Physikalisches Institut II, Erlangen (Germany); Trusov, S. [Forschungszentrum Rossendorf, Institut fuer Kern- und Hadronenphysik, Dresden (Germany); Uzikov, Yu. [JINR, Laboratory of Nuclear Problems, Dubna (Russian Federation); M. V. Lomonosov Moscow State University, Department of Physics, Moscow (Russian Federation); Wilkin, C. [UCL, Physics and Astronomy Department, London (United Kingdom)

    2013-04-15

    The unpolarised differential cross section and the two deuteron tensor analysing powers A{sub xx} and A{sub yy} of the vector dp {yields} {l_brace}pp{r_brace}{sub s}n charge-exchange reaction have been measured with the ANKE spectrometer at the COSY storage ring. Using deuteron beams with energies 1.2, 1.6, 1.8, and 2.27GeV, data were obtained for small momentum transfers to a {l_brace}pp{r_brace}{sub s} system with low excitation energy. The results at the three lower energies are consistent with impulse approximation predictions based upon the current knowledge of the neutron-proton amplitudes. However, at 2.27GeV, where these amplitudes are far more uncertain, agreement requires a reduction in the overall double-spin-flip contribution, with an especially significant effect in the longitudinal direction. These conclusions are supported by measurements of the deuteron-proton spin-correlation parameters C{sub x,x} and C{sub y,y} that were carried out in the vector dvector p {yields} {l_brace}pp{r_brace}{sub s}n reaction at 1.2 and 2.27GeV. The values obtained for the proton analysing power A{sub y}{sup p} also suggest the need for a radical re-evaluation of the neutron-proton elastic scattering amplitudes at the higher energy. It is therefore clear that such measurements can provide a valuable addition to the neutron-proton database in the charge-exchange region. (orig.)

  10. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

    2015-01-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  11. The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2017-09-07

    A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

  12. Theory of proton coupled electron transfer reactions: Assessing the Born-Oppenheimer approximation for the proton motion using an analytically solvable model

    International Nuclear Information System (INIS)

    Zheng Renhui; Jing Yuanyuan; Chen Liping; Shi Qiang

    2011-01-01

    Graphical abstract: An analytically solvable model was employed to study proton coupled electron transfer reactions. Approximated theories are assessed, and vibrational coherence is observed in case of small reorganization energy. Research highlights: → The Duschinsky rotation effect in PCET reactions. → Assessment of the BO approx. for proton motion using an analytically solvable model. → Vibrational coherence in PCET in the case of small reorganization energy. - Abstract: By employing an analytically solvable model including the Duschinsky rotation effect, we investigated the applicability of the commonly used Born-Oppenheimer (BO) approximation for separating the proton and proton donor-acceptor motions in theories of proton coupled electron transfer (PCET) reactions. Comparison with theories based on the BO approximation shows that, the BO approximation for the proton coordinate is generally valid while some further approximations may become inaccurate in certain range of parameters. We have also investigated the effect of vibrationally coherent tunneling in the case of small reorganization energy, and shown that it plays an important role on the rate constant and kinetic isotope effect.

  13. Phase transitions and radiative proton-capture nuclear reactions in metallic hydrogen

    International Nuclear Information System (INIS)

    Setsuo, Ichimaru

    2002-01-01

    Protons being the lightest nuclei, metallic hydrogen exhibits the features of the quantum liquids most relevant to the enormously enhanced nuclear reactions; thermonuclear and pycno-nuclear rates and associated enhancement factors of radiative proton captures of high-Z nuclei as well as of deuterons are evaluated. Atomic states of high-Z impurities are determined in a way consistent with the equations of state and screening characteristics of the metallic hydrogen. Rates of pycno-nuclear p-d reactions are prodigiously high at densities ≥ 20 g/cm 3 , pressures ≥ 1 Gbar, and temperatures ≥ 950 K near the conditions of solidification. It is also predicted that proton captures of nuclei such as C, N, O, and F may take place at considerable rates owing to strong screening by K-shell electrons, if the densities ≥ 60-80 g/cm 3 , the pressures ≥ 7-12 Gbar, and the temperatures just above solidification. Phase diagrams of metallic hydrogen describing solidification thus count essentially in the pycno-nuclear processes. A novel scheme of pycno-nuclear fusion reactors that utilizes p-d reactions in metallic hydrogen is presented; it eliminates those ferocious problems inherent in the conventional thermonuclear-fusion reactors employing d-t reactions: The fusion yields of p-d reactions, i.e., stable 3 He and γ -rays (at 5.494 MeV), would not produce hazardous radioactive byproducts; absent likewise are the instabilities associated with confinement of the plasmas at ultrahigh temperatures. (author)

  14. Deamidation reactions of protonated asparagine and glutamine investigated by ion spectroscopy.

    Science.gov (United States)

    Kempkes, Lisanne J M; Martens, Jonathan K; Grzetic, Josipa; Berden, Giel; Oomens, Jos

    2016-02-28

    Deamidation of Asn and Gln residues is a primary route for spontaneous post-translational protein modification. Several structures have been proposed for the deamidation products of the protonated amino acids. Here we verify these structures by ion spectroscopy, as well as the structures of parallel and sequential fragmentation products. Infrared ion spectroscopy using the free electron laser FELIX has been applied to the reaction products from deamidation of protonated glutamine and asparagine in a tandem mass spectrometer. IR spectra were recorded over the 800-1900 cm(-1) spectral range by infrared multiple-photon dissociation (IRMPD) spectroscopy. Molecular structures of the fragment ions are derived from comparison of the experimental spectra with spectra predicted for different candidate structures by density functional theory (DFT) calculations. [AsnH(+) -NH3](+) is found to possess a 3-aminosuccinic anhydride structure protonated on the amino group. The dissociation reaction involving loss of H2O and CO forms a linear immonium ion. For [GlnH(+)-NH3](+), the N-terminal nitrogen acts as the nucleophile leading to an oxo-proline product ion structure. For [GlnH(+)-NH3](+), a sequential loss of [CO + H2O] is found, leading to a pyrolidone-like structure. We also confirm by IR spectroscopy that dehydration of protonated aspartic acid (AspH(+)) and glutamic acid (GluH(+)) leads to identical structures as to those found for the loss of NH3 from AsnH(+) and GlnH(+). The structure determined for AsnH(+) is in agreement with the suggested structure derived from measured and computed activation energies. IR ion spectra for the NH3 -loss product from GlnH(+) establish that a different reaction mechanism occurs for this species as compared to AsnH(+). For both amino acids, loss of NH3 occurs from the side chain. Copyright © 2016 John Wiley & Sons, Ltd.

  15. Double proton transfer reactions in the formic acid dimer in solution

    International Nuclear Information System (INIS)

    Kohanoff, J.; Estrin, D.A.; Laria, D.; Abashkin, Y.

    2000-06-01

    The issue of multiple proton transfer (PT) reactions in solution is addressed by performing molecular dynamics simulations for a formic acid dimer embedded in a water cluster. The reactant species is treated quantum mechanically, within a density functional approach, while the solvent is represented by a classical model. By constraining different distances within the dimer we analyze the PT process in a variety of situations representative of more complex environments. Free energy profiles are presented, and analyzed in terms of typical solvated configurations extracted from the simulations. A decrease in the PT barrier height upon solvation is rationalized in terms of a transition state which is more polarized than the stable states. The dynamics of the double PT process is studied in a low-barrier case and correlated with that of the polarization fluctuations of the solvent. Cooperative effects in the motion of the two protons are observed in two different situations: when the solvent polarization does not favor the transfer of one of the two protons and when the motion of the two protons is not synchronized. This body of observations is correlated with structural and dynamical local properties of the solvent in the vicinity of the reactant. (author)

  16. Electron transfer reactions of 1-phenyl-4-vinylpyrazole mediated by cerium(IV) ammonium nitrate

    International Nuclear Information System (INIS)

    Pitarch-Vinuesa, M.; Miranda, M.A.; Medio-Simon, M.; Sepulveda-Arques, J.

    1993-01-01

    The title compound is converted into the cyclic ethers 5 and the alcohol 6 upon treatment with ceric ammonium nitrate in acetone. Using methanol as a solvent the dimethoxy derivative 9 and the nitrate ester 10 are formed. No cross cycloaddition is observed in the presence of olefins such as ethyl vinyl ether, DMAD, or indene; however, with cyclopentadiene as co-reagent a mixture of the exo-endo Diels-Alder adducts 14 involving the vinylic system of 1 as 2π component is obtained. The results are rationalized through the intermediacy of the radical cation 1 .+ , generated by single electron transfer (SET) from the neutral precursor 1 to Ce(IV)

  17. Excitation functions of radionuclides produced by proton induced reactions on gadolinium targets

    International Nuclear Information System (INIS)

    Challana, M.B.; Comsana, M.N.H.; Moawadb, G.S.; Abou-Zeid, M.A.

    2008-01-01

    Cross section study for proton induced reaction on natural Gadolinium targets were performed. Excitation functions for the reactions n atGd(p,x) 152m+g , 154m,154g Tb from threshold up to E p = 18 MeV have been measured employing the stacked foil activation technique, and using high resolution HPGe gamma spectrometry. Utilizing the simultaneous measurement of the excitation function of n atCu(p,x) 62 Zn, n atCu(p,x) 63 Zn, and n atCu(p,x) 65 Zn as monitor reactions. The theoretical analysis of the excitation functions has been done employing both ALICE-91 and EMPIRE-II codes. In general, theoretical calculations agree well with the experimental data. A significant contribution of pre-equilibrium component has been observed at these energies

  18. Theoretical study of cross sections of proton-induced reactions on cobalt

    Directory of Open Access Journals (Sweden)

    Mustafa Yiğit

    2018-04-01

    Full Text Available Nuclear fusion may be among the strongest sustainable ways to replace fossil fuels because it does not contribute to acid rain or global warming. In this context, activated cobalt materials in corrosion products for fusion energy are significant in determination of dose levels during maintenance after a coolant leak in a nuclear fusion reactor. Therefore, cross-section studies on cobalt material are very important for fusion reactor design. In this article, the excitation functions of some nuclear reaction channels induced by proton particles on 59Co structural material were predicted using different models. The nuclear level densities were calculated using different choices of available level density models in ALICE/ASH code. Finally, the newly calculated cross sections for the investigated nuclear reactions are compared with the experimental values and TENDL data based on TALYS nuclear code. Keywords: Cobalt, Nuclear Structural Materials, Reaction Cross Section, TENDL Database

  19. Parity nonconserving asymmetries in the resonance scattering and nuclear reactions induced by polarized protons

    International Nuclear Information System (INIS)

    Dumitrescu, O.; Horoi, M.; Carstoiu, F.; Stratan, G.

    1989-01-01

    The parity-nonconserving nucleon-nucleon (PNC-NN) interaction studied in nuclear systems provides an unique window on ΔS=0 hadronic weak processes. To check the predictions concerning the interactions between weak hadronic currents, low energy nuclear physics processes appear to be very suitable. Considering the nuclear reactions induced by polarized protons as low energy nuclear processes we derive expressions for the longitudinal and irregular transverse PNC analysing powers, when the reactions take place via parity mixed resonances. Applications for 13 C(p-vector,p) 13 C, 15 N(p-vector,p) 15 N and 15 N(p-vector,α) 12 C resonance reactions are done. (author). 23 refs, 4 figs, 2 tabs

  20. C-H activation in reactions of protonated hydrogen peroxide with propane

    Science.gov (United States)

    Adlhart, Christian; Uggerud, Einar

    2006-08-01

    Reactions between deuterium labelled alkanes and H2OOH+ have been investigated by conducting gas phase reactions within the cell of an FT-ICR mass spectrometer. Propane is exceptional in giving off a hydride (deuteride) thereby producing the propyl cation and two water molecules, as well as demonstrating high activity for proton induced H/D exchange. The detailed mechanistic scenario has been modelled using accurate quantum chemical methods (MP2 and G3). The calculations show that hydrogen exchange takes place via a synchronous flip-flop mechanism. Results of reactions with partially deuteriated propanes demonstrate quite exceptional regioselectivity for hydride abstraction in favour of the secondary positions (2-H) compared to the primary (1-H). This observation is understood on the basis of transition state theory.

  1. Effect of the method to prepare platinum-based nanoparticles versus electro-reduction of nitrates and proton adsorption; Efecto de la ruta de preparacion de nanoparticulas basadas en platino versus la electro-reduccion de nitratos y la adsorcion de protones

    Energy Technology Data Exchange (ETDEWEB)

    Estudillo-Wong, L.A.; Torres-Santillan, E.; Arce-Estrada, E.M.; J.R. Vargas-Garcia [Escuela Superior de Ingenieria Quimica e Industrias Extractivas (ESIQIE), IPN, Mexico D.F. (Mexico)]. E-mail: amanzor@ipn.mx; Alonso-Vante, N. [Universite de Poitiers, Poitiers (France); Manzo-Robledo, A. [Escuela Superior de Ingenieria Quimica e Industrias Extractivas (ESIQIE), IPN, Mexico D.F. (Mexico)

    2009-09-15

    The electro-reduction of nitrate ions (ERN) was carried out in an alkaline medium on platinum-tin nanoparticles, synthesized with metal organic chemical vapor deposition (MOCVD) and carbonyl complex route (CCR) and supported on carbon nanotubes (CNT) and Vulcan carbon. These catalysts were deposited on 4.0 mm diameter vitreous carbon. Cyclic voltametry was used to evaluate this reduction reaction. Different current magnitudes for hydrogen evolution reaction (HER) and ERN were found. Nevertheless, the proton and ion nitrate adsorption processes on the surface of the catalysts evaluated presented a potential range of -0.7 to -1.0V/SCE, indicating that the reaction mechanism is similar. Studies of nitrate concentrations indicate that the magnitude of the reduction current decreases and, in addition, different magnitudes are presented according to the catalyst/substrate used. These variations are explained by local disorder, due to the nature of the substrate, and the size of the nanoparticles resulting from the preparation method. Indirectly, the kinetic parameters calculated enable clarifying these suppositions. [Spanish] La electro-reduccion de iones nitrato (NER) sobre nano-particulas de platino-(estano) sintetizadas via MOCVD (metal organic chemical vapor deposition) y via carbonilo (carbonyl complex route, CCR) soportadas sobre nano-tubos de carbon (NTC) y carbon Vulcan (C), fue llevada a cabo en medio alcalino. Estos catalizadores fueron depositados sobre carbon vitreo de 4.0mm de diametro. La tecnica de voltametria ciclica fue utilizada para evaluar dicha reaccion de reduccion. Diferentes magnitudes de corriente versus la reaccion de evolucion de hidrogeno (HER) y la NER fueron encontradas. Sin embargo, los procesos de adsorcion de protones e iones nitrato en la superficie de los catalizadores evaluados se presentan en un intervalo de potencial de -0.7 a -1.0V/SCE, indicando que el mecanismo de reaccion es similar. Estudios en funcion de la concentracion de

  2. Proton induced nuclear reactions on cadmium up 17 MeV

    International Nuclear Information System (INIS)

    Al-Abyad, M.

    2012-01-01

    The cross-sections of proton induced reactions on nat Cd targets was studied in the energy range from threshold up to 17 MeV, using a stacked-foil irradiation technique and classical gamma-spectroscopy. We measured the formation cross-sections of the radioisotopes 109g,110m,110,111g,113m,114m,115m,116m In The obtained excitation functions were compared with the earlier published data and the theoretical model calculations by the codes ALICE-IPPE, EMPIRE and TALYS .

  3. Remeasurement and compilation of excitation function of proton induced reactions on iron for activation techniques

    International Nuclear Information System (INIS)

    Takacs, S.; Vasvary, L.; Tarkanyi, F.

    1994-01-01

    Excitation functions of proton induced reactions on nat Fe(p, xn) 56 Co have been remeasured in the energy region up to 18 MeV using stacked foil technique and standard high resolution gamma-ray spectrometry at the Debrecen MGC-20E cyclotron. Compilation of the available data measured between 1959 and 1993 has been made. The corresponding excitation functions have been reviewed, critical comparison of all the available data was done to obtain the most accurate data set. The feasibility of the evaluated data set was checked by reproducing experimental calibration curves for TLA by calculation. (orig.)

  4. Production of terbium-152 by heavy ion reactions and proton induced spallation

    CERN Document Server

    Allen, B J; Sarkar, S; Beyer, G; Morel, Christian; Byrne, A P

    2001-01-01

    Terbium-152 (Tb-152) is of potential value as a radiotracer for radiolanthanides in positron emission tomography. We report the production of Tb-152 by heavy ion reactions at the ANU Tandem accelerator, and by the spallation method at the CERN proton accelerator using the on-line ISOLDE separator, obtaining microcurie and millicurie yields, respectively. After purification, a phantom image in PET is obtained which shows the feasibility of using Tb-152 for monitoring the kinetics of Tb-149 and other radiolanthanides. However, the current availability of this radioisotope will be restricted to major nuclear physics research centres. (7 refs).

  5. Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets

    Energy Technology Data Exchange (ETDEWEB)

    Celler, A; Hou, X [University of British Columbia, Vancouver, BC, Canada, (Canada); Benard, F; Ruth, T, E-mail: aceller@physics.ubc.ca, E-mail: xinchi@phas.ubc.ca, E-mail: fbenard@bccrc.ca, E-mail: truth@triumf.ca [BC Cancer Agency, Vancouver, BC (Canada)

    2011-09-07

    Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and {sup 100}Mo(p,2n){sup 99m}Tc reaction has been considered. In this context, the production yields of {sup 99m}Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of {sup 99m}Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for {sup 99m}Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of {sup 99m}Tc and its ratio relative to {sup 99g}Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

  6. Reactions of acids with naphthyridine-functionalized ferrocenes: protonation and metal extrusion.

    Science.gov (United States)

    Sadhukhan, Nabanita; Sarkar, Mithun; Ghatak, Tapas; Rahaman, S M Wahidur; Barbour, Leonard J; Bera, Jitendra K

    2013-02-04

    Reaction of 1,8-naphthyrid-2-yl-ferrocene (FcNP) with a variety of acids affords protonated salts at first, whereas longer reaction time leads to partial demetalation of FcNP resulting in a series of Fe complexes. The corresponding salts [FcNP·H][X] (X = BF(4) or CF(3)SO(3) (1)) are isolated for HBF(4) and CF(3)SO(3)H. Reaction of FcNP with equimolar amount of CF(3)CO(2)H for 12 h affords a neutral complex [Fe(FcNP)(2)(O(2)CCF(3))(2)(OH(2))(2)] (2). Use of excess acid gave a trinuclear Fe(II) complex [Fe(3)(H(2)O)(2)(O(2)CCF(3))(8)(FcNP·H)(2)] (3). Three linear iron atoms are held together by four bridging trifluoroacetates and two aqua ligands in a symmetric fashion. Reaction with ethereal solution of HCl afforded [(FcNP·H)(3)(Cl)][FeCl(4)](2) (4) irrespective of the amount of the acid used. Even the picric acid (HPic) led to metal extrusion giving rise to [Fe(2)(Cl)(2)(FcNP)(2)(Pic)(2)] (5) when crystallized from dichloromethane. Metal extrusion was also observed for CF(3)SO(3)H, but an analytically pure compound could not be isolated. The demetalation reaction proceeds with an initial proton attack to the distal nitrogen of the NP unit. Subsequently, coordination of the conjugate base to the electrophilic Fe facilitates the release of Cp rings from metal. The conjugate base plays an important role in the demetalation process and favors the isolation of the Fe complex as well. The 1,1'-bis(1,8-naphthyrid-2-yl)ferrocene (FcNP(2)) does not undergo demetalation under identical conditions. Two NP units share one positive charge causing the Fe-Cp bonds weakened to an extent that is not sufficient for demetalation. X-ray structure of the monoprotonated FcNP(2) reveals a discrete dimer [(FcNP(2)·H)](2)[OTf](2) (6) supported by two N-H···N hydrogen bonds. Crystal packing and dispersive forces associated with intra- and intermolecular π-π stacking interactions (NP···NP and Cp···NP) allow the formation of the dimer in the solid-state. The protonation and

  7. Thermonuclear reaction rates for proton induced reactions on 41K and neutron induced reactions on 41Ca

    International Nuclear Information System (INIS)

    Sevior, M.E.; Anderson, M.R.; Mitchell, L.W.; Kennett, S.R.; Sargood, D.G.

    1981-01-01

    The yield of γ-rays from the reaction 41 K(p,γ) 42 Ca has been measured as a function of bombarding energy over the range 0.68-2.48 MeV and from the reaction 41 K(p,αγ) 38 Ar over the range 1.20-2.48 MeV, and the yield of neutrons from the reaction 41 K(p,n) 41 Ca has been measured from threshold to a bombarding energy of 2.48 MeV. The energy dependence of the cross sections is compared with statistical-model calculations with global optical model parameters in all particle channels. The calculations seriously overestimate the cross section for the neutron channel and underestimate those for the other channels. A reduction in the imaginary well depth in the neutron channel leads to good agreement with all the data. Statistical-model calculations with this modified set of parameters are then carried out to provide cross sections for the astrophysically interesting reactions 41 Ca(n,p) 41 K, 41 Ca(n,α) 38 Ar, and 41 Ca(n,γ) 42 Ca. Thermonuclear reaction rates are calculated for all six reactions over the temperature range 5 x 10 8 - 10 1 0K which includes the range of temperatures of interest in nucleosynthesis calculations

  8. Intramolecular proton transfer and tunnelling reactions of hydroxyphenylbenzoxazole derivatives in Xenon at 15 K

    Energy Technology Data Exchange (ETDEWEB)

    Walla, Peter J. [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany) and Department for Biophysical Chemistry, Technical University of Brunswick, Institute for Physical and Theoretical Chemistry, Hans-Sommerstr. 10, D-38106 Braunschweig (Germany)]. E-mail: pwalla@gwdg.de; Nickel, Bernhard [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany)

    2005-06-06

    We investigated the site dependence and the tunnelling processes of the intramolecular proton and deuteron transfer in the triplet state of the compounds 2-(2'-hydroxy-4'-methylphenyl)benzoxazole (m-MeHBO) and 2-(2'-hydroxy-3'-methylphenyl)benzoxazoles (o-MeHBO) and their deuterio-oxy analogues in a solid xenon matrix. After singlet excitation there occurs an ultrafast intramolecular enol {yields} keto proton transfer and subsequent intersystem crossing mainly to the keto triplet state. In the triplet state of m-MeHBO, the proton transfer back to the lower enol triplet state is governed by tunnelling processes. In o-MeHBO, however, the enol triplet state is higher and therefore normally no tunnel reaction can be observed. Because of the external heavy atom-effect in a xenon matrix, we were able to investigate the reverse enol-keto-tunnelling after exciting directly the enol triplet state of deuterated o-MeHBO. The time constants of the reverse enol-keto tautomerization are similar to those of the normal keto-enol tautomerization. In a xenon matrix, the observed site-selective phosphorescence spectra are very well-resolved vibrationally. This allowed the study of the tunnel rates in different well-defined sites. The vibrational energies obtained in the spectra are in good agreement with vibrational energies found in resonant Raman and IR spectra of 2-(2'-hydroxyphenyl)benzoxazole (HBO)

  9. Determination of nitrite/nitrate in human biological material by the simple Griess reaction.

    Science.gov (United States)

    Guevara, I; Iwanejko, J; Dembińska-Kieć, A; Pankiewicz, J; Wanat, A; Anna, P; Gołabek, I; Bartuś, S; Malczewska-Malec, M; Szczudlik, A

    1998-06-22

    Since a number of pathological processes such as septic shock, inflammation, graft rejection, diabetes, etc. are associated with a release of nitric oxide (NO), rapid and accurate methods of monitoring of NO concentration are of interest. Various methods for measurement of nitrite and nitrate (NO2-, NO3- ) -- the stable metabolites of NO -- are commonly used for this purpose. In this paper we have shown that the proper Griess procedure for nitrite determination significantly increases the sensitivity of this method. This procedure, supplemented with deproteinization and reduction of nitrates to nitrites in the presence of NADPH-sensitive reductase, can be successfully applied for measurement of NOx levels in human body fluids (serum, urine and CSF). Deproteinization of samples with methanol/diethylether is required and does not influence the sensitivity of detection of NO metabolites. The recovery of the method is 88%+/-6% (n = 30). The NOx concentrations measured by this procedure ranged from 25.0 to 39.0 micromol/l in blood, 4.6 to 14.6 micromol/l in CSF and 0.37 to 2.52 mmol/l (adjusted to creatinine concentration) in urine. The coefficient of variation for this method was between 1.3-2.2%. This method can also be recommended for measurement of NOx produced by cells in tissue cell culture.

  10. Cross section measurements of proton capture reactions on Se isotopes relevant to the astrophysical p process

    Science.gov (United States)

    Foteinou, V.; Harissopulos, S.; Axiotis, M.; Lagoyannis, A.; Provatas, G.; Spyrou, A.; Perdikakis, G.; Zarkadas, Ch.; Demetriou, P.

    2018-03-01

    Cross sections of proton capture reactions on 74Se, 78Se, and 80Se have been measured at incident beam energies from 2 to 6 MeV, 1.7 to 3 MeV, and 1.5 to 3.5 MeV, respectively. In the case of Se,8078, cross sections were obtained from in-beam γ -angular distribution measurements, whereas for the 74Se isotope they were derived from off-beam activity measurements. The measured cross sections were compared with calculations performed with the nuclear reaction code talys (version 1.6). A good agreement between theory and experiment was found. Astrophysical S factors and reaction rates deduced from the experimental and calculated cross sections were also compared and the impact of different nuclear ingredients in the calculations on the reaction rates was investigated. It was found that, for certain combinations of nuclear input models, the reaction rates obtained at temperatures relevant to p -process nucleosynthesis differ by a factor 2 at the most, differences that are well within the acceptable deviations of calculated p -nuclei abundances and observations.

  11. Operando Phonon Studies of the Protonation Mechanism in Highly Active Hydrogen Evolution Reaction Pentlandite Catalysts.

    Science.gov (United States)

    Zegkinoglou, Ioannis; Zendegani, Ali; Sinev, Ilya; Kunze, Sebastian; Mistry, Hemma; Jeon, Hyo Sang; Zhao, Jiyong; Hu, Michael Y; Alp, E Ercan; Piontek, Stefan; Smialkowski, Mathias; Apfel, Ulf-Peter; Körmann, Fritz; Neugebauer, Jörg; Hickel, Tilmann; Roldan Cuenya, Beatriz

    2017-10-18

    Synthetic pentlandite (Fe 4.5 Ni 4.5 S 8 ) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be beneficial for its catalytic performance, but the role of sulfur vacancies and the mechanism determining the reaction kinetics are still unknown. We have performed electrochemical operando studies of the vibrational dynamics of pentlandite under hydrogen evolution reaction conditions using 57 Fe nuclear resonant inelastic X-ray scattering. Comparing the measured Fe partial vibrational density of states with density functional theory calculations, we have demonstrated that hydrogen atoms preferentially occupy substitutional positions replacing pre-existing sulfur vacancies. Once all vacancies are filled, the protonation proceeds interstitially, which slows down the reaction. Our results highlight the beneficial role of sulfur vacancies in the electrocatalytic performance of pentlandite and give insights into the hydrogen adsorption mechanism during the reaction.

  12. Two-proton pickup studies with the (6Li,8B) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Weisenmiller, R.B.

    1976-12-03

    The (/sup 6/Li,/sup 8/B) reaction has been investigated on targets of /sup 26/Mg, /sup 24/Mg, /sup 16/O, /sup 13/C, /sup 12/C, /sup 11/B, /sup 10/B, and /sup 9/Be at a bombarding energy of 80.0 MeV, and on targets of /sup 16/O, /sup 12/C, /sup 9/Be, /sup 7/Li, and /sup 6/Li at a bombarding energy of 93.3 MeV. Only levels consistent with direct, single-step two-proton pickup reaction mechanisms were observed to be strongly populated. On T/sub z/ = 0 targets, the spectroscopic selectivity of this reaction resembles that of the analogous (p,t) reaction. Additionally, these data demonstrate the dominance of spatially symmetric transfer of the two protons. On T/sub z/ greater than 0 targets the (/sup 6/Li,/sup 8/B) reaction was employed to locate two previously unreported levels (at 7.47 +- 0.05 MeV and 8.86 +- 0.07 MeV) in the T/sub z/ = 2 nuclide /sup 24/Ne and to establish the low-lying 1p-shell states in the T/sub z/ = /sup 3///sub 2/ nuclei /sup 11/Be, /sup 9/Li, and /sup 7/He. However, no evidence was seen for any narrow levels in the T/sub z/ = /sup 3///sub 2/ nuclide /sup 5/H nor for any narrow excited states in /sup 7/He. The angular distributions reported here are rather featureless and decrease monotonically with increasing angle. This behavior can be shown by a semi-classical reaction theory to be a consequence of the reaction kinematics. A semi-classical approach also suggests that the kinematic term in the transition matrix element is only weakly dependent upon the angular momentum transfer (which is consistent with simple Distorted Wave Born Approximation calculations). However, only qualitative agreement was obtained between the observed relative transition yields and semi-classical predictions, using the two-nucleon coefficients of fractional parentage of Cohen and Kurath, probably due to the limitations of the semi-classical reaction theory.

  13. Laboratory Research. [spectroscopic analysis, photochemical reactions, and proton irradiation of ice

    Science.gov (United States)

    Donn, B.

    1981-01-01

    To properly interpret the rapidly growing body of data from comet observations, many types of laboratory measurements are needed. These include: (1) molecular spectroscopy in the visible, ultraviolet, infrared and microwave region of the spectra; (2) laser fluorescent spectroscopy of photofragments; (3) laboratory cross-section or reaction rate measurements using flow tube techniques, fluorescent spectroscopy detection for neutrals and ion-molecule reaction techniques; (4) experiments to simulate solar-wind interactions with comets; (5) studies of the properties and behavior of ice mixtures; (6) experiments on the sublimation rate of ice, and the phase transition from amorphous to crystalline ice; (7) investigations of the irradiation of ice; and (8) the electron impact dissociation and excitation of molecules of cometary interest. A nearly completed experiment on the proton irradiation of ice is described.

  14. Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

    Science.gov (United States)

    Erickson, M. H.; Wallace, H. W.; Jobson, B. T.

    2012-02-01

    A new approach was developed to measure the total abundance of long chain alkanes (C12 and above) in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS). These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1), monocyclic aromatics, and an ion group with formula CnH2n-1 (m/z 97, 111, 125, 139). The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m-3 to 100 μg m-3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.

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

    Science.gov (United States)

    Doan, Thuc N.; Fujihara, Akimasa

    2018-03-01

    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 d-glucose units, such as d-maltose or 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+( l-Trp)( d-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+( d-Trp)( d-maltose). For 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 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.

  16. Effect of free-particle collisions in high energy proton and pion-induced nuclear reactions

    International Nuclear Information System (INIS)

    Jacob, N.P. Jr.

    1975-07-01

    The effect of free-particle collisions in simple ''knockout'' reactions of the form (a,aN) and in more complex nuclear reactions of the form (a,X) was investigated by using protons and pions. Cross sections for the 48 Ti(p,2p) 47 Sc and the 74 Ge(p,2p) 73 Ga reactions were measured from 0.3 to 4.6 GeV incident energy. The results indicate a rise in (p,2p) cross section for each reaction of about (25 +- 3) percent between the energies 0.3 and 1.0 GeV, and are correlated to a large increase in the total free-particle pp scattering cross sections over the same energy region. Results are compared to previous (p,2p) excitation functions in the GeV energy region and to (p,2p) cross section calculations based on a Monte Carlo intranuclear cascade-evaporation model. Cross section measurements for (π/sup +-/, πN) and other more complex pion-induced spallation reactions were measured for the light target nuclei 14 N, 16 O, and 19 F from 45 to 550 MeV incident pion energy. These measurements indicate a broad peak in the excitation functions for both (π,πN) and (π,X) reactions near 180 MeV incident energy. This corresponds to the large resonances observed in the free-particle π + p and π - p cross sections at the same energy. Striking differences in (π,πN) cross section magnitudes are observed among the light nuclei targets. The experimental cross section ratio sigma(π - ,π - n)/sigma(π + ,πN) at 180 MeV is 1.7 +- 0.2 for all three targets. The experimental results are compared to previous pion and analogous proton-induced reactions, to Monte Carlo intranuclear cascade-evaporation calculations, and to a semi-classical nucleon charge exchange model. (108 references) (auth)

  17. Study of proton-deuteron break-up reaction in exclusive experiment at 1 GeV

    International Nuclear Information System (INIS)

    Aleshin, N.P.; Belostotskij, S.L.; Dotsenko, Yu.V.

    1987-07-01

    The exclusive proton-deuteron break-up reaction pD yields ppn was studied at 1 GeV. Differential cross sections and polarizations of the final protons were measured in the range of neutron-spectator momenta 0 3 3 <0.2 GeV/c, respectively. The data obtained are well described within the framework of impulse approximation with the Paris wave function of the deuteron. (author)

  18. Extension of PENELOPE to protons: simulation of nuclear reactions and benchmark with Geant4.

    Science.gov (United States)

    Sterpin, E; Sorriaux, J; Vynckier, S

    2013-11-01

    Describing the implementation of nuclear reactions in the extension of the Monte Carlo code (MC) PENELOPE to protons (PENH) and benchmarking with Geant4. PENH is based on mixed-simulation mechanics for both elastic and inelastic electromagnetic collisions (EM). The adopted differential cross sections for EM elastic collisions are calculated using the eikonal approximation with the Dirac-Hartree-Fock-Slater atomic potential. Cross sections for EM inelastic collisions are computed within the relativistic Born approximation, using the Sternheimer-Liljequist model of the generalized oscillator strength. Nuclear elastic and inelastic collisions were simulated using explicitly the scattering analysis interactive dialin database for (1)H and ICRU 63 data for (12)C, (14)N, (16)O, (31)P, and (40)Ca. Secondary protons, alphas, and deuterons were all simulated as protons, with the energy adapted to ensure consistent range. Prompt gamma emission can also be simulated upon user request. Simulations were performed in a water phantom with nuclear interactions switched off or on and integral depth-dose distributions were compared. Binary-cascade and precompound models were used for Geant4. Initial energies of 100 and 250 MeV were considered. For cases with no nuclear interactions simulated, additional simulations in a water phantom with tight resolution (1 mm in all directions) were performed with FLUKA. Finally, integral depth-dose distributions for a 250 MeV energy were computed with Geant4 and PENH in a homogeneous phantom with, first, ICRU striated muscle and, second, ICRU compact bone. For simulations with EM collisions only, integral depth-dose distributions were within 1%/1 mm for doses higher than 10% of the Bragg-peak dose. For central-axis depth-dose and lateral profiles in a phantom with tight resolution, there are significant deviations between Geant4 and PENH (up to 60%/1 cm for depth-dose distributions). The agreement is much better with FLUKA, with deviations within

  19. Extension of PENELOPE to protons: Simulation of nuclear reactions and benchmark with Geant4

    International Nuclear Information System (INIS)

    Sterpin, E.; Sorriaux, J.; Vynckier, S.

    2013-01-01

    Purpose: Describing the implementation of nuclear reactions in the extension of the Monte Carlo code (MC) PENELOPE to protons (PENH) and benchmarking with Geant4.Methods: PENH is based on mixed-simulation mechanics for both elastic and inelastic electromagnetic collisions (EM). The adopted differential cross sections for EM elastic collisions are calculated using the eikonal approximation with the Dirac–Hartree–Fock–Slater atomic potential. Cross sections for EM inelastic collisions are computed within the relativistic Born approximation, using the Sternheimer–Liljequist model of the generalized oscillator strength. Nuclear elastic and inelastic collisions were simulated using explicitly the scattering analysis interactive dialin database for 1 H and ICRU 63 data for 12 C, 14 N, 16 O, 31 P, and 40 Ca. Secondary protons, alphas, and deuterons were all simulated as protons, with the energy adapted to ensure consistent range. Prompt gamma emission can also be simulated upon user request. Simulations were performed in a water phantom with nuclear interactions switched off or on and integral depth–dose distributions were compared. Binary-cascade and precompound models were used for Geant4. Initial energies of 100 and 250 MeV were considered. For cases with no nuclear interactions simulated, additional simulations in a water phantom with tight resolution (1 mm in all directions) were performed with FLUKA. Finally, integral depth–dose distributions for a 250 MeV energy were computed with Geant4 and PENH in a homogeneous phantom with, first, ICRU striated muscle and, second, ICRU compact bone.Results: For simulations with EM collisions only, integral depth–dose distributions were within 1%/1 mm for doses higher than 10% of the Bragg-peak dose. For central-axis depth–dose and lateral profiles in a phantom with tight resolution, there are significant deviations between Geant4 and PENH (up to 60%/1 cm for depth–dose distributions). The agreement is much

  20. A Simulation Study for Radiation Treatment Planning Based on the Atomic Physics of the Proton-Boron Fusion Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sunmi; Yoon, Do-Kun; Shin, Han-Back; Jung, Joo-Young; Kim, Moo-Sub; Kim, Kyeong-Hyeon; Jang, Hong-Seok; Suh, Tae Suk [the Catholic University of Korea, Seoul (Korea, Republic of)

    2017-03-15

    The purpose of this research is to demonstrate, based on a Monte Carlo simulation code, the procedure of radiation treatment planning for proton-boron fusion therapy (PBFT). A discrete proton beam (60 - 120 MeV) relevant to the Bragg peak was simulated using a Monte Carlo particle extended (MCNPX, Ver. 2.6.0, National Laboratory, Los Alamos NM, USA) simulation code. After computed tomography (CT) scanning of a virtual water phantom including air cavities, the acquired CT images were converted using the simulation source code. We set the boron uptake regions (BURs) in the simulated water phantom to achieve the proton-boron fusion reaction. Proton sources irradiated the BUR, in the phantom. The acquired dose maps were overlapped with the original CT image of the phantom to analyze the dose volume histogram (DVH). We successfully confirmed amplifications of the proton doses (average: 130%) at the target regions. From the DVH result for each simulation, we acquired a relatively accurate dose map for the treatment. A simulation was conducted to characterize the dose distribution and verify the feasibility of proton boron fusion therapy (PBFT). We observed a variation in proton range and developed a tumor targeting technique for treatment that was more accurate and powerful than both conventional proton therapy and boron-neutron capture therapy.

  1. A simulation study for radiation treatment planning based on the atomic physics of the proton-boron fusion reaction

    Science.gov (United States)

    Kim, Sunmi; Yoon, Do-Kun; Shin, Han-Back; Jung, Joo-Young; Kim, Moo-Sub; Kim, Kyeong-Hyeon; Jang, Hong-Seok; Suh, Tae Suk

    2017-03-01

    The purpose of this research is to demonstrate, based on a Monte Carlo simulation code, the procedure of radiation treatment planning for proton-boron fusion therapy (PBFT). A discrete proton beam (60 - 120 MeV) relevant to the Bragg peak was simulated using a Monte Carlo n-particle extended (MCNPX, Ver. 2.6.0, National Laboratory, Los Alamos NM, USA) simulation code. After computed tomography (CT) scanning of a virtual water phantom including air cavities, the acquired CT images were converted using the simulation source code. We set the boron uptake regions (BURs) in the simulated water phantom to achieve the proton-boron fusion reaction. Proton sources irradiated the BUR, in the phantom. The acquired dose maps were overlapped with the original CT image of the phantom to analyze the dose volume histogram (DVH). We successfully confirmed amplifications of the proton doses (average: 130%) at the target regions. From the DVH result for each simulation, we acquired a relatively accurate dose map for the treatment. A simulation was conducted to characterize the dose distribution and verify the feasibility of proton-boron fusion therapy (PBFT). We observed a variation in proton range and developed a tumor-targeting technique for treatment that was more accurate and powerful than both conventional proton therapy and boron-neutron capture therapy.

  2. Safety in the Chemical Laboratory: Nitric Acid, Nitrates, and Nitro Compounds.

    Science.gov (United States)

    Bretherick, Leslie

    1989-01-01

    Discussed are the potential hazards associated with nitric acid, inorganic and organic nitrate salts, alkyl nitrates, acyl nitrates, aliphatic nitro compounds, aromatic nitro compounds, and nitration reactions. (CW)

  3. The Generation of Dehydroalanine Residues in Protonated Polypeptides: Ion/Ion Reactions for Introducing Selective Cleavages

    Science.gov (United States)

    Peng, Zhou; Bu, Jiexun; McLuckey, Scott A.

    2017-09-01

    We examine a gas-phase approach for converting a subset of amino acid residues in polypeptide cations to dehydroalanine (Dha). Subsequent activation of the modified polypeptide ions gives rise to specific cleavage N-terminal to the Dha residue. This process allows for the incorporation of selective cleavages in the structural characterization of polypeptide ions. An ion/ion reaction within the mass spectrometer between a multiply protonated polypeptide and the sulfate radical anion introduces a radical site into the multiply protonated polypeptide reactant. Subsequent collisional activation of the polypeptide radical cation gives rise to radical side chain loss from one of several particular amino acid side chains (e.g., leucine, asparagine, lysine, glutamine, and glutamic acid) to yield a Dha residue. The Dha residues facilitate preferential backbone cleavages to produce signature c- and z-ions, demonstrated with cations derived from melittin, mechano growth factor (MGF), and ubiquitin. The efficiencies for radical side chain loss and for subsequent generation of specific c- and z-ions have been examined as functions of precursor ion charge state and activation conditions using cations of ubiquitin as a model for a small protein. It is noted that these efficiencies are not strongly dependent on ion trap collisional activation conditions but are sensitive to precursor ion charge state. Moderate to low charge states show the greatest overall yields for the specific Dha cleavages, whereas small molecule losses (e.g., water/ammonia) dominate at the lowest charge states and proton catalyzed amide bond cleavages that give rise to b- and y-ions tend to dominate at high charge states. [Figure not available: see fulltext.

  4. Silylium ion-catalyzed challenging Diels-Alder reactions: the danger of hidden proton catalysis with strong Lewis acids.

    Science.gov (United States)

    Schmidt, Ruth K; Müther, Kristine; Mück-Lichtenfeld, Christian; Grimme, Stefan; Oestreich, Martin

    2012-03-07

    The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Brønsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)(3)P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Brønsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the

  5. Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide

    Science.gov (United States)

    Chang, Yao-Feng; Fowler, Burt; Chen, Ying-Chen; Zhou, Fei; Pan, Chih-Hung; Chang, Ting-Chang; Lee, Jack C.

    2016-02-01

    We realize a device with biological synaptic behaviors by integrating silicon oxide (SiOx) resistive switching memory with Si diodes. Minimal synaptic power consumption due to sneak-path current is achieved and the capability for spike-induced synaptic behaviors is demonstrated, representing critical milestones for the use of SiO2-based materials in future neuromorphic computing applications. Biological synaptic behaviors such as long-term potentiation (LTP), long-term depression (LTD) and spike-timing dependent plasticity (STDP) are demonstrated systematically using a comprehensive analysis of spike-induced waveforms, and represent interesting potential applications for SiOx-based resistive switching materials. The resistive switching SET transition is modeled as hydrogen (proton) release from (SiH)2 to generate the hydrogen bridge defect, and the RESET transition is modeled as an electrochemical reaction (proton capture) that re-forms (SiH)2. The experimental results suggest a simple, robust approach to realize programmable neuromorphic chips compatible with large-scale CMOS manufacturing technology.

  6. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. The use of low energy, ion induced nuclear reactions for proton radiotherapy applications

    Science.gov (United States)

    Horn, K. M.; Doyle, B.; Segal, M. N.; Hamm, R. W.; Adler, R. J.; Glatstein, E.

    1995-12-01

    Medical radiotherapy has traditionally relied upon the use of external photon beams and internally implanted radioisotopes as the chief means of irradiating tumors. However, advances in accelerator technology and the exploitation of novel means of producing radiation may provide useful alternatives to some current modes of medical radiation delivery — with reduced total dose to surrounding healthy tissue, reduced expense, or increased treatment accessibility. This paper will briefly overview currently established modes of radiation therapy, techniques still considered experimental but in clinical use and innovative concepts under study that may enable new forms of treatment or enhance existing ones. The potential role of low energy, ion-induced nuclear reactions in radiotherapy applications is examined specifically for the 650 keV d( 3He,p) 4 He nuclear reaction. This examination will describe the basic physics associated with this reaction's production of 17.4 MeV protons and the processes used to fabricate the necessary materials used in the technique. Calculations of the delivered radiation dose, heat generation, and required exposure times are presented. Experimental data is also presented validating the dose calculations. The design of small, lower cost ion accelerators, as embodied in "nested"-tandem and radio frequency quadrupole accelerators is examined, as is the potential use of high-output 3He and deuterium ion sources. Finally, potential clinical applications are discussed in terms of the advantages and disadvantages of this technique with respect to current radiotherapy methods and equipment.

  8. The use of low energy, ion induced nuclear reactions for proton radiotherapy applications

    International Nuclear Information System (INIS)

    Horn, K.M.; Doyle, B.; Segal, M.N.; Adler, R.J.; Glatstein, E.

    1995-01-01

    Medical radiotherapy has traditionally relied upon the use of external photon beams and internally implanted radioisotopes as the chief means of irradiating tumors. However, advances in accelerator technology and the exploitation of novel means of producing radiation may provide useful alternatives to some current modes of medical radiation delivery with reduced total dose to surrounding healthy tissue, reduced expense, or increased treatment accessibility. This paper will briefly overview currently established modes of radiation therapy, techniques still considered experimental but in clinical use, innovative concepts under study that may enable new forms of treatment or enhance existing ones. The potential role of low energy, ion-induced nuclear reactions in radiotherapy applications is examined specifically for the 650 keV d( 3 He,p) 4 He nuclear reaction. This examination will describe the basic physics associated with this reaction's production of 17.4 MeV protons and the processes used to fabricate the necessary materials used in the technique. Calculations of the delivered radiation dose, heat generation, and required exposure times are presented. Experimental data are also presented validating the dose calculations. The design of small, lower cost ion accelerators, as embodied in 'nested'-tandem and radio frequency quadrupole accelerators is examined, as is the potential use of high-output 3 He and deuterium ion sources. Finally, potential clinical applications are discussed in terms of the advantages and disadvantages of this technique with respect to current radiotherapy methods and equipment

  9. New calculations of cyclotron production cross sections of some positron emitting radioisotopes in proton induced reactions

    International Nuclear Information System (INIS)

    Tel, E.; Aydin, E.G.; Kaplan, A.; Aydin, A.

    2009-01-01

    In this study, new calculations on the excitation functions of 13 C(p, n) 13 N, 14 N (p, α) 11 C, 15 N(p, n) 15 O, 16 O(p, α) 13 N, 18 O(p, n) 18 F, 62 Ni(p, n) 62 Cu, 68 Zn(p, n) 68 Ga and 72 Ge(p, n) 72 As reactions have been carried out in the 5-40 MeV incident proton energy range. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve hybrid model, geometry dependent hybrid model, the cascade exciton model and full exciton model. Equilibrium effects were calculated according to Weisskopf-Ewing model. The calculated results have been compared with experimental data taken from literature. (author)

  10. Measurement of the Induced Proton Polarization Pn in the 12C(e, e', p) reaction

    International Nuclear Information System (INIS)

    Woo, R.J.; Barkhuff, David; Bertozzi, William; Jian-ping Chen; Dan Dale; G. Dodson; K.A. Dow; Marty Epstein; Manouchehr Farkhondeh; Mike Finn; Shalev Gilad; Mark K. Jones; Kyungseon Joo; James Kelly; Stanley Kowalski; Bob Lourie; Richard Madey; Dimitri Margaziotis; Pete Markowitz; Justin McIntyre; Christoph Mertz; Brian Milbrath; Joseph Mitchell; Charles F. Perdrisat; Vina Punjabi; Paul Rutt; Adam Sarty; D. Tieger; C. Tschalaer; William Turchinetz; Paul E. Ulmer; S.P. Van Verst; C. Vellidis; Glen Warren; Lawrence Weinstein

    1998-01-01

    The first measurements of the induced proton polarization Pn for the 12C(e,e',p) reaction are reported. The experiment was performed at quasifree kinematics for energy and momentum transfer (w,q) = (294 MeV, 765 MeV/c) and sampled a missing momentum range of 0-250 MeV/c. The induced polarization arises from final-state interactions and for these kinematics is dominated by the real part of the spin-orbit optical potential. The distorted-wave impulse approximation provides good agreement with data for the 1 p3/2 shell. The data for the continuum suggest that both the 1s1/2 shell and underlying l > 1 configurations contribute

  11. Proton induced reactions on natural Pb targets. A potential new cyclotron method for 201Tl production

    International Nuclear Information System (INIS)

    Lagunas-Solar, M.C.; Little, F.E.; Jungerman, J.A.

    1981-01-01

    The basis for a new cyclotron method for production of no-carrier-added 201 Tl, from its grandparent 201 Bi via the Pb(p,xn) 201 Bi → 201 Pb → 201 Tl reaction is presented here. Thick-target yields (μCi/μAh) for the 201 Pb and 200 Pb induced radioactivities were measured over the 65- to 43-MeV proton-energy range. The experimental data indicate that the 201 Tl yields could be optimized by using Pb targets enriched in 206 Pb, 207 Pb, and, or 208 Pb, which are expected to provide greater overall yields than current methods, as well as material of high-chemical, radiochemical and radionuclidic quality for radiopharmaceutical production. (author)

  12. Formaldehyde measurements by Proton transfer reaction – Mass Spectrometry (PTR-MS: correction for humidity effects

    Directory of Open Access Journals (Sweden)

    A. Vlasenko

    2010-08-01

    Full Text Available Formaldehyde measurements can provide useful information about photochemical activity in ambient air, given that HCHO is formed via numerous oxidation processes. Proton transfer reaction mass spectrometry (PTR-MS is an online technique that allows measurement of VOCs at the sub-ppbv level with good time resolution. PTR-MS quantification of HCHO is hampered by the humidity dependence of the instrument sensitivity, with higher humidity leading to loss of PTR-MS signal. In this study we present an analytical, first principles approach to correct the PTR-MS HCHO signal according to the concentration of water vapor in sampled air. The results of the correction are validated by comparison of the PTR-MS results to those from a Hantzsch fluorescence monitor which does not have the same humidity dependence. Results are presented for an intercomparison made during a field campaign in rural Ontario at Environment Canada's Centre for Atmospheric Research Experiments.

  13. Fragment formation in GeV-energy proton and light heavy-ion induced reactions

    International Nuclear Information System (INIS)

    Murakami, T.; Haga, M.; Haseno, M.

    2002-01-01

    We have investigated similarities and differences among the fragment formation processes in GeV-energy light-ion and light heavy-ion induced reactions. We have newly measured inclusive and exclusive energy spectra of intermediate mass fragments (3 ≤ Z ≤ 30; IMFs) for 8-GeV 16 O and 20 Ne and 12-GeV 20 Ne induced target multifragmentations (TMFs) in order to compare them with those previously measured for 8- and 12-GeV proton induced TMFs. We fond noticeable difference in their spectrum shapes and magnitudes but all of them clearly indicate the existence of sideward-peaked components, indicating fragment formations are mainly dictated not by a incident energy per nucleon but by a total energy of the projectile. (author)

  14. Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

    Science.gov (United States)

    Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

    2018-03-22

    The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

  15. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  16. Kinetics and selectivity of the oxidation of methylbenzenes in Co(III)-CH3COOH-CF3COOH solutions. Comparison with nitration and hydroxylation reactions

    International Nuclear Information System (INIS)

    Rudakov, E.S.; Lobachev, V.L.

    1989-01-01

    Data have been obtained concerning the kinetics, substrate selectivity, and kinetic isotope effect for the first stage in the oxidation of a series of arenes, from benzene to hexamethylbenzene, by Co(III) acetate in CH 3 COOH-CF 3 COOH (1.9 M) solutions at 25 degree C. A similarity was noted between substrate selectivity for reactions of alkylbenzenes with Co(III) and electrophilic nitration reactions, which occur via an electron transfer step. It was also found that substrate selectivity for these reactions differs significantly from that found for electrophilic hydroxylation reactions, which occur via an intermediate slow step involving σ-complex formation

  17. Tunable excited-state intramolecular proton transfer reactions with Nsbnd H or Osbnd H as a proton donor: A theoretical investigation

    Science.gov (United States)

    Li, Yuanyuan; Wen, Keke; Feng, Songyan; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Guo, Xugeng; Zhang, Jinglai

    2017-12-01

    Excited-state intramolecular proton transfer (ESIPT) reactions occurring in the S1 state for five molecules, which possess five/six-membered ring intramolecular Nsbnd H···N or Osbnd H···N hydrogen bonds bearing quinoline or 2-phenylpyridine moiety, have been described in detail by the time-dependent density functional theory (TD-DFT) approach using the B3LYP hybrid functional. For the five molecules, the constrained potential energy profiles along the ESIPT reactions show that proton transfer is barrierless in molecules possessing six-membered ring intramolecular H-bonds, which is smoother than that with certain barriers in five-membered ring H-bonding systems. For the latter, chemical modification by a more strong acid group can lower the ESIPT barrier significantly, which harnesses the ESIPT reaction from a difficult type to a fast one. The energy barrier of the ESIPT reaction depends on the intensity of the intramolecular H-bond, which can be measured with the topological descriptors by topology analysis of the bond critical point (BCP) of the intramolecular H-bond. It is found that when the value of electron density ρ(r) at BCP is bigger than 0.025 a.u., the corresponding molecule might go through an ultrafast and barrierless ESIPT process, which opens a new scenario to explore the ESIPT reactions.

  18. Sequential deuterium exchange reactions of protonated benzenes with D2O in the gas phase by ion cyclotron resonance spectroscopy

    International Nuclear Information System (INIS)

    Freiser, B.S.; Woodin, R.L.; Beauchamp, J.L.

    1975-01-01

    Results are reported results on a novel deuterium exchange reaction, observed using ion cyclotron resonance (ICR) spectroscopy. In apparent contrast to previously reported results sequential reactions of protonated aromatic compounds with D 2 O in the gas phase occur which lead to various degrees of ring deuteration. For example, reactions in a mixture of benzene and D 2 O produce C 6 H 6 D + , which in further reaction with D 2 O undergoes rapid stepwise exchange of H for D. From the data summarized for the halo and alkyl substituted benzenes it is apparent that deuterium exchange varies significantly for different structural isomers. Thus while o- and p-difluorobenzene exchange all hydrogens rapidly, the meta isomer slowly exchanges only a single hydrogen. Species such as the benzoyl cation, radical cations, and C 7 H 7 + derived from toluene and cycloheptatriene do not undergo exchange. It appears that ring protonation is a necessary condition for exchange to occur

  19. Geographical provenancing of purple grape juices from different farming systems by proton transfer reaction mass spectrometry using supervised statistical techniques

    NARCIS (Netherlands)

    Granato, Daniel; Koot, Alex; Ruth, van S.M.

    2015-01-01

    BACKGROUND: Organic, biodynamic and conventional purple grape juices (PGJ; n = 79) produced in Brazil and Europe were characterized by volatile organic compounds (m/z 20-160) measured by proton transfer reaction mass spectrometry (PTR-MS), and classification models were built using supervised

  20. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  1. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

  2. Measurement and calculation of cross section for (p,x) reactions on natural Fe for 650 MeV protons

    International Nuclear Information System (INIS)

    Janczyszyn, J.; Pohorecki, W.; Domanska, G.; Loska, L.; Taczanowski, S.; Shvetsov, V.

    2006-01-01

    Cross sections for production of radionuclides in (p,x) reactions on natural iron were measured for protons of 650 ± 4 MeV with the use of HPGe gamma spectrometry and calculated with the MCNPX code. The determined cross section values were compared with the computed and other experimental ones

  3. Activation cross-sections on cadmium: Proton induced nuclear reactions up to 80 MeV

    International Nuclear Information System (INIS)

    Tarkanyi, F.; Kiraly, B.; Ditroi, F.; Takacs, S.; Csikai, J.; Hermanne, A.; Uddin, M.S.; Hagiwara, M.; Baba, M.; Ido, T.; Shubin, Yu.N.; Kovalev, S.F.

    2006-01-01

    Cross-sections of proton induced nuclear reactions on natural cadmium were measured up to 80 MeV using the standard stacked foil irradiation technique and high resolution gamma-ray spectroscopy. Experimental cross-sections and derived integral yields are reported for the nat Cd(p,xn) 107g,108m,108g,109g,110m,110g,111g,112m,113m,114m,115m,116m1 In, nat Cd(p,x) 107,109,111m,115g Cd and nat Cd(p,x) 104g,105g,106m,110m,111g,113g Ag reactions. Earlier experimental data measured on natural cadmium were found only for 109,110,111,113,114 In in the literature. The experimental data are analyzed and compared to the results of the theoretical model code ALICE-IPPE. Applications of the new cross-sections for data validation, medical radioisotope production, thin layer activation and dose calculation are discussed.

  4. Polarizations for proton knockout reactions from s1/2 orbits at 1 GeV

    International Nuclear Information System (INIS)

    Andreev, V.A.; Andronenko, M.N.; Amalsky, G.M.; Belostotski, S.L.; Domchenkov, O.A.; Fedorov, O.Ya.; Izotov, A.A.; Jgoun, A.A.; Kisselev, A.Yu.; Kopytin, M.A.; Miklukho, O.V.; Naryshkin, Yu.G.; Prokofiev, A.N.; Prokofiev, D.A.; Sulimov, V.V.; Shvedchikov, A.V.; Trush, S.I.; Vikhrov, V.V.; Zhdanov, A.; Hatanaka, K.

    2004-01-01

    The polarization of protons emitted in (p,2p) reactions has been measured for three kinds of targets at 1 GeV. The values of the polarization that we obtain are significantly smaller than the values predicted using the nucleon-nucleon (NN) interaction in free space, and the discrepancy between the two is seen to increase monotonically as a function of the effective mean density, which is defined as a measure of the sensitivity of a reaction to density-dependent terms of the interaction. The experimental data are also compared with a model calculation that includes a relativistic effect, and it is found that inclusion of this effect is able to account for about half of the density-dependent discrepancy between the experimental results and the values predicted with the free space NN interaction. These results, in conjunction with the previous results at 392 MeV, indicate that this discrepancy is not caused by a contribution of multistep processes and provide further evidence that there exists a medium effect

  5. Recent progress in the development of a polarized proton target for reactions with radioactive ion beams

    International Nuclear Information System (INIS)

    Urrego-Blanco, J.P.; Bingham, C.R.; Brandt, B. van den; Galindo-Uribarri, A.; Gomez del Campo, J.; Hautle, P.; Konter, J.A.; Padilla-Rodal, E.; Schmelzbach, P.A.

    2007-01-01

    Polarization observables in nuclear reactions with stable beams have provided important information concerning structural properties of nuclei and reaction mechanisms and hold great promise in the context of exotic nuclei. We report on the development of a polarized target based on plastic foils of 20-200 μm thickness to be used with radioactive ion beams. The operation of such a target requires a moderately high magnetic field and very low temperatures. The plastic foil is placed inside a chamber attached to the mixing chamber of a 3 He- 4 He dilution refrigerator. Cooling of the foil is achieved via a superfluid film of 4 He that can be supplied through two capillaries. The chamber has two thin, highly uniform silicon nitride windows. An NMR coil is attached to the target to monitor the polarization. Results of a first test to characterize the target system, using the elastic scattering of 38 MeV 12 C by protons in inverse kinematics are presented

  6. Investigation of proton induced reactions on niobium at low and medium energies

    International Nuclear Information System (INIS)

    Ditroi, F.; Hermanne, A.; Corniani, E.; Takacs, S.; Tarkanyi, F.; Csikai, J.; Shubin, Yu. N.

    2009-01-01

    Niobium is a metal with important technological applications: use as alloying element to increase strength of super alloys, as thin layer for tribological applications, as superconductive material, in high temperature engineering systems, etc. In the frame of a systematic study of activation cross-sections of charged particle induced reactions on structural materials proton induced excitation functions on Nb targets were determined with the aim of applications in accelerator and reactor technology and for thin layer activation (TLA). The charged particle activation cross-sections on this element are also important for yield calculation of medical isotope production ( 88,89 Zr, 86,87,88 Y) and for dose estimation in PET targetry. As niobium is a monoisotopic element it is an ideal target material to test nuclear reaction theories. We present here the experimental excitation functions of 93 Nb(p,x) 90,93m Mo, 92m,91m,90 Nb, 88,89 Zr and 88 Y in the energy range 0-37 MeV. The results were compared with the theoretical cross-sections calculated by means of the code ALICE-IPPE, EMPIRE-3, TALYS and with the literature data. The theory reproduces the shape of the measured results well and magnitude is also acceptable. Thick target yields calculated from our fitted cross-section give reliable estimations for production of medically relevant radioisotopes and for dose estimation in accelerator technology.

  7. Measurement of the proton total reaction cross section for 159Tb, 181Ta and 197Au between 20 and 48 MeV

    International Nuclear Information System (INIS)

    Abegg, R.; Birchall, J.; Davison, N.E.; Jong, M.S. de; Ginther, D.L.; Hasell, D.K.; Nasr, T.N.; Oers, W.T.H. van; Carlson, R.F.; Cox, A.J.

    1979-01-01

    Proton total reaction cross sections have been measured for the nuclei 159 Tb, 181 Ta and 197 Au at seven proton energies between 20 and 48 MeV using an attenuation technique. The experimentally determined energy dependence of the total reaction cross sections is compared with results obtained for black nucleus and optical model calulations. (Auth.)

  8. Differential nitrate accumulation, nitrate reduction, nitrate reductase ...

    African Journals Online (AJOL)

    For most of the cultivated crops, nitrate is the major source of nitrogen. Most steps in the nitrate assimilatory pathway are nitrate inducible. In this study, Cucurbita pepo were grown in washed sand per pot at three potassium and sodium nitrate supplies (25, 50 and 100 mM) to investigate the effects of nitrate salts supply on ...

  9. Compound and precompound emission in reactions of Zn isotopes with protons and alpha particles

    International Nuclear Information System (INIS)

    Lux, C.R.

    1975-01-01

    Targets of 64 Zn, 66 Zn, 68 Zn, and 70 Zn were bombarded by 12.5 MeV protons and 18.0 MeV alpha particles. Energy spectra and angular distributions of protons and alpha particles emitted in these reactions were measured. Integrated cross sections were determined from the experimental spectra. The assumption was made that emission in the backward direction was due to compound emission and that any ''excess'' cross section in the forward direction was due to precompound emission. Then an experimental percent precompound emission was calculated. It ranged from 2 to 95 percent. A constant temperature analysis was performed on all 150 0 and 30 0 spectra. The nuclear temperature of the 30 0 spectra was from 0.1 to 2.0 MeV higher, indicating more precompound emission in the 30 0 than in the 150 0 spectra. The ratios of (GAMMA/sub p//GAMMA/sub n/) and (GAMMA/sub α//GAMMA/sub n/) for 150 0 were adequately fit by evaporation theory indicating that a compound mechanism can account for the data. The spin-dependent statistical model was then used to fit the 150 0 spectra. Good fits were obtained using parameters that are in agreement with those calculated by Gilbert and Cameron. The spin-dependent statistical model was then combined with the precompound Quasi-Free Scattering Model and fits were made to the experimental data. Good fits were obtained and a calculated percent precompound emission wasobtained. This ranged from 1 to 95 percent and compared favorably with the percentages obtained experimentally

  10. Parameterization of N2O5 reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate

    Directory of Open Access Journals (Sweden)

    P. V. Bhave

    2008-09-01

    Full Text Available A parameterization was developed for the heterogeneous reaction probability (γ of N2O5 as a function of temperature, relative humidity (RH, particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH4HSO4, (NH42SO4, and NH4NO3 were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH4HSO4 and (NH42SO4 particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 80% of the laboratory data within a factor of two and 63% within a factor of 1.5. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, RH, sulfate, nitrate, and ammonium. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our equations lay the foundation for future research that will parameterize the suppression of γ when inorganic ammoniated particles are mixed or coated with organic material. Our analyses draw attention to a major uncertainty in the available laboratory data at high RH and highlight a critical need for future laboratory measurements of γ at low temperature and high RH to improve model simulations of N2O5 hydrolysis during wintertime conditions.

  11. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    Energy Technology Data Exchange (ETDEWEB)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Ino, Takashi; Kawai, Masayoshi [High Energy Accelerator Research Organization, Tsukuba, Ibaraki (Japan); Jerde, Eric; Glasgow, David [Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the {sup 115}In(n,n'){sup 115m}In, {sup 93}Nb(n,2n){sup 92m}Nb, and {sup 209}Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured {sup 115}In(n,n'){sup 115m}In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  12. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    International Nuclear Information System (INIS)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro; Jerde, Eric; Glasgow, David

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the 115 In(n,n') 115m In, 93 Nb(n,2n) 92m Nb, and 209 Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured 115 In(n,n') 115m In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  13. Mixed quantum classical calculation of proton transfer reaction rates: from deep tunneling to over the barrier regimes.

    Science.gov (United States)

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-07

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

  14. Multi-capillary-column proton-transfer-reaction time-of-flight mass spectrometry.

    Science.gov (United States)

    Ruzsanyi, Veronika; Fischer, Lukas; Herbig, Jens; Ager, Clemes; Amann, Anton

    2013-11-05

    Proton-transfer-reaction time-of-flight mass-spectrometry (PTR-TOFMS) exhibits high selectivity with a resolution of around 5000 m/Δm. While isobars can be separated with this resolution, discrimination of isomeric compounds is usually not possible. The coupling of a multi-capillary column (MCC) with a PTR-TOFMS overcomes these problems as demonstrated in this paper for the ketone isomers 3-heptanone and 2-methyl-3-hexanone and for different aldehydes. Moreover, fragmentation of compounds can be studied in detail which might even improve the identification. LODs for compounds tested are in the range of low ppbv and peak positions of the respective separated substances show good repeatability (RSD of the peak positions <3.2%). Due to its special characteristics, such as isothermal operation, compact size, the MCC setup is suitable to be installed inside the instrument and the overall retention time for a complete spectrum is only a few minutes: this allows near real-time measurements in the optional MCC mode. In contrast to other methods that yield additional separation, such as the use of pre-cursor ions other than H3O(+), this method yields additional information without increasing complexity. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

  15. Triacetone triperoxide detection using low reduced-field proton transfer reaction mass spectrometer

    Science.gov (United States)

    Shen, Chengyin; Li, Jianquan; Han, Haiyan; Wang, Hongmei; Jiang, Haihe; Chu, Yannan

    2009-08-01

    Proton transfer reaction mass spectrometry (PTR-MS) was applied to on-line detection of the explosive triacetone triperoxide (TATP) using a discharge gas of water vapor or alternative ammonia in the ion source. The dependence of ionic intensity on reduced-field in the drift tube was investigated, and the results indicate that an irregular operation using low reduced-field can enhance TATP detection due to reduced collision-induced dissociation in the drift tube. When water vapor is used as the discharge gas, the characteristic ions for TATP identification are [TATP + H]+ which are detectable at a reduced-field about 50 Td. If ammonia is the discharge gas, PTR-MS exhibits a better sensitivity, the explosive TATP can be discriminated according to the adduct ions [TATP + NH4]+, and a limit of detection at ppb level can be achieved at a reduced-field around 100 Td in this PTR-MS apparatus. PTR-MS is suggested as a potential tool for on-site detection of the explosive TATP with the advantages of rapid response and high sensitivity without sample pretreatment.

  16. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry

    Science.gov (United States)

    Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia

    2008-08-01

    The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

  17. Production of residual nuclides by proton-induced reactions on target W at the energy of 72 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Moazzem Hossain [Univ. of Chittagong, Dept. of Physics, Chittagong (Bangladesh); Kuhnhenn, Jochen; Herpers, Ulrich [Univ. of Cologne, Dept. of Nuclear Chemistry, Cologne (Germany); Michel, Rolf [University of Hannover, Centre for Radiation Protection and Radioecology (Germany); Kubik, Peter [Paul Scherrer Inst., c/o Institute for Particle Physics, ETH Hoenggerberg, Zuerich (Switzerland)

    2002-08-01

    Investigations of cross-sections for residual nuclide production on the target element W by proton-induced reactions were performed by irradiating the target with 72 MeV protons using the cyclotron facilities at Paul-Scherrer Institute, Zurich, Switzerland. Residual nuclides were measured by gamma-spectrometry of HpGe detectors calibrated with standard gamma sources. The measured data contains 104 individual cross-sections for 20 identified nuclides in the proton energies between 52.5 - 68.9 MeV. These nuclear data is important in the study of spallation neutron source and in accelerator driven technologies such as waste transmutation and energy amplification. The present data are compared with the shape of the excitation functions of earlier only one measurement at higher energies and they are in good agreement to each other. (author)

  18. Differential nitrate accumulation, nitrate reduction, nitrate reductase ...

    African Journals Online (AJOL)

    use

    2011-12-07

    Dec 7, 2011 ... nitrate salts supply on nitrate accumulation, amino acid biosynthesis, total protein production, nitrate reductase activity and carbohydrate biosynthesis in the roots and leaves of the plants. The results indicate that both sodium and potassium nitrate supplementation had stimulatory effects on all of the.

  19. Proton conductive Pt-Co nanoparticles anchoring on citric acid functionalized graphene for efficient oxygen reduction reaction

    Science.gov (United States)

    Zhao, Yige; Liu, Jingjun; Wu, Yijun; Wang, Feng

    2017-08-01

    Designing highly efficient electro-catalysts for the oxygen reduction reaction (ORR) has been regarded as a demanding task in the development of renewable energy sources. However, little attention has been paid on improving Pt-based catalysts by promoting proton transfer from the electrolyte solutions to the catalyst layer at the cathode. Herein, we design proton conductive Pt-Co alloy nanoparticles anchoring on citric acid functionalized graphene (Pt-Co/CA-G) catalysts for efficient ORR. The facile modification approach for graphene can introduce oxygenated functional groups on the graphene surface to promote proton transfer as well as keeping the high electron conductivity without destroying the graphene original structure. The electrochemical results show that the Pt-Co/CA-G catalyst exhibits more excellent ORR activity and stability than the commercial Pt/C catalyst, which can be attributed to its improved proton transfer ability. The fast proton transfer comes from the hydrogen-bonding networks formed by the interaction between the oxygenated functional groups and water molecules. This work provides not only a novel and simple approach to modify graphene but also an effective strategy to improve Pt-based catalysts for the ORR.

  20. Production of He-, Ne-, Ar-, Kr-, and Xe-isotopes by proton-induced reactions on lead

    International Nuclear Information System (INIS)

    Leya, I.; Michel, R.

    2003-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr-, and Xe-isotopes from lead from the respective reaction thresholds up to 2.6 GeV. The production of noble gas isotopes in lead by proton-induced reactions is of special importance for design studies of accelerator driven systems and energy amplifiers. In order to minimise the influences of secondary particles on the production of residual nuclides a new Mini-Stack approach was used instead of the well-known stacked-foil techniques for all experiments with proton energies above 200 MeV. With some exceptions our database for the proton-induced production of noble gas isotopes from lead is consistent and nearly complete. In contradistinction to the production of He from Al and Fe, where the cross sections obtained by thin-target irradiation experiments are up to a factor of 2 higher than the NESSI data, both datasets agree for the He production from lead. (orig.)

  1. Percolation-fission model study of the fragment mass distribution for the 1 GeV proton induced reaction

    International Nuclear Information System (INIS)

    Katsuma, Masahiko; Kobayashi, Hiroshi; Sawada, Tetsuo; Sasa, Toshinobu

    2005-01-01

    The 1 GeV proton induced reaction on 208 Pb targets is analyzed by using the percolation model combined with the Atchison fission model. The fragment mass distribution and the isotopic production cross sections obtained from our model are compared with the experimental data. The trends of the fragment mass distribution for the 1 GeV proton induced reaction can be reproduced by our calculation in some degree. The order of magnitude for the calculated isotopic production cross sections at the calculated peak positions is similar to that of the experimental peak values. The calculated peak positions of the isotopic production cross sections are shifted to the heavier region than those of the experimental data. (author)

  2. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  3. Measurements of Volatile Organic Compounds Using Proton Transfer Reaction - Mass Spectrometry during the MILAGRO 2006 Campaign

    Science.gov (United States)

    Fortner, E. C.; Zheng, J.; Zhang, R.; Berk Knighton, W.; Volkamer, R. M.; Sheehy, P.; Molina, L.; André, M.

    2009-01-01

    Volatile organic compounds (VOCs) were measured by proton transfer reaction - mass spectrometry (PTR-MS) on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of the Megacity Initiative - Local and Global Research Observations (MILAGRO) 2006 field campaign. Thirty eight individual masses were monitored during the campaign and many species were quantified including methanol, acetaldehyde, toluene, the sum of C2 benzenes, the sum of C3 benzenes, acetone, isoprene, benzene, and ethyl acetate. The VOC measurements were analyzed to gain a better understanding of the type of VOCs present in the MCMA, their diurnal patterns, and their origins. Diurnal profiles of weekday and weekend/holiday aromatic VOC concentrations showed the influence of vehicular traffic during the morning rush hours and during the afternoon hours. Plumes including elevated toluene as high as 216 parts per billion (ppb) and ethyl acetate as high as 183 ppb were frequently observed during the late night and early morning hours, indicating the possibility of significant industrial sources of the two compounds in the region. Wind fields during those peak episodes revealed no specific direction for the majority of the toluene plumes but the ethyl acetate plumes arrived at the site when winds were from the Southwest or West. The PTR-MS measurements combined with other VOC measuring techniques at the field site as well as VOC measurements conducted in other areas of the Mexico City Metropolitan Area (MCMA) will help to develop a better understanding of the spatial pattern of VOCs and its variability in the MCMA.

  4. Calibration and intercomparison of acetic acid measurements using proton transfer reaction mass spectrometry (PTR-MS)

    Science.gov (United States)

    Haase, K.B.; Keene, W.C.; Pszenny, A.A.P.; Mayne, H.R.; Talbot, R.W.; Sive, B.C.

    2012-01-01

    Acetic acid is one of the most abundant organic acids in the ambient atmosphere, with maximum mixing ratios reaching into the tens of parts per billion by volume (ppbv) range. The identities and associated magnitudes of the major sources and sinks for acetic acid are poorly characterized, due in part to the limitation in available measurement techniques. This paper demonstrates that Proton Transfer Reaction Mass Spectrometry (PTR-MS) can reliably quantify acetic acid vapor in ambient air. Three different PTR-MS configurations were calibrated at low ppbv mixing ratios using permeation tubes, which yielded calibration factors between 7.0 and 10.9 normalized counts per second per ppbv (ncps ppbv−1) at a drift tube field strength of 132 townsend (Td). Detection limits ranged from 0.06 to 0.32 ppbv with dwell times of 5 s. These calibration factors showed negligible humidity dependence. Using the experimentally determined calibration factors, PTR-MS measurements of acetic acid during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign were validated against results obtained using Mist Chambers coupled with Ion Chromatography (MC/IC). An orthogonal least squares linear regression of paired data yielded a slope of 1.14 ± 0.06 (2σ), an intercept of 0.049 ± 20 (2σ) ppbv, and an R2 of 0.78. The median mixing ratio of acetic acid on Appledore Island, ME during the ICARTT campaign was 0.530 ± 0.025 ppbv with a minimum of 0.075 ± 0.004 ppbv, and a maximum of 3.555 ± 0.171 ppbv.

  5. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici

    2014-09-01

    Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  6. Presolvated electron reactions with methyl acetoacetate: electron localization, proton-deuteron exchange, and H-atom abstraction.

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D

    2014-09-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•--CH2-COOCH3) in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-COOCH3. The ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments.

  7. Angular distributions of protons from the c13(d, p)c14 and c12(d, p)c13 reactions

    NARCIS (Netherlands)

    Koudijs, B.; Endt, P.M.; Hart, J.M. van der; Palmen, P.J.W.

    Angular distributions have been measured of protons from the groundstate transitions of the reactions C13(d, p)C14 and C12(d, p)C13 at a deuteron bombarding energy of 470 keV. The target consisted of barium carbonate enriched to 56% in C13 content. The angular distribution of C13(d, p)C14 protons

  8. Contribution to the analysis of dileptons production reactions in proton-proton collision with HADES; Contribution a l'analyse de reactions de production de dileptons en collision proton-proton avec HADES

    Energy Technology Data Exchange (ETDEWEB)

    Moriniere, E

    2008-03-15

    The most recent analysis of dilepton spectra, produced in heavy ion collisions, have shown the need for a precise knowledge of all dilepton production channels. The experimental HADES facility, installed on the GSI accelerator site, is appropriate for that goal. Thus, the Dalitz decay branching ratio of {delta} resonance ({delta} {yields} Ne{sup +}e{sup -}), which has never been measured, is studied in this work. Moreover, the pp {yields} p/ {delta}{sup +} {yields} ppe{sup +-} reaction could allow to provide some information about the internal resonance structure and more precisely, about the electromagnetic transition N - A form factors. The analysis of simulations shows the feasibility of this experiment, estimates the counting yield as well as the Signal over Background ratio. This analysis shows also the great importance of the momentum resolution of the detector for the success of this experiment. The momentum resolution must be investigated. In this work, an attempt to find out the most important contributions to the measured resolution is presented. The calibration step, which provides the relation between electronic time and physical time, the detector alignment (global, relative or internal) as well as the tracking method are studied. Some methods for improvement of these different contributions are proposed in order to reach the optimal resolution. (author)

  9. Does excited-state proton-transfer reaction contribute to the emission behaviour of 4-aminophthalimide in aqueous media?

    Science.gov (United States)

    Khara, Dinesh Chandra; Banerjee, Sanghamitra; Samanta, Anunay

    2014-06-23

    4-Aminophthalimide (AP) is an extensively used molecule both for fundamental studies and applications primarily due to its highly solvent-sensitive fluorescence properties. The fluorescence spectrum of AP in aqueous media was recently shown to be dependent on the excitation wavelength. A time-dependent blue shift of its emission spectrum is also reported. On the basis of these findings, the excited-state solvent-mediated proton-transfer reaction of the molecule, which was proposed once but discarded at a later stage, is reintroduced. We report on the fluorescence behaviour of AP and its imide-H protected derivative, N-BuAP, to prove that a solvent-assisted excited-state keto-enol transformation does not contribute to the steady-state and time-resolved emission behaviour of AP in aqueous media. Our results also reveal that the fluorescence of AP in aqueous media arises from two distinct hydrogen-bonded species. The deuterium isotope effect on the fluorescence quantum yield and lifetime of AP, which was thought to be a reflection of the excited-state proton-transfer reaction in the system, is explained by considering the difference in the influence of H(2)O and D(2)O on the nonradiative rates and ground-state exchange of the proton with the solvent. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Kinetics and Mechanism of Deoxygenation Reactions over Proton-Form and Molybdenum-Modified Zeolite Catalysts

    Science.gov (United States)

    Bedard, Jeremy William

    The depletion of fossil fuel resources and the environmental consequences of their use have dictated the development of new sources of energy that are both sustainable and economical. Biomass has emerged as a renewable carbon feedstock that can be used to produce chemicals and fuels traditionally obtained from petroleum. The oxygen content of biomass prohibits its use without modification because oxygenated hydrocarbons are non-volatile and have lower energy content. Chemical processes that eliminate oxygen and keep the carbon backbone intact are required for the development of biomass as a viable chemical feedstock. This dissertation reports on the kinetic and mechanistic studies conducted on high and low temperature catalytic processes for deoxygenation of biomass precursors to produce high-value chemicals and fuels. Low temperature, steady state reaction studies of acetic acid and ethanol were used to identify co-adsorbed acetic acid/ethanol dimers as surface intermediates within specific elementary steps involved in the esterification of acetic acid with ethanol on zeolites. A reaction mechanism involving two dominating surface species, an inactive ethanol dimeric species adsorbed on Bronsted sites inhibiting ester formation and a co-adsorbed complex of acetic acid and ethanol on the active site reacting to produce ethyl acetate, is shown to describe the reaction rate as a function of temperature (323 -- 383 K), acetic acid (0.5 -- 6.0 kPa), and ethanol (5.0 -- 13.0 kPa) partial pressure on proton-form BEA, FER, MFI, and MOR zeolites. Measured differences in rates as a function of zeolite structure and the rigorous interpretation of these differences in terms of esterification rate and equilibrium constants is presented to show that the intrinsic rate constant for the activation of the co-adsorbed complex increases in the order FER < MOR < MFI < BEA. High temperature co-processing of acetic acid, formic acid, or carbon dioxide with methane (CH3COOH/CH4 = 0

  11. Protonation reactions of electron adducts of acrylamide derivatives. A pulse radiolytic-kinetic spectrophotometric study

    International Nuclear Information System (INIS)

    Madhavan, V.; Lichtin, N.N.; Hayon, E.

    1974-01-01

    The absorption spectra of electron adducts of a number of α,β-unsaturated carboxamides and of methyl methacrylate, as well as of two isomeric types of protonated electron adducts, have been characterized by means of the technique of pulse radiolysis-kinetic absorption spectrophotometry. Spectra of the electron adducts are characterized by bands in the uv (epsilon/sub max/ approximately 10 4 M -1 cm -1 ) and in the visible (epsilon/sub max/ approximately 10 3 M -1 cm -1 ). The position of the uv band shifts 10--30 nm to shorter wavelength upon reversible protonation. Fast reversible protonation of electron adducts takes place at the carbonyl oxygen. The pK/sub a/ values of the electron adducts vary linearly with the pK/sub a/ values of the corresponding carboxylic acids: for acrylamide, 7.9; methacrylamide, 8.0; trans-crotonamide, 8.5; β,β-dimethylacrylamide, 9.5; N,N-dimethylacrylamide, 8.5; trans-cinnamamide, 7.2; methyl methacrylate, approximately7. Slower irreversible protonation of the electron adducts takes place at the β-carbon atom and is subject to general acid catalysis which obeys the Bronsted catalysis law. Uncatalyzed specific rates of β protonation of anion radicals (in units of 10 5 sec -1 ) are: for acrylamide, 1.4; for methacrylamide, 13; for trans-crotonamide, 0.22; for β,β-dimethylacrylamide, 0.21; for N,N-dimethylacrylamide, 3.7; for trans-cinnamamide, less than or equal to approximately .01; for methyl methacrylate, 4.5. The second-order decay of reversibly protonated electron adducts competes with irreversible β protonation. (U.S.)

  12. Differential nitrate accumulation, nitrate reduction, nitrate reductase ...

    African Journals Online (AJOL)

    use

    2011-12-07

    Dec 7, 2011 ... reductase activity and nitrite accumulation depend on the exogenous nitrate. Nitrite itself is reduced to ammonium by palstidic nitrite reductase. Nitrite reductase is activated by both nitrate and nitrite ions by positive feed forward, whereas nitrate metabolites, most likely ammonium and glutamine; down.

  13. Validation of GEANT4 simulations for {sup 62,63}Zn yield estimation in proton induced reactions of natural copper

    Energy Technology Data Exchange (ETDEWEB)

    Rostampour, Malihe [Department of Physics, Arak University, P.O. Box: 38156, Arak (Iran, Islamic Republic of); Sadeghi, Mahdi, E-mail: msadeghi@nrcam.org [Medical Physics Department, School of Medicine, Iran University of Medical Sciences, P.O. Box: 14155-6183, Tehran (Iran, Islamic Republic of); Aboudzadeh, Mohammadreza [Radiation Application Research School, Nuclear Science and Technology Research Institute, P.O. Box: 11365-8486, Tehran (Iran, Islamic Republic of); Hamidi, Saeid [Department of Physics, Arak University, P.O. Box: 38156, Arak (Iran, Islamic Republic of); Hosseini, Seyedeh Fatemeh [Department of Physics, Payame Noor University, P.O. Box: 19395-3697, Tehran (Iran, Islamic Republic of)

    2017-03-01

    A useful approach to optimize of radioisotope production is the use of Monte Carlo simulations prior to experimentation. In this paper, the GEANT4 code was employed to calculate the saturation yields of {sup 62,63}Zn from proton-induced reactions of natural copper, enriched {sup 63}Cu and {sup 65}Cu. In addition, the saturation yields of the investigated radio-nuclides were calculated using the stopping power from the SRIM-2013 and reported experimental data for cross sections. The simulated saturation yields were compared with experimental values. Good agreement between the experimental and corresponding simulated data demonstrated that GEANT4 provides a suitable tool for radionuclide simulation production using proton irradiation.

  14. Capture reactions into borromean two-proton systems at rp-waiting points

    DEFF Research Database (Denmark)

    Hove, D.; Jensen, A. S.; Fynbo, H. O. U.

    2016-01-01

    a linear dependence between two- and three-body energies with the same slope, but the absolute value slightly dependent on partial wave structure. Using these relations we predict low-lying excited states in the isotones following the critical waiting points. The capture rate for producing a borromean......We investigate even-even two-proton borromean systems at prominent intermediate heavy waiting points for the rapid proton capture process. The most likely single-particle levels are used to calculate three-body energy and structure as a function of proton-core resonance energy. We establish...... bound state is described both based on a full three-body calculation and on a very simple analytic rate expression for temperatures about $1-5$~GK. This rate is valid for both direct and sequential capture paths, and it only depends on the three-body resonance energy. As a result the relevant path...

  15. An efficient synthesis of β-amino ketone compounds through one-pot three-component Mannich-type reactions using bismuth nitrate as catalyst

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2015-07-01

    Full Text Available Three components one-pot Mannich reaction of aromatic ketone, aromatic aldehyde and aromatic amines has been efficiently catalyzed by recyclable bismuth nitrate (Bi(NO33, BN at ambient temperature to give various β-amino carbonyl compounds in high yields. This method has advantages of mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-amino carbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to moderate yields by this methodology.

  16. Proton transfer and unimolecular decay in the low-energy-reaction dynamics of H3O+ with acetone

    International Nuclear Information System (INIS)

    Creasy, W.R.; Farrar, J.M.

    1983-01-01

    The title reaction has been studied at collision energies of 0.83 and 2.41 eV. Direct reaction dynamics have been observed at both energies and an increasingly high fraction of the total energy appears in product translation as the collision energy increases. This result is consistent with the concept of induced repulsive energy release, which becomes more effective as trajectories sample the corner of the potential energy surface. At the higher collision energy, the protonated acetone cation undergoes two unimolecular decay channels: C-C bond cleavage to CH 3 CO + and CH 4 , and C-O bond cleavagto C 3 H 5 + (presumably to allyl cation) and H 2 O. The CH 3 CO + channel, endothermic relative to ground state protonated acetone cations by 0.74 eV, appears to liberate 0.4 eV in relative product translation while the C 3 H 5 + channel, endothermic by 2.17 eV, liberates only 0.07 eV in relative translation. These results are discussed in terms of the location on the reaction coordinate and magnitudes of potential energy barriers to 1,3-hydrogen atoms shifts which must precede the bond cleavage processes

  17. Direct nuclear reactions with polarized protons: an experimental study of Ge and Se

    International Nuclear Information System (INIS)

    Moonen, W.H.L.

    1986-01-01

    The present investigation, is concerned with excited states of some transitional nuclides, which, through the experimental improvements, became accessible for polarized proton experiments. The aim was to see how nuclei behave when they have a proton and/or neutron number inbetween 28 and 50. Another aim was the completion of the picture of even-even nuclei in general where the research started with the nuclei Fe (Z=26) and Ni (Z=28). Therefore some nuclei were chosen which follow this series: Ge, Z=32, N=38,40,42,44; Se, Z=34, N=42,44,46. (Auth.)

  18. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  19. Excitation functions of natZn(p,x) nuclear reactions with proton beam energy below 18 MeV

    OpenAIRE

    Asad, A. H.; Chan, S.; Morandeau, L.; Cryer, D.; Smith, S. V.; Price, R. I.

    2015-01-01

    Introduction We measured the excitation functions of natZn (p,x) reactions up to 17.6 MeV using the stacked-foils activation technique. High-purity natural zinc (and copper) foils were irradiated with proton beams from an 18MeV medical cyclotron, the predominant purpose of which is to provide a routine regional service for clinical PET radiopharmaceuticals. Thick-target integral yields were also deduced from the measured excitation functions of the produced radioisotopes. These results we...

  20. Photon and neutral pion distributions in 60 and 200 A.GeV 16O + nucleus and proton + nucleus reactions

    International Nuclear Information System (INIS)

    Albrecht, R.; Bock, R.; Claesson, G.; Gutbrod, H.H.; Kolb, B.W.; Lund, I.; Schmidt, H.R.; Siemiarczuk, T.; Awes, T.C.; Baktash, C.; Ferguson, R.L.; Lee, I.Y.; Plasil, F.; Young, G.R.; Beckmann, P.; Berger, F.; Dragon, L.; Glasow, R.; Kampert, K.H.; Loehner, H.; Peitzmann, T.; Purschke, M.; Santo, R.; Franz, A.; Kristiansson, P.; Poskanzer, A.M.; Ritter, H.G.; Garpman, S.; Gustafsson, H.A.; Oskarsson, A.; Otterlund, I.; Persson, S.; Stenlund, E.; Obenshain, F.E.; Sorensen, S.P.

    1987-12-01

    Transverse momentum (p T ) distributions of inclusive photons and neutral pions at midrapidity are measured with a lead glass calorimeter in 60 and 200 A.GeV 16 O + nucleus and proton + nucleus reactions. The variation of the average transverse momentum is investigated as function of centrality, determined by measurements of the remaining energy of the projectile and the charged particle multiplicity. For small values of the entropy, deduced from the multiplicity density, an increase in average p T is observed levelling off for larger values of entropy. The target-mass and energy dependence of π 0 p T distributions are presented. (orig.)

  1. Photon and neutral pion distributions in 60 and 200 A GeV 16O + nucleus and proton + nucleus reactions

    International Nuclear Information System (INIS)

    Albrecht, R.; Bock, R.; Claesson, G.; Gutbrod, H.H.; Kolb, B.W.; Lund, I.; Schmidt, H.R.; Siemiarczuk, T.; Awes, T.C.; Baktash, C.; Ferguson, R.L.; Lee, I.Y.; Plasil, F.; Young, G.R.; Beckmann, P.; Berger, F.; Dragon, L.; Glasow, R.; Kampert, K.H.; Loehner, H.; Peitzmann, T.; Purschke, M.; Santo, R.; Franz, A.; Kristiansson, P.; Poskanzer, A.M.; Ritter, H.G.; Garpman, S.; Gustafsson, H.A.; Oskarsson, A.; Otterlund, I.; Persson, S.; Stenlund, E.; Obenshain, F.E.; Sorensen, S.P.

    1988-01-01

    Transverse momentum (p T ) distributions of inclusive photons and neutral pions at midrapidity are measured with a lead glass calorimeter in 60 and 200 A GeV 16 O+ nucleus and proton + nucleus reactions. The variation of the average transverse momentum is investigated as function of centrality, determined by measurements of the remaining energy of the projectile and the charged particle multiplicity. For small values of the entropy, deduced from the multiplicity density, and increase in average p T is observed levelling off for larger values of entropy. The target-mass and energy dependence of π 0 p T distributions are presented. (orig.)

  2. Cross-sections of spallation residues produced in 1A GeV 208Pb on proton reactions

    International Nuclear Information System (INIS)

    Wlazlo, W.; Uniwersytet Jagiellonski, Cracow; Enqvist, T.; Armbruster, P.

    2000-02-01

    Spallation residues produced in 1 GeV per nucleon 208 Pb on proton reactions have been studied using the fragment separator facility at GSI. Isotopic production cross-sections of elements from 61 Pm to 82 Pb have been measured down to 0.1 mb with a high accuracy. The recoil kinetic energies of the produced fragments were also determined. The obtained cross-sections agree with most of the few existing gamma-spectroscopy data. Data are compared with different intranuclear-cascade and evaporation-fission models. Drastic deviations were found for a standard code used in technical applications. (orig.)

  3. A beam detector for pion experiments and analysis of the inclusive Λ production in proton-proton reactions with HADES

    Energy Technology Data Exchange (ETDEWEB)

    Lalik, Rafal Tomasz

    2016-06-02

    This thesis presents the work focused on two topics related to the physics performed at the HADES detector. In the first part, the development of the tracking detector playing an important role of online beam monitoring and the momentum reconstruction device in the secondary pion beam experiment is presented. Such a detector must fulfill various requirements regarding the operation in the vacuum, with accelerator beams and high count rates. Two detection stations employing double sided silicons strip sensors with an active area of 10 cm x 10 cm and position resolution of 780 μm, providing momentum resolution below 0.5 % and capable for operating with beams up to 32 x 10{sup 6} particles/s total and 2 x 10{sup 6} particles/s in a single channel have been constructed, tested and used in the pion beam experiments. In the first chapter, general information about the production of the secondary, in particular, pion beams is presented. Further, description how the momentum is reconstructed using the information obtained from the tracking detector, and description of most important components of the system, namely the silicon sensor and front end electronics used for its readout is presented. In the second chapter, development of the detector, including all the components used or constructed for this particular purpose is presented. This section also includes description of the laboratory tests and calibrations performed to characterize the detector. In the end of the section, results from two of the beam runs employed for the tests of the detector are presented and discussed. The last third chapter presents results from the commissioning of the tracking detector in the final configuration. Momentum reconstruction feasibility is presented. The second part of the thesis focuses on the analysis of inclusive production of the Λ hyperons in the nuclear reactions at the HADES energies. The aims of the analysis are to extract the differential cross-section of Λ production in

  4. A beam detector for pion experiments and analysis of the inclusive Λ production in proton-proton reactions with HADES

    International Nuclear Information System (INIS)

    Lalik, Rafal Tomasz

    2016-01-01

    This thesis presents the work focused on two topics related to the physics performed at the HADES detector. In the first part, the development of the tracking detector playing an important role of online beam monitoring and the momentum reconstruction device in the secondary pion beam experiment is presented. Such a detector must fulfill various requirements regarding the operation in the vacuum, with accelerator beams and high count rates. Two detection stations employing double sided silicons strip sensors with an active area of 10 cm x 10 cm and position resolution of 780 μm, providing momentum resolution below 0.5 % and capable for operating with beams up to 32 x 10 6 particles/s total and 2 x 10 6 particles/s in a single channel have been constructed, tested and used in the pion beam experiments. In the first chapter, general information about the production of the secondary, in particular, pion beams is presented. Further, description how the momentum is reconstructed using the information obtained from the tracking detector, and description of most important components of the system, namely the silicon sensor and front end electronics used for its readout is presented. In the second chapter, development of the detector, including all the components used or constructed for this particular purpose is presented. This section also includes description of the laboratory tests and calibrations performed to characterize the detector. In the end of the section, results from two of the beam runs employed for the tests of the detector are presented and discussed. The last third chapter presents results from the commissioning of the tracking detector in the final configuration. Momentum reconstruction feasibility is presented. The second part of the thesis focuses on the analysis of inclusive production of the Λ hyperons in the nuclear reactions at the HADES energies. The aims of the analysis are to extract the differential cross-section of Λ production in pp center

  5. Sensitive detection of n-alkanes using a mixed ionization mode proton-transfer-reaction mass spectrometer

    Directory of Open Access Journals (Sweden)

    O. Amador-Muñoz

    2016-11-01

    Full Text Available Proton-transfer-reaction mass spectrometry (PTR-MS is a technique that is widely used to detect volatile organic compounds (VOCs with proton affinities higher than water. However, n-alkanes generally have a lower proton affinity than water and therefore proton transfer (PT by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+ in the reaction chamber (drift tube. There are very few studies on O2+ detection of alkanes and the mixed mode has never been proposed before. We determined the optimum conditions and the resulting reaction mechanisms, allowing detection of n-alkanes from n-pentane to n-tridecane. These compounds are mostly emitted by evaporative/combustion process from fossil fuel use. The charge transfer (CT mechanism observed with O2+ was the main reaction channel for n-heptane and longer n-alkanes, while for n-pentane and n-hexane the main reaction channel was hydride abstraction (HA. Maximum sensitivities were obtained at low E ∕ N ratios (83 Td, low water flow (2 sccm and high O2+ ∕ NO+ ratios (Uso =  180 V. Isotopic 13C contribution was taken into account by subtracting fractions of the preceding 12C ion signal based on the number of carbon atoms and the natural abundance of 13C (i.e., 5.6 % for n-pentane and 14.5 % for n-tridecane. After accounting for isotopic distributions, we found that PT cannot be observed for n-alkanes smaller than n-decane. Instead, protonated water clusters of n-alkanes (M  ⋅  H3O+ species were observed with higher abundance using lower O2+ and higher water cluster fractions. M  ⋅  H3O+ species are probably the source for the M + H+ species observed from n-decane to n-tridecane. Normalized sensitivities to O2+ or to the sum of O2++

  6. New Oxime Ligand with Potential for Proton-Coupled Electron-Transfer Reactions

    DEFF Research Database (Denmark)

    Deville, Claire; Sundberg, Jonas; McKenzie, Christine Joy

    such that a pyridine group is sterically restricted so it does not coordinate. Instead it can act as proximal base for accepting the oxime proton. [1] M. H. V. Huynh, T. J. Meyer, Chem. Rev. 2007, 107, 5004-5064. [2] T. Irebo, O. Johansson, L. Hammarström, J. Am. Chem. Soc., 2008, 130, 9194-9195....

  7. Deamidation reactions of protonated asparagine and glutamine investigated by ion spectroscopy

    NARCIS (Netherlands)

    Kempkes, L.J.M.; Martens, J.K.; Grzetic, J.; Berden, G.; Oomens, J.

    2016-01-01

    RATIONALE: Deamidation of Asn and Gln residues is a primary route for spontaneous post-translational protein modification. Several structures have been proposed for the deamidation products of the protonated amino acids. Here we verify these structures by ion spectroscopy, as well as the structures

  8. Time resolved investigations on biogenic trace gases exchanges using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Karl, T.

    2000-02-01

    Volatile organic compounds (VOCs) released from vegetation, including wound-induced VOCs, can have important effects on atmospheric chemistry. The analytical methods for measuring wound-induced VOCs, especially the hexenal family of VOCs (hexenals, hexenols and hexenyl esters) but also compounds like acetaldehyde, are complicated by their chemical instability and the transient nature of their formation after leaf and stem wounding. The goal of this thesis was to assess, quantify and complement our understanding on the origin of tropospheric VOCs. This thesis demonstrates that formation and emission of hexenal family compounds can be monitored on-line using proton-transfer-reaction mass spectrometry (PTR-MS), avoiding the need for preconcentration or chromatography. These measurements revealed the rapid emission of the parent compound, (Z)-3-hexenal, within 1-2 seconds of wounding of leaves from various woody and nonwoody plants, and its metabolites including (E)-2-hexenal, hexenols and hexenyl acetates. Emission of (Z)-3-hexenal from detached, drying leaves averaged 500 μg (gram dry weight)-1. PTR-MS showed to be a useful tool for the analysis of VOC emissions resulting from grazing, herbivory, harvesting and senescing leaves. The release of reactive VOCs during lawn mowing was observed in on-line ambient air measurements in July and August 1998 in the outskirts of Innsbruck. Also obtained were data on emission rates of reactive aldehydes (hexenyl compounds) and other abundant VOCs such as methanol, acetaldehyde and acetone from drying grass in various chamber experiments. Fluxes were measured after cutting of grass using eddy covariance measurements and the micrometeorological gradient method (Obhukov-Similarity-Method). Comparison of data obtained by these different methods showed satisfactory agreement. The highest fluxes for methanol during drying were 5 mg/m2h, for (Z)-3-hexenal 1.5 mg/m2h. Experiments conducted on the Sonnblick Observatory in Fall and Winter

  9. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    Science.gov (United States)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce

  10. Bismuth nitrate as an efficient recyclable catalyst for the one-pot multi component synthesis of 1,4-dihydropyridine derivatives through unsymmetrical Hantzsch reaction

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2016-09-01

    Full Text Available Bismuth nitrate catalyzed efficient Hantzsch reaction via four-component coupling reactions of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione (dimedone, ethyl acetoacetate and ammonium acetate at 80 °C temperature was described as the preparation of 1,4-dihydropyridine derivatives. 2-Amino-4-phenyl-3-cyano-7,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline derivatives are also prepared under the same experimental conditions using aldehydes, dimedone, malononitrile and ammonium acetate in good yield. The higher catalytic activity of Bi(NO3·5H2O is ascribed to its high acidity, thermal stability and water tolerance. The process presented here is operationally simple, environmentally benign and has excellent yield. Furthermore, the catalyst can be recovered conveniently and reused efficiently.

  11. Parameterization of N2O5 Reaction Probabilities on the Surface of Particles Containing Ammonium, Sulfate, and Nitrate

    Science.gov (United States)

    A comprehensive parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity, particle composition, and phase state, for use in advanced air quality models. The reaction probabilities o...

  12. Analysis for fragmentation products of proton-induced reactions on Pb with energy up to GeV

    CERN Document Server

    Fan Sheng; LiZhuXia; Zhao Zhi Xiang

    2002-01-01

    The mass and charge distribution of residual products produced in the spallation reaction needs to be studied because it can provide useful information for the disposal of nuclear and the radiation damage in the spallation target. The mass and charge distribution of the spallation products is studied by using quantum molecular dynamic (QMD) models. The simulation results are well agreed with the experimental data of the spallation fragment and empirical formula. However, QMD model does not include the fission process; the calculations can not reproduce the fission fragment. The fission model is introduced into QMD model to investigate the fragment products from proton-induced reactions on Pb. The results are in good agreement with the experimental data

  13. Excitation functions for proton-induced reactions on natural hafnium: Production of 177Lu for medical use

    Science.gov (United States)

    Siiskonen, T.; Huikari, J.; Haavisto, T.; Bergman, J.; Heselius, S.-J.; Lill, J.-O.; Lönnroth, T.; Peräjärvi, K.; Vartti, V.-P.

    2009-11-01

    There is an increasing interest in using radioisotopes of rare earth elements for internal radiotherapy and for imaging in nuclear medicine. 177Lu is one of the promising radionuclides. This article reports on the first measurements of the excitation function for the production of 177Lu with proton-beam energies up to 17 MeV on natural hafnium targets. The experimental cross sections for the reaction natHf(p,x) 177Lu were obtained by the activation of a stacked-foil target and subsequent gamma spectrometry. Theoretical cross sections were calculated up to 35 MeV with the EMPIRE nuclear reaction model code. The measured and calculated cross sections were used for deriving the thick-target yields and for estimating the production of other nuclides than 177Lu. Measured production cross sections of 175,176,177,178Ta on the same target are also presented.

  14. Neutronigen target study and realization for medical cyclotron using proton reactions on lithium deuteride

    International Nuclear Information System (INIS)

    Filhol, J.M.

    1984-02-01

    The new idea, used for this source realization, consists of replacing the classical beryllium targets (usuals in neutronotherapy cyclotrons) by a half-thick lithium deuteride target. The target is bombarded by high energy 150 MeV) protons which are beyond the target, deviated out of the neutron beam by a permanent magnet, before to be stopped in a graphite block. Target cooling conditions study and optimisation is presented, followed by the proton deflection block study and realization. The permanent magnet used (SmCo 5 ) is adapted to this target use conditions. Many series of neutronic and dosimetric characteristics measurements allow to verify the theoretical predictions concerning the neutron flux obtained [fr

  15. Proton-transfer and H2-elimination reactions of trimethylamine alane: role of dihydrogen bonding and Lewis acid-base interactions.

    Science.gov (United States)

    Filippov, Oleg A; Tsupreva, Victoria N; Golubinskaya, Lyudmila M; Krylova, Antonina I; Bregadze, Vladimir I; Lledos, Agusti; Epstein, Lina M; Shubina, Elena S

    2009-04-20

    Proton-transfer and H(2)-elimination reactions of aluminum hydride AlH(3)(NMe(3)) (TMAA) with XH acids were studied by means of IR and NMR spectroscopy and DFT calculations. The dihydrogen-bonded (DHB) intermediates in the interaction of the TMAA with XH acids (CH(3)OH, (i)PrOH, CF(3)CH(2)OH, adamantyl acetylene, indole, 2,3,4,5,6-pentafluoroaniline, and 2,3,5,6-tetrachloroaniline) were examined experimentally at low temperatures, and the spectroscopic characteristics, dihydrogen bond strength and structures, and the electronic and energetic characteristics of these complexes were determined by combining experimental and theoretical approaches. The possibility of two different types of DHB complexes with polydentate proton donors (typical monodentate and bidentate coordination with the formation of a symmetrical chelate structure) was shown by DFT calculations and was experimentally proven in solution. The DHB complexes are intermediates of proton-transfer and H(2)-elimination reactions. The extent of this reaction is very dependent on the acid strength and temperature. With temperature increases the elimination of H(2) was observed for OH and NH acids, yielding the reaction products with Al-O and Al-N bonds. The reaction mechanism was computationally studied. Besides the DHB pathway for proton transfer, another pathway starting from a Lewis complex was discovered. Preference for one of the pathways is related to the acid strength and the nucleophilicity of the proton donor. As a consequence of the dual Lewis acid-base nature of neutral aluminum hydride, participation of a second ROH molecule acting as a bifunctional catalyst forming a six-member cycle connecting aluminum and hydride sites notably reduces the reaction barrier. This mechanism could operate for proton transfer from weak OH acids to TMAA in the presence of an excess of proton donor.

  16. A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2015-03-21

    The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

  17. Spectroscopy and secondary reactions of proton-rich nuclei and the search for new isotopes

    International Nuclear Information System (INIS)

    Blank, B.; Andriamonje, S.; Czajkowski, S.; Davi, F.; Del Moral, R.; Dufour, J.P.; Fleury, A.

    1995-01-01

    Two experiments performed at GSI and GANIL are reviewed. Using a primary beam of 58 Ni at 650 MeV/nucleon impinging on a beryllium target, production cross sections of proton-rich fragments from projectile fragmentation have been measured at the projectile-fragment separator FRS at GSI. The production rates measured demonstrate that counting rates much higher than expected can be obtained at the proton drip line. The results from spectroscopy measurements show that no Thomas-Ehrmann effect is present in our data which means that the decay energies and masses can be well predicted by using e.g. the IMME. The partial charge-changing cross sections show an odd-even staggering which is much more pronounced when approaching the proton drip line. An experiment performed at the SISSI/LISE facility at GANIL is also presented. Using an 78 Kr primary beam, 5 new isotopes: 60 Ga, 64 As, 69,70 Kr, and 74 Sr have been observed. No evidence have been found for 69 Br which has been observed with a few counts at MSU. (authors). 22 refs., 9 figs

  18. Protective effect of transparent film dressing on proton therapy induced skin reactions

    Directory of Open Access Journals (Sweden)

    Whaley Jonathan T

    2013-01-01

    Full Text Available Abstract Objective Proton therapy can result in clinically significant radiation dermatitis. In some clinical scenarios, such as lung or breast cancer, the risk of severe radiation dermatitis may limit beam arrangement and prescription doses. Patients undergoing proton therapy for prostate cancer commonly develop mild radiation dermatitis. Herein, we report the outcomes of two prostate cancer patients whose radiation dermatitis appears to have been substantially diminished by transparent film dressings (Beekley stickers. Methods This is a descriptive report of the skin toxicity observed in two patients undergoing proton therapy for prostate cancer at a single institution in 2011. A phantom dosimetric study was performed to evaluate the impact of a transparent film dressing on a beam’s spread out Bragg peak (SOBP. Results Two patients with low risk prostate cancer were treated with proton therapy to a total dose of 79.2Gy (RBE in 1.8 Gy (RBE fractions using two opposed lateral beams daily. Both patients had small circular (2.5 cm diameter transparent adhesive markers placed on their skin to assist with daily alignment. Patient 1 had markers in place bilaterally for the entirety of treatment. Patient 2 had a marker in place for three weeks on one side and six weeks on the other. Over the course of therapy, both men developed typical Grade 1 radiation dermatitis (asymptomatic erythema on their hips; however, in both patients, the erythema was substantially decreased beneath the markers. Patient 2 demonstrated less attenuation and thus greater erythema in the skin covered for three weeks compared to the skin covered for six weeks. The difference in skin changes between the covered and uncovered skin persisted for at least 1 month. A phantom study of double scattered beam SOBP with and without the marker in the beam path showed no gross dosimetric effect. Conclusions Transparent adhesive markers appear to have attenuated radiation dermatitis in

  19. Protective effect of transparent film dressing on proton therapy induced skin reactions

    International Nuclear Information System (INIS)

    Whaley, Jonathan T; Kirk, Maura; Cengel, Keith; McDonough, James; Bekelman, Justin; Christodouleas, John P

    2013-01-01

    Proton therapy can result in clinically significant radiation dermatitis. In some clinical scenarios, such as lung or breast cancer, the risk of severe radiation dermatitis may limit beam arrangement and prescription doses. Patients undergoing proton therapy for prostate cancer commonly develop mild radiation dermatitis. Herein, we report the outcomes of two prostate cancer patients whose radiation dermatitis appears to have been substantially diminished by transparent film dressings (Beekley stickers). This is a descriptive report of the skin toxicity observed in two patients undergoing proton therapy for prostate cancer at a single institution in 2011. A phantom dosimetric study was performed to evaluate the impact of a transparent film dressing on a beam’s spread out Bragg peak (SOBP). Two patients with low risk prostate cancer were treated with proton therapy to a total dose of 79.2Gy (RBE) in 1.8 Gy (RBE) fractions using two opposed lateral beams daily. Both patients had small circular (2.5 cm diameter) transparent adhesive markers placed on their skin to assist with daily alignment. Patient 1 had markers in place bilaterally for the entirety of treatment. Patient 2 had a marker in place for three weeks on one side and six weeks on the other. Over the course of therapy, both men developed typical Grade 1 radiation dermatitis (asymptomatic erythema) on their hips; however, in both patients, the erythema was substantially decreased beneath the markers. Patient 2 demonstrated less attenuation and thus greater erythema in the skin covered for three weeks compared to the skin covered for six weeks. The difference in skin changes between the covered and uncovered skin persisted for at least 1 month. A phantom study of double scattered beam SOBP with and without the marker in the beam path showed no gross dosimetric effect. Transparent adhesive markers appear to have attenuated radiation dermatitis in these two patients without affecting the SOBP. One patient may

  20. Low-lying states and structure of the exotic 8He via direct reactions on the proton

    International Nuclear Information System (INIS)

    Skaza, F.; Lapoux, V.; Keeley, N.; Alamanos, N.; Auger, F.; Beaumel, D.; Becheva, E.; Blumenfeld, Y.; Delaunay, F.; Drouart, A.; Gillibert, A.; Giot, L.; Khan, E.; Nalpas, L.; Pakou, A.; Pollacco, E.; Raabe, R.; Roussel-Chomaz, P.; Rusek, K.; Scarpaci, J.-A.; Sida, J.-L.; Stepantsov, S.; Wolski, R.

    2007-01-01

    The structure of the light exotic nucleus 8 He was investigated using direct reactions of the 8 He SPIRAL beam on a proton-rich target. The (p,p') scattering to the 2 1 + state, the (p,d) 7 He and (p,t) 6 He transfer reactions, were measured at the energy E lab =15.7 A.MeV. The light charged particles (p,d,t) were detected in the MUST Si-strip telescope array. The excitation spectrum of 8 He was extracted from the (p,p') reaction. Above the known 2 1 + excited state at 3.6 MeV, a second resonance was found around 5.4 MeV. The cross sections were analyzed within the coupled-reaction channels framework, using microscopic potentials. It is inferred that the 8 He ground state has a more complex neutron-skin structure than suggested by previous α+4n models assuming a pure (1p 3/2 ) 4 configuration

  1. Neutron-proton bremsstrahlung from intermediate energy heavy-ion reactions as a probe of the nuclear symmetry energy?

    International Nuclear Information System (INIS)

    Yong, G.-C.; Li Baoan; Chen Liewen

    2008-01-01

    Hard photons from neutron-proton bremsstrahlung in intermediate energy heavy-ion reactions are examined as a potential probe of the nuclear symmetry energy within a transport model. Effects of the symmetry energy on the yields and spectra of hard photons are found to be generally smaller than those due to the currently existing uncertainties of both the in-medium nucleon-nucleon cross sections and the photon production probability in the elementary process pn→pnγ. Very interestingly, nevertheless, the ratio of hard photon spectra R 1/2 (γ) from two reactions using isotopes of the same element is not only approximately independent of these uncertainties but also quite sensitive to the symmetry energy. For the head-on reactions of 132 Sn + 124 Sn and 112 Sn + 112 Sn at E beam /A=50 MeV, for example, the R 1/2 (γ) displays a rise up to 15% when the symmetry energy is reduced by about 20% at ρ=1.3ρ 0 which is the maximum density reached in these reactions

  2. Modeling of the symmetry factor of electrochemical proton discharge via the Volmer reaction

    DEFF Research Database (Denmark)

    Björketun, Mårten E.; Tripkovic, Vladimir; Skúlason, Egill

    2013-01-01

    A scheme for evaluating symmetry factors of elementary electrode reactions using a density functional theory (DFT) based model of the electrochemical double layer is presented. As an illustration, the symmetry factor is determined for hydrogen adsorption via the electrochemical Volmer reaction...

  3. Modeling Proton- and Light Ion-Induced Reactions at Low Energies in the MARS15 Code

    Energy Technology Data Exchange (ETDEWEB)

    Rakhno, I. L. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Mokhov, N. V. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Gudima, K. K. [National Academy of Sciences, Cisineu (Moldova)

    2015-04-25

    An implementation of both ALICE code and TENDL evaluated nuclear data library in order to describe nuclear reactions induced by low-energy projectiles in the Monte Carlo code MARS15 is presented. Comparisons between results of modeling and experimental data on reaction cross sections and secondary particle distributions are shown.

  4. Rotational dependence of the proton-transfer reaction HBr+ + CO2-->HOCO+ + Br. I. Energy versus angular momentum effects.

    Science.gov (United States)

    Paetow, Lisa; Unger, Franziska; Beichel, Witali; Frenking, Gernot; Weitzel, Karl-Michael

    2010-05-07

    Cross sections for the endothermic proton-transfer reactions of rotationally state-selected HBr(+) and DBr(+) ions with CO(2) were measured in a guided ion beam apparatus in order to determine the influence of rotational excitation and collision energy in the center of mass (c.m.) system on the cross section. Ab initio calculations were performed to obtain energetic information about reactants, intermediates, and products. In the experiment HBr(+) and DBr(+) ions were prepared with the same mean rotational quantum number but different mean rotational energies as the rotational constants differ by about a factor of two. The mean rotational energy was varied from 1.4 to 66.3 meV for HBr(+) and from 0.7 to 43.0 meV for DBr(+). Collision energies (E(c.m.)) ranged from 0.32 to 1.00 eV. Under all conditions considered, an increase in the rotational excitation leads to a decrease in the cross section for both reactions. However, the effect is more pronounced for the higher collision energies. For E(c.m.)=1.00 and 0.85 eV; a comparison between the results for HBr(+) and DBr(+) indicates that the cross section is dominated by effects of rotational energy rather than angular momentum. For lower collision energies the cross sections for the deuteron transfer and the proton transfer are in best agreement if not compared for the same c.m. collision energy but for the same value of the difference between the collision energy and the reaction enthalpy.

  5. Reaction channel coupling effects for nucleons on 16O: Induced undularity and proton-neutron potential differences

    Science.gov (United States)

    Keeley, N.; Mackintosh, R. S.

    2018-01-01

    Background: Precise fitting of scattering observables suggests that the nucleon-nucleus interaction is l dependent. Such l dependence has been shown to be S -matrix equivalent to an undulatory l -independent potential. The undulations include radial regions where the imaginary term is emissive. Purpose: To study the dynamical polarization potential (DPP) generated in proton-16O and neutron-16O interaction potentials by coupling to pickup channels. Undulatory features occurring in these DPPs can be compared with corresponding features of empirical optical model potentials (OMPs). Furthermore, the additional inclusion of coupling to vibrational states of the target will provide evidence for dynamically generated nonlocality. Methods: The fresco code provides the elastic channel S -matrix Sl j for chosen channel couplings. Inversion, Sl j→V (r ) +l .s VSO(r ) , followed by subtraction of the bare potential, yields an l -independent and local representation of the DPP due to the chosen couplings. Results: The DPPs have strongly undulatory features, including radial regions of emissivity. Certain features of empirical DPPs appear, e.g., the full inverted potential has emissive regions. The DPPs for different collective states are additive except near the nuclear center, whereas the collective and reaction channel DPPs are distinctly nonadditive over a considerable radial range, indicating dynamical nonlocality. Substantial differences between the DPPs due to pickup coupling for protons and neutrons occur; these imply a greater difference between proton and neutron OMPs than the standard phenomenological prescription. Conclusions: The onus is on those who object to undularity in the local and l -independent representation of nucleon elastic scattering to show why such undulations do not occur. This work suggests that it is not legitimate to halt model-independent fits to high-quality data at the appearance of undularity.

  6. Laboratory studies in support of the detection of biogenic unsaturated alcohols by proton transfer reaction-mass spectrometry

    Science.gov (United States)

    Demarcke, M.; Amelynck, C.; Schoon, N.; Dhooghe, F.; Rimetz-Planchon, J.; van Langenhove, H.; Dewulf, J.

    2010-02-01

    The effect of the ratio of the electric field to the buffer gas number density (E/N) in the drift tube reactor of a proton transfer reaction-mass spectrometer (PTR-MS) on the product ion distributions of seven common biogenic unsaturated alcohols (2-methyl-3-buten-2-ol, 1-penten-3-ol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 1-octen-3-ol, 6-methyl-5-hepten-2-ol and linalool) has been investigated. At low E/N values, the dominant product ion is the dehydrated protonated alcohol. Increasing E/N results in more extensive fragmentation for all compounds. For cis-3-hexenol and 6-methyl-5-hepten-2-ol the contribution of the protonated molecule can be enhanced by reducing E/N with respect to commonly used PTR-MS E/N values (120-130 Td). Significant differences have been found between some of the isomeric species studied, opening a way for selective detection. The C10 alcohol linalool mainly results in product ions at m/z 137 and 81, which are also PTR-MS fingerprints of monoterpenes. This may complicate monoterpene quantification when linalool and monoterpenes are simultaneously present in sampled air. Furthermore the influence of the water vapour pressure in the PTR-MS inlet line on the product ion distributions has been determined. Some major fingerprint ions of the unsaturated alcohols were found to depend significantly on the water vapour pressure in the inlet line and this should be taken into account for accurate quantification of these species by PTR-MS.

  7. Fundamentals on the biochemistry of peroxynitrite and protein tyrosine nitration

    Directory of Open Access Journals (Sweden)

    Silvina Bartesaghi

    2018-04-01

    Full Text Available In this review we provide an analysis of the biochemistry of peroxynitrite and tyrosine nitration. Peroxynitrite is the product of the diffusion-controlled reaction between superoxide (O2•- and nitric oxide (•NO. This process is in competition with the enzymatic dismutation of O2•- and the diffusion of •NO across cells and tissues and its reaction with molecular targets (e.g. guanylate cyclase. Understanding the kinetics and compartmentalization of the O2•- / •NO interplay is critical to rationalize the shift of •NO from a physiological mediator to a cytotoxic intermediate. Once formed, peroxynitrite (ONOO- and ONOOH; pKa = 6,8 behaves as a strong one and two-electron oxidant towards a series of biomolecules including transition metal centers and thiols. In addition, peroxynitrite anion can secondarily evolve to secondary radicals either via its fast reaction with CO2 or through proton-catalyzed homolysis. Thus, peroxynitrite can participate in direct (bimolecular and indirect (through secondary radical intermediates oxidation reactions; through these processes peroxynitrite can participate as cytotoxic effector molecule against invading pathogens and/or as an endogenous pathogenic mediator. Peroxynitrite can cause protein tyrosine nitration in vitro and in vivo. Indeed, tyrosine nitration is a hallmark of the reactions of •NO-derived oxidants in cells and tissues and serves as a biomarker of oxidative damage. Protein tyrosine nitration can mediate changes in protein structure and function that affect cell homeostasis. Tyrosine nitration in biological systems is a free radical process that can be promoted either by peroxynitrite-derived radicals or by other related •NO-dependent oxidative processes. Recently, mechanisms responsible of tyrosine nitration in hydrophobic biostructures such as membranes and lipoproteins have been assessed and involve the parallel occurrence and connection with lipid

  8. Cross-sections of (p, xn) nuclear reactions on Pb and Bi by 100 MeV protons

    Energy Technology Data Exchange (ETDEWEB)

    Oranj, Leila Mokhtari; Jung, Nam Suk; Oh, Joo Hee; Lee, Arim; Kim, Dong Hyun; Bae, Oryun; Lee, Hee Seock [POSTECH, Pohang (Korea, Republic of)

    2016-04-15

    The development of high-intensity and high-energy accelerator is gaining interest in Korea, in recent years. Rare Isotope Science Project (RISP), Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL), Korea Heavy Ion Medical Accelerator (KHIMA) facilities are being designed. In the frame of above projects, for the safety issue and shielding analysis of the accelerator facility, extensive studies including experimental and simulation on the production yields of residual nuclei induced in the accelerator materials such as Pb, Cu and Bi by protons and heavy ions are in progress. In this work, we measured cross-sections of {sup na}'tPb(p,xn){sup 206,205,204,20{sup ,202}}Bi and {sup 209}Bi(p, xn){sup 207,206,205,204},{sup 203}Po nuclear reactions by the 100-MeV protons. The present experimental data are in good agreement with the results of Titarenkoet al. and Gloris et al.. Experimental data were higher than theoretical data. In other words, results of TALYS code and data in TENDL library underestimated the measured crosss sections and library of TALYS code and TENDL need to be improved.

  9. Effect of NaCl Salts on the Activation Energy of Excited-State Proton Transfer Reaction of Coumarin 183.

    Science.gov (United States)

    Joung, Joonyoung F; Kim, Sangin; Park, Sungnam

    2015-12-17

    Coumarin 183 (C183) was used as a photoacid to study excited-state proton transfer (ESPT) reactions. Here, we studied the effect of ions on the ESPT of C183 in aqueous NaCl solutions using a steady-state fluorescence spectroscopy and time-correlated single photon counting (TCSPC) method. The acid dissociation equilibrium of excited-state C183 and the activation energy for the ESPT of C183 were determined as a function of NaCl concentration. The change in the equilibrium constant was found to be correlated with the solvation energy of deprotonated C183. Frequency-resolved TCSPC signals measured at several temperatures were analyzed by using a global fitting analysis method which enabled us to extract all the rate constants involving the ESPT reaction and the spectra of individual species. The activation energy for the ESPT reaction of C183 was highly dependent on NaCl concentration. Quantum chemical calculations were used to calculate the local hydrogen-bond (H-bond) configurations around C183 in aqueous NaCl solutions. It was found that the activation energy for the ESPT was determined by the local H-bond configurations around C183 which were significantly influenced by the dissolved ions.

  10. Proton NMR investigation of the electron-exchange reaction between hexaammineruthenium(II) and hexaammineruthenium(III) ions

    Energy Technology Data Exchange (ETDEWEB)

    Smolenaers, P.J.; Beattie, J.K.

    1986-06-18

    The rate of the electron-self-exchange reaction between (Ru(NH/sub 3/)/sub 6/)/sup 3 +/ and (Ru(NH/sub 3/)/sub 6/)/sup 2 +/ has been measured by proton NMR line broadening. The system is complicated by the equation of (Ru(NH/sub 3/)/sub 6/)/sup 2 +/, which results in reduction of the small amount of (Ru(NH/sub 3/)/sub 6/)/sup 3 +/ present. To reduce this difficulty, measurements were performed at 4/sup 0/C. Rate constants are (6.6 +/- 1.0) x 10/sup 3/ and (9.9 +/- 0.2) X 10/sup 3/ M/sup -1/ s/sup -1/ for solutions of 0.125 and 0.250 M (Ru(NH/sub 3/)/sub 6/)Cl/sub 2/, respectively. These rate constants are in order-of-magnitude agreement with those previously reported. The reaction appears to be catalyzed by chloride ion. A rate constant for the uncatalyzed reaction at 4/sup 0/C and an ionic strength approx.0.5 M is estimated to be 3.3 x 10/sup 3/ M/sup -1/ s/sup -1/. The activation enthalpy is about 5 kcal mol/sup -1/.

  11. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  12. Measurement of excitation functions in proton induced reactions on natural copper from their threshold to 43 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Shahid, Muhammad; Kim, Kwangsoo [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Naik, Haladhara [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Zaman, Muhammad [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Yang, Sung-Chul [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 305-353 (Korea, Republic of); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2015-01-01

    We have measured the production cross-sections of the residual radionuclides from proton-induced reactions of {sup nat}Cu by using a stacked-foil activation and off-line γ-ray spectrometric technique in the energy range from their respective threshold to 43 MeV at the MC-50 cyclotron of the Korea Institute of Radiological and Medical Sciences. The measured results were compared with the earlier reported data as well as with the theoretical values obtained from the TENDL-2013 library based on the TALYS 1.6 code. The integral yields for thick target of the investigated radio-nuclides were calculated from the measured excitation function and the stopping power of {sup nat}Cu.

  13. Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Lukasz JOZWIAK

    2017-02-01

    Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

  14. Catalytic hydrogen/oxygen reaction assisted the proton exchange membrane fuel cell (PEMFC) startup at subzero temperature

    Science.gov (United States)

    Sun, Shucheng; Yu, Hongmei; Hou, Junbo; Shao, Zhigang; Yi, Baolian; Ming, Pingwen; Hou, Zhongjun

    Fuel cells for automobile application need to operate in a wide temperature range including freezing temperature. However, the rapid startup of a proton exchange membrane fuel cell (PEMFC) at subfreezing temperature, e.g., -20 °C, is very difficult. A cold-start procedure was developed, which made hydrogen and oxygen react to heat the fuel cell considering that the FC flow channel was the characteristic of microchannel reactor. The effect of hydrogen and oxygen reaction on fuel cell performance at ambient temperature was also investigated. The electrochemical characterizations such as I- V plot and cyclic voltammetry (CV) were performed. The heat generated rate for either the single cell or the stack was calculated. The results showed that the heat generated rate was proportional to the gas flow rate when H 2 concentration and the active area were constant. The fuel cell temperature rose rapidly and steadily by controlling gas flow rate.

  15. Study of the excited levels of 11C and 12C by the analysis of protons induced reactions

    International Nuclear Information System (INIS)

    Rihet, Y.

    1984-07-01

    The present work is a study of 11 and 12 C excited states by reactions of non polarised protons on 10 B and 11 B. R-matrix analysis of the 10 B excitation curves in the range E p = 0 to 8 MeV was used to establish parameters of 41 levels in 11 C. Isobaric multiplets of T = 1/2 and T = 3/2 states in A = 11 nuclei are deduced. Analysis of 11 B excitation curves in the E p = 0.5 to 7.4 MeV range led to parameter values of 60 levels in 12 C. T = 1 states in A = 12 isobaric nuclei are discussed [fr

  16. Study of proton-induced reactions and correlation with fast-neutron scattering

    International Nuclear Information System (INIS)

    Hansen, L.F.

    1982-01-01

    The generation of cross sections for fast neutron-nucleon interactions obtained from elastic and charge-exchange proton data is discussed in terms of the Lane model formalism. A general description of the interaction of nucleons with nuclei is presented in terms of the optical model and the extended (or coupled-channel) optical model, together with the relation of these models to microscopic calculations of the nucleon-nucleon interaction. Comparisons between neutron elastic data and calculations carried out with optical model potentials obtained from (p,p) and (p,n) data are presented for a large number of nuclei. The validity of the Lane model and the importance of coupled effects in the actinide region are shown in a detailed comparison of calculations for elastic and inelastic neutron differential cross sections and measurements for 232 Th and 238 U

  17. Search for proton emission in {sup 54}Ni and multi-nucleon transfer reactions in the actinide region

    Energy Technology Data Exchange (ETDEWEB)

    Geibel, Kerstin

    2012-06-15

    The first part of the thesis presents the investigation of fusion-evaporation reactions in order to verify one-proton emission from the isomeric 10{sup +} state in the proton rich nucleus {sup 54}Ni. Between the years 2006 and 2009 a series of experimental studies were performed at the Tandem accelerator in the Institut fuer Kernphysik (IKP), University of Cologne. These experiments used fusion-evaporation reactions to populate {sup 54}Ni via the two-neutron-evaporation channel of the compound nucleus {sup 56}Ni. The cross section for the population of the ground state of {sup 54}Ni was predicted to be in orders of microbarn. This required special care with respect to the sensitivity of the experimental setup, which consisted of a double-sided silicon-strip detector (DSSSD), a neutron-detector array and HPGe detectors. In two experiments the excitation functions of the reactions ({sup 32}S+{sup 24}Mg) and ({sup 28}Si+{sup 28}Si) were determined to find the optimal experimental conditions for the population of {sup 54}Ni. A final experiment employed a {sup 28}Si beam at an energy of 70 MeV, impinging on a {sup 28}Si target. With a complex analysis it is possible to obtain a background-free energy spectrum of the DSSSD. An upper cross section limit for the population of the 10{sup +} state in {sup 54}Ni is established at σ({sup 54}Ni(10{sup +})) ≤ (13.9 ± 7.8) nbarn. In the second part of the thesis the population of actinide nuclei by multi-nucleon transfer reactions is investigated. Two experiments, performed in 2007 and 2008 at the CLARA-PRISMA setup at the Laboratori Nazionali di Legnaro, are analyzed with respect to the target-like reaction products. In both experiments {sup 238}U was used as target. A {sup 70}Zn beam with 460 MeV and a {sup 136}Xe beam with 926 MeV, respectively, impinged on the target, inducing transfer reactions. Kinematic correlations between the reaction partners are used to obtain information on the unobserved target-like reaction

  18. On-line analysis of organic compounds in diesel exhaust using a proton transfer reaction mass spectrometer (PTR-MS)

    Science.gov (United States)

    Jobson, B. T.; Alexander, M. L.; Maupin, G. D.; Muntean, G. G.

    2005-08-01

    Chemical ionization mass spectrometry using H3O+ proton transfer in an ion drift tube (PTR-MS) was used to measure volatile organic compound (VOC) concentrations on-line in diesel engine exhaust as a function of engine load. The purpose of the study was to evaluate the PTR-MS instrument as an analytical tool for diesel engine emissions abatement research. Measured sensitivities determined from gas standards were found to agree well with calculated sensitivities for non-polar species. A slight humidity dependent sensitivity was observed for non-polar species, implying that reactions with H+(H2O)2 were important for some organics. The diesel exhaust mass spectra were complex but displayed a pattern of strong ion signals at 14n + 1 (n = 3.8) masses, with a relative ion abundance similar to that obtained from electron impact ionization of alkanes. Laboratory experiments verified that C8-C16 n-alkanes and C8-C13 1-alkenes react with H3O+ in dissociative proton transfer reaction resulting in alkyl cation ion products, primarily m/z 41, 43, 57, 71 and 85. Monitoring the sum of these ion signals may be useful for estimating alkane emissions from unburnt diesel fuel. Alkane fragmentation likely simplified the diesel exhaust mass spectrum and reduced potential mass interferences with isobaric aromatic compounds. Concentrations of aldehydes and ketones dominated those of aromatic species with formaldehyde and acetaldehyde estimated to be the most abundant VOCs in the PTR-MS mass spectrum at all engine loads. The relative abundances of benzene and toluene increased with engine load indicating their pyrogenic origin. The relative abundance of alkanes, aromatics, aldehydes and alcohols was broadly consistent with literature publications of diesel exhaust analysis by gas chromatography. About 75% of the organic ion signal could be assigned. On-line analysis of diesel exhaust using this technology may be valuable tool for diesel engine emission research.

  19. Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

    Science.gov (United States)

    Gupta, S; Basant, N; Mohan, D; Singh, K P

    2016-07-01

    Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

  20. The Trojan Horse Method Applied to the Astrophysically Relevant Proton Capture Reactions on Li Isotopes

    Science.gov (United States)

    Tumino, A.; Spitaleri, C.; Musumarra, A.; Pellegriti, M. G.; Pizzone, R. G.; Rinollo, A.; Romano, S.; Pappalardo, L.; Bonomo, C.; Del Zoppo, A.; Di Pietro, A.; Figuera, P.; La Cognata, M.; Lamia, L.; Cherubini, S.; Rolfs, C.; Typel, S.

    2005-12-01

    The 7Li(p,α)4He 6Li(d,α)4He and 6Li(p,α)3He reactions was performed and studied in the framework of the Trojan Horse Method applied to the d(7Li,αα)n, 6Li(6Li,αα)4He and d(6Li,α3He)n three-body reactions respectively. Their bare astrophysical S-factors were extracted and from the comparison with the behavior of the screened direct data, an independent estimate of the screening potential was obtained.

  1. Proton transfer and isotope-induced reaction in aniline cluster ions

    Czech Academy of Sciences Publication Activity Database

    Lengyel, Jozef; Poterya, Viktoriya; Fárník, Michal

    2015-01-01

    Roč. 50, č. 3 (2015), s. 643-649 ISSN 1076-5174 R&D Projects: GA ČR GA14-14082S Institutional support: RVO:61388955 Keywords : isotope effect * intracluster reaction * Electron ionization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.541, year: 2015

  2. Proton, deuteron and triton emission in 14N + Ag reaction at 52 MeV/nucleon

    International Nuclear Information System (INIS)

    Aleksakhin, V.Yu.; Gostkin, M.I.; Gudima, K.K.

    1998-01-01

    Inclusive energy spectra of p, d, t and multiplicities from the reaction 14 N(Ag, X), X = p, d, t at E/A = 52 MeV were measured. The experimental data are compared with Dubna version of the Cascade Model (DCM) and are analyzed in the framework of the moving source model

  3. /sup 3/He breakup reaction by 65 MeV protons in the FSI region

    Energy Technology Data Exchange (ETDEWEB)

    Okihana, A.; Takashima, R.; Fukunaga, K.; Kakigi, S.; Ohsawa, T.; Sekioka, T.; Yokota, H.

    1987-02-16

    The angular distributions of the differential cross sections and the analyzing powers for the /sup 3/He(p,p)dp and /sup 3/He(p,pd)/sup 1/H reactions have been measured in the FSI region. The multiple scattering calculation including to double scattering terms has reproduced the differential cross sections well.

  4. Tandem mass spectrometry and hydrogen/deuterium exchange studies of protonated species of 1,1'-bis(diphenylphosphino)-ferrocene oxidative impurity generated during a Heck reaction.

    Science.gov (United States)

    Wu, Lianming; Hernandez-Soto, Heriberto; Liu, David Q; Vogt, Frederick G; O'Neill-Slawecki, Stacy A; Su, Qiaogong

    2008-01-01

    Oxidation of 1,1'-bis(diphenylphosphino)-ferrocene (DPPF) was found to occur when it served as the ligand for Pd(II)(CH3COO)2 in a Heck reaction. This oxidative impurity of DPPF, referred to as DPPF(O), was identified by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) and exact mass measurements. Protonated DPPF(O) exhibited unique fragmentation pathways in the gas phase. Hydrogen/deuterium (H/D) exchange experiments provided important insights into the dissociation mechanisms of protonated DPPF(O), suggesting the existence of isomeric structures of the product ions by retaining or losing a proton (or deuteron) upon collision-induced dissociation (CID). The specific fate of the proton (or deuteron) upon CID is postulated to be dependent on the distance between the exchangeable proton (or deuteron) and the sites of bond cleavage. Density functional theory (DFT) calculations at the B3LYP/LANL2DZ level of theory showed that oxygen in DPPF(O) plays a pivotal role in invoking pi-cation interactions between the p-type lone pair electrons (n pi) in oxygen and the anti-bonding orbital of Fe(II), accounting for the major fragmentation pathways of protonated DPPF(O). Facile formation of organometallic distonic ions in dissociation of protonated DPPF(O), and especially of protonated DPPF, could be useful for further exploration of their chemical properties by gas-phase ion/molecule reactions. Copyright (c) 2008 John Wiley & Sons, Ltd.

  5. Potential Mechanisms of Hematological Adverse Drug Reactions in Patients Receiving Clozapine in Combination With Proton Pump Inhibitors.

    Science.gov (United States)

    Wiciński, Michał; Węclewicz, Mateusz M; Miętkiewicz, Mateusz; Malinowski, Bartosz; Grześk, Elżbieta; Klonowska, Joanna

    2017-03-01

    Clozapine is a second-generation antipsychotic which has proven efficacy in treating the symptoms of schizophrenia. Although clozapine therapy is associated with a number of adverse drug reactions, it is frequently used. One of the most common adverse drug reactions is gastroesophageal reflux disease which is an indication for treatment with proton pump inhibitors (PPIs). Coadministration of clozapine and PPIs increases the risk of hematological adverse drug reactions, including neutropenia and agranulocytosis. The mechanism in idiosyncratic agranulocytosis is not dose related and involves either a direct toxic or an immune-allergic effect. It is suspected that the clozapine metabolites nitrenium ion and N-desmethylclozapine may cause apoptosis or impair growth of granulocytes. Formation of N-desmethylclozapine is correlated with activity of the cytochrome P450 enzymes 1A2 and 3A4 (CYP1A2 and CYP3A4). Nitrenium ion is produced by the flavin-containing monooxygenase system of leukocytes. A drug interaction between clozapine and a PPI is a consequence of the induction of common metabolic pathways either by the PPI or clozapine. Findings to date suggest that indirect induction of flavin-containing monooxygenase by omeprazole through the aryl hydrocarbon receptor increases the expression of the enzyme mRNA and in the long term may cause the increase in activity. Moreover, induction of CYP1A2, especially by omeprazole and lansoprazole, may increase the serum concentration of N-desmethylclozapine, which can accumulate in lymphocytes and may achieve toxic levels. Another hypothesis that may explain hematological adverse drug reactions is competitive inhibition of CYP2C19, which may contribute to increased serum concentrations of toxic metabolites.

  6. Spallation reaction study for fission products in nuclear waste: Cross section measurements for {sup 137}Cs and {sup 90}Sr on proton and deuteron

    Energy Technology Data Exchange (ETDEWEB)

    Wang, H., E-mail: wanghe@ribf.riken.jp [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Otsu, H.; Sakurai, H.; Ahn, D.S. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Aikawa, M. [Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doornenbal, P.; Fukuda, N.; Isobe, T. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawakami, S. [Department of Applied Physics, University of Miyazaki, Miyazaki 889-2192 (Japan); Koyama, S. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kubo, T.; Kubono, S.; Lorusso, G. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Maeda, Y. [Department of Applied Physics, University of Miyazaki, Miyazaki 889-2192 (Japan); Makinaga, A. [Graduate School of Medicine, Hokkaido University, North-14, West-5, Kita-ku, Sapporo 060-8648 (Japan); Momiyama, S. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Nakano, K. [Department of Advanced Energy Engineering Science, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Niikura, M. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Shiga, Y. [Department of Physics, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima, Tokyo 171-8501 (Japan); RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Söderström, P.-A. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); and others

    2016-03-10

    We have studied spallation reactions for the fission products {sup 137}Cs and {sup 90}Sr for the purpose of nuclear waste transmutation. The spallation cross sections on the proton and deuteron were obtained in inverse kinematics for the first time using secondary beams of {sup 137}Cs and {sup 90}Sr at 185 MeV/nucleon at the RIKEN Radioactive Isotope Beam Factory. The target dependence has been investigated systematically, and the cross-section differences between the proton and deuteron are found to be larger for lighter spallation products. The experimental data are compared with the PHITS calculation, which includes cascade and evaporation processes. Our results suggest that both proton- and deuteron-induced spallation reactions are promising mechanisms for the transmutation of radioactive fission products.

  7. Spallation reaction study for fission products in nuclear waste: Cross section measurements for 137Cs and 90Sr on proton and deuteron

    Directory of Open Access Journals (Sweden)

    H. Wang

    2016-03-01

    Full Text Available We have studied spallation reactions for the fission products 137Cs and 90Sr for the purpose of nuclear waste transmutation. The spallation cross sections on the proton and deuteron were obtained in inverse kinematics for the first time using secondary beams of 137Cs and 90Sr at 185 MeV/nucleon at the RIKEN Radioactive Isotope Beam Factory. The target dependence has been investigated systematically, and the cross-section differences between the proton and deuteron are found to be larger for lighter spallation products. The experimental data are compared with the PHITS calculation, which includes cascade and evaporation processes. Our results suggest that both proton- and deuteron-induced spallation reactions are promising mechanisms for the transmutation of radioactive fission products.

  8. XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration.

    Science.gov (United States)

    Galbraith, M C E; Smeenk, C T L; Reitsma, G; Marciniak, A; Despré, V; Mikosch, J; Zhavoronkov, N; Vrakking, M J J; Kornilov, O; Lépine, F

    2017-08-02

    Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH 3 + fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.

  9. Dissipative effects in fission investigated with proton-on-lead reactions

    Directory of Open Access Journals (Sweden)

    Rodríguez-Sánchez J. L.

    2016-01-01

    Full Text Available The complete kinematic measurement of the two fission fragments permitted us to investigate dissipative effects at large deformations, between the saddle-point and the corresponding scission configurations. Up to now, this kind of study has only been performed with fusionfission reactions using a limited number of observables, such as the mass distribution of the fission fragments or the neutron multiplicities. However, the large angular momenta gained by the compound nucleus could affect the conclusions drawn from such experiments. In this work, the use of spallation reactions, where the fissioning systems are produced with low angular momentum, small deformations and high excitation energies, favors the study of dissipation, and allowed us to define new observables, such as postscission neutron multiplicities and the neutron excess of the final fission fragments as a function of the atomic number of the fissioning system. These new observables are used to investigate the dissipation at large deformations.

  10. Measurements of the proton total reaction cross section for 24Mg, 646668Zn and 140Ce between 17.5 and 48 MeV

    International Nuclear Information System (INIS)

    Davison, N.E.; Hasell, D.K.; Sourkes, A.M.; Oers, W.T.H. van

    1977-01-01

    Measurements of proton total reaction cross sections have been made for the deformed nuclei 24 Mg, 64 66 68 Zn and 140 Ce in the energy range 17.5 to 48 MeV using an attenuation technique. The cross sections are compared with various theoretical predictions and with existing data. (Auth.)

  11. Measurements of proton total reaction cross sections for 6Li,7Li,14N,20Ne and 40Ar between 23 and 49 MeV

    International Nuclear Information System (INIS)

    Carlson, R.F.; Cox, A.J.; Nasr, T.N.; De Jong, M.S.; Ginther, D.I.; Hasell, D.K.; Sourkes, A.M.; Van Oers, W.T.H.; Margaziotis, D.J.

    1985-01-01

    Measurements of proton total reaction cross sections for 6 Li, 7 Li, 14 N, 20 Ne and 40 Ar have been made in the energy range 23 to 49 MeV, using a variation of a standard attenuation technique. The measured cross sections are compared with optical-model and nuclear-transparency calculations. (orig.)

  12. Reaction cross sections for protons on {sup 12}C, {sup 40}Ca, {sup 90}Zr and {sup 208}Pb at energies between 80 and 180 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Auce, A.; Ingemarsson, A.; Johansson, R. [and others

    2005-04-01

    Results of reaction cross section measurements on {sup 12}C, {sup 40}Ca, {sup 90}Zr and {sup 208}Pb at incident proton energies between 80 and 180 MeV and for {sup 58}Ni at 81 MeV are presented. The experimental procedure is described and the results are compared with earlier measurements and predictions using macroscopic and microscopic models.

  13. On the nucleon effective mass role to the high energy proton spallation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Santos, B.M., E-mail: biank_ce@if.uff.br [Instituto de Física, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza, 24210-346 Niterói, RJ (Brazil); Instituto Militar de Engenharia, Praça General Tibúrcio 80, 22290-270 Rio de Janeiro, RJ (Brazil); Pinheiro, A.R.C. [Centro Brasileiro de Pesquisas Físicas, Rua Dr. Xavier Sigaud 150, 22290-180 Rio de Janeiro, RJ (Brazil); Universidade Federal do Acre, BR 364 km 04, 69920-900 Rio Branco, AC (Brazil); Gonçalves, M. [Comissão Nacional de Energia Nuclear, Rua General Severiano 90, 22290-901 Rio de Janeiro, RJ (Brazil); Duarte, S.B. [Centro Brasileiro de Pesquisas Físicas, Rua Dr. Xavier Sigaud 150, 22290-180 Rio de Janeiro, RJ (Brazil); Cabral, R.G. [Instituto Militar de Engenharia, Praça General Tibúrcio 80, 22290-270 Rio de Janeiro, RJ (Brazil)

    2016-04-15

    We explore the effect of the nucleon effective mass to the dynamic evolution of the rapid phase of proton–nucleus spallation reactions. The analysis of the relaxation time for the non-equilibrium phase is studied by variations in the effective mass parameter. We determine the final excitation energy of the hot residual nucleus at the end of cascade phase and the de-excitation of the nuclear system is carried out considering the competition of particle evaporation and fission processes. It was shown that the excitation energy depends of the hot compound residual nucleus at the end of the rapid phase on the changing effective mass. The multiplicity of particles was also analyzed in cascade and evaporation phase of the reaction. The use of nucleon effective mass during cascade phase can be considered as an effect of the many-body nuclear interactions not included explicitly in a treatment to the nucleon–nucleon interaction inside the nucleus. This procedure represents a more realistic scenario to obtain the neutron multiplicity generated in this reaction, which is a benchmark for the calculation of the neutronic in the ADS reactors.

  14. Theoretical Study of the Mechanism Behind the para-Selective Nitration of Toluene in Zeolite H-Beta

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Amity; Govind, Niranjan; Subramanian, Lalitha

    2011-11-28

    Periodic density functional theory calculations were performed to investigate the origin of the favorable para-selective nitration of toluene exhibited by zeolite H-beta with acetyl nitrate nitration agent. Energy calculations were performed for each of the 32 crystallographically unique Bronsted acid sites of a beta polymorph B zeolite unit cell with multiple Bronsted acid sites of comparable stability. However, one particular aluminum T-site with three favorable Bronsted site oxygens embedded in a straight 12-T channel wall provides multiple favorable proton transfer sites. Transition state searches around this aluminum site were performed to determine the barrier to reaction for both para and ortho nitration of toluene. A three-step process was assumed for the nitration of toluene with two organic intermediates: the pi- and sigma-complexes. The rate limiting step is the proton transfer from the sigma-complex to a zeolite Bronsted site. The barrier for this step in ortho nitration is shown to be nearly 2.5 times that in para nitration. This discrepancy appears to be due to steric constraints imposed by the curvature of the large 12-T pore channels of beta and the toluene methyl group in the ortho approach that are not present in the para approach.

  15. Detection of nerve agents using proton transfer reaction mass spectrometry with ammonia as reagent gas.

    Science.gov (United States)

    Ringer, Joachim M

    2013-01-01

    The chemical warfare agents (CWA) Sarin, Soman, Cyclosarin and Tabun were characterised by proton transfer mass spectrometry (PTRMS). It was found that PTRMS is a suitable technique to detect nerve agents highly sensitively, highly selectively and in near real-time. Methods were found to suppress molecule fragmentation which is significant under PTRMS hollow cathode ionisation conditions. In this context, the drift voltage (as one of the most important system parameters) was varied and ammonia was introduced as an additional chemical reagent gas. Auxiliary chemicals such as ammonia affect ionisation processes and are quite common in context with detectors for CWAs based on ion mobility spectrometry (IMS). With both, variation of drift voltage and ammonia as the reagent gas, fragmentation can be suppressed effectively. Suppression of fragmentation is crucial particularly concerning the implementation of an algorithm for automated agent identification in field applications. On the other hand, appearance of particular fragments might deliver additional information. Degradation and rearrangement products of nerve agents are not distinctive for the particular agent but for the chemical class they belong to. It was found that switching between ammonia doped and ordinary water ionisation chemistry can easily be performed within a few seconds. Making use of this effect it is possible to switch between fragment and molecular ion peak spectra. Thus, targeted fragmentation can be used to confirm identification based only on single peak detection. PTRMS turned out to be a promising technique for future CWA detectors. In terms of sensitivity, response time and selectivity (or confidence of identification, respectively) PTRMS performs as a bridging technique between IMS and GC-MS.

  16. Supra-molecular hydrogen-bonding patterns in the N(9)-H protonated and N(7)-H tautomeric form of an N(6) -benzoyl-adenine salt: N (6)-benzoyl-adeninium nitrate.

    Science.gov (United States)

    Karthikeyan, Ammasai; Jeeva Jasmine, Nithianantham; Thomas Muthiah, Packianathan; Perdih, Franc

    2016-02-01

    In the title molecular salt, C12H10N5O(+)·NO3 (-), the adenine unit has an N (9)-protonated N(7)-H tautomeric form with non-protonated N(1) and N(3) atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intra-molecular N(7)-H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyl-adeninium cations also form base pairs through N-H⋯O and C-H⋯N hydrogen bonds involving the Watson-Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra-molecular ribbon with R 2 (2)(9) rings. Benzoyl-adeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N-H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π-π stacking inter-actions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol-ecules generate a three-dimensional supra-molecular architecture.

  17. Supra­molecular hydrogen-bonding patterns in the N(9)—H protonated and N(7)—H tautomeric form of an N6-benzoyl­adenine salt: N 6-benzoyl­adeninium nitrate

    Science.gov (United States)

    Karthikeyan, Ammasai; Jeeva Jasmine, Nithianantham; Thomas Muthiah, Packianathan; Perdih, Franc

    2016-01-01

    In the title molecular salt, C12H10N5O+·NO3 −, the adenine unit has an N 9-protonated N(7)—H tautomeric form with non-protonated N1 and N3 atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intra­molecular N7—H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyl­adeninium cations also form base pairs through N—H⋯O and C—H⋯N hydrogen bonds involving the Watson–Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra­molecular ribbon with R 2 2(9) rings. Benzoyl­adeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N—H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π–π stacking inter­actions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol­ecules generate a three-dimensional supra­molecular architecture. PMID:26958373

  18. Laboratory and Ambient Studies of the Products of Gas-Phase Hydroxyl and Nitrate Ion Radical-Initiated Reactions with Selected PAHs

    Science.gov (United States)

    Zimmermann, Kathryn Jean

    Nitrated polycyclic aromatic hydrocarbon (nitro-PAH) product distributions from the gas-phase hydroxyl (OH) and nitrate (NO3) radical-initiated reactions with selected PAHs, as well as the heterogeneous reactions of surface-bound PAHs with N2O5 and HNO3, were investigated. Chapter 2 presents formation yields of nitro-PAHs from the gas-phase OH radical-initiated reactions of 1,7- and 2,7-dimethylnaphthalene (DMN) as a function of NO 2 concentration over the range 0.04-0.14 ppmv. The measured formation yields of dimethylnitronaphthalenes (DMNNs) under conditions that the OH-DMN adducts reacted solely with NO2 were 0.252 ± 0.094% for Σ1,7-DMNNs and 0.010 ± 0.005% for Σ2,7-DMNNs. 1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) was the major nitro-isomer formed, with a limiting high-NO 2 concentration yield of 0.212 ± 0.080% and with equal reactions of the 1,7-DMN-OH adduct with NO2 and O2 occurring in air at 60 ± 39 ppbv of NO2, indicating that the OH-DMN adduct reaction with NO2 can be important at NO2 concentrations commonly found in urban atmospheres. Although the yields of the DMNNs are low, ≤0.3%, the DMNN (and ethylnitronaphthalene) profiles from chamber experiments match well with those observed in polluted urban areas under conditions where OH radical-initiated chemistry is dominant, such as Mexico City, Mexico. Chapter 3 examines the nitro-PAH products of gas-phase OH and NO 3 radicals and heterogeneous N2O5 reactions with fluoranthene, pyrene, benz[a]anthracene, chrysene, and triphenylene. Analysis of nitro-PAHs in the NIST diesel particulate SRM (1975) and selected ambient samples are also presented. 2-Nitrofluoranthene (2-NFL) was the most abundant nitro-PAH in Riverside, CA and Mexico City, and the mw 273 nitro-PAHs were observed in lower concentrations. However, in Tokyo, Japan, concentrations of 1- + 2-nitrotriphenylene (NTP) were more similar to those of 2-NFL. Comparing specific nitro-PAH ratios in ambient particulate samples from Tokyo, Mexico City

  19. Production Cross–Section Calculations of Medical 177Lu Using Neutron and Proton Induced Reactions

    Directory of Open Access Journals (Sweden)

    Mert ŞEKERCİ

    2016-11-01

    Full Text Available Abstract. In this study, we aimed to investigate the alternative ways to produce 177Lu, an isotope which has a growing rate of usage in radionuclide therapy applications. For this purpose; we analyzed the 176Lu (n,γ177Lu, 176Yb (n,γ177Yb 177Lu, 181Ta (n,n+α177-MLu, natW(p,x177Lu reactions with the TALYS 1.6 and EMPIRE 3.2 theoretical nuclear reaction codes. Obtained results with the TALYS 1.6 and EMPIRE 3.2 codes are also compared with the experimental data exists in the literature for each reaction.Keywords: 177Lu, Cross–Section, TALYS 1.6, EMPIRE 3.2. Özet. Bu çalışmada, radyonüklit terapi uygulamalarında giderek artan bir kullanım oranına sahip olan 177Lu izotopu için alternatif üretim yollarının araştırılması amaçlanmıştır. Bu amaçla; 176Lu(n,γ177Lu, 176Yb(n,γ177Yb 177Lu, 181Ta(n,n+α177-MLu, natW(p,x177Lu reaksiyonları TALYS 1.6 ve EMPIRE 3.2 teorik nükleer reaksiyon kodları kullanılarak analiz edilmiştir. Ayrıca, TALYS 1.6 ve EMPIRE 3.2 kodları ile elde edilen bulgular her bir reaksiyon için literatürde mevcut deneysel veriler ile karşılaştırılmıştır. Anahtar Kelimeler: 177Lu, Tesir Kesiti, TALYS 1.6, EMPIRE 3.2.

  20. Use of Rapid Reduced Electric Field Switching to Enhance Compound Specificity for Proton Transfer Reaction-Mass Spectrometry.

    Science.gov (United States)

    González-Méndez, Ramón; Watts, Peter; Reich, D Fraser; Mullock, Stephen J; Cairns, Stuart; Hickey, Peter; Brookes, Matthew; Mayhew, Chris Anthony

    2018-04-09

    The high sensitivity of Proton Transfer Reaction-Mass Spectrometry (PTR-MS) makes it a suitable analytical tool for detecting trace compounds. Its specificity is primarily determined by the accuracy of identifying the m/z of the product ions specific to a particular compound. However, specificity can be enhanced by changing the product ions (concentrations and types) through modifying the reduced electric field. For current PTR-MS systems this is not possible for trace compounds that would only be present in the reaction chamber of a PTR-MS for a short time (seconds). For such circumstances it is necessary to change the reduce electric field swiftly if specificity enhancements are to be achieved. In this paper we demonstrate such a novel approach, which permits any compound that may only be present in the drift tube for seconds to be thoroughly investigated. Specifically, we have developed hardware and software which permits the reaction region's voltages to be rapidly switched at a frequency of 0.1-5 Hz. We show how this technique can be used to provide a higher confidence in the identification of compounds than is possible by keeping to one reduced electric field value through illustrating the detection of explosives. Although demonstrated for homeland security applications, this new technique has applications in other analytical areas and disciplines where rapid changes in a compound's concentration can occur, e.g. in the Earth's atmosphere, plant emissions and in breath. Importantly, this adaptation provides a method for improved selectivity without expensive instrumental changes or the need for high mass resolution instruments.

  1. Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

    2016-01-01

    Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

  2. Theoretical study on the excited-state intramolecular proton-transfer reaction of 10-hydroxybenzo[h]quinoline in methanol and cyclohexane

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Meng [Department of Chemistry, Liaoning University, Shenyang 110036 (China); State Key Lab of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Zhao, Jinfeng [Department of Physics, Liaoning University, Shenyang 110036 (China); State Key Lab of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Cui, Yanling; Wang, Qianyu [Department of Physics, Liaoning University, Shenyang 110036 (China); Dai, Yumei [Normal College, Shenyang University, Shenyang 110044 (China); Song, Peng, E-mail: songpeng@lnu.edu.cn [Department of Physics, Liaoning University, Shenyang 110036 (China); Xia, Lixin, E-mail: lixinxia@lnu.edu.cn [Department of Chemistry, Liaoning University, Shenyang 110036 (China)

    2015-05-15

    The dynamics of the excited-state intramolecular proton-transfer (ESIPT) reaction of 10-hydroxybenzoquinoline (HBQ) in different solvents, have been investigated based on the time-dependent density functional theory (TD-DFT) in detail. Upon excitation, the intramolecular hydrogen bond between the hydroxyl and phenanthrene functionality is significantly strengthened in the S{sub 1} state, which can be used as a reasonable tendency for facilitating the ESIPT process. In addition, the calculated vertical excitation energies in the S{sub 0} state and S{sub 1} state reproduce the experimental UV–vis absorbance and fluorescence emission spectra well. Through calculating the fluorescence spectra of the HBQ chromophore, two outcomes for this chromophore were found in the S{sub 1} state, which demonstrates that the ESIPT process occurs. The potential energy curves have been calculated to account for the mechanism of the proton-transfer process in the excited-state. As a result, the barrierless ESIPT process can occur in the S{sub 1} state with proton transfer from the O atom to the N atom. And maybe the ESIPT process is easier in methanol solvent due to the higher potential energy difference. - Highlights: • The hydrogen bond between the hydroxyl and phenanthrene is strengthened. • The hydrogen bond facilitates the proton transfer from the hydroxyl group to the N atom. • The spontaneous excited-state intramolecular proton transfer reaction can be observed.

  3. Depth profiles of production yields of natPb(p, xn206,205,204,203,202 Bi reactions using 100-MeV proton beam

    Directory of Open Access Journals (Sweden)

    Oranj Leila Mokhtari

    2017-01-01

    Full Text Available In this study, results of the experimental study on the depth profiles of production yields of 206,205,204,203,202Bi radio-nuclei in the natural Pb target irradiated by a 100-MeV proton beam are presented. Irradiation was performed at proton linac facility (KOMAC in Korea. The target, irradiated by 100-MeV protons, was arranged in a stack consisting of natural Pb, Al, Au foils and Pb plates. The proton beam intensity was determined by activation analysis method using 27Al(p, 3p1n24Na, 197Au(p, p1n196Au, and 197Au(p, p3n194Au monitor reactions and also using dosimetry method by a Gafchromic film. The production yields of produced Bi radio-nuclei in the natural Pb foils and monitor reactions were measured by gamma-ray spectroscopy. Monte Carlo simulations were performed by FLUKA, PHITS, and MCNPX codes and compared with the measurements in order to verify validity of physical models and nuclear data libraries in the Monte Carlo codes. A fairly good agreement was observed between the present experimental data and the simulations by FLUKA, PHITS, and MCNPX. However, physical models and the nuclear data relevant to the end of range of protons in the codes need to be improved.

  4. Gamow-Teller transitions and neutron-proton-pair transfer reactions

    Science.gov (United States)

    Van Isacker, P.; Macchiavelli, A. O.

    2018-05-01

    We propose a schematic model of nucleons moving in spin-orbit partner levels, j = l ±1/2, to explain Gamow-Teller and two-nucleon transfer data in N = Z nuclei above 40Ca. Use of the LS coupling scheme provides a more transparent approach to interpret the structure and reaction data. We apply the model to the analysis of charge-exchange, 42Ca(3He,t)42Sc, and np-transfer, 40Ca(3He,p)42Sc, reactions data to define the elementary modes of excitation in terms of both isovector and isoscalar pairs, whose properties can be determined by adjusting the parameters of the model (spin-orbit splitting, isovector pairing strength and quadrupole matrix element) to the available data. The overall agreement with experiment suggests that the approach captures the main physics ingredients and provides the basis for a boson approximation that can be extended to heavier nuclei. Our analysis also reveals that the SU(4)-symmetry limit is not realized in 42Sc.

  5. Measurements of cross-sections of the proton-induced activation reactions

    CERN Document Server

    Uddin, M S; Ditrói, F; Hagiwara, M; Tarkanyi, F

    2005-01-01

    Excitation functions for the /sup 89/Y(p, x)/sup 89,88,86/Zr, /sup 89 /Y(p, x)/sup 88,87,87m,86/Y, /sup 89/Y(p, x)/sup 85,83,82/Sr and /sup 89/Y(p, x)/sup 84,83/Rb reactions were measured by a stacked foil activation technique in the energy range 15-80 MeV. The production for the long lived products like /sup 88/Zr, and /sup 88/Y are significantly larger than that of /sup nat/Mo+p, /sup nat/Nb+p and /sup nat/Zr+p processes. The productions of the medical isotopes, /sup 85/Sr and /sup 83/Sr are also effective by Y+p process using 80 MeV beam. The model calculations using ALICE-IPPE code compiled in MENDL-2P have the general trend of the measured results.

  6. Synthesis of cerous ammonium nitrate using ceric ammonium nitrate and anhydrous ammonia as a reducing agent

    International Nuclear Information System (INIS)

    Bourleaux, G.; Colombet, P.; Rouxel, J.; Gradeff, P.S.; Mauermann, H.

    1988-01-01

    The reduction of ceric ammonium nitrate by anhydrous ammonia has been studied. The reaction yields cerous ammonium nitrate complex. This is an easy method to prepare an anhydrous Ce (III) salt, suitable for synthesis of organo cerium (III) derivatives [fr

  7. Reactions of formic acid with protonated water clusters: Implications of cluster growth in the atmosphere

    Science.gov (United States)

    Goken, E. G.; Castleman, A. W.

    2010-08-01

    Obtaining direct and detailed chemical information about the initial stages of nucleation continues to be a challenging task, but it is necessary for improved understanding of the growth process of particles in the atmosphere. To elucidate the role of organic molecules, specifically formic acid, in nucleation and particle growth, the present work uses a flow tube reactor to study formic acid-water interactions using water cluster distributions of 2-30 water molecules. The reactions studied herein are compared to methanol-water interactions to provide evidence of a change to the stable clathrate-like structure of the H+(H2O)21 "magic" cluster. Intensity ratios of the form R = I[H+(H2O)n]/I[H+(H2O)n+1] are used to identify prominent clusters in spectra containing pure water, methanol-water mixed clusters, and formic acid-water mixed clusters. Relative concentration flow rates of 12.5, 25, 50, and 125.5 standard cubic centimeters per minute (sccm) of formic acid were added to a pure water distribution, and the resultant spectra were compared to those from methanol relative concentrations of 25, 50, and 100 sccm. The formic acid-water mixed cluster distributions observed in these reactions do not contain a prominent peak in the intensity ratio graphs, indicating a disruption in the clathrate structure of the 21-molecule cluster while a prominent peak for 21-molecule cluster is observed in the methanol system. Also observed was an increase in intensity with increased cluster size, which indicates that formic acid-water mixed clusters could serve as a prenucleation embryo for the nucleation of water molecules and a possible particle growth pathway.

  8. 48Ca(d,n)49Sc reaction at E/sub d/=20 MeV; proton single-particle states in 49Sc

    International Nuclear Information System (INIS)

    Iwasaki, Y.; Galonsky, A.; Weber, D.J.

    1980-01-01

    The 48 Ca(d,n) 49 Sc reaction has been studied at E/sub d/=20 MeV. Angular distributions of differential cross sections have been obtained for 14 transitions to states in 49 Sc up to an excitation energy of 7.1 MeV. A distorted-wave Born-approximation analysis has been made of the experimental data. With respect to states corresponding to the same proton single-particle orbital, relative values of derived spectroscopic factors are generally in good agreement with those obtained from ( 3 He,d) reaction data. There are remarkable differences between the results from the 48 Ca(d,n) 49 Sc reaction and the 48 Ca( 3 He,d) 49 Sc, however, regarding the dependence of the relative spectroscopic factors on proton single-particle orbitals

  9. Cross sections for nuclide production in proton- and deuteron-induced reactions on 93Nb measured using the inverse kinematics method

    Directory of Open Access Journals (Sweden)

    Nakano Keita

    2017-01-01

    Full Text Available Isotopic production cross sections were measured for proton- and deuteron-induced reactions on 93Nb by means of the inverse kinematics method at RIKEN Radioactive Isotope Beam Factory. The measured production cross sections of residual nuclei in the reaction 93Nb + p at 113 MeV/u were compared with previous data measured by the conventional activation method in the proton energy range between 46 and 249 MeV. The present inverse kinematics data of four reaction products (90Mo, 90Nb, 88Y, and 86Y were in good agreement with the data of activation measurement. Also, the model calculations with PHITS describing the intra-nuclear cascade and evaporation processes generally well reproduced the measured isotopic production cross sections.

  10. On-line Analysis of Organic Compounds in Diesel Exhaust Using a Proton Transfer Reaction Mass Spectrometer (PTR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Jobson, B Tom T.; Alexander, M. Lizabeth; Maupin, Gary D.; Muntean, George G.

    2005-08-01

    Chemical ionization mass spectrometry using H3O+ proton transfer in an ion drift tube (PTR-MS) was used to measure volatile organic compound (VOC) concentrations on-line in diesel engine exhaust as a function on engine load. The purpose of the study was to evaluate the PTR-MS instrument as an analytical tool for diesel engine emissions abatement research. Measured sensitivities determined from gas standards were found to be between 30% and 100% greater than calculated sensitivities. A slight humidity dependent sensitivity was observed for non-polar species, implying that reactions with H+(H2O)2 were important for some organics. The mass spectra of diesel exhaust were complex but displayed a pattern of strong ion signals at 14n+1 (n=3..8) masses, with a relative ion abundance similar to that obtained from electron impact ionization of alkanes. Laboratory experiments verified that C8-C16 n-alkanes and C8-C13 1-alkenes react with H3O+ in dissociative proton transfer reaction resulting in alkyl cation ion products, primarily m/z 41, 43, 57, 71 and 85. Monitoring the sum of these ions signals may be useful for estimating alkane emissions from unburnt diesel fuel. Alkane fragmentation likely simplified the diesel exhaust mass spectrum and reduced potential mass interferences with isobaric aromatic compounds. It is shown that the relative abundances of VOCs changed as a function of engine load. Concentrations of aldehydes and ketones dominated those of aromatic species with formaldehyde and acetaldehyde estimated to be the most abundant VOCs in the PTR-MS mass spectrum at all engine loads. The relative abundances of benzene and toluene increased with engine load indicating their pyrogenic origin. The relative abundance of alkanes, aromatics, aldehydes, and alcohols was broadly consistent with literature publications of diesel exhaust analysis by gas chromatography. About 75% of the organic ion signal could be assigned. On line analysis of diesel exhaust using this

  11. Spallation reaction study for fission products in nuclear waste: Cross section measurements for 137Cs, 90Sr and 107Pd on proton and deuteron

    Directory of Open Access Journals (Sweden)

    Wang He

    2017-01-01

    Full Text Available Spallation reactions for the long-lived fission products 137Cs, 90Sr and 107Pd have been studied for the purpose of nuclear waste transmutation. The cross sections on the proton- and deuteron-induced spallation were obtained in inverse kinematics at the RIKEN Radioactive Isotope Beam Factory. Both the target and energy dependences of cross sections have been investigated systematically. and the cross-section differences between the proton and deuteron are found to be larger for lighter fragments. The experimental data are compared with the SPACS semi-empirical parameterization and the PHITS calculations including both the intra-nuclear cascade and evaporation processes.

  12. Continuous monitoring of the zinc-phosphate acid-base cement setting reaction by proton nuclear magnetic relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Apih, T.; Lebar, A.; Pawlig, O.; Trettin, R.

    2001-06-15

    Proton nuclear magnetic relaxation is a well-established technique for continuous and non destructive monitoring of hydration of conventional Portland building cements. Here, we demonstrate the feasibility of nuclear magnetic resonance (NMR) monitoring of the setting reaction of zinc-phosphate acid-base dental cements, which harden in minutes as compared to days, as in the case of Portland cements. We compare the setting of cement powder (mainly, zinc oxide) prepared with clinically used aluminum-modified orthophosphoric acid solution with the setting of a model system where cement powder is mixed with pure orthophosphoric acid solution. In contrast to previously published NMR studies of setting Portland cements, where a decrease of spin-lattice relaxation time is attributed to enhanced relaxation at the growing internal surface, spin-lattice relaxation time T{sub 1} increases during the set of clinically used zinc-phosphate cement. Comparison of these results with a detailed study of diffusion, viscosity, and magnetic-field dispersion of T{sub 1} in pure and aluminum-modified orthophosphoric acid demonstrates that the increase of T{sub 1} in the setting cement is connected with the increase of molecular mobility in the residual phosphoric acid solution. Although not taken into account so far, such effects may also significantly influence the relaxation times in setting Portland cements, particularly when admixtures with an effect on water viscosity are used. {copyright} 2001 American Institute of Physics.

  13. Competitive roles of reagent vibration and translation in the exothermic proton transfer reaction H+2+Ar→HAr++H

    International Nuclear Information System (INIS)

    Bilotta, R.M.; Farrar, J.M.

    1981-01-01

    We present a crossed beam study of the title reaction at fixed collision energies of 1.2 and 2.3 eV with reagent H + 2 average vibrational energies of 0.44 and 0.89 eV; we also present data at fixed total energies with variable proportions of reagent vibrational and translational energy. At fixed collision energy, reagent vibrational excitation is found to have negligible effect on the total cross section for proton transfer. At fixed total energy, a decrease in reagent vibrational excitation with a corresponding increase in reagent translation leads to partial disposal of the incremental translation in product translation: At a total energy of 3.5 eV, 50% of this incremental reagent translation appears as product translation. At a total energy of 4.6 eV, 78% of the incremental translation appears in product translation. The experimental data are discussed in terms of induced attractive and repulsive energy release on an attractive potential surface. The role of noncollinear geometries and compressed reactant configurations is judged to be of substantial importance in assessing product rotational excitation and dissociation

  14. Continuous monitoring of the zinc-phosphate acid-base cement setting reaction by proton nuclear magnetic relaxation

    International Nuclear Information System (INIS)

    Apih, T.; Lebar, A.; Pawlig, O.; Trettin, R.

    2001-01-01

    Proton nuclear magnetic relaxation is a well-established technique for continuous and non destructive monitoring of hydration of conventional Portland building cements. Here, we demonstrate the feasibility of nuclear magnetic resonance (NMR) monitoring of the setting reaction of zinc-phosphate acid-base dental cements, which harden in minutes as compared to days, as in the case of Portland cements. We compare the setting of cement powder (mainly, zinc oxide) prepared with clinically used aluminum-modified orthophosphoric acid solution with the setting of a model system where cement powder is mixed with pure orthophosphoric acid solution. In contrast to previously published NMR studies of setting Portland cements, where a decrease of spin-lattice relaxation time is attributed to enhanced relaxation at the growing internal surface, spin-lattice relaxation time T 1 increases during the set of clinically used zinc-phosphate cement. Comparison of these results with a detailed study of diffusion, viscosity, and magnetic-field dispersion of T 1 in pure and aluminum-modified orthophosphoric acid demonstrates that the increase of T 1 in the setting cement is connected with the increase of molecular mobility in the residual phosphoric acid solution. Although not taken into account so far, such effects may also significantly influence the relaxation times in setting Portland cements, particularly when admixtures with an effect on water viscosity are used. [copyright] 2001 American Institute of Physics

  15. Helium production for 0.8-2.5 GeV proton induced spallation reactions, damage induced in metallic window materials

    International Nuclear Information System (INIS)

    Hilscher, D.; Herbach, C.-M.; Jahnke, U.; Tishchenko, V.; Enke, M.; Filges, D.; Goldenbaum, F.; Neef, R.-D.; Nuenighoff, K.; Paul, N.; Schaal, H.; Sterzenbach, G.; Letourneau, A.; Boehm, A.; Galin, J.; Lott, B.; Peghaire, A.; Pienkowski, L.

    2001-01-01

    Production cross-sections for neutrons and charged particles as well as excitation energy distributions in spallation reactions were measured recently by the NESSI-collaboration and have been employed to test different intra nuclear cascade models and the subsequent evaporation. The INCL/GEMINI code, which describes best the experimental data has been employed to calculate the damage cross-sections in Fe and Ta as well as the He/dpa ratio as a function of proton energy. For the same amount of neutron production in a typical target of a spallation neutron source the proton beam induced radiation damage in an Fe window is shown to decrease almost linearly with proton energy. For heavier materials such as Ta a similar decrease of the radiation damage is found only for energies above about 3 GeV

  16. Separation and preparation of xanthochymol and guttiferone E by high performance liquid chromatography and high speed counter-current chromatography combined with silver nitrate coordination reaction.

    Science.gov (United States)

    Li, Jun; Gao, Ruixi; Zhao, Dan; Huang, Xianju; Chen, Yu; Gan, Fei; Liu, Hui; Yang, Guangzhong

    2017-08-18

    Xanthochymol (XCM) and guttiferone E (GFE), a pair of π bond benzophenone isomers from Garcinia xanthochymus, were once reported to be difficult or impossible to separate. The present study reports the successful separation of these two isomers through high performance liquid chromatography (HPLC), as well as their effective isolation using high speed counter-current chromatography (HSCCC) based on the silver nitrate (AgNO 3 ) coordination reaction. First, an effective HPLC separation system was developed, achieving a successful baseline separation with resolution of 2.0. Based on the partition coefficient (K) resolved by HPLC, the two-phase solvent system was determined as n-hexane, methanol and water with the uncommon volume ratio of 4:6:1. A crude extract of Garcinia xanthochymus (0.2g) was purified by normal HSCCC and refined with AgNO 3 -HSCCC. Monomers of XCM and GFE were identified by HPLC, mass spectrometry (MS) and nuclear magnetic resonance (NMR). The results demonstrate the separation and isolation of π bond benzophenone isomers using ordinary octadecyl silane (C 18 ) columns and HSCCC. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The proton spectral function of 40Ca and 48Ca studied with the (e,e'p) reaction

    International Nuclear Information System (INIS)

    Kramer, G.J.

    1990-01-01

    This thesis presents the results of an experimental study into the occupation of the orbitals around the Fermi level for 40 Ca and 48 Ca with quasi-elastic proton knock-out (e,e'p). Experiments have been carried out with the 500 MeV electron beam of the linear accelerator MEA at NIKHEF, Amsterdam. For 40 Ca the mechanism of the (e,e'p) reaction has been studied by comparing the measured momentum distributions of some strong transitions to discrete states in 39K , with various theoretical calculations. From this it has been concluded that uncertainties caused by deviations of the impulse approximation can be minimized if the measurements are carried out under parallel kinematical conditions. The spectroscopic strengths of the shell-model orbitals in states just below the Fermi level, for 40 Ca the 1d 3/2 , 1d 5/2 and 2s 1/2 orbitals, turned out to amount 50 to 70% of the IPSM limit. A small part of the missing strength has been found in the 1f 7/2 and 2p 3/2 orbitals which are just above the Fermi level (resp. 11 and 2% of the 2j+1 limit), which is an indication for ground state correlations. The spectroscopic strengths for the 1d 3/2 , 2s 1/2 and 1d 3/2 orbitals of 48 Ca turned out to be the same as for 40C a within the actual measuring accuracy. Above the Fermi level only strength in the 1f 7/2 orbital has been found (1% of the 2j+1 limit). The spectroscopic strengths determined with (e,e'p) experiments are about a factor two smaller than those obtained from (d, 3 He) experiments. This discrepancy has been studied by reviewing the model dependency of the DWBA analysis for the (d, 3 He) reaction with special emphasis on the sensitivities of the spectroscopic factors to the various approximations made in this theory. It is also investigated which part of the bound state wave function is probed by the (e,e'p) and the (d, 3 He) reactions in order to understand the model sensitivities arising from the exact shape of the bound state wave function. (H.W.).97 refs.; 48

  19. Reactions between aromatic hydrocarbons and heterocycles: covalent and proton-bound dimer cations of benzene/pyridine.

    Science.gov (United States)

    El-Shall, M Samy; Ibrahim, Yehia M; Alsharaeh, Edreese H; Meot-Ner Mautner, Michael; Watson, Simon P

    2009-07-29

    negatively charged C atoms of the ring. In contrast, the more stable proton-bound PyH(+) x Py dimer contains a linear NH(+)...N hydrogen bond. The formation of the (benzene/pyridine)(*+) adduct may represent a general class of addition reactions that can form complex heterocyclic species in ionizing environments.

  20. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    Energy Technology Data Exchange (ETDEWEB)

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayon, Victor M.; Largo, Antonio, E-mail: alargo@qf.uva.es [Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain)

    2012-04-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the higher energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  1. Measurement of cross-sections for produced radionuclide in proton induced reactions on natHf up to 45 MeV

    International Nuclear Information System (INIS)

    Shahid, Muhammad; Kim, Kwangsoo; Naik, Haladhara; Kim, Guinyun

    2014-01-01

    We measured production cross-sections of Hf, Lu, and Ta radioisotopes from proton-induced reaction of nat Hf by using a stacked-foil activation and off-line γ-ray spectrometric technique at the MC-50 cyclotron of the Korea Institute of Radiological and Medical Sciences. The results were compared with the reported experimental data as well as the theoretical calculations based on the TALYS 1.4 code. The present results in the energy region from the threshold energy to 45 MeV are in general good agreement with the other experimental data and calculated results. The present experimental results will play an important role in enrichment of the literature data base for proton-induced reactions on natural hafnium leading to various applications. Some of the investigated radionuclides (e.g. 177g Lu) have remarkable applications in the field of nuclear medicine, a thin layer activation analysis, and a trace element analysis

  2. Study of the inclusive reaction $K^{+}p \\rightarrow K^{0}$ + anything at 5, 8.2 and 16 GeV/c in the proton fragmentation region

    CERN Document Server

    Ciapetti, G; Colley, D C; Dunwoodie, W M; Ginestet, J; Goldschmidt-Clermont, Yves; Grant, A; Grard, F; Henri, V; Herquet, P; James, M; Jones, G T; Manesse, D; Sekera, Z; Sené, M; Sherbatt, D; Stergiou, Athanase; Tuominiemi, J; Verbeure, F; Vignaud, D; Windmolders, R; Yamdagni, N

    1975-01-01

    The inclusive reaction $K^+p \\to K^0X$ is studied at 5, 8.2 and 16 GeV/c. The inclusive cross sections as well as the inclusive transverse and longitudinal distributions are given. The energy dependence of the structure function in the proton fragmentation region is found to be consistent with s/sup -1/-behaviour indicating the presence of f'- phi exchange in the missing mass channel with a relative contribution of 50-70%.

  3. Measurement of double differential charged-particle emission cross sections for reactions induced by 26 MeV protons and FKK model analysis

    International Nuclear Information System (INIS)

    Watanabe, Y.; Aoto, A.; Kashimoto, H.

    1994-01-01

    Double differential charged-particle emission cross sections of proton-induced reactions have been measured for nat C, 27 Al, nat Si, 98 Mo, 106 Pd, 159 Tb and 181 Ta at energies around 26 MeV. Several (p,p') and (p,n) data for 98 Mo and 106 Pd in the incident energy range from 12 to 26 MeV are analysed in terms of the Feshbach-Kerman-Koonin model, in order to study preequilibrium nucleon emission from nucleon-induced reactions

  4. Thermodynamics and Reaction Mechanisms of Decomposition of the Simplest Protonated Tripeptide, Triglycine: A Guided Ion Beam and Computational Study

    Science.gov (United States)

    Mookherjee, Abhigya; Van Stipdonk, Michael J.; Armentrout, P. B.

    2017-04-01

    We present a thorough characterization of fragmentations observed in threshold collision-induced dissociation (TCID) experiments of protonated triglycine (H+GGG) with Xe using a guided ion beam tandem mass spectrometer (GIBMS). Kinetic energy-dependent cross-sections for 10 ionic products are observed and analyzed to provide 0 K barriers for six primary products: [b2]+, [y1 + 2H]+, [b3]+, CO loss, [y2 + 2H]+, and [a1]+; three secondary products: [a2]+, [a3]+, and [y2 + 2H - CO]+; and two tertiary products: high energy [y1 + 2H]+ and [a2 - CO]+ after accounting for multiple ion-molecule collisions, internal energy of reactant ions, unimolecular decay rates, competition between channels, and sequential dissociations. Relaxed potential energy surface scans performed at the B3LYP-D3/6-311+G(d,p) level of theory are used to identify transition states (TSs) and intermediates of the six primary and one secondary products. Geometry optimizations and single point energy calculations were performed at several levels of theory. These theoretical energies are compared with experimental energies and are found to give reasonably good agreement, in particular for the M06-2X level of theory. This good agreement between experiment and theory validates the reaction mechanisms explored computationally here and elsewhere and allows identification of the product structures formed at threshold energies. The present work presents the first measurement of absolute experimental threshold energies of important sequence ions and non-sequence ions: [y1 + 2H]+, [b3]+, CO loss, [a1]+, and [a3]+, and refines those for [b2]+ and [y2 + 2H]+ previously measured.

  5. Iridium-decorated palladium-platinum core-shell catalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

    Science.gov (United States)

    Wang, Chen-Hao; Hsu, Hsin-Cheng; Wang, Kai-Ching

    2014-08-01

    Carbon-supported Pt, Pd, Pd-Pt core-shell (Pt(shell)-Pd(core)/C) and Ir-decorated Pd-Pt core-shell (Ir-decorated Pt(shell)-Pd(core)/C) catalysts were synthesized, and their physical properties, electrochemical behaviors, oxygen reduction reaction (ORR) characteristics and proton exchange membrane fuel cell (PEMFC) performances were investigated herein. From the XRD patterns and TEM images, Ir-decorated Pt(shell)-Pd(core)/C has been confirmed that Pt was deposited on the Pd nanoparticle which had the core-shell structure. Ir-decorated Pt(shell)-Pd(core)/C has more positive OH reduction peak than Pt/C, which is beneficial to weaken the binding energy of Pt-OH during the ORR. Thus, Ir-decorated Pt(shell)-Pd(core)/C has higher ORR activity than Pt/C. The maximum power density of H2-O2 PEMFC using Ir-decorated Pt(shell)-Pd(core)/C is 792.2 mW cm(-2) at 70°C, which is 24% higher than that using Pt/C. The single-cell accelerated degradation test of PEMFC using Ir-decorated Pt(shell)-Pd(core)/C shows good durability by the potential cycling of 40,000 cycles. This study concludes that Ir-decorated Pt(shell)-Pd(core)/C has the low Pt content, but it can facilitate the low-cost and high-efficient PEMFC. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Measurements of Volatile Organic Compounds Using Proton Transfer Reaction – Mass Spectrometry during the MILAGRO 2006 Campaign

    Directory of Open Access Journals (Sweden)

    E. C. Fortner

    2009-01-01

    Full Text Available Volatile organic compounds (VOCs were measured by proton transfer reaction – mass spectrometry (PTR-MS on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of the Megacity Initiative – Local and Global Research Observations (MILAGRO 2006 field campaign. Thirty eight individual masses were monitored during the campaign and many species were quantified including methanol, acetaldehyde, toluene, the sum of C2 benzenes, the sum of C3 benzenes, acetone, isoprene, benzene, and ethyl acetate. The VOC measurements were analyzed to gain a better understanding of the type of VOCs present in the MCMA, their diurnal patterns, and their origins. Diurnal profiles of weekday and weekend/holiday aromatic VOC concentrations showed the influence of vehicular traffic during the morning rush hours and during the afternoon hours. Plumes including elevated toluene as high as 216 parts per billion (ppb and ethyl acetate as high as 183 ppb were frequently observed during the late night and early morning hours, indicating the possibility of significant industrial sources of the two compounds in the region. Wind fields during those peak episodes revealed no specific direction for the majority of the toluene plumes but the ethyl acetate plumes arrived at the site when winds were from the Southwest or West. The PTR-MS measurements combined with other VOC measuring techniques at the field site as well as VOC measurements conducted in other areas of the Mexico City Metropolitan Area (MCMA will help to develop a better understanding of the spatial pattern of VOCs and its variability in the MCMA.

  7. Muscular Adverse Drug Reactions Associated with Proton Pump Inhibitors: A Disproportionality Analysis Using the Italian National Network of Pharmacovigilance Database.

    Science.gov (United States)

    Capogrosso Sansone, Alice; Convertino, Irma; Galiulo, Maria Teresa; Salvadori, Stefano; Pieroni, Stefania; Knezevic, Tamara; Mantarro, Stefania; Marino, Alessandra; Hauben, Manfred; Blandizzi, Corrado; Tuccori, Marco

    2017-10-01

    Proton pump inhibitors (PPIs) have been implicated in the occurrence of moderate to severe myopathies in several case reports. This study was performed to assess the reporting risk of muscular adverse drug reactions (ADRs) associated with PPIs in the Italian National Network of Pharmacovigilance database. A disproportionality analysis (case/non-case) was performed using spontaneous reports collected in the database between July 1983 and May 2016. Reporting odds ratio (ROR) and 95% confidence intervals (CIs) were calculated as a measure of disproportionality. In a secondary and tertiary analysis, we explored the association of PPIs with muscular ADRs after taking into account the masking effect of statins. Moreover, the possibility of an interaction between PPIs and statins, leading to the occurrence of muscular ADRs, was also tested. The study was carried out on 274,108 reports. The ROR of muscular ADRs for PPIs, adjusted for age and gender, was 1.484 (95% CI 1.204-1.829; p < 0.001), whereas the ROR for rhabdomyolysis was 0.621 (95% CI 0.258-1.499). Similar results were obtained in the secondary analysis. The tertiary analysis, where PPIs were considered regardless of whether their role was suspected or concomitant, showed a potential disproportionate reporting for the combination PPIs-rhabdomyolysis (ROR 1.667, 95% CI 1.173-2.369; p < 0.01). The PPIs-statins combination was not associated with an enhanced ROR of muscular ADRs/rhabdomyolysis compared with statins alone. This explorative study suggests that the class of PPIs could be involved in reports of muscular ADRs, rather than any other ADR, more frequently than any non-statin drug. Our results must be corroborated by further studies.

  8. FA-SIFT study of reactions of protonated water and ethanol clusters with [alpha]-pinene and linalool in view of their selective detection by CIMS

    Science.gov (United States)

    Dhooghe, F.; Amelynck, C.; Rimetz-Planchon, J.; Schoon, N.; Vanhaecke, F.

    2010-02-01

    The use of protonated water clusters and protonated ethanol clusters as reagent ions has been evaluated for the resolution of an interference encountered in CIMS when measuring monoterpenes (C10H16) and linalool (C10H18O) simultaneously. To this end, the reactions of H3O+.(H2O)n (n = 1-3), (C2H5OH)mH+ (m = 1-3) and (C2H5OH.H2O)H+ with [alpha]-pinene and linalool have been characterized in a flowing afterglow-selected ion flow tube (FA-SIFT) instrument at a SIFT He buffer gas pressure of 1.43 hPa and a temperature of 298 K. All reactions with linalool were found to occur at the collision limit. The reaction of (C2H5OH)2H+ with [alpha]-pinene proceeds at half the collision rate and both the reactions of (C2H5OH)3H+ and H3O+.(H2O)3 with [alpha]-pinene have a very low rate constant. All other reactions involving [alpha]-pinene proceed at the collision rate. The reactions of H3O+.H2O, H3O+.(H2O)2, C2H5OH2+, (C2H5OH.H2O)H+ and (C2H5OH)2H+ with [alpha]-pinene mainly proceed by proton transfer. Additionally, ligand switching channels have been observed for the reactions of (C2H5OH)2H+ and H3O+.(H2O)2 with [alpha]-pinene. Protonated linalool was observed as a minor product for the reactions of (C2H5OH.H2O)H+ and H3O+.(H2O)n (n = 1-3) with linalool. For all linalool reactions, a contribution of the dissociative proton transfer product at m/z 137 was found and this ion was the main product ion for the reactions with H3O+.H2O, C2H5OH2+ and (C2H5OH.H2O)H+. For the (C2H5OH.H2O)H+/linalool reaction, ligand switching with both water and ethanol has been observed. Major ligand switching channels were observed for the reactions of (C2H5OH)2H+, (C2H5OH)3H+ and H3O+.(H2O)2 with linalool. Also, for the H3O+.(H2O)3/linalool reaction, several ligand switching channels have been observed. These results are discussed in view of their applicability for the selective detection of monoterpenes and linalool with CIMS instrumentation such as SIFT-MS, PTR-MS and APCI-MS.

  9. Proton Transport

    Science.gov (United States)

    Pohorille, Andrew; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    The transport of protons across membranes is an essential process for both bioenergetics of modern cells and the origins of cellular life. All living systems make use of proton gradients across cell walls to convert environmental energy into a high-energy chemical compound, adenosine triphosphate (ATP), synthesized from adenosine diphosphate. ATP, in turn, is used as a source of energy to drive many cellular reactions. The ubiquity of this process in biology suggests that even the earliest cellular systems were relying on proton gradient for harvesting environmental energy needed to support their survival and growth. In contemporary cells, proton transfer is assisted by large, complex proteins embedded in membranes. The issue addressed in this Study was: how the same process can be accomplished with the aid of similar but much simpler molecules that could have existed in the protobiological milieu? The model system used in the study contained a bilayer membrane made of phospholipid, dimyristoylphosphatidylcholine (DMPC) which is a good model of the biological membranes forming cellular boundaries. Both sides of the bilayer were surrounded by water which simulated the environment inside and outside the cell. Embedded in the membrane was a fragment of the Influenza-A M$_2$ protein and enough sodium counterions to maintain system neutrality. This protein has been shown to exhibit remarkably high rates of proton transport and, therefore, is an excellent model to study the formation of proton gradients across membranes. The Influenza M$_2$ protein is 97 amino acids in length, but a fragment 25 amino acids long. which contains a transmembrane domain of 19 amino acids flanked by three amino acids on each side. is sufficient to transport protons. Four identical protein fragments, each folded into a helix, aggregate to form small channels spanning the membrane. Protons are conducted through a narrow pore in the middle of the channel in response to applied voltage. This

  10. Tailoring medium energy proton beam to induce low energy nuclear reactions in ⁸⁶SrCl₂ for production of PET radioisotope ⁸⁶Y.

    Science.gov (United States)

    Medvedev, Dmitri G; Mausner, Leonard F; Pile, Philip

    2015-07-01

    This paper reports results of experiments at Brookhaven Linac Isotope Producer (BLIP) aiming to investigate effective production of positron emitting radioisotope (86)Y by the low energy (86)Sr(p,n) reaction. BLIP is a facility at Brookhaven National Laboratory designed for the proton irradiation of the targets for isotope production at high and intermediate proton energies. The proton beam is delivered by the Linear Accelerator (LINAC) whose incident energy is tunable from 200 to 66 MeV in approximately 21 MeV increments. The array was designed to ensure energy degradation from 66 MeV down to less than 20 MeV. Aluminum slabs were used to degrade the proton energy down to the required range. The production yield of (86)Y (1.2+/-0.1 mCi (44.4+/-3.7) MBq/μAh) and ratio of radioisotopic impurities was determined by assaying an aliquot of the irradiated (86)SrCl2 solution by gamma spectroscopy. The analysis of energy dependence of the (86)Y production yield and the ratios of radioisotopic impurities has been used to adjust degrader thickness. Experimental data showed substantial discrepancies in actual energy propagation compared to energy loss calculations. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. A product study of the isoprene+NO3 reaction

    Directory of Open Access Journals (Sweden)

    R. C. Cohen

    2009-07-01

    Full Text Available Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS and reactive nitrogen products were observed using Thermal Dissociation–Laser Induced Fluorescence (TD-LIF. The organic nitrate yield is found to be 65±12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK is found to be ∼10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.

  12. Nuclear structure of weakly bound radioactive nuclei through elastic and and inelastic scattering on proton. Impacts of the couplings induced by these exotic nuclei on direct reactions; Structure de noyaux radioactifs faiblement lies par diffusions elastiques et inelastiques sur proton. Effets des couplages induits par ces noyaux exotiques sur les reactions directes

    Energy Technology Data Exchange (ETDEWEB)

    Lapoux, V

    2005-09-15

    Information on the structure, spectroscopy and target interaction potentials of exotic nuclei can be inferred by interpreting measured data from direct reactions on proton such as elastic or inelastic scattering of proton (p,p') or one-nucleon transfer reaction (p,d). A series of experimental results has been obtained at the GANIL facilities on the setting composed of the MUST telescope array used for the detection of light charged-particles and of CATS beam detectors. This setting aims at measuring reactions on light proton or deuteron targets through reverse kinematics. Particularly, results on C{sup 10}, C{sup 11} and on direct reactions with the He{sup 8} beam of Spiral are presented. The first chapter is dedicated to the description of the most important theories concerning the nucleus. The experimental tools used to probe the nucleus are reported in the second chapter. The third and fourth chapters present the framework that has allowed us to analyse results from (p,p') and (p,d) reactions on weakly bound exotic nuclei. The last chapter is dedicated to the description of future experimental programs. (A.C.)

  13. Rapid "breath-print" of liver cirrhosis by proton transfer reaction time-of-flight mass spectrometry. A pilot study.

    Directory of Open Access Journals (Sweden)

    Filomena Morisco

    Full Text Available UNLABELLED: The aim of the present work was to test the potential of Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS in the diagnosis of liver cirrhosis and the assessment of disease severity by direct analysis of exhaled breath. Twenty-six volunteers have been enrolled in this study: 12 patients (M/F 8/4, mean age 70.5 years, min-max 42-80 years with liver cirrhosis of different etiologies and at different severity of disease and 14 healthy subjects (M/F 5/9, mean age 52.3 years, min-max 35-77 years. Real time breath analysis was performed on fasting subjects using a buffered end-tidal on-line sampler directly coupled to a PTR-ToF-MS. Twelve volatile organic compounds (VOCs resulted significantly differently in cirrhotic patients (CP compared to healthy controls (CTRL: four ketones (2-butanone, 2- or 3- pentanone, C8-ketone, C9-ketone, two terpenes (monoterpene, monoterpene related, four sulphur or nitrogen compounds (sulfoxide-compound, S-compound, NS-compound, N-compound and two alcohols (heptadienol, methanol. Seven VOCs (2-butanone, C8-ketone, a monoterpene, 2,4-heptadienol and three compounds containing N, S or NS resulted significantly differently in compensate cirrhotic patients (Child-Pugh A; CP-A and decompensated cirrhotic subjects (Child-Pugh B+C; CP-B+C. ROC (Receiver Operating Characteristic analysis was performed considering three contrast groups: CP vs CTRL, CP-A vs CTRL and CP-A vs CP-B+C. In these comparisons monoterpene and N-compound showed the best diagnostic performance. CONCLUSIONS: Breath analysis by PTR-ToF-MS was able to distinguish cirrhotic patients from healthy subjects and to discriminate those with well compensated liver disease from those at more advanced severity stage. A breath-print of liver cirrhosis was assessed for the first time.

  14. Analysis of expiration gas in intensive care patients with SIRS/sepsis using proton-transfer-reaction-mass-spectrometry

    International Nuclear Information System (INIS)

    Bodrogi, F.B.M.

    2003-11-01

    In 1971, Pauling and co-workers were the first to detect volatile organic compounds (VOC) in human breath. Since then, a number of technical applications for breath gas analyses have been designed and processed, among them gas chromatography and proton transfer reaction-mass spectrometry (PTR-MS). Due to this technical progress it is meanwhile possible to correlate different kinds and stages of diseases with measurable changes in the patient's VOC profile. The aim of the present study was to investigate the composition of VOC in exhaled air of patients with sepsis via PTR-MS. To isolate distinct volatile organic compounds that may serve as clinical markers for the onset, the progress, as well as the outcome of the disease, the results obtained from septic patients were compared with two different control groups: 25 healthy, non-smoking volunteers enrolled in the day-case-surgery and 25 post-operative in-patients residing in post-anaesthetic care units (PACU). PTR-MS is capable to analyze VOC according to their molecular weight with a range between 21-230 Da. A total of 210 different masses has been detected in the present study. 54 masses were significantly different in exhaled air of septic patients as compared to healthy controls as well as post-operative patients. Among them, mass 69 representing isoprene might be of special interest for the diagnosis of sepsis. Although no exact biochemical properties of isoprene have been described to date, it is known that isoprene synthesis is increased in plants following exposure to oxidative stress. Chronic, systemic infectious diseases like sepsis are accompanied by the production of reactive oxygen species, indicating that isoprene might be increased in the course of sepsis, too. In the present study, isoprene values were markedly higher in septic patients as compared to PACU residents (3.3-fold increase in mean value) and to healthy volunteers (2.2-fold increase in mean value). In addition (and in contrast to other VOC

  15. Formation of short-lived positron emitters in reactions of protons of energies up to 200 MeV with the target elements carbon, nitrogen and oxygen

    CERN Document Server

    Kettern, K; Qaim, S M; Shubin, Yu N; Steyn, G F; Van der Walt, T N; 10.1016/j.apradiso.2004.02.007

    2004-01-01

    Excitation functions were measured by the stacked-foil technique for proton induced reactions on carbon, nitrogen and oxygen leading to the formation of the short-lived positron emitters /sup 11/C (T/sub 1 /2/=20.38 min) and /sup 13/N (T/sub 1/2/=9.96 min). The energy region covered extended up to 200 MeV. The product activity was measured non-destructively via gamma -ray spectrometry. A careful decay curve analysis of the positron annihilation radiation was invariably performed. The experimental results were compared with theoretical data obtained using the modified hybrid nuclear model code ALICE-IPPE for intermediate energies. The agreement was found to be generally satisfactory. The data are of importance in proton therapy.

  16. Model-Independent Analysis of the Neutron-Proton Final-State Interaction Region in the $\\pi\\pi \\to pn\\pi^+$ Reaction

    CERN Document Server

    Uzikov, Yu N

    2001-01-01

    Experimental data on the \\pi\\pi\\to pn\\pi^+ reaction measured in an exclusive two-arm experiment at 800 MeV show a narrow peak arising from the strong proton-neutron final-state interaction. It was claimed, within the framework of a certain model, that this peak contained up to a 25 % spin-singlet final-state contribution. By comparing the data with those of \\pi\\pi\\to d\\pi^+ in a largely model-independent way, it is here demonstrated that at all the angles measured the whole of the peak could be explained as being due to spin-triplet final states, with the spin-singlet being at most a few percent. Good qualitative agreement with the measured proton analysing power is also found within this approach.

  17. Measurement of activation reaction rate distribution on a mercury target with a lead-reflector and light-water-moderator for high energy proton bombardment using AGS accelerator

    International Nuclear Information System (INIS)

    Kasugai, Yoshimi; Takada, Hiroshi; Meigo, Shin-ichiro

    2001-02-01

    Characteristic of spallation neutrons driven by GeV protons from a mercury target with a lead-reflector and light-water-moderator was studied experimentally using the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Several reaction rates along with the mercury target were measured with the activation method at incident proton energies of 1.94, 12 and 24 GeV. Indium, niobium, aluminum, cobalt, nickel and bismuth were used as activation detectors to cover the threshold energy of between 0.33 and 40.9 MeV. This report summarizes the experimental procedure with all the measured data. (author)

  18. The rate of second electron transfer to QB(-) in bacterial reaction center of impaired proton delivery shows hydrogen-isotope effect.

    Science.gov (United States)

    Maróti, Ágnes; Wraight, Colin A; Maróti, Péter

    2015-02-01

    The 2nd electron transfer in reaction center of photosynthetic bacterium Rhodobacter sphaeroides is a two step process in which protonation of QB(-) precedes interquinone electron transfer. The thermal activation and pH dependence of the overall rate constants of different RC variants were measured and compared in solvents of water (H2O) and heavy water (D2O). The electron transfer variants where the electron transfer is rate limiting (wild type and M17DN, L210DN and H173EQ mutants) do not show solvent isotope effect and the significant decrease of the rate constant of the second electron transfer in these mutants is due to lowering the operational pKa of QB(-)/QBH: 4.5 (native), 3.9 (L210DN), 3.7 (M17DN) and 3.1 (H173EQ) at pH7. On the other hand, the proton transfer variants where the proton transfer is rate limiting demonstrate solvent isotope effect of pH-independent moderate magnitude (2.11±0.26 (WT+Ni(2+)), 2.16±0.35 (WT+Cd(2+)) and 2.34±0.44 (L210DN/M17DN)) or pH-dependent large magnitude (5.7 at pH4 (L213DN)). Upon deuteration, the free energy and the enthalpy of activation increase in all proton transfer variants by about 1 kcal/mol and the entropy of activation becomes negligible in L210DN/M17DN mutant. The results are interpreted as manifestation of equilibrium and kinetic solvent isotope effects and the structural, energetic and kinetic possibility of alternate proton delivery pathways are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Optimization of the pion beam for the HADES detector and determination of the {eta} form factor in proton-proton reactions at 2.2 GeV; Optimierung des Pionenstrahls zum HADES-Detektor und Bestimmung des {eta}-Formfaktors in Proton-Proton-Reaktionen bei 2.2 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Spruck, Bjoern

    2008-02-08

    This thesis contains two tasks. The first part focuses on the development and optimization of the pion beam facility for the HADES experiment. The second part describes the measurement of the electromagnetic transition form factor of the {eta} meson in proton-proton reactions. To investigate pion-nucleon reaction, a secondary pion beam is required. The pions are produced by a heavy ion beam impinging on a beryllium target. In order to determine the profile of the beam focus, two scintillating fiber detectors have been built as part of this thesis and are read out with recently developed electronics. The measured size of the beam focus appeared to be not acceptable, which can be attributed to the achromatic magnetic focusing in the beam line. Simulations have shown, that an additional quadrupole magnet directly in front of HADES would solve this problem and improve the beam quality. A test experiment including this new quadrupole has been performed and the analysis is still in progress. Preliminary results show a significant reduction of the momentum dependency of the focus. The size of the actual beam spot has been deduced to 14 mm by using an indirect tracking approach. For deducing the electromagnetic structure of hadrons, a first step has been done by analyzing the {eta} Dalitz decay in p+p reactions at 2.2 GeV kinetic energy to determine the electromagnetic transition form factor of the {eta} meson. A fit to the data leads to a form factor slope of b=2.2{sub -1.4}{sup +1.2} GeV{sup -2}. This corresponds to a pole mass of {lambda}=680{sub -130}{sup +460} MeV/c{sup 2}. It has been shown, that a semi-exclusive analysis of the {eta} Dalitz decay within the event hypothesis framework including a kinematical fit is feasible. (orig.)

  20. Pre-equilibrium proton emission in 40Ar and 132Xe induced reactions at 44 MeV/u

    International Nuclear Information System (INIS)

    Alba, R.; Ciniglione, R.; Del Zoppo, A.; Agodi, C.; Finocchiaro, P.; Loukachine, K.; Maiolino, C.; Piattelli, P.; Santonocito, D.; Sapienza, P.; Bellia, G.; Migneco, E.; Manduci, L.; Moroni, A.; Iori, I.; Milan Univ.

    1994-01-01

    Proton emission in heavy ion collisions has already been observed, even at rather large polar angles. A standard data analysis based on three moving sources has evidenced the presence of a half-beam velocity source (IS) interpreted in terms of pre-equilibrium emission from the participant zone of the colliding system. We have performed an experimental study of the fast protons production with the aim of investigating its impact parameter dependence. The data shows clearly that the mean multiplicity of the IS protons increases strongly with the centrality of the collision as expected in the hypothesis that their origin is the projectile-target overlap region. (D.L.). 8 refs., 1 fig

  1. Proton transfer in methylmalonyl-CoA epimerase from Propionibacterium shermanii. The reaction of (2R)-methylmalonyl-CoA in tritiated water.

    Science.gov (United States)

    Fuller, J Q; Leadlay, P F

    1983-01-01

    The reaction catalysed by methylmalonyl-CoA epimerase from Propionibacterium shermanii was studied in tritiated water, in the direction with (2R)-methylmalonyl-CoA as substrate, under 'irreversible' conditions. After partial reaction, even when most of the substrate had been converted into product (isolated as propionyl-CoA) essentially no solvent tritium appeared in residual (2R)-methylmalonyl-CoA. The product, however, did contain tritium, and the specific radioactivity of the (2S)-epimer was deduced to be 0.33 times that of the solvent. These results provide further support for the mechanism proposed for the epimerase-catalysed reaction in the accompanying paper [Leadlay & Fuller (1983) Biochem. J. 213, 635-642], in which two enzyme bases act respectively as proton donor and acceptor. The observed low discrimination against solvent tritium entering the product can be accounted for by a mechanism in which the release of product is slow, and the re-protonation step on the enzyme is reversible, without leading to isotopic exchange with the solvent. PMID:6311170

  2. Proton therapy

    Science.gov (United States)

    Proton beam therapy; Cancer - proton therapy; Radiation therapy - proton therapy; Prostate cancer - proton therapy ... that use x-rays to destroy cancer cells, proton therapy uses a beam of special particles called ...

  3. Light particle production in spallation reactions induced by protons of 0.8-2.5 GeV incident kinetic energy

    International Nuclear Information System (INIS)

    Herbach, Claus-Michael; Enke, Michael; Boehm, Andreas

    2002-01-01

    Absolute production cross sections have been measured simultaneously for neutrons and light charged particles in 0.8-2.5 GeV proton induced spallation reactions for a series of target nuclei from aluminum up to uranium. The high detection efficiency both for neutral and charged evaporative particles provides an event-wise access to the amount of projectile energy dissipated into nuclear excitation. Various intra nuclear cascade plus evaporation models have been confronted with the experimental data showing large discrepancies for hydrogen and helium production. (author)

  4. Transverse spin effects in proton-proton scattering and $Q \\bar Q$ production

    OpenAIRE

    Goloskokov, S. V.

    2002-01-01

    We discuss transverse spin effects caused by the spin-flip part of the Pomeron coupling with the proton. The predicted spin asymmetries in proton-proton scattering and QQ production in proton-proton and lepton-proton reactions are not small and can be studied in future polarized experiments.

  5. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb

    NARCIS (Netherlands)

    Erasmus, Sara W.; Muller, Magdalena; Alewijn, Martin; Koot, Alex H.; Ruth, van Saskia M.; Hoffman, Louwrens C.

    2017-01-01

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile

  6. Guanine radical reaction processes: a computational description of proton transfer in X-irradiated 9-ethylguanine single crystals.

    Science.gov (United States)

    Jayatilaka, Nayana; Nelson, William H

    2008-12-25

    Computational methods based on DFT procedures have been used to investigate proton-transfer processes in irradiated 9-ethylguanine crystals. Previous experimental results from X-irradiation and study of this system at 10 K found significant concentrations of two main products, R1, formed by N7-hydrogenation of the purine ring, and R2, the primary one-electron oxidation product (Jayatilaka, N.; Nelson, W. H. J. Phys. Chem. B 2007, 111, 7887). The objective of this work is to describe the processes leading to these products using computational methods that take into account molecular packing and bulk dielectric properties. The basic concept is that a proton will transfer following ionization if the net electronic energy of the system, consisting of the donor plus the acceptor plus any intervening molecules, becomes lower. Three approaches were used to investigate this concept, two based on energies computed for single molecules and one based on energies computed for two-molecule clusters arranged as in the crystals. The results are that the methods successfully predict the observed behavior, that it is energetically favorable on one-electron reduction for proton H1 to transfer from a neutral molecule to N7 of the neighbor, forming the N7-hydrogenated product, and that there is virtually no energy advantage for a proton to transfer upon one-electron oxidation. The results also support the proposal that the C8 H-addition radical, found only upon irradiation at 300 K, was the product of intramolecular transfer of the H7 proton to C8 in a process apparently requiring sufficient thermal energy for activation. Finally, the computations predict hyperfine couplings and tensors in very good agreement with those from experiment, thereby providing additional evidence for the success of the computations in describing the experimental observations.

  7. Electrostatics of the photosynthetic bacterial reaction center. Protonation of Glu L 212 and Asp L 213 - A new method of calculation.

    Science.gov (United States)

    Ptushenko, Vasily V; Cherepanov, Dmitry A; Krishtalik, Lev I

    2015-12-01

    Continuum electrostatic calculation of the transfer energies of anions from water into aprotic solvents gives the figures erroneous by order of magnitude. This is due to the hydrogen bond disruption that suggests the necessity to reconsider the traditional approach of the purely electrostatic calculation of the transfer energy from water into protein. In this paper, the method combining the experimental estimates of the transfer energies from water into aprotic solvent and the electrostatic calculation of the transfer energies from aprotic solvent into protein is proposed. Hydrogen bonds between aprotic solvent and solute are taken into account by introducing an imaginary aprotic medium incapable to form hydrogen bonds with the solute. Besides, a new treatment of the heterogeneous intraprotein dielectric permittivity based on the microscopic protein structure and electrometric measurements is elaborated. The method accounts semi-quantitatively for the electrostatic effect of diverse charged amino acid substitutions in the donor and acceptor parts of the photosynthetic bacterial reaction center from Rhodobacter sphaeroides. Analysis of the volatile secondary acceptor site QB revealed that in the conformation with a minimal distance between quinone QB and Glu L 212 the proton uptake upon the reduction of QB is prompted by Glu L 212 in alkaline and by Asp L 213 in slightly acidic regions. This agrees with the pH dependences of protonation degrees and the proton uptake. The method of pK calculation was applied successfully also for dissociation of Asp 26 in bacterial thioredoxin. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Semivolatile organic compounds monitored using a proton transfer reaction mass spectrometer at 200m above ground in rural Netherlands

    Science.gov (United States)

    Strickland, Jessica; Klinger, Andreas; Herbig, Jens; Holzinger, Rupert

    2017-04-01

    Semi-volatile organic compounds (SVOCs) are anthropogenically and naturally occurring chemical compounds that have vapor pressures such that they exist in both the gas and condensed phase at room temperature. Due to the fact SVOCs condense easily, they are interesting in the context of organic aerosol formation and these compounds impact atmospheric properties and human health. Proton Transfer Reaction Mass Spectrometry (PTR-MS, resolution 1200 FWHM) is a method that facilitates deeper analysis of SVOCs. Our setup, consisting of a PTR-MS with a time of flight mass spectrometer coupled to a denuder sampler (DS) was stationed as part of the European ACTRIS-2 program at 200m atop the Cabauw tower in the Netherlands as of September, 2016. The DS consists of three denuders in series. The first two denuders are coated with dimethylpolysiloxane (DB1, OD 4mm, 3cm long) and consists of an assemblage of micro-channels (ID 80 micrometer). The third denuder is an activated charcoal monolith of the same dimensions but with larger (thus fewer) channels (ID 800 micrometer). The air sampled at 800mL/min is pulled through these denuders as laminar flow and the SVOCs will collide and condense on the wall. Undesirable wall losses are minimized by using a short and high flow inlet lines. The collected SVOCs are thermally desorbed under a Nitrogen (N2) gas flow and transferred to the PTR-MS through heated lines to avoid re-condensation. Evaluation of the full mass spectra revealed over 200 different compounds in the range 15-500 Da. The majority of the mass of SVOCs was contained in m/z > 100 and typical mixing ratios of the detected SVOCs were a few pmol/mol in ambient air. Discernible contamination from the DB1 coating was detected and therefore, different blank methods have been tested and evaluated using a student T-test. Proper blank correction is an important issue of this method and will be discussed in detail. Data from October 19th, 2016, are used as case studies for analyzing

  9. Calculation of proton induced reaction on 209Bi in energy region from 7 to 250 MeV

    International Nuclear Information System (INIS)

    Gao Bo; Sun Xiuquan

    2000-01-01

    Cross sections of p + 209 Bi reaction are calculated from 7 to 250 MeV based on various nuclear reaction models, i.e., the optical model, evaporation model, exciton model, as well as the direct reaction theory. The comparison of the calculated results with the experimental data shows that author's calculations are quite reasonable. Moreover, excitation functions for the reactions producing some long-lived radioactive nuclei and neutron multiplicity are predicted

  10. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

    2000-01-01

    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and

  11. Copper nitrate: a privileged reagent for organic synthesis.

    Science.gov (United States)

    Gao, Mingchun; Ye, Rongxuan; Shen, Weijia; Xu, Bin

    2018-04-18

    Copper has been explored as an ideal candidate for replacing noble metals in organic synthesis, especially for practical large scale preparation. Recent decades have witnessed the renaissance and improvement of copper-catalyzed and copper-mediated organic reactions. Copper nitrate is a common inorganic copper salt which has been proved to be a ubiquitous reactant in organic synthesis due to its commercial availability, stability, inexpensiveness and environmentally benign nature. Copper nitrate could be used as a nitration reagent, oxidant, catalyst or promoter, and Lewis acid as well. Remarkably, great attention has been devoted to the efficient transformation of copper nitrate into functionalized or complicated compounds through various reaction types including cyclization, C-H activation, difunctionalization, nitration, rearrangement and asymmetric synthesis with chiral ligands. Further modification of copper nitrate, such as solid-supported copper nitrate or copper nitrate complexes, extends its applications in organic synthesis. The present review highlights recent advances of copper nitrate in organic synthesis, along with the mechanisms.

  12. Study of nuclear reactions involving heavy nuclei and intermediate- and high-energy protons and an application in nuclear reactor physics (ADS)

    International Nuclear Information System (INIS)

    Matuoka, Paula Fernanda Toledo

    2016-01-01

    In the present work, intermediate- and high-energy nuclear reactions involving heavy nuclei and protons were studied with the Monte Carlo CRISP (Rio - Ilheus - Sao Paulo Collaboration) model. The most relevant nuclear processes studied were intranuclear cascade and fission-evaporation competition. Preliminary studies showed fair agreement between CRISP model calculation and experimental data of multiplicity of evaporated neutrons (E < 20 MeV) from the p(1200 MeV) + 208 Pb reaction and of spallation residues from the p(1000 MeV) + 208 Pb reaction. The investigation of neutron multiplicity from proton-induced fission of 232 Th up to 85 MeV showed that it was being overestimated by CRISP model; on the other hand, fission cross section were being underestimated. This behavior is due to limitations of the intranuclear cascade model for low-energies (around 50 MeV). The p(1200 MeV) + 208 Pb reaction was selected for the study of a spallation neutron source. High-energy neutrons (E > 20 MeV) were emitted mostly in the intranuclear cascade stage, while evaporation presented larger neutron multiplicity. Fission cross section of 209 mb and spallation cross section of 1788 mb were calculated { both in agreement with experimental data. The fission process resulted in a symmetric mass distribution. Another Monte Carlo code, MCNP, was used for radiation transport in order to understand the role of a spallation neutron source in a ADS (Accelerator Driven System) nuclear reactor. Initially, a PWR reactor was simulated to study the isotopic compositions in spent nuclear fuel. As a rst attempt, a spallation neutron source was adapted to an industrial size nuclear reactor. The results showed no evidence of incineration of transuranic elements and modifications were suggested. (author)

  13. Measurement of cross-sections for produced radionuclide in proton induced reactions on {sup nat}Hf up to 45 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Shahid, Muhammad; Kim, Kwangsoo [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Naik, Haladhara [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2014-03-01

    We measured production cross-sections of Hf, Lu, and Ta radioisotopes from proton-induced reaction of {sup nat}Hf by using a stacked-foil activation and off-line γ-ray spectrometric technique at the MC-50 cyclotron of the Korea Institute of Radiological and Medical Sciences. The results were compared with the reported experimental data as well as the theoretical calculations based on the TALYS 1.4 code. The present results in the energy region from the threshold energy to 45 MeV are in general good agreement with the other experimental data and calculated results. The present experimental results will play an important role in enrichment of the literature data base for proton-induced reactions on natural hafnium leading to various applications. Some of the investigated radionuclides (e.g. {sup 177g}Lu) have remarkable applications in the field of nuclear medicine, a thin layer activation analysis, and a trace element analysis.

  14. Connection between Koba-Nielsen-Olesen distributions in totally inclusive and single-proton semi-inclusive reactions

    International Nuclear Information System (INIS)

    Lam, C.S.; Yeung, P.S.

    1983-01-01

    We obtain Koba-Nielsen-Olesen multiplicity distributions for p+p→anything from a model relating them to the multiplicity distributions and the proton spectrum in p+p→p+anything. The agreement with data for 100< or approx. =P/sub lab/< or approx. =1000 GeV/c is good; comparison with a similar model of Gouljanos, Sticker, and White and the validity of such models at √s = 540 GeV are discussed

  15. On-line and precise measurement of iron wear using thin layer activation reactions by proton beam

    International Nuclear Information System (INIS)

    Kosako, Toshiso; Nishimura, Kazuo.

    1990-01-01

    For the purpose of the on-line measurement of iron wear, thin layer activation (TLA) method or surface layer activation (SLA) method has been carried out since early 1970s. This method uses the irradiation of charged particle beam like protons from an accelerator onto a metal surface to produce a thin activated layer of several tens μm. The wear of this activated layer is measured by nondestructive on-line method with a radiation detector. There are two methods of the measurement. One is the activity loss measurement on the surface, and the other is the activity measurement of the metal debris collected in a filter. The former method is considered here. The purpose it to measure the wear of engine cam noses to help the development of good engine oil. Proton beam irradiation with a tandem van de Graaff accelerator, wear calibration using a gamma ray spectrometer, on-line wear measurement of cam noses of car engines by TLA method and so on are reported. The 7.00 MeV proton beam from a van de Graaff accelerator was used for activation, and Co-56, Co-57 and Co-58 were obtained in thin layers. (K.I.)

  16. Spectrophotometric determination of nitrate in vegetables using ...

    African Journals Online (AJOL)

    A rapid and sensitive spectrophotometric method for the determination of nitrate in vegetables is described. The method is based on the measurement of the absorbance of yellow sodium nitrophenoxide formed via the reaction of phenol with the vegetable-based nitrate in presence of sulphuric acid. The analytical ...

  17. Spectrophotometric Determination of Nitrate in Vegetables Using ...

    African Journals Online (AJOL)

    DR. MIKE HORSFALL

    ABSTRACT: A rapid and sensitive spectrophotometric method for the determination of nitrate in vegetables is described. The method is based on the measurement of the absorbance of yellow sodium nitrophenoxide formed via the reaction of phenol with the vegetable-based nitrate in presence of sulphuric acid.

  18. In honour of N. Yngve Öhrn: surveying proton cancer therapy reactions with Öhrn's electron nuclear dynamics method. Aqueous clusters radiolysis and DNA-base damage by proton collisions

    Science.gov (United States)

    Mclaurin, Patrick M.; Privett, Austin J.; Stopera, Christopher; Grimes, Thomas V.; Perera, Ajith; Morales, Jorge A.

    2015-02-01

    Proton cancer therapy (PCT) utilises high-energy H+ projectiles to cure cancer. PCT healing arises from its DNA damage in cancerous cells, which is mostly inflicted by the products from PCT water radiolysis reactions. While clinically established, a complete microscopic understanding of PCT remains elusive. To help in the microscopic elucidation of PCT, Professor Öhrn's simplest-level electron nuclear dynamics (SLEND) method is herein applied to H+ + (H2O)3-4 and H+ + DNA-bases at ELab = 1.0 keV. These are two types of computationally feasible prototypes to study water radiolysis reactions and H+-induced DNA damage, respectively. SLEND is a time-dependent, variational, non-adiabatic and direct-dynamics method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction. Additionally, our SLEND + effective-core-potential method is herein employed to simulate some computationally demanding PCT reactions. Due to these attributes, SLEND proves appropriate for the simulation of various types of PCT reactions accurately and feasibly. H+ + (H2O)3-4 simulations reveal two main processes: H+ projectile scattering and the simultaneous formation of H and OH fragments; the latter process is quantified through total integrals cross sections. H+ + DNA-base simulations reveal atoms and groups displacements, ring openings and base-to-proton electron transfers as predominant damage processes. The authors warmly dedicate this SLEND investigation in honour of Professor N. Yngve Öhrn on the occasion of his 80th birthday celebration during the 54th Sanibel Symposium in St. Simons' Island, Georgia, on February 16-21, 2014. Associate Professor Jorge A. Morales was a former chemistry PhD student under the mentorship of Professor Öhrn and Dr Ajith Perera took various quantum chemistry courses taught by Professor Öhrn during his chemistry PhD studies. Both Jorge and Ajith look back to those great times of their scientific formation under

  19. Substrate-dependent modulation of the enzymatic catalytic activity: reduction of nitrate, chlorate and perchlorate by respiratory nitrate reductase from Marinobacter hydrocarbonoclasticus 617.

    Science.gov (United States)

    Marangon, Jacopo; Paes de Sousa, Patrícia M; Moura, Isabel; Brondino, Carlos D; Moura, José J G; González, Pablo J

    2012-07-01

    The respiratory nitrate reductase complex (NarGHI) from Marinobacter hydrocarbonoclasticus 617 (Mh, formerly Pseudomonas nautica 617) catalyzes the reduction of nitrate to nitrite. This reaction is the first step of the denitrification pathway and is coupled to the quinone pool oxidation and proton translocation to the periplasm, which generates the proton motive force needed for ATP synthesis. The Mh NarGH water-soluble heterodimer has been purified and the kinetic and redox properties have been studied through in-solution enzyme kinetics, protein film voltammetry and spectropotentiometric redox titration. The kinetic parameters of Mh NarGH toward substrates and inhibitors are consistent with those reported for other respiratory nitrate reductases. Protein film voltammetry showed that at least two catalytically distinct forms of the enzyme, which depend on the applied potential, are responsible for substrate reduction. These two forms are affected differentially by the oxidizing substrate, as well as by pH and inhibitors. A new model for the potential dependence of the catalytic efficiency of Nars is proposed. Copyright © 2012. Published by Elsevier B.V.

  20. Protonic equilibria in the reductive half-reaction of the medium-chain acyl-CoA dehydrogenase

    OpenAIRE

    Rudik, Irina; Ghisla, Sandro; Thorpe, Colin

    1998-01-01

    Oxidation of thioester substrates in the medium-chain acyl-CoA dehydrogenase involves α-proton abstraction by the catalytic base, Glu376, with transfer of a β-hydride equivalent to the flavin prosthetic group. Polarization of bound acyl-CoA derivatives by the recombinant human liver enzyme has been studied with 4-thia-trans-2-enoyl-CoA analogues. Polarization is maximal at low pH, with an apparent pK of 9.2 for complexes with the C8 analogue, and progressively lower pK values as the length of...

  1. Optimum conditions for cotton nitrate reductase extraction and ...

    African Journals Online (AJOL)

    GREGO

    mM of glutamine in the extraction buffer stimulates significantly, in vitro, the reduction of nitrate. Enzyme activity is moreover optimal when 1 M of exogenous nitrate, as substrate, is added to the reaction medium. At these optimum conditions of nitrate reductase activity determination, the substrate was completely reduced ...

  2. Electrophilic and free radical nitration of benzene and toluene with various nitrating agents*

    Science.gov (United States)

    Olah, George A.; Lin, Henry C.; Olah, Judith A.; Narang, Subhash C.

    1978-01-01

    Electrophilic nitration of toluene and benzene was studied under various conditions with several nitrating systems. It was found that high orthopara regioselectivity is prevalent in all reactions and is independent of the reactivity of the nitrating agent. The methyl group of toluene is predominantly ortho-para directing under all reaction conditions. Steric factors are considered to be important but not the sole reason for the variation in the ortho/para ratio. The results reinforce our earlier views that, in electrophilic aromatic nitrations with reactive nitrating agents, substrate and positional selectivities are determined in two separate steps. The first step involves a π-aromatic-NO2+ ion complex or encounter pair, whereas the subsequent step is of arenium ion nature (separate for the ortho, meta, and para positions). The former determines substrate selectivity, whereas the latter determines regioselectivity. Thermal free radical nitration of benzene and toluene with tetranitromethane in sharp contrast gave nearly statistical product distributions. PMID:16592503

  3. Analytical detection of explosives and illicit, prescribed and designer drugs using proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Bishu; Petersson, Fredrik; Juerschik, Simone [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Sulzer, Philipp; Jordan, Alfons [IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Maerk, Tilmann D. [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Watts, Peter; Mayhew, Chris A. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 4TT (United Kingdom)

    2011-07-01

    This work demonstrates the extremely favorable features of Proton Transfer Reaction Time-of-flight Mass Spectrometry (PTR-TOF-MS) for the detection and identification of solid explosives, chemical warfare agent simulants and illicit, prescribed and designer drugs in real time. Here, we report the use of PTR-TOF, for the detection of explosives (e.g., trinitrotoluene, trinitrobenzene) and illicit, prescribed and designer drugs (e.g., ecstasy, morphine, heroin, ethcathinone, 2C-D). For all substances, the protonated parent ion (as we used H{sub 3}O{sup +} as a reagent ion) could be detected, providing a high level of confidence in their identification since the high mass resolution allows compounds having the same nominal mass to be separated. We varied the E/N from 90 to 220 T{sub d} (1 T{sub d}=10{sup -17} Vcm{sup -1}). This allowed us to study fragmentation pathways as a function of E/N (reduced electric field). For a few compounds rather unusual E/N dependencies were also discovered.

  4. Immediate-type hypersensitivity reactions to proton pump inhibitors: usefulness of skin tests in the diagnosis and assessment of cross-reactivity.

    Science.gov (United States)

    Kepil Özdemir, S; Yılmaz, I; Aydin, Ö; Büyüköztürk, S; Gelincik, A; Demirtürk, M; Erdoğdu, D; Cömert, S; Erdoğan, T; Karakaya, G; Kalyoncu, A F; Oner Erkekol, F; Dursun, A B; Misirligil, Z; Bavbek, S

    2013-08-01

    Data are limited about the value of skin tests in the diagnosis of proton pump inhibitor (PPI)-induced hypersensitivity reactions and the cross-reactivity between PPIs. We aimed to assess the role of skin testing in the diagnosis of PPI-related immediate hypersensitivity reactions and the cross-reactivity patterns among PPIs. The study was designed in a prospective, national, multicentre nature. Sixty-five patients with a suggestive history of a PPI-induced immediate hypersensitivity reaction and 30 control subjects were included. Standardized skin prick and intradermal tests were carried out with a panel of PPIs. Single-blind, placebo-controlled oral provocation tests (OPTs) with the PPIs other than the culprit PPI that displayed negative results in skin tests (n = 61) and diagnostic OPTs with the suspected PPI (n = 12) were performed. The suspected PPIs were lansoprazole (n = 52), esomeprazole (n = 11), pantoprazole (n = 9), rabeprazole (n = 2), and omeprazole (n = 1). The sensitivity, specificity, and negative and positive predictive values of the skin tests with PPIs were 58.8%, 100%, 70.8%, and 100%, respectively. Fifteen of the 31 patients with a hypersensitivity reaction to lansoprazole had a positive OPT or skin test result with at least one of the alternative PPIs (8/52 pantoprazole, 6/52 omeprazole, 5/52 esomeprazole, 3/52 rabeprazole). Considering the high specificity, skin testing seems to be a useful method for the diagnosis of immediate-type hypersensitivity reactions to PPIs and for the evaluation of cross-reactivity among PPIs. However, OPT should be performed in case of negativity on skin tests. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  5. a Study of the Reactions Positive Pion-Proton ---> Positive Pion-Proton Neutral Pion (fast) and Positive Pion-Proton ---> Positive Pion-Neutron Positive Pion Neutral Pion (fast) at 15.7 Gev/c.

    Science.gov (United States)

    Glanzman, Thomas Lynn

    The reactions (pi)('+)p (--->) (pi)('+)p(pi)('0) and (pi)('+)p (--->) (pi)('+)n(pi)('+)(pi)('0) are studied at 15.7 GeV/c using the SLAC 1 meter Hybrid Bubble Chamber facility with the addition of a large lead glass photon detector. The 677,000 pictures taken represent a 22.8 event/(mu)b untriggered sensitivity. The present analysis consists of 38,900 2-prong events with an identified and fully measured (pi)('0). Systematics for incorporating lead glass data for neutral particles with charged particle information from the bubble chamber are developed. Several resonance channels in the (pi)('+)p(pi)('0) final state are observed. Isolation of the (pi)('+)p ( --->) (DELTA)('++)(pi)('0) events yielded a production cross section of (32.6 (+OR-) 3.5) (mu)b. The production mechanism for the (DELTA)('++), as studied through the spin density matrix elements and t-distribution, is found to be in good agreement with the Regge Pole Model. The appearance of dual solutions for the Regge amplitudes does not rule out a photon-like (rho) meson (helicity = (+OR-) 1) mediating this reaction. Production of the (rho)('+) meson in the reaction (pi)('+)p (--->) (rho)('+)p is observed with a cross section of (20.6 (+OR-) 7.4) (mu)b. An analysis of the spin density matrix elements indicates an approximately equal contribution of (pi) and (omega) exchange mediating (rho)('+) production. The reaction (pi)('+)p (--->) g('+)(1700)p is seen with a partial cross section of (3.2 (+OR-) 1.1) (mu)b for (pi)('+)(pi)('0) decays with a forward (pi)('0). No other resonance behavior with a cross section greater than 1.4 (mu)b/0.2 GeV/c('2) is observed in this system above a mass of 1.8 GeV/c('2). The first study of the reaction (pi)('+)p (-- ->) (rho)('+)(pi)('+)n was made in this experiment and found to have a cross section of (90.2 (+OR-) 10.6) (mu)b. The spin density matrix elements are fitted, and exchange properties of this reaction studied. This reaction is seen to favor (pi)-exchange as the

  6. Protein Tyrosine Nitration: Selectivity, physicochemical and biological consequences, denitration and proteomics methods for the identification of tyrosine-nitrated proteins

    NARCIS (Netherlands)

    Abello, N.; Kerstjens, H.A.M.; Postma, D.S; Bischoff, Rainer

    2009-01-01

    Protein tyrosine nitration (PTN) is a post-translational modification occurring under the action of a nitrating agent. Tyrosine is modified in the 3-position of the phenolic ring through the addition of a nitro group (NO2). In the present article, we review the main nitration reactions and elucidate

  7. Protein Tyrosine Nitration : Selectivity, Physicochemical and Biological Consequences, Denitration, and Proteomics Methods for the Identification of Tyrosine-Nitrated Proteins

    NARCIS (Netherlands)

    Abello, Nicolas; Kerstjens, Huib A. M.; Postma, Dirkje S.; Bischoff, Rainer

    Protein tyrosine nitration (PTN) is a post-translational modification occurring under the action of a nitrating agent. Tyrosine is modified in the 3-position of the phenolic ring through the addition of a nitro group (NO(2)). In the present article, we review the main nitration reactions and

  8. Calculations of nuclear data for the reactions of neutrons and protons with heavy nuclei at energy from 1 MeV up to 2 GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-01-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 1 MeV to 2 GeV. At energies from 1 to 20 MeV the statistical model code STAPRE was used for calculations of the neutron cross-sections for fission, (n,2n) and (n,3n) reaction cross-sections for 71 actinide isotopes. In the energy region from 10 to 100 MeV the nuclear theory code GNASH was used to calculate the neutron fission and (n,xn) cross-sections for 238 U, 235 U, 239 Pu, 232 Th, 237 Np, 238 Pu, 241 Am, 243 Am, 245 Cm and 246 Cm. At energies from 100 MeV to 2 GeV the intranuclear cascade-exciton model including the fission process was applied to calculations of the interactions of protons and neutrons with actinides and the calculated results are compared with experimental data. (author)

  9. Subthreshold particle production mechanisms in cold nuclear matter: neutral pion and photon production in proton-nucleus reactions at 190 MeV

    International Nuclear Information System (INIS)

    Aphecetche, L.

    1998-01-01

    The production of photons and neutral pions in the cold nuclear matter and in particular the production under the threshold, has been studied. Particles produced under the threshold in heavy ion collisions, are in fact the only sources of information on the hot nuclear matter characteristics, that is created during the collisions. The proton-nuclei reactions have been studied at 190 MeV with the TAPS collaboration, at the AGOR accelerator (KVI). The concomitant measure of photons and neutral pions allowed the cross sections determination of direct photons production, with a contribution estimation of the photons resulting from the neutral pions decay, to the measured photons spectrum. The great number of measured particles allowed to study the differential cross sections development in function of the nuclei target mass. (A.L.B.)

  10. Experimental cross-sections for proton induced nuclear reactions on mercury up to 65 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Hermanne, A., E-mail: aherman@vub.ac.be [Cyclotron Laboratory, Vrije Universiteit Brussel (VUB), Brussels (Belgium); Tárkányi, F.; Takács, S.; Ditrói, F.; Szücs, Z.; Brezovcsik, K. [Institute of Nuclear Research, Hungarian Academy of Sciences (ATOMKI), Debrecen (Hungary)

    2016-07-01

    Cross-sections for formation of activation products induced by protons on natural mercury targets were measured. Results for {sup 196m,196g,197g}(cum), {sup 198m,198g,199g}(cum), {sup 200g}(cum), {sup 201,202}Tl, {sup 194g}(cum), {sup 195g}(cum), {sup 196g}(cum), {sup 198m,199g}(cum) Au and {sup 195m,197m,203}Hg are presented up to 65 MeV incident particle energy, many of these for the first time. The experimental data are compared with literature values and with the predictions of the TALYS 1.6 code (results taken from TENDL-2015 on-line library), thick target yields were derived and possible applications in biomedical sciences are discussed.

  11. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  12. Theoretical Study of the Mechanism Behind the para-Selective Nitration of Toluene in Zeolite H-Beta

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Amity; Govind, Niri; Subramanian, Lalitha

    2008-10-24

    In this work, we investigate the origin of the favorable para-selective nitration of toluene exhibited by H- beta zeolite solid acid catalyst. Periodic density functional theory calculations were performed to study the toluene nitration by acetyl nitrate within the pore system of a model H-beta structure. Firstly, energetics were calculated for each of the 32 crystallographically unique Br¿nsted acid sites of a beta polymorph B zeolite unit cell. These calculations revealed more than one favorable Br¿nsted acid site. However, steric and mechanistic considerations could be used to argue that one particular aluminum site with three favorable Br¿nsted site oxygens comprising a 12-T pore wall would be a likely site for nitration to take place. Transition state searches around this aluminum site were performed to determine the barrier to reaction for both para and ortho nitration of the toluene. A three-step process was assumed for the nitration of toluene with two organic intermediates: the ¼-complex and the ¾-complex (i.e., Wheland or arenium complex). The rate limiting step of the three-step process is the transfer of the proton from the ¾-complex to a Br¿nsted site on the zeolite cage. The barrier for this step in the ortho nitration case is shown to be nearly 2.5 times that for the para nitration case. The reason for the discrepancy appears to be a subtle steric constraint imposed by the curvature of the 12-T pore system of the beta zeolite and the methyl group of the toluene in the case of the ortho approach.

  13. Theoretical Study of the Mechanism Behind the para-Selective Nitration of Toluene in Zeolite H-Beta

    International Nuclear Information System (INIS)

    Andersen, Amity; Govind, Niri; Subramanian, Lalitha

    2008-01-01

    In this work, we investigate the origin of the favorable para-selective nitration of toluene exhibited by H- beta zeolite solid acid catalyst. Periodic density functional theory calculations were performed to study the toluene nitration by acetyl nitrate within the pore system of a model H-beta structure. Firstly, energetics were calculated for each of the 32 crystallographically unique Broensted acid sites of a beta polymorph B zeolite unit cell. These calculations revealed more than one favorable Broensted acid site. However, steric and mechanistic considerations could be used to argue that one particular aluminum site with three favorable Broensted site oxygens comprising a 12-T pore wall would be a likely site for nitration to take place. Transition state searches around this aluminum site were performed to determine the barrier to reaction for both para and ortho nitration of the toluene. A three-step process was assumed for the nitration of toluene with two organic intermediates: the π-complex and the σ-complex (i.e., Wheland or arenium complex). The rate limiting step of the three-step process is the transfer of the proton from the σ-complex to a Broensted site on the zeolite cage. The barrier for this step in the ortho nitration case is shown to be nearly 2.5 times that for the para nitration case. The reason for the discrepancy appears to be a subtle steric constraint imposed by the curvature of the 12-T pore system of the beta zeolite and the methyl group of the toluene in the case of the ortho approach

  14. Radiation chemistry of nitrate ices

    International Nuclear Information System (INIS)

    Kishore, K.; Moorthy, P.N.; Rao, K.N.

    1978-01-01

    The yields of various products formed in γ-irradiated nitrate ices, viz NO 2 - , H 2 O 2 , O 2 and H 2 , have been measured at different nitrate concentrations. Daniel's method of partition of yields has been employed to evaluate the direct and indirect effect contributions to the yields of the first three products. G(H 2 ) is close to zero at all nitrate concentrations above approximately 0.5 mol dm -3 . The mechanism of product formation has been discussed in the light of various reactions put forth to explain the radiolysis of fluid aqueous nitrate solutions. The effect of various scavengers for the primary species on the product yields has also been investigated. From this it is inferred that nitrate is able to scavenge both the reducing species, viz. H and e - sub(m) giving nitrite and possibly also the holes (h + sub(m)) giving O 2 , and excited water molecules (H 2 O*) giving H 2 O 2 and additional nitrite. (author)

  15. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb.

    Science.gov (United States)

    Erasmus, Sara W; Muller, Magdalena; Alewijn, Martin; Koot, Alex H; van Ruth, Saskia M; Hoffman, Louwrens C

    2017-10-15

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile fingerprints were affected by the origin of the meat. The classification of the origin of the lamb was achieved by examining the calculated and recorded fingerprints in combination with chemometrics. Four different partial least squares discriminant analysis (PLS-DA) models were fitted to the data to classify lamb meat and fat samples into "region of origin" (six different regions) and "origin" (Karoo vs. Non-Karoo). The estimation models classified samples 100% correctly. Validation of the first two models gave 42% (fat) and 58% (meat) correct classification of region, while the second two models performed better with 92% (fat) and 83% (meat) correct classification of origin. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Preliminary study on 2-dimensional distributions of 10B reaction rate in a water phantom with boron-doped CR-39 for 7Li(p, n)7Be neutrons by 1.95 MeV protons

    International Nuclear Information System (INIS)

    Hasegawa, Y.; Tanaka, K.; Tsuruta, T.

    2000-01-01

    In an Accelerator-based neutron irradiation field using 7 Li(p, n) 7 Be neutrons by 1.95 MeV protons, the distributions of 10 B reaction rates and thermal neutron fluence in a water phantom were measured using Boron-doped CR-39 and Au activation analysis, respectively. Comparing the results of the measurements, we discussed the validity of the evaluation method of 10 B reaction rate using thermal neutron fluence. (author)

  17. Angular distributions of the quasifree deuteron-proton and deuteron-neutron scattering in the reaction dd → dpn

    International Nuclear Information System (INIS)

    Schneider, H.

    1978-06-01

    The mechanism of the quasifree scattering (QFS) in the reaction dd → dpn has been investigated systematically by means of kinematically complete coincidence experiments using 52 MeV deuterons. In order to measure the angular distributions of the quasifree dp scattering and the quasifree dn scattering, the kinematical conditions were chosen to favour quasifree scattering of deuterons on bound nucleons of the target deuteron. (orig.) [de

  18. Correction: The stability and generation pattern of thermally formed isocyanic acid (ICA) in air - potential and limitations of proton transfer reaction-mass spectrometry (PTR-MS) for real-time workroom atmosphere measurements.

    Science.gov (United States)

    Jankowski, Mikolaj Jan; Olsen, Raymond; Thomassen, Yngvar; Molander, Paal

    2018-02-21

    Correction for 'The stability and generation pattern of thermally formed isocyanic acid (ICA) in air - potential and limitations of proton transfer reaction-mass spectrometry (PTR-MS) for real-time workroom atmosphere measurements' by Mikolaj Jan Jankowski et al., Environ. Sci.: Processes Impacts, 2016, 18, 810-818.

  19. A selected ion flow tube study of the ion molecule association reactions of protonated (MH+), nitrosonated (MNO+) and dehydroxidated (M-OH)(+) carboxylic acids (M) with H2O

    Czech Academy of Sciences Publication Activity Database

    Brůhová Michalčíková, R.; Španěl, Patrik

    2014-01-01

    Roč. 368, JUL 2014 (2014), s. 15-22 ISSN 1387-3806 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : ion molecule reactions * proton transfer * selected ion flow tube mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

  20. Calculations of neutron and proton induced reaction cross sections for actinides in the energy region from 10MeV to 1GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-06-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 10MeV to 1GeV. At energies up to 100MeV the nuclear theory code GNASH was used for nuclear data calculation for neutrons incident for on 238 U, 233-236 U, 238-242 Pu, 237 Np, 232 Th, 241-243 Am and 242-247 Cm. At energies from 100MeV to 1GeV the intranuclear cascade exciton model including the fission process was applied to calculations of protons and neutrons with 233 U, 235 U, 238 U, 232 Th, 232 Pa, 237 Np, 238 Np, 239 Pu, 241 Am, 242 Am and 242-248 Cm. Determination of parameter systematics was a major effort in the present work that was aimed at improving the predictive capability of the models used. An emphasis was placed upon a simultaneous analysis of data for a variety of reaction channels for the nuclei considered, as well as of data that are available for nearby nuclei or for other incident particles. Comparisons with experimental data available on multiple reaction cross sections, isotope yields, fission cross sections, particle multiplicities, secondary particle spectra, and double differential cross sections indicate that the calculations reproduce the trends, and often the details, of the measurements data. (author) 82 refs

  1. Calculations of neutron and proton induced reaction cross sections for actinides in the energy region from 10 MeV to 1 GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-01-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 10 MeV to 1 GeV. At energies up to 100 MeV the nuclear theory code GNASH was used for nuclear data calculation for incident neutrons for 238 U, 233-236 U, 238-242 Pu, 237 Np, 232 Th, 241-243 Am and 242-247 Cm. At energies from 100 MeV to 1 GeV the intranuclear cascade exciton model including the fission process was applied to calculations of protons and neutrons with 233 U, 235 U, 238 U, 232 Th, 232 Pa, 237 Np, 238 Np, 239 Pu, 241 Am, 242 Am and 242-248 Cm. Determination of parameter systematics was a major effort in the present work that was aimed at improving the predictive capability of the models used. An emphasis was made on a simultaneous analysis of data for a variety of reaction channels for the nucleus considered, as well as of data that are available for nearby nuclei or other incident particles. Comparison with experimental data available on multiple reaction cross sections, isotope yields, fission cross sections, particle multiplicities, secondary particle spectra, and double differential cross sections indicates that the calculations reproduce the trends, and often the details, of the experimental data. (author)

  2. Proton scattering on unstable nuclei: study of {sup 40}S(p,p`) and {sup 43}Ar(p,p`) reactions, development of detection system MUST; Diffusion de protons par des noyaux instables: Etudes des reactions {sup 40}S(p,p`) et {sup 43}Ar(p,p`), developpement du systeme de detection MUST

    Energy Technology Data Exchange (ETDEWEB)

    Marechal, F

    1998-02-06

    We measured for the first time the elastic and inelastic proton scattering on the {sup 40}S unstable nucleus. The experiment was performed in inverse kinematics at the NSCL AT Michigan State University with a {sup 40}S secondary beam bombarding a CH{sub 2} target at 30 MeV/A. We obtained the elastic scattering angular distribution and two points of the inelastic distribution to the first 2{sup +} excited state found to be located at 860{+-}90 KeV. With a coupled channel analysis, the {beta}{sub 2} quadrupolar deformation parameter is found to be equal to 0.35{+-}0.05. This value can be compared to 0.28{+-}0.02 obtained by coulomb excitation. A macroscopic analysis allowed us to extract the neutron and proton transition matrix element ratio M{sub n}/M{sub p} which is equal to 1.88{+-}0.38. This value, greater than N/Z, could indicate an isovector effect in the first 2{sup +} state excitation which could be due to a difference between the neutron and proton vibrations. The microscopic analysis gives the possibility to test the densities and the transition densities to the first 2{sup +} state. The calculated densities for the {sup 40}S nucleus show a neutron skin. However the microscopic analysis yields a M{sub n}/M{sub p} ratio of 1.40{+-}0.20. A similar elastic and inelastic proton scattering experiment allowed us to get a deformation parameter of 0.25{+-}0.03 for the {sup 43}Ar nucleus. To develop the study of direct reactions induced by radioactive beams at GANIL, we have developed and built, in collaboration with the CEA-Saclay and the CEA-Bruyeres, the new detector MUST.It is based on the silicon strip technology, and is dedicated to the measurement of recoiling light particles emitted in these reactions. The results obtained with a {sup 40}Ar beam at 77 Me V/A, have shown the good performances of the detector for the particle identification as well as for the resolutions, and allow us to consider now a large experimental programme concerning these direct

  3. Investigation of sulfate and nitrate formation on mineral dust particles by receptor modeling

    Energy Technology Data Exchange (ETDEWEB)

    Hien, P.D.; Bac, V.T.; Thinh, N.T.H. [Vietnam Atomic Energy Commission, Hanoi (Vietnam)

    2005-12-01

    The formation of sulfate and nitrate by heterogeneous reactions of gaseous precursors on mineral dust particles was investigated using positive matrix factorization (PMF) of coarse PM10 (particulate diameters from 2.2 to 10 {mu} m) collected at urban (Hanoi) and rural (Lucnam) sites in northern Vietnam. Air samples were analyzed for ionic and elemental components using ion chromatography and proton induced X-ray emission methods. PMF revealed six similar sources/types of coarse PM10 at the two sites, namely soil dust containing nitrate and sulfate, coal fly ash from distant and local sources, soil dust containing organic matter and ammonium sulfate and marine aerosol. Traffic (road) dust was found only at the urban site. From the PMF factor models, the yields of NO{sub 3}{sup -}, SO{sub 4}{sup 2-} and NH{sub 4}{sup +} can be estimated and their possible chemical forms in different particulate types can be suggested. The yields of nitrate and sulfate formation on mineral dust particles increase with the (Ca)/(Si) ratio, which is greater in soil dust than in coal fly ash. Nitrate is bound to Ca-richest soil dust particles. Ammonium was found in dust particles containing soil organic matter, which also hold the largest amount of sulfate. The comparison of urban and rural receptor models provided synergy for the source identification and insights into the properties of mineral dust particles relevant to their interactions with acidic gases in ambient air.

  4. Use of Proton-Transfer-Reaction Mass Spectrometry to Characterize Volatile Organic Compound Sources at the La Porte Super Site During the Texas Air Quality Study 2000

    Energy Technology Data Exchange (ETDEWEB)

    Karl, Thomas G.; Jobson, B Tom T.; Kuster, W. C.; Williams, Eric; Stutz, Jochen P.; Shetter, Rick; Hall, Samual R.; Goldan, P. D.; Fehsenfeld, Fred C.; Lindinger, Werner

    2003-08-19

    Proton-transfer-reaction mass spectrometry (PTR-MS) was deployed for continuous real-time monitoring of volatile organic compounds (VOCs) at a site near the Houston Ship Channel during the Texas Air Quality Study 2000. Overall, 28 ions dominated the PTR-MS mass spectra and were assigned as anthropogenic aromatics (e.g., benzene, toluene, xylenes) and hydrocarbons (propene, isoprene), oxygenated compounds (e.g., formaldehyde, acetaldehyde, acetone, methanol, C7 carbonyls), and three nitrogencontaining compounds (e.g., HCN, acetonitrile and acrylonitrile). Biogenic VOCs were minor components at this site. Propene was the most abundant lightweight hydrocarbon detected by this technique with concentrations up to 100+ nmol mol-1, and was highly correlated with its oxidation products, formaldehyde (up to ~40 nmol mol-1) and acetaldehyde (up to ~80 nmol/mol), with typical ratios close to 1 in propene-dominated plumes. In the case of aromatic species the high time resolution of the obtained data set helped in identifying different anthropogenic sources (e.g., industrial from urban emissions) and testing current emission inventories. A comparison with results from complimentary techniques (gas chromatography, differential optical absorption spectroscopy) was used to assess the selectivity of this on-line technique in a complex urban and industrial VOC matrix and give an interpretation of mass scans obtained by ‘‘soft’’ chemical ionization using proton-transfer via H3O+. The method was especially valuable in monitoring rapidly changing VOC plumes which passed over the site, and when coupled with meteorological data it was possible to identify likely sources.

  5. In situ formation of a 3D core-shell and triple-conducting oxygen reduction reaction electrode for proton-conducting SOFCs

    Science.gov (United States)

    Zhang, Zhenbao; Wang, Jian; Chen, Yubo; Tan, Shaozao; Shao, Zongping; Chen, Dengjie

    2018-05-01

    BaZrxCeyY1-x-yO3-δ are recognized proton-conducting electrolyte materials for proton-conducting solid oxide fuel cells (H+-SOFCs) below 650 °C. Here Co cations are incorporated into the BaZr0.4Ce0.4Y0.2O3-δ (BZCY) scaffold to generate a 3D core-shell and triple-conducting (H+/O2-/e-) electrode in situ via infiltrating and reactive sintering. The core is the bulk BZCY scaffold, while the shell is composed of the cubic Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ, cubic spinel Co3O4 and cubic fluorite (Ce, Zr, Y)O2. The obtained electrode exhibits an excellent compatibility with the BZCY electrolyte, and performs well in yielding a low and stable polarization resistance for oxygen reduction reaction for intermediate-temperature H+-SOFCs. In particular, it achieves polarization resistances as low as 0.094 and 0.198 Ω cm2 at 650 and 600 °C in wet air (3% H2O) when the sintering temperature for the electrode is 900 °C. In addition, a symmetrical cell also exhibits operation stability of 70 h at 650 °C. Furthermore, a fuel cell assembled with the 3D core-shell and triple-conducting electrode delivers a peak power density of ∼330 mW cm-2 at 650 °C. The substantially improved electrochemical performance and high stability are ascribed to the unique core-shell structure and the formation of Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ in the shell.

  6. (d ,n ) proton-transfer reactions on 9Be, 11B, 13C, N,1514, and 19F and spectroscopic factors at Ed=16 MeV

    Science.gov (United States)

    Febbraro, M.; Becchetti, F. D.; Torres-Isea, R. O.; Riggins, J.; Lawrence, C. C.; Kolata, J. J.; Howard, A. M.

    2017-08-01

    The (d ,n ) reaction has been studied with targets of 9Be, 11B, 13C, N,1514, and 19F at Ed=16 MeV using a deuterated liquid-scintillator array. Advanced spectral unfolding techniques with accurately measured scintillator response functions were employed to extract neutron energy spectra without the need for long-path neutron time-of-flight. An analysis of the proton-transfer data at forward angles to the ground states of the final nuclei, using finite-range distorted-wave Born approximation analysis with common bound-state, global, and local optical-model parameter sets, yields a set of self-consistent spectroscopic factors. These are compared with the results of several previous time-of-flight measurements, most done many years ago for individual nuclei at lower energy and often analyzed using zero-range transfer codes. In contrast to some of the earlier published data, our data generally compare well with simple shell-model predictions, with little evidence for uniform quenching (reduction from shell-model values) that has previously been reported from analysis of nucleon knock-out reactions. Data for low-lying excited states in 14N from 13C(d ,n ) also is analyzed and spectroscopic information relevant to nuclear astrophysics obtained. A preliminary study of the radioactive ion beam induced reaction 7Be(d ,n ) , E (7Be)=30 MeV was carried out and indicates further improvements are needed for such measurements, which require detection of neutrons with En<2 MeV .

  7. Yttrium Nitrate mediated Nitration of Phenols at room temperature in ...

    Indian Academy of Sciences (India)

    chromatographic purification. 2.1 Procedure for Nitration of Phenol. Phenol (94 mg, 1 mmol) dissolved in 3 mL glacial acetic acid in a 50 mL test tube was treated with solid Y(NO3)3.6H2O. (383 mg, 1 mmol) with constant shaking at RT for 10 min. The reaction was monitored by TLC at 10% EtOAc in. Petroleum benzene.

  8. Spectrophotometric study on the proton transfer reaction between 2-amino-4-methylpyridine with 2,6-dichloro-4-nitrophenol in methanol, acetonitrile and the binary mixture 50% methanol + 50% acetonitrile

    Science.gov (United States)

    Al-Ahmary, Khairia M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

    2016-02-01

    Proton transfer reaction between 2-amino-4-methylpyridine (2AMP) as the proton acceptor with 2,6-dichloro-4-nitrophenol (DCNP) as the proton donor has been investigated spectrophotometrically in methanol (MeOH), acetonitrile (AN) and a binary mixture composed of 50% MeOH and 50% AN (AN-Me). The composition of the complex has been investigated utilizing Job's and photometric titration methods to be 1:1. Minimum-maximum absorbance equation has been applied to estimate the formation constant of the proton transfer reaction (KPT) where it reached high values in the investigated solvent confirming its high stability. The formation constant recorded higher value in AN compared with MeOH and mixture of AN-Me. Based on the formation of stable proton transfer complex, a sensitive spectrophotometric method was suggested for quantitative determination of 2AMP. The Lambert-Beer's law was obeyed in the concentration range 0.5-8 μg mL- 1 with small values of limits of detection and quantification. The solid complex between 2AMP with DCNP has been synthesized and characterized by elemental analysis to be 1:1 in concordant with the molecular stoichiometry in solution. Further analysis of the solid complex was carried out using infrared and 1H NMR spectroscopy.

  9. Primary hydrogen isotope effect in the nitration of polymethylbenzenes with nitric acid

    International Nuclear Information System (INIS)

    Mishina, Tadashi

    1980-01-01

    The side-chain nitrooxylation (formation of benzyl nitrate) of specifically deuterated polymethylbenzenes with nitric acid in nitromethane has been investigated. The kinetic isotope effect (KIE) of hydrogen in the reaction was determined by means of MS and NMR spectroscopy. For 6-X-Pentamethylbenzenes (1, X=CH 3 ; 2, X=H; 3, X=COCH 3 ; 4, X=COC(CH 3 ) 3 ), KIE was 2.88(0 0 C), 1.69 and 1.74 (0 and 25 0 C), 2.01 (25 0 C), and 1.46 (25 0 C), respectively, by the intramolecular competition between the methyl group and the trideuteriomethyl group. For 1,2,3,5-tetramethylbenzene (5), the intermolecular KIE obtained by means of high performance liquid chromatograph (HPLC) was 1.2(0 0 C). No hydrogen exchange was detected in the course of the reaction. These relatively large primary KIEs indicate that the proton removal is partly involved in the rate-determination. This is quite different from ordinary ring nitration of simple arenes. A range of the KIE values is discussed in terms of proton acidity, stability of the arenium ion, as well as steric circumstance. (author)

  10. Legacy Nitrate Impacts on Groundwater and Streams

    Science.gov (United States)

    Tesoriero, A. J.; Juckem, P. F.; Miller, M. P.

    2017-12-01

    Decades of recharge of high-nitrate groundwater have created a legacy—a mass of high-nitrate groundwater—that has implications for future nitrate concentrations in groundwater and in streams. In the United States, inorganic nitrogen fertilizer applications to the land surface have increased ten-fold since 1950, resulting in sharp increases in nitrate concentrations in recharging groundwater, which pose a risk to deeper groundwater and streams. This study assesses the factors that control time lags and eventual concentrations of legacy nitrate in groundwater and streams. Results from the USGS National Water-Quality Assessment Project are presented which elucidate nitrate trends in recharging groundwater, delineate redox zones and assess groundwater and stream vulnerability to legacy nitrate sources on a regional scale. This study evaluated trends and transformations of agricultural chemicals based on groundwater age and water chemistry data along flow paths from recharge areas to streams at 20 study sites across the United States. Median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years, from 4 to 7.5 mg N/L. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the redox zones encountered along flow paths and on the age distribution of nitrate discharging to supply wells and streams. Delineating redox zones on a regional scale is complicated by the spatial variability of reaction rates. To overcome this limitation, we applied logistic regression and machine learning techniques to predict the probability of a specific redox condition in groundwater in the Chesapeake Bay watershed and the Fox-Wolf-Peshtigo study area in Wisconsin. By relating redox-active constituent concentrations in groundwater samples to indicators of residence time and/or electron donor availability, we were able to delineate redox zones on a regional scale

  11. Potential energy surface of the reaction of imidazole with peroxynitrite: Density functional theory study

    Science.gov (United States)

    Gogonea, Valentin

    This article presents a theoretical investigation of the reaction mechanism of imidazole nitration by peroxynitrite using density functional theory calculations. Understanding this reaction mechanism will help in elucidating the mechanism of guanine nitration by peroxynitrite, which is one of the assumed chemical pathways for damaging DNA in cells. This work focuses on the analysis of the potential energy surface (PES) for this reaction in the gas phase. Calculations were carried out using Hartree-Fock (HF) and density functional theory (DFT) Hamiltonians with double-zeta basis sets ranging from 6-31G(d) to 6-31++G(d,p), and the triple-zeta basis set 6-311G(d). The computational results reveal that the reaction of imidazole with peroxynitrite in gas phase produces the following species: (i) hydroxide ion and 2-nitroimidazole, (ii) hydrogen superoxide ion and 2-nitrosoimidazole, and (iii) water and 2-nitroimidazolide. The rate-determining step is the formation of a short-lived intermediate in which the imidazole C2 carbon is covalently bonded to peroxynitrite nitrogen. Three short-lived intermediates were found in the reaction path. These intermediates are involved in a proton-hopping transport from C2 carbon to the terminal oxygen of the OO moiety of peroxynitrite via the nitroso (ON) oxygen. Both HF and DFT calculations (using the Becke3-Lee-Yang-Parr functional) lead to similar reaction paths for proton transport, but the landscape details of the PES for HF and DFT calculations differ. This investigation shows that the reaction of imidazole with peroxynitrite produces essentially the same types of products (nitro- and nitroso-) as observed experimentally in the reaction of guanine with peroxynitrite, which makes the former reaction a good model to study by computation the essential characteristics of the latter reaction. Nevertheless, the computationally determined activation energy for imidazole nitration by peroxynitrite in the gas phase is 84.1 kcal

  12. Modeled Wet Nitrate Deposition

    Data.gov (United States)

    U.S. Environmental Protection Agency — Modeled data on nitrate wet deposition was obtained from Dr. Jeff Grimm at Penn State Univ. Nitrate wet depostion causes acidification and eutrophication of surface...

  13. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources of...

  14. Nitrate accumulation in spinach

    NARCIS (Netherlands)

    Steingröver, Eveliene Geertruda

    1986-01-01

    Leafy vegetables, like spinach, may contain high concentrations of nitrate. In the Netherlands, about 75% of mean daily intake of nitrate orginates from the consumption of vegatables. Hazards to human health are associated with the reduction of nitrate to nitrite. Acute nitrite poisoning causes

  15. Study of the production of residual evaporation nuclei issued from the spallation reaction of uranium-238 by 1 GeV protons; Etude de la production de noyaux residuels d'evaporation issus de la reaction de spallation de l'uranium-238 par des protons a 1 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Taieb, J

    2000-10-01

    The spallation reaction by high energy protons is one of the envisaged nuclear reactions for production of exotic nuclei. We have measured the production of more than 300 different evaporation residues issued by the spallation reaction of Uranium-238 by 1 GeV protons. We used the reverse kinematics technique in order to produce the relativistic nuclei and therefore to be able to detect those nuclides within a very short time, shorter in most cases than the radioactive disintegration period. The achieved nuclear charge and mass resolution are excellent. They allow a good accuracy on the values of the measured cross-sections (10 to 15%). We have observed for the first time the nuclide Actinium-235 obtained consequently to the loss of 3 protons by the projectile. The measured isotopic distribution are strongly influenced by the mechanism of fission which leads to a strong reduction of the production of the heavy neutron deficient isotopes. We have compared our results to some other measurements achieved with radio-chemical methods at a similar energy. We observed a systematic disagreement of about 40%. Some comparison with the available systematics show that those are presently not able to reproduce the data with a reasonable precision. We could also measure the recoil momentum distribution for each studied isotopes. We show that Goldhaber's model agrees very well with the experiment in case. of 'cold' channels where the evaporation of particles never occurs. On the other hand, when the produced pre-fragment is excited the data show that Goldhaber's model does not reproduce.the data showing the limitation of such an approach. We finally tried to reproduce the measurement of evaporation residue cross-section thanks to the coupling of intra-nuclear cascade and statistical evaporation codes. The influence of the fission process is rather important is the system p+U; we therefore had to account for the dynamical aspect of the fission. We also showed

  16. Nitração aromática: substituição eletrofílica ou reação com transferência de elétrons? Aromatic nitration: electrophilic substitution or reaction with electron transfer?

    Directory of Open Access Journals (Sweden)

    Sheila Pressentin Cardoso

    2001-06-01

    Full Text Available Aromatic nitration is one of the most relevant class of reactions in organic chemistry. It has been intensively studied by both experimental, including works in the condensed as well as in the gas phase, and theoretical procedures. However, the published results do not seem to converge to an unique mechanism. Electrophilic substitution and electron transfer, in an exclusive way, are both proposed as the main mechanism for the reaction. We review these proposals and discuss the most recent findings.

  17. Valence and inner proton hole states in 207Tl via the (d,3He) reaction at 108 MeV

    International Nuclear Information System (INIS)

    Langevin-Joliot, H.; Gerlic, E.; Guillot, J.; Van de Wiele, J.

    1983-01-01

    The excitation energy spectra of the residual nucleus 207 Tl have been investigated up to 14 MeV using the (d, 3 He) reaction at 108 MeV. New groups and high lying structures are first observed up to 8.3 MeV, in addition to the five known low lying levels. Beyond a minimum at 7.13 MeV, weaker structures are observed riding over an asymetric bump located around 9 MeV. DWBA analysis of angular distributions have allowed l attributions and the determination of valence and inner hole spectroscopic factors. It is found that the valence levels at 1.33 MeV, 1.67 MeV and 3.47 MeV exhaust respectively about 65%, 60% and 45% of the 1hsub(11/2), 2dsub(5/2) and 1gsub(7/2) sum rules. The missing strengths are found below 8.3 MeV. The 2dsub(5/2) and 1gsub(7/2) holes contribute mainly to some well concentrated groups, whereas the 1hsub(11/2) strength is distributed more smoothly. Small contributions of 1gsub(9/2) and 2p strengths are tentatively identified below 7.13 MeV. The highest lying energy region up to 14 MeV may approximately account for the 1gsub(9/2) and (1fsub(5/2)) total sum-rule and about 70% of the 2p strength. The 1gsub(9/2) strength gives the largest contribution to the asymetric bump around 9 MeV. The deduced experimental strength functions are compared with theoretical calculations

  18. Cross sections of proton-induced reactions on {sup 152}Gd, {sup 155}Gd and {sup 159}Tb with emphasis on the production of selected Tb radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Steyn, G.F., E-mail: deon@tlabs.ac.za [iThemba Laboratory for Accelerator Based Sciences, P.O. Box 722, Somerset West 7129 (South Africa); Vermeulen, C. [iThemba Laboratory for Accelerator Based Sciences, P.O. Box 722, Somerset West 7129 (South Africa); Szelecsényi, F.; Kovács, Z. [Cyclotron Application Department, ATOMKI, P.O. Box 51, H-4001 Debrecen (Hungary); Hohn, A. [Department of Nuclear Medicine, University Medical Centre Rostock, Rostock (Germany); Meulen, N.P. van der [Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, 5232 Villigen-PSI (Switzerland); Center of Radiopharmaceutical Science, Paul Scherrer Institute, 5232 Villigen-PSI (Switzerland); Schibli, R. [Center of Radiopharmaceutical Science, Paul Scherrer Institute, 5232 Villigen-PSI (Switzerland); Walt, T.N. van der [Faculty of Applied Sciences, Cape Peninsula University of Technology, P.O. Box 1906, Bellville 7535 (South Africa)

    2014-01-15

    Cross sections are presented for various Dy, Tb and Gd radionuclides produced in the proton bombardment of {sup 159}Tb as well as for the reactions {sup 152}Gd(p,4n){sup 149}Tb and {sup 155}Gd(p,4n){sup 152}Tb up to 66 MeV. The experimental excitation functions are compared with theoretical predictions by means of the geometry-dependent hybrid (GDH) model as implemented in the code ALICE/ASH, as well as with values from the TENDL-2012 library and previous literature experimental data, where available. Physical yields have been derived for the production of some of the medically important radioterbiums, namely {sup 149}Tb (radionuclide therapy), {sup 152}Tb (PET) and {sup 155}Tb (SPECT). The indirect production of high-purity {sup 155}Tb via the decay of its precursor {sup 155}Dy is reported. The possibility of a large-scale production facility based on a commercial 70 MeV cyclotron is also discussed.

  19. Production cross sections of products in the proton induced reactions on {sup nat}Nd in the energy region up to 45 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Sung-Chul [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 305-353 (Korea, Republic of); Kim, Kwangsoo [Department of Physics and Center for High Energy Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Song, Tae-Yung; Lee, Young-Ouk [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 305-353 (Korea, Republic of); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics and Center for High Energy Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2015-11-01

    The production cross sections of {sup 141,143,144,146,148m,148g,149,150}Pm, {sup 139m,147,149}Nd, {sup 138m,142g}Pr, and {sup 139g}Ce in the {sup nat}Nd(p,x) reactions were determined by a stacked-foil activation technique for the proton energy range up to 45 MeV using the MC-50 cyclotron of Korea Institute of Radiological and Medical Sciences. The measured cross sections were compared with literature data as well as data from the TENDL-2014 library based on TALYS 1.6. The production cross sections of the above radionuclides are slightly higher than the literature data but are in general agreement with values in TENDL-2014 library except for {sup 148m}Pm, {sup 148g}Pm, {sup 139m}Nd, and {sup 142g}Pr. The thick target integral yields of the produced radionuclides were also deducted from the measured cross sections.

  20. Direct sampling of sub-µm atmospheric particulate organic matter in sub-ng m-3 mass concentrations by proton-transfer-reaction mass spectrometry

    Science.gov (United States)

    Armin, W.; Mueller, M.; Klinger, A.; Striednig, M.

    2017-12-01

    A quantitative characterization of the organic fraction of atmospheric particulate matter is still challenging. Herein we present the novel modular "Chemical Analysis of Aerosol Online" (CHARON) particle inlet system coupled to a new-generation proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF 6000 X2, Ionicon Analytik, Austria) that quantitatively detects organic analytes in real-time and sub-pptV levels by chemical ionization with hydronium reagent ions. CHARON consists of a gas-phase denuder for stripping off gas-phase analytes (efficiency > 99.999%), an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. With typical particle enrichment factors of around 30 for particle diameters (DP) between 120 nm and 1000 nm (somewhat reduced enrichment for 60 nm 6000) and excellent mass accuracies (< 10 ppm) chemical compositions can be assigned and included in further analyses. In addition to a detailed characterization of the CHARON PTR-TOF 6000 X2 we will present first results on the chemical composition of sub-µm particulate organic matter in the urban atmosphere in Innsbruck (Austria).

  1. Real-time monitoring of respiratory absorption factors of volatile organic compounds in ambient air by proton transfer reaction time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhonghui [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Yanli [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Yan, Qiong [Department of Respiratory Diseases, Guangzhou No. 12 People' s Hospital, Guangzhou 510620 (China); Zhang, Zhou [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Wang, Xinming, E-mail: wangxm@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China)

    2016-12-15

    Respiratory absorption factors (AFs) are essential parameters in the evaluation of human health risks from toxic volatile organic compounds (VOCs) in ambient air. A method for the real time monitoring of VOCs in inhaled and exhaled air by proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) has been developed to permit the calculation of respiratory AFs of VOCs. Isoprene was found to be a better breath tracer than O{sub 2}, CO{sub 2}, humidity, or acetone for distinguishing between the expiratory and inspiratory phases, and a homemade online breath sampling device with a buffer tube was used to optimize signal peak shapes. Preliminary tests with seven subjects exposed to aromatic hydrocarbons in an indoor environment revealed mean respiratory AFs of 55.0%, 55.9%, and 66.9% for benzene, toluene, and C8-aromatics (ethylbenzene and xylenes), respectively. These AFs were lower than the values of 90% or 100% used in previous studies when assessing the health risks of inhalation exposure to hazardous VOCs. The mean respiratory AFs of benzene, toluene and C8-aromatics were 66.5%, 70.2% and 82.3% for the three female subjects; they were noticeably much higher than that of 46.4%, 45.2% and 55.3%, respectively, for the four male subjects.

  2. Spray Inlet Proton Transfer Reaction Mass Spectrometry (SI-PTR-MS) for Rapid and Sensitive Online Monitoring of Benzene in Water.

    Science.gov (United States)

    Zou, Xue; Kang, Meng; Li, Aiyue; Shen, Chengyin; Chu, Yannan

    2016-03-15

    Rapid and sensitive monitoring of benzene in water is very important to the health of people and for environmental protection. A novel and online detection method of spray inlet proton transfer reaction mass spectrometry (SI-PTR-MS) was introduced for rapid and sensitive monitoring of trace benzene in water. A spraying extraction system was coupled with the self-developed PTR-MS. The benzene was extracted from the water sample in the spraying extraction system and continuously detected with PTR-MS. The flow of carrier gas and salt concentration in water were optimized to be 50 sccm and 20% (w/v), respectively. The response time and the limit of detection of the SI-PTR-MS for detection of benzene in water were 55 s and 0.14 μg/L at 10 s integration time, respectively. The repeatability of the SI-PTR-MS was evaluated, and the relative standard deviation of five replicate determinations was 4.3%. The SI-PTR-MS system was employed for monitoring benzene in different water matrices, such as tap water, lake water, and wastewater. The results indicated that the online SI-PTR-MS can be used for rapid and sensitive monitoring of trace benzene in water.

  3. Thermal desorption extraction proton transfer reaction mass spectrometer (TDE-PTR-MS) for rapid determination of residual solvent and sterilant in disposable medical devices.

    Science.gov (United States)

    Wang, Yujie; Shen, Chengyin; Li, Jianquan; Wang, Hongmei; Wang, Hongzhi; Jiang, Haihe; Chu, Yannan

    2011-07-15

    Thermal desorption extraction proton transfer reaction mass spectrometer (TDE-PTR-MS) has been exploited to provide rapid determination of residual solvent and sterilant like cyclohexanone (CHX) and ethylene oxide (EO) in disposable medical devices. Two novel methods are proposed for the quantification of residual chemicals in the polyvinyl chloride infusion sets with our homemade PTR-MS. In the first method, EO residue in the solid infusion sets (y, mgset(-1)) is derived through the determination of EO gas concentration within its packaging bag (x, ppm) according to the correlative equation of y=0.00262x. In the second one, residual EO and CHX in the solid infusion sets are determined through a time integral of their respective mass emission rates. The validity of the proposed methods is demonstrated by comparison with the experimental results from the exhaustive extraction method. Due to fast response, absolute concentration determination and high sensitivity, the TDE-PTR-MS is suggested to be a powerful tool for the quality inspection of disposable medical devices including the quantitative determination of residual solvent and sterilant like CHX and EO. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Rotational dependence of the proton-transfer reaction HBr+ + CO2 → HOCO+ + Br. II. Comparison of HBr+ (2Π(3/2)) and HBr+ (2Π(1/2)).

    Science.gov (United States)

    Paetow, Lisa; Unger, Franziska; Beutel, Bernd; Weitzel, Karl-Michael

    2010-12-21

    The effects of reactant ion rotational excitation on the exothermic proton-transfer reactions of HBr(+)((2)Π(1/2)) and DBr(+)((2)Π(1/2)), respectively, with CO(2) were studied in a guided ion beam apparatus. Cross sections are presented for collision energies in the center of mass system E(c.m.) in the range of 0.23 to 1.90 eV. The HBr(+)/DBr(+) ions were prepared in a state-selective manner by resonance enhanced multiphoton ionization. The mean rotational energy was varied from 3.4 to 46.8 meV for HBr(+)((2)Π(1/2)) and from 1.8 to 40.9 meV for DBr(+)((2)Π(1/2)). Both reactions studied are inhibited by collision energy, as expected for exothermic reactions. For all collision energies considered, the cross section decreases with increasing rotational energy of the ion, but the degree of the rotational dependence differs depending on the collision energy. For E(c.m.) = 0.31 eV, the cross sections of the deuteron transfer are significantly larger than those of the proton transfer. For higher E(c.m.) they differ very little. The current results for the exothermic proton transfer are systematically compared to previously published data for the endothermic proton transfer starting from HBr(+)((2)Π(3/2)) [L. Paetow et al., J. Chem. Phys. 132, 174305 (2010)]. Additional new data regarding the latter reaction are presented to further confirm the conclusions. The dependences on rotational excitation found cannot be explained by the corresponding change in the total energy of the system. For both the endothermic and the exothermic reaction, the cross section is maximized for the smallest rotational energy, at least well above the threshold.

  5. Structural Basis of Eukaryotic Nitrate Reduction: Crystal Structures of the Nitrate Reductase Active Site

    Science.gov (United States)

    Fischer, Katrin; Barbier, Guillaume G.; Hecht, Hans-Juergen; Mendel, Ralf R.; Campbell, Wilbur H.; Schwarz, Guenter

    2005-01-01

    Nitrate assimilation in autotrophs provides most of the reduced nitrogen on earth. In eukaryotes, reduction of nitrate to nitrite is catalyzed by the molybdenum-containing NAD(P)H:nitrate reductase (NR; EC 1.7.1.1-3). In addition to the molybdenum center, NR contains iron-heme and flavin adenine dinucleotide as redox cofactors involved in an internal electron transport chain from NAD(P)H to nitrate. Recombinant, catalytically active Pichia angusta nitrate-reducing, molybdenum-containing fragment (NR-Mo) was expressed in P. pastoris and purified. Crystal structures for NR-Mo were determined at 1.7 and 2.6 Å. These structures revealed a unique slot for binding nitrate in the active site and identified key Arg and Trp residues potentially involved in nitrate binding. Dimeric NR-Mo is similar in overall structure to sulfite oxidases, with significant differences in the active site. Sulfate bound in the active site caused conformational changes, as compared with the unbound enzyme. Four ordered water molecules located in close proximity to Mo define a nitrate binding site, a penta-coordinated reaction intermediate, and product release. Because yeast NAD(P)H:NR is representative of the family of eukaryotic NR, we propose a general mechanism for nitrate reduction catalysis. PMID:15772287

  6. Ammonium nitrate explosion hazards

    Directory of Open Access Journals (Sweden)

    Negovanović Milanka

    2015-01-01

    Full Text Available Ammonium nitrate (AN primarily is used as a fertilizer but it is also very important compound in the production of industrial explosives. The application of ammonium nitrate in the production of industrial explosives was related with the early era of Nobel dynamite and widely increased with the appearance of blasting agents such as ANFO and Slurry, in the middle of the last Century. Throughout the world millions of tons of ammonium nitrate are produced annually and handled without incident. Although ammonium nitrate generally is used safely, accidental explosions involving AN have high impact resulting in loss of lives and destruction of property. The paper presents the basic properties of ammonium nitrate as well as hazards in handling of ammonium nitrate in order to prevent accidents. Several accidents with explosions of ammonium nitrate resulted in catastrophic consequences are listed in the paper as examples of non-compliance with prescribed procedures.

  7. Influence of isovector pairing and particle-number projection effects on spectroscopic factors for one-pair like-particle transfer reactions in proton-rich even-even nuclei

    Science.gov (United States)

    Benbouzid, Y.; Allal, N. H.; Fellah, M.; Oudih, M. R.

    2018-04-01

    Isovector neutron-proton (np) pairing and particle-number fluctuation effects on the spectroscopic factors (SF) corresponding to one-pair like-particle transfer reactions in proton-rich even-even nuclei are studied. With this aim, expressions of the SF corresponding to two-neutron stripping and two-proton pick-up reactions, which take into account the isovector np pairing effect, are established within the generalized BCS approach, using a schematic definition proposed by Chasman. Expressions of the same SF which strictly conserve the particle number are also established within the Sharp-BCS (SBCS) discrete projection method. In both cases, it is shown that these expressions generalize those obtained when only the pairing between like particles is considered. First, the formalism is tested within the Richardson schematic model. Second, it is applied to study even-even proton-rich nuclei using the single-particle energies of a Woods-Saxon mean-field. In both cases, it is shown that the np pairing effect and the particle-number projection effect on the SF values are important, particularly in N = Z nuclei, and must then be taken into account.

  8. Photochemical reduction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  9. Native-Like and Denatured Cytochrome c Ions Yield Cation-to-Anion Proton Transfer Reaction Products with Similar Collision Cross-Sections

    Science.gov (United States)

    Laszlo, Kenneth J.; Buckner, John H.; Munger, Eleanor B.; Bush, Matthew F.

    2017-07-01

    The relationship between structures of protein ions, their charge states, and their original structures prior to ionization remains challenging to decouple. Here, we use cation-to-anion proton transfer reactions (CAPTR) to reduce the charge states of cytochrome c ions in the gas phase, and ion mobility to probe their structures. Ions were formed using a new temperature-controlled nanoelectrospray ionization source at 25 °C. Characterization of this source demonstrates that the temperature of the liquid sample is decoupled from that of the atmospheric pressure interface, which is heated during CAPTR experiments. Ionization from denaturing conditions yields 18+ to 8+ ions, which were each isolated and reacted with monoanions to generate all CAPTR products with charge states of at least 3+. The highest, intermediate, and lowest charge-state products exhibit collision cross-section distributions that are unimodal, multimodal, and unimodal, respectively. These distributions depend strongly on the charge state of the product, although those for the intermediate charge-state products also depend on that of the precursor. The distributions of the 3+ products are all similar, with averages that are less than half that of the 18+ precursor ions. Ionization of cytochrome c from native-like conditions yields 7+ and 6+ ions. The 3+ CAPTR products from these precursors have slightly more compact collision cross-section distributions that are indistinguishable from those for the 3+ CAPTR products from denaturing conditions. More broadly, these results indicate that the collision cross-sections of ions of this single domain protein depend strongly on charge state for charge states greater than 4.

  10. In cleanroom, sub-ppb real-time monitoring of volatile organic compounds using proton-transfer reaction/time of flight/mass spectrometry

    Science.gov (United States)

    Hayeck, Nathalie; Maillot, Philippe; Vitrani, Thomas; Pic, Nicolas; Wortham, Henri; Gligorovski, Sasho; Temime-Roussel, Brice; Mizzi, Aurélie; Poulet, Irène

    2014-04-01

    Refractory compounds such as Trimethylsilanol (TMS) and other organic compounds such as propylene glycol methyl ether acetate (PGMEA) used in the photolithography area of microelectronic cleanrooms have irreversible dramatic impact on optical lenses used on photolithography tools. There is a need for real-time, continuous measurements of organic contaminants in representative cleanroom environment especially in lithography zone. Such information is essential to properly evaluate the impact of organic contamination on optical lenses. In this study, a Proton-Transfer Reaction-Time-of-Flight Mass spectrometer (PTR-TOF-MS) was applied for real-time and continuous monitoring of fugitive organic contamination induced by the fabrication process. Three types of measurements were carried out using the PTR-TOF-MS in order to detect the volatile organic compounds (VOCs) next to the tools in the photolithography area and at the upstream and downstream of chemical filters used to purge the air in the cleanroom environment. A validation and verification of the results obtained with PTR-TOF-MS was performed by comparing these results with those obtained with an off-line technique that is Automated Thermal Desorber - Gas Chromatography - Mass Spectrometry (ATD-GC-MS) used as a reference analytical method. The emerged results from the PTR-TOF-MS analysis exhibited the temporal variation of the VOCs levels in the cleanroom environment during the fabrication process. While comparing the results emerging from the two techniques, a good agreement was found between the results obtained with PTR-TOF-MS and those obtained with ATD-GC-MS for the PGMEA, toluene and xylene. Regarding TMS, a significant difference was observed ascribed to the technical performance of both instruments.

  11. Characterization of biomass burning smoke from cooking fires, peat, crop residue and other fuels with high resolution proton-transfer-reaction time-of-flight mass spectrometry

    Science.gov (United States)

    Stockwell, C. E.; Veres, P. R.; Williams, J.; Yokelson, R. J.

    2014-08-01

    We deployed a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to measure biomass burning emissions from peat, crop-residue, cooking fires, and many other fire types during the fourth Fire Lab at Missoula Experiment (FLAME-4) laboratory campaign. A combination of gas standards calibrations and composition sensitive, mass dependent calibration curves were applied to quantify gas-phase non-methane organic compounds (NMOCs) observed in the complex mixture of fire emissions. We used several approaches to assign best identities to most major "exact masses" including many high molecular mass species. Using these methods approximately 80-96% of the total NMOC mass detected by PTR-TOF-MS and FTIR was positively or tentatively identified for major fuel types. We report data for many rarely measured or previously unmeasured emissions in several compound classes including aromatic hydrocarbons, phenolic compounds, and furans; many of which are suspected secondary organic aerosol precursors. A large set of new emission factors (EFs) for a range of globally significant biomass fuels is presented. Measurements show that oxygenated NMOCs accounted for the largest fraction of emissions of all compound classes. In a brief study of various traditional and advanced cooking methods, the EFs for these emissions groups were greatest for open 3-stone cooking in comparison to their more advanced counterparts. Several little-studied nitrogen-containing organic compounds were detected from many fuel types that together accounted for 0.1-8.7% of the fuel nitrogen and some may play a role in new particle formation.

  12. Rapid characterization of dry cured ham produced following different PDOs by proton transfer reaction time of flight mass spectrometry (PTR-ToF-MS).

    Science.gov (United States)

    Del Pulgar, José Sánchez; Soukoulis, Christos; Biasioli, Franco; Cappellin, Luca; García, Carmen; Gasperi, Flavia; Granitto, Pablo; Märk, Tilmann D; Piasentier, Edi; Schuhfried, Erna

    2011-07-15

    In the present study, the recently developed proton transfer reaction time of flight mass spectrometry (PTR-ToF-MS) technique was used for the rapid characterization of dry cured hams produced according to 4 of the most important Protected Designations of Origin (PDOs): an Iberian one (Dehesa de Extremadura) and three Italian ones (Prosciutto di San Daniele, Prosciutto di Parma and Prosciutto Toscano). In total, the headspace composition and respective concentration for nine Spanish and 37 Italian dry cured ham samples were analyzed by direct injection without any pre-treatment or pre-concentration. Firstly, we show that the rapid PTR-ToF-MS fingerprinting in conjunction with chemometrics (Principal Components Analysis) indicates a good separation of the dry cured ham samples according to their production process and that it is possible to set up, using data mining methods, classification models with a high success rate in cross validation. Secondly, we exploited the higher mass resolution of the new PTR-ToF-MS, as compared with standard quadrupole based versions, for the identification of the exact sum formula of the mass spectrometric peaks providing analytical information on the observed differences. The work indicates that PTR-ToF-MS can be used as a rapid method for the identification of differences among dry cured hams produced following the indications of different PDOs and that it provides information on some of the major volatile compounds and their link with the implemented manufacturing practices such as rearing system, salting and curing process, manufacturing practices that seem to strongly affect the final volatile organic profile and thus the perceived quality of dry cured ham. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. On-line measurements of nitro organic compounds emitted from automobiles by proton transfer reaction mass spectrometry: Laboratory experiments and a field measurement

    Science.gov (United States)

    Inomata, S.; Tanimoto, H.; Fujitani, Y.; Fushimi, A.; Sato, K.; Sekimoto, K.; Yamada, H.; Hori, S.; Shimono, A.; Hikida, T.

    2011-12-01

    On-line measurements of nitro organic compounds in automobile exhaust were carried out by proton transfer reaction mass spectrometry (PTR-MS) with a chassis dynamometer. Diesel vehicles with oxidation catalyst system (diesel vehicle A) and with diesel PM-NOx reduction system ((diesel vehicle B) and a gasoline vehicle were used as a test vehicle. In the case of the diesel vehicle A, the emissions of nitromethane, nitrophenol (NPh), C7-, C8-, C9-, and C10-nitrophenols, and dihydroxynitrobenzenes (DHNB) were observed in the diesel exhaust from the experiment under the constant driving at 60 km hr-1. Temporal variations of mixing ratios for nitromethane, NPh, and DHNB along with related volatile organic compounds (VOCs) were measured during a transient driving cycle. The time-resolved measurement revealed that the nitromethane emission was strongly correlated with the emissions of CO, benzene, and acetone, which are relatively quickly produced in acceleration processes and appeared as sharp peaks. On the other hand, the NPh emission was moderately correlated with the emissions of acetic acid and phenol, which peaks were broad. The emission of nitromethane was observed from the exhaust of the diesel vehicle B but the emission of other nitro organic compounds was not observed. This suggests that the emission of nitro organic compounds besides nitromethane may depend on the diesel exhaust aftertreatment devices. The emission of nitromethane was also observed from the exhaust of the gasoline vehicle with cold start. An in-situ measurement of nitro organic compounds and their related VOCs was carried out at the crossing of an urban city, Kawasaki. Nitromethane was observed at the crossing and we found that the concentration of nitrometane varied rapidly. During the measurement, the maximum of the concentration of nitrometane reached 5 ppbv. Not only nitrophenols but also nitroaromatics were sometimes detected in the field measurement.

  14. Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke; Li, Yifan; Yu, Shule; Cullen, David A.; Retterer, Scott T.; Toops, Todd J.; Bender, Guido; Pivovar, Bryan S.; Green, Johney B.; Zhang, Feng-Yuan

    2018-05-01

    Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layers at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.

  15. Protonation mechanism and location of rate-determining steps for the Ascaris suum nicotinamide adenine dinucleotide-malic enzyme reaction from isotope effects and pH studies

    Energy Technology Data Exchange (ETDEWEB)

    Kiick, D.M.; Harris, B.G.; Cook, P.F.

    1986-01-14

    The pH dependence of the kinetic parameters and the primary deuterium isotope effects with nicotinamide adenine dinucleotide (NAD) and also thionicotinamide adenine dinucleotide (thio-NAD) as the nucleotide substrates were determined in order to obtain information about the chemical mechanism and location of rate-determining steps for the Ascaris suum NAD-malic enzyme reaction. The maximum velocity with thio-NAD as the nucleotide is pH-independent from pH 4.2 to 9.6, while with NAD, V decreases below a pK of 4.8. V/K for both nucleotides decreases below a pK of 5.6 and above a pK of 8.9. Both the tartronate pKi and V/Kmalate decrease below a pK of 4.8 and above a pK of 8.9. Oxalate is competitive vs. malate above pH 7 and noncompetitive below pH 7 with NAD as the nucleotide. The oxalate Kis increases from a constant value above a pK of 4.9 to another constant value above a pK of 6.7. The oxalate Kii also increases above a pK of 4.9, and this inhibition is enhanced by NADH. In the presence of thio-NAD the inhibition by oxalate is competitive vs. malate below pH 7. For thio-NAD, both DV and D(V/K) are pH-independent and equal to 1.7. With NAD as the nucleotide, DV decreases to 1.0 below a pK of 4.9, while D(V/KNAD) and D(V/Kmalate) are pH-independent. Above pH 7 the isotope effects on V and the V/K values for NAD and malate are equal to 1.45, the pH-independent value of DV above pH 7. Results indicate that substrates bind to only the correctly protonated form of the enzyme. Two enzyme groups are necessary for binding of substrates and catalysis. Both NAD and malate are released from the Michaelis complex at equal rates which are equal to the rate of NADH release from E-NADH above pH 7. Below pH 7 NADH release becomes more rate-determining as the pH decreases until at pH 4.0 it completely limits the overall rate of the reaction.

  16. Protonation mechanism and location of rate-determining steps for the Ascaris suum nicotinamide adenine dinucleotide-malic enzyme reaction from isotope effects and pH studies

    International Nuclear Information System (INIS)

    Kiick, D.M.; Harris, B.G.; Cook, P.F.

    1986-01-01

    The pH dependence of the kinetic parameters and the primary deuterium isotope effects with nicotinamide adenine dinucleotide (NAD) and also thionicotinamide adenine dinucleotide (thio-NAD) as the nucleotide substrates were determined in order to obtain information about the chemical mechanism and location of rate-determining steps for the Ascaris suum NAD-malic enzyme reaction. The maximum velocity with thio-NAD as the nucleotide is pH-independent from pH 4.2 to 9.6, while with NAD, V decreases below a pK of 4.8. V/K for both nucleotides decreases below a pK of 5.6 and above a pK of 8.9. Both the tartronate pKi and V/Kmalate decrease below a pK of 4.8 and above a pK of 8.9. Oxalate is competitive vs. malate above pH 7 and noncompetitive below pH 7 with NAD as the nucleotide. The oxalate Kis increases from a constant value above a pK of 4.9 to another constant value above a pK of 6.7. The oxalate Kii also increases above a pK of 4.9, and this inhibition is enhanced by NADH. In the presence of thio-NAD the inhibition by oxalate is competitive vs. malate below pH 7. For thio-NAD, both DV and D(V/K) are pH-independent and equal to 1.7. With NAD as the nucleotide, DV decreases to 1.0 below a pK of 4.9, while D(V/KNAD) and D(V/Kmalate) are pH-independent. Above pH 7 the isotope effects on V and the V/K values for NAD and malate are equal to 1.45, the pH-independent value of DV above pH 7. Results indicate that substrates bind to only the correctly protonated form of the enzyme. Two enzyme groups are necessary for binding of substrates and catalysis. Both NAD and malate are released from the Michaelis complex at equal rates which are equal to the rate of NADH release from E-NADH above pH 7. Below pH 7 NADH release becomes more rate-determining as the pH decreases until at pH 4.0 it completely limits the overall rate of the reaction

  17. Anoxic Activated Sludge Monitoring with Combined Nitrate and Titrimetric Measurements

    DEFF Research Database (Denmark)

    Petersen, B.; Gernaey, Krist; Vanrolleghem, P.A.

    2002-01-01

    was with the carbon source in excess, since excess nitrate provoked nitrite build-up thereby complicating the data interpretation. A conceptual model could quantitatively describe the experimental observations and thus link the experimentally measured proton production with the consumption of electron acceptor......An experimental procedure for anoxic activated sludge monitoring with combined nitrate and titrimetric measurements is proposed and evaluated successfully with two known carbon sources, (-)acetate and dextrose. For nitrate measurements an ion-selective nitrate electrode is applied to allow...... for frequent measurements, and thereby the possibility for detailed determination of the denitrification biokinetics. An internal nitrate electrode calibration is implemented in the experiments to avoid the often-encountered electrode drift problem. It was observed that the best experimental design...

  18. Antimony doped tin oxides and their composites with tin pyrophosphates as catalyst supports for oxygen evolution reaction in proton exchange membrane water electrolysis

    DEFF Research Database (Denmark)

    Xu, Junyuan; Li, Qingfeng; Hansen, Martin Kalmar

    2012-01-01

    based on tin pyrophosphates as the catalyst support. The materials showed an overall conductivity of 0.57 S cm−1 at 130 °C under the water vapor atmosphere with a contribution of the proton conduction. Using this composite support, iridium oxide nanoparticle catalysts were prepared and characterized......Proton exchange membrane water electrolysers operating at typically 80 °C or at further elevated temperatures suffer from insufficient catalyst activity and durability. In this work, antimony doped tin oxide nanoparticles were synthesized and further doped with an inorganic proton conducting phase...

  19. 100-MeV proton beam intensity measurement by Au activation analysis using {sup 197}Au(p, pn){sup 196}Au and {sup 197}Au(p, p3n){sup 194}Au reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari Oranj, Leila [Division of Advanced Nuclear Engineering, POSTECH, Pohang 37673 (Korea, Republic of); Jung, Nam-Suk; Oh, Joo-Hee [Pohang Accelerator Laboratory, POSTECH, Pohang 37673 (Korea, Republic of); Lee, Hee-Seock, E-mail: lee@postech.ac.kr [Pohang Accelerator Laboratory, POSTECH, Pohang 37673 (Korea, Republic of)

    2016-05-15

    The proton beam intensity of a 100-MeV proton linac at the Korea Multi-purpose Accelerator Complex (KOMAC) was measured by an Au activation analysis using {sup 197}Au(p, pn){sup 196}Au and {sup 197}Au(p, p3n){sup 194}Au reactions to determine the accuracy and precision of beam intensity measurement using Gafchromic film dosimetry method. The target, irradiated by 100-MeV protons, was arranged in a stack consisting of Au, Al foils and Pb plates. The yields of produced radio-nuclei in Au foils were obtained by gamma-ray spectroscopy. The FLUKA code was employed to calculate the energy spectrum of protons onto the front surface of Au foils located at three different depth points of the target and also to investigate the condition of incident beam on the target. A good agreement was found between the beam intensity measurements using the activation analysis method at three different depth points of the target. An excellent agreement was also observed between the beam intensity measurements using the Au activation analysis method and the dosimetry method using Gafchromic film.

  20. determination of nitrite, nitrate and total nitrogen in vegetable samples

    African Journals Online (AJOL)

    The above colour reaction system has been applied successfully for the determination of nitrite, nitrate and total nitrogen in vegetable samples. Unreduced samples give direct measure for nitrite whilst reduction of samples by copperized-cadmium column gives total nitrogen content and their difference shows nitrate content ...

  1. Aromatic nitrations by mixed acid. Fast liquid-liquid regime

    NARCIS (Netherlands)

    Zaldivar, J.M.; Zaldivar, J.M.; Molga, E.J.; Alos, M.A.; Hernandez, H.; Westerterp, K.R.

    1996-01-01

    Aromatic nitration by mixed acid was selected as a specific case of heterogeneous liquid-liquid reaction. An extensive experimental programme was followed using adiabatic and heat flow calorimetry and pilot reactor experiments, supported by chemical analysis. A series of nitration experiments was

  2. Nitrate leaching index

    Science.gov (United States)

    The Nitrate Leaching Index is a rapid assessment tool that evaluates nitrate (NO3) leaching potential based on basic soil and climate information. It is the basis for many nutrient management planning efforts, but it has considerable limitations because of : 1) an oversimplification of the processes...

  3. Agricultural nitrate pollution

    DEFF Research Database (Denmark)

    Anker, Helle Tegner

    2015-01-01

    Despite the passing of almost 25 years since the adoption of the EU Nitrates Directive, agricultural nitrate pollution remains a major concern in most EU Member States. This is also the case in Denmark, although a fairly strict regulatory regime has resulted in almost a 50 per cent reduction...

  4. Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer

    Science.gov (United States)

    Ma, Yan; Diao, Yiwei; Zhang, Bingjie; Wang, Weiwei; Ren, Xinrong; Yang, Dongsen; Wang, Ming; Shi, Xiaowen; Zheng, Jun

    2016-12-01

    A proton transfer reaction ion-drift chemical ionization mass spectrometer (PTR-ID-CIMS) equipped with a hydronium (H3+O) ion source was developed and deployed near an industrial zone in the Yangtze River Delta (YRD) region of China in spring 2015 to investigate industry-related emissions of volatile organic compounds (VOCs). Air pollutants including formaldehyde (HCHO), aromatics, and other trace gases (O3 and CO) were simultaneously measured. Humidity effects on the sensitivity of the PTR-ID-CIMS for HCHO detection were investigated and quantified. The performances of the PTR-ID-CIMS were also validated by intercomparing with offline HCHO measurement technique using 2,4-dinitrophenylhydrazone (DNPH) cartridges and the results showed fairly good agreement (slope = 0.81, R2 = 0.80). The PTR-ID-CIMS detection limit of HCHO (10 s, three-duty-cycle averages) was determined to be 0.9-2.4 (RH = 1-81.5 %) parts per billion by volume (ppbv) based on 3 times the standard deviations of the background signals. During the field study, observed HCHO concentrations ranged between 1.8 and 12.8 ppbv with a campaign average of 4.1 ± 1.6 ppbv, which was comparable with previous HCHO observations in other similar locations of China. However, HCHO diurnal profiles showed few features of secondary formation. In addition, time series of both HCHO and aromatic VOCs indicated strong influence from local emissions. Using a multiple linear regression fit model, on average the observed HCHO can be attributed to secondary formation (13.8 %), background level (27.0 %), and industry-related emissions, i.e., combustion sources (43.2 %) and chemical productions (16.0 %). Moreover, within the plumes the industry-related emissions can account for up to 69.2 % of the observed HCHO. This work has provided direct evidence of strong primary emissions of HCHO from industry-related activities. These primary HCHO sources can potentially have a strong impact on local and regional air pollution formation

  5. Pre-equilibrium proton emission in {sup 40}Ar and {sup 132}Xe induced reactions at 44 MeV/u

    Energy Technology Data Exchange (ETDEWEB)

    Alba, R.; Ciniglione, R.; Del Zoppo, A.; Agodi, C.; Finocchiaro, P.; Loukachine, K.; Maiolino, C.; Piattelli, P.; Santonocito, D.; Sapienza, P. [Istituto Nazionale di Fisica Nucleare, Catania (Italy); Bellia, G.; Migneco, E. [Istituto Nazionale di Fisica Nucleare, Catania (Italy)]|[Catania Univ. (Italy). Ist. di Fisica; Peghaire, A. [Grand Accelerateur National d`Ions Lourds (GANIL), 14 - Caen (France); Manduci, L.; Moroni, A. [Istituto Nazionale di Fisica Nucleare, Milan (Italy); Iori, I. [Istituto Nazionale di Fisica Nucleare, Milan (Italy)]|[Milan Univ. (Italy). Ist. di Fisica

    1994-04-01

    Proton emission in heavy ion collisions has already been observed, even at rather large polar angles. A standard data analysis based on three moving sources has evidenced the presence of a half-beam velocity source (IS) interpreted in terms of pre-equilibrium emission from the participant zone of the colliding system. We have performed an experimental study of the fast protons production with the aim of investigating its impact parameter dependence. The data shows clearly that the mean multiplicity of the IS protons increases strongly with the centrality of the collision as expected in the hypothesis that their origin is the projectile-target overlap region. (D.L.). 8 refs., 1 fig.

  6. Study of spallation reactions, neutron production and transport in thick lead target and uranium blanket irradiated with 0.7 GeV protons

    International Nuclear Information System (INIS)

    Svoboda, O.; Adam, J.; Bielewicz, M.

    2009-01-01

    Neutron activation detectors were used to study a neutron field in the setup 'Energy plus Transmutation' consisting of thick lead target and natural uranium blanket. This setup was exposed to 0.7 GeV proton beam from the Nuclotron accelerator. The experiment was a part of the systematic study using proton and deuteron beams within the energy range from 0.7 to 2.52 GeV. The experimental data were compared with the results of the MCNPX simulations and with the data of other experiments. Good agreement within the statistical and systematical uncertainties was observed

  7. Sodium nitrate combustion limit tests

    International Nuclear Information System (INIS)

    Beitel, G.A.

    1976-04-01

    Sodium nitrate is a powerful solid oxidant. Energetically, it is capable of exothermically oxidizing almost any organic material. Rate-controlling variables such as temperature, concentration of oxidant, concentration of fuel, thermal conductivity, moisture content, size, and pressure severely limit the possibility of a self-supported exothermic reaction (combustion). The tests reported in this document were conducted on one-gram samples at atmospheric pressure. Below 380 0 C, NaNO 3 was stable and did not support combustion. At moisture concentrations above 22 wt percent, exothermic reactions did not propagate in even the most energetic and reactive compositions. Fresh resin and paraffin were too volatile to enable a NaNO 2 -supported combustion process to propagate. Concentrations of NaNO 3 above 95 wt percent or below 35 wt percent did not react with enough energy release to support combustion. The influence of sample size and confining pressure, both important factors, was not investigated in this study

  8. Study of the inclusive reactions K/sup +/p to K/sup 0/+anything at 5, 82 and 16 GeV/c in the proton fragmentation region

    CERN Document Server

    Dunwoodie, W M; Colley, D C; Ginestet, J; Goldschmidt-Clermont, Yves; Grant, A; Grard, F; Henri, V; Herquet, P; James, M; Jones, G T; Manesse, D; Sekera, Z; Sené, M; Sherbatt, D; Stergiou, Athanase; Tuominiemi, J; Verbeure, F; Vignaud, D; Windmolders, R

    1975-01-01

    The inclusive reaction K/sup +/p to K/sup 0/x is studied at 5, 8.2 and 16 GeV/c. The inclusive cross sections as well as the inclusive transverse and longitudinal distributions are given. The energy dependence of the structure function in the proton fragmentation region is found to be consistent with s/sup -1/-behaviour indicating the presence of f'- phi exchange in the missing mass channel, with a relative contribution of 30-50%. (0 refs).

  9. VT Nitrate Leaching Index

    Data.gov (United States)

    Vermont Center for Geographic Information — (Link to Metadata) Nitrate Leaching Index data for the state of Vermont. This is a derivative product based on the SSURGO soils data for all counties except Essex...

  10. Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)

    2016-10-15

    Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

  11. Proton adsorption onto alumina: extension of multisite complexation (MUSIC) theory

    Energy Technology Data Exchange (ETDEWEB)

    Nagashima, K.; Blum, F.D.

    1999-09-01

    The adsorption isotherm of protons onto a commercial {gamma}-alumina sample was determined in aqueous nitric acid with sodium nitrate as a background electrolyte. Three discrete regions could be discerned in the log-log plots of the proton isotherm determined at the solution pH 5 to 2. The multisite complexation (MUSIC) model was modified to analyze the simultaneous adsorption of protons onto various kinds of surface species.

  12. Protonated nitrosamide

    DEFF Research Database (Denmark)

    Egsgaard, H.; Carlsen, L.; Øgaard Madsen, J.

    1994-01-01

    The protonated nitrosamide, NH3NO+, has been generated by chemical ionization mass spectrometry. Although a direct search for this species in ammonia flames has proved negative, fast proton transfer to major flame constituents is supported experimentally as well as by MO calculations....

  13. Hydrogen-bond dynamics and proton transfer in nanoconfinement

    NARCIS (Netherlands)

    van der Loop, T.H.

    2015-01-01

    Proton transfer is of fundamental importance to both biology and chemistry. Much is known about proton transfer in large water volumes but often proton transfer reactions take place in very small nanometer sized volumes for example between lipid layers and in proton channels in mitochondria and

  14. Capture reactions

    NARCIS (Netherlands)

    Endt, P.M.

    1956-01-01

    Capture reactions will be considered here from the viewpoint of the nuclear spectroscopist. Especially important to him are the capture of neutrons, protons, and alpha particles, which may proceed through narrow resonances, offering a well defined initial state for the subsequent deexcitation

  15. Tyrosine nitration affects thymidylate synthase properties.

    Science.gov (United States)

    Dąbrowska-Maś, Elżbieta; Frączyk, Tomasz; Ruman, Tomasz; Radziszewska, Karolina; Wilk, Piotr; Cieśla, Joanna; Zieliński, Zbigniew; Jurkiewicz, Agata; Gołos, Barbara; Wińska, Patrycja; Wałajtys-Rode, Elżbieta; Leś, Andrzej; Nizioł, Joanna; Jarmuła, Adam; Stefanowicz, Piotr; Szewczuk, Zbigniew; Rode, Wojciech

    2012-01-14

    Highly purified preparations of thymidylate synthase, isolated from calf thymus, and L1210 parental and FdUrd-resistant cells, were found to be nitrated, as indicated by a specific reaction with anti-nitro-tyrosine antibodies, suggesting this modification to appear endogenously in normal and tumor tissues. Each human, mouse and Ceanorhabditis elegans recombinant TS preparation, incubated in vitro in the presence of NaHCO(3), NaNO(2) and H(2)O(2) at pH 7.5, underwent tyrosine nitration, leading to a V(max)(app) 2-fold lower following nitration of 1 (with human or C. elegans TS) or 2 (with mouse TS) tyrosine residues per monomer. Enzyme interactions with dUMP, meTHF or 5-fluoro-dUMP were not distinctly influenced. Nitration under the same conditions of model tripeptides of a general formula H(2)N-Gly-X-Gly-COOH (X = Phe, Tyr, Trp, Lys, Arg, His, Ser, Thr, Cys, Gly), monitored by NMR spectroscopy, showed formation of nitro-species only for H-Gly-Tyr-Gly-OH and H-Gly-Phe-Gly-OH peptides, the chemical shifts for nitrated H-Gly-Tyr-Gly-OH peptide being in a very good agreement with the strongest peak found in (15)N-(1)H HMBC spectrum of nitrated protein. MS analysis of nitrated human and C. elegans proteins revealed several thymidylate synthase-derived peptides containing nitro-tyrosine (at positions 33, 65, 135, 213, 230, 258 and 301 in the human enzyme) and oxidized cysteine (human protein Cys(210), with catalytically critical Cys(195) remaining apparently unmodified) residues.

  16. Neutron production in spallation reactions of 0.9 and 1.5 GeV protons on a thick lead target. Comparison between experimental data and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    Krasa, A.; Krizek, F.; Wagner, V.; Kugler, A.; Henzl, V.; Henzlova, D.; Majerle, M.; Adam, J.; Caloun, P.; Bradnova, V.; Chultem, D.; Kalinnikov, V.G.; Krivopustov, M.I.; Solnyshkin, A.A.; Stegajlov, V.I.; Tsupko-Sitnikov, V.M.; Tumehndehlgehr, Ts.; Vasil'ev, S.I.

    2005-01-01

    This paper reports on two experiments performed at the Synchrophasotron/Nuclotron accelerator complex at JINR. Relativistic protons with energies 885 MeV and 1.5 GeV hit a massive cylindrical lead target. The spatial and energetic distributions of the neutron field produced by the spallation reactions were measured by the activation of Al, Au, Bi, Co, and Cu foils placed on the surface of the target and close to it. The yields of the radioactive nuclei produced by threshold reactions in these foils were determined by the analyses of their γ spectra. The comparison with Monte-Carlo based simulations was performed both with the LAHET+MCNP code and the MCNPX code

  17. Extension of the energy range of the experimental activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium up to 65MeV.

    Science.gov (United States)

    Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

    2015-04-01

    Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65MeV by using stacked foil irradiation and gamma spectrometry experimental methods. Experimental cross-sections data for the formation of the radionuclides (159)Dy, (157)Dy, (155)Dy, (161)Tb, (160)Tb, (156)Tb, (155)Tb, (154m2)Tb, (154m1)Tb, (154g)Tb, (153)Tb, (152)Tb and (151)Tb are reported in the 36-65MeV energy range, and compared with an old dataset from 1964. The experimental data were also compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS nuclear reaction model code as listed in the latest on-line libraries TENDL 2013. Copyright © 2015. Published by Elsevier Ltd.

  18. Nuclear model analysis of excitation functions of proton induced reactions on ⁸⁶Sr, ⁸⁸Sr and natZr: Evaluation of production routes of ⁸⁶Y.

    Science.gov (United States)

    Zaneb, H; Hussain, M; Amjed, N; Qaim, S M

    2015-10-01

    The proton induced nuclear reactions on (86)Sr, (88)Sr and (nat)Zr were investigated for the production of (86)Y. The literature data were compared with the results of nuclear model calculations using the codes ALICE-IPPE, TALYS 1.6 and EMPIRE 3.2. The thick target yields of (86)Y were calculated from the recommended excitation functions. Analysis of radioyttrium impurities was also performed. A comparison of the various production routes showed that for medical applications of (86)Y, the reaction (86)Sr(p,n)(86)Y is the method of choice, which gives efficient yield with minimum impurities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Comparison of Solar Energetic Particle Events and Impulsive Nitrate Increases in Greenland Ice Cores

    Science.gov (United States)

    Spence, H. E.; Kepko, L.; Shea, M. A.; Smart, D. F.

    2004-12-01

    Using nitrate measurements from Greenland ice cores we examine the correlation of nitrate spikes and solar proton events. We choose a few large space-age events for analysis, focusing particular attention on the amplitude and timing of the nitrate increase in relation to the onset and characteristics of the SEP event. A time delay between nitrate spikes and SEP onset has previously been observed to be a few weeks, which is much faster than current atmospheric downward transport theory allows. Independent confirmation or invalidation of the previous analysis of this short delay has not been attempted before.

  20. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

    International Nuclear Information System (INIS)

    Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

    1995-01-01

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

  1. Feasibility studies for the measurement of the time-like electromagnetic form factors of the proton in reactions of anti pp → μ{sup +}μ{sup -} at the PANDA-experiment at FAIR

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, Iris; Dbeyssi, Alaa; Khaneft, Dmitry; Maas, Frank; Zambrana, Manuel; Mora Espi, Maria Carmen; Morales Morales, Cristina; Lin, Dexu; Froehlich, Bertold; Capozza, Luigi; Noll, Oliver; Deiseroth, Malte; Ahmed, Samer; Ahmadi, Heybat; Valente, Roserio; Rodriguez Pineiro, David [Helmholtz-Institut Mainz (Germany); GSI Darmstadt (Germany); Collaboration: PANDA-Collaboration

    2015-07-01

    The measurement of the time-like electromagnetic form factors (TL em FF), G{sub E} and G{sub M}, using reactions of anti pp → l{sup +}l{sup -} (l=e,μ) gives access to the structure of the proton. It will be the first time measurement of TL em FF of the proton accessing the muons in the final state. One advantage of using this channel is that radiative corrections due to final state radiation are suppressed by the heavy mass of the muon. Measuring anti pp → μ{sup +}μ{sup -} will also serve as a consistency check of the TL em FF data from anti pp → e{sup +}e{sup -}. Feasibility studies for the individual extraction of G{sub E} and G{sub M} out of the measured angular distribution are in progress for the muonic channel using the software package PANDARoot. Due to the strong hadronic background, mainly reactions of anti pp → π{sup +}π{sup -}, a very good signal-to-background separation is needed. For the analysis of both signal and background channel different multivariate classification methods are used. The current status of the studies is presented.

  2. Evaluation of proton induced reactions on sup 1 sup 0 sup 0 Mo. New cross sections for production of sup 9 sup 9 sup m Tc and sup 9 sup 9 Mo

    CERN Document Server

    Takács, S; Tarkanyi, F; Hermanne, A; Sonck, M

    2003-01-01

    The use of the sup 9 sup 9 Mo -> sup 9 sup 9 sup m Tc generator in nuclear medicine is well established world wide. The production of the sup 9 sup 9 Mo (T sub 1 sub / sub 2 = 66 h) parent as a fission product of sup 2 sup 3 sup 5 U is largely based on the use of reactor technology. From the early 1990's accelerator based production methods to provide either direct produced sup 9 sup 9 sup m Tc or the parent sup 9 sup 9 Mo, were studied and suggested as potential alternatives to the reactor based production of sup 9 sup 9 Mo. A possible pathway for the charged particle production of sup 9 sup 9 sup m Tc and sup 9 sup 9 Mo is irradiation of molybdenum metal with protons via the reaction sup 1 sup 0 sup 0 Mo(p,2n) sup 9 sup 9 sup m Tc and sup 1 sup 0 sup 0 Mo(p,pn) sup 9 sup 9 Mo, respectively. The earlier published excitation functions show large differences in their maximum that result in large differences in the calculated yields. Study the excitation function for these proton-induced reactions was decided. ...

  3. Compensatory periplasmic nitrate reductase activity supports anaerobic growth of Pseudomonas aeruginosa PAO1 in the absence of membrane nitrate reductase

    Science.gov (United States)

    Van Alst, Nadine E.; Sherrill, Lani A.; Iglewski, Barbara H.; Haidaris, Constantine G.

    2009-01-01

    Nitrate serves as a terminal electron acceptor under anaerobic conditions in Pseudomonas aeruginosa. Reduction of nitrate to nitrite generates a transmembrane proton motive force allowing ATP synthesis and anaerobic growth. Inner membrane-bound nitrate reductase NarGHI is encoded within the narK1K2GHJI operon and the periplasmic nitrate reductase NapAB is encoded within the napEFDABC operon. The role of the two dissimilatory nitrate reductases in anaerobic growth, and the regulation of their expression were examined by using a set of deletion mutants in P. aeruginosa PAO1. NarGHI mutants were unable to grow anaerobically, but plate cultures remained viable up to 120 hr. In contrast, nitrate sensor-response regulator mutant ΔnarXL displayed growth arrest initially, but resumed growth after 72 hr and reached early stationary phase in liquid culture after 120 hr. Genetic, transcriptional, and biochemical studies demonstrated that anaerobic growth recovery by the NarXL mutant was the result of NapAB periplasmic nitrate reductase expression. A novel transcriptional start site for napEFDABC expression was identified in the NarXL mutant grown anaerobically. Furthermore, mutagenesis of a consensus NarL-binding site monomer upstream of the novel transcriptional start site restored anaerobic growth recovery in the NarXL mutant. The data suggest that during anaerobic growth of wild type P. aeruginosa PAO1, nitrate response regulator NarL directly represses expression of periplasmic nitrate reductase, while inducing maximal expression of membrane nitrate reductase. PMID:19935885

  4. Protonation and Photocatalytic Activity of the Rb2La2Ti3O10 Layered Oxide in the Reaction of Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Ivan A. Rodionov

    2017-01-01

    Full Text Available The Rb2La2Ti3O10 layered oxide was synthesized by the solid-state method. Three phases with different protonation degrees and intercalated water contents were obtained from the initial compound by the treatment with distilled water and hydrochloric acid. The obtained samples were characterized by powder X-ray diffraction, SEM, X-ray microanalysis, BET, DRS, and TG. It was found that the complete ion exchange of Rb+ for H+ in the layered oxide Rb2La2Ti3O10 proceeds through the formation of two metastable intermediate phases with average protonation degrees of 0.5 and 0.75, which successively transform from one to another. Each of these phase transformations is accompanied not only by the contraction of the interlayer distance but also by the displacement of adjacent perovskite layers by 1/2 of the cell parameter which results in the change in the space group. The photocatalytic activity of obtained samples decreases with the increase in the protonation degree, which correlates with the decrease in the intercalated water content.

  5. Amperometric nitrate biosensor based on Carbon nanotube/Polypyrrole/Nitrate reductase biofilm electrode

    Energy Technology Data Exchange (ETDEWEB)

    Can, Faruk; Korkut Ozoner, Seyda; Ergenekon, Pinar; Erhan, Elif, E-mail: e.erhan@gyte.edu.tr

    2012-01-01

    This study describes the construction and characterization of an amperometric nitrate biosensor based on the Polypyrrole (PPy)/Carbon nanotubes (CNTs) film. Nitrate reductase (NR) was both entrapped into the growing PPy film and chemically immobilized via the carboxyl groups of CNTs to the CNT/PPy film electrode. The optimum amperometric response for nitrate was obtained in 0.1 M phosphate buffer solution (PBS), pH 7.5 including 0.1 M lithium chloride and 7 mM potassium ferricyanide with an applied potential of 0.13 V (vs. Ag/AgCl, 3 M NaCl). Sensitivity was found to be 300 nA/mM in a linear range of 0.44-1.45 mM with a regression coefficient of 0.97. The biosensor response showed a higher linear range in comparison to standard nitrate analysis methods which were tested in this study and NADH based nitrate biosensors. A minimum detectable concentration of 0.17 mM (S/N = 3) with a relative standard deviation (RSD) of 5.4% (n = 7) was obtained for the biosensor. Phenol and glucose inhibit the electrochemical reaction strictly at a concentration of 1 {mu}g/L and 20 mg/L, respectively. The biosensor response retained 70% of its initial response over 10 day usage period when used everyday. - Highlights: Black-Right-Pointing-Pointer K{sub 3}Fe(CN){sub 6} has been used for the first time as mediator for nitrate reductase. Black-Right-Pointing-Pointer Better performance was obtained in comparison to other nitrate biosensor studies operated with various mediators. Black-Right-Pointing-Pointer Analytical parameters were better than standard nitrate analysis methods.

  6. Amperometric nitrate biosensor based on Carbon nanotube/Polypyrrole/Nitrate reductase biofilm electrode

    International Nuclear Information System (INIS)

    Can, Faruk; Korkut Ozoner, Seyda; Ergenekon, Pinar; Erhan, Elif

    2012-01-01

    This study describes the construction and characterization of an amperometric nitrate biosensor based on the Polypyrrole (PPy)/Carbon nanotubes (CNTs) film. Nitrate reductase (NR) was both entrapped into the growing PPy film and chemically immobilized via the carboxyl groups of CNTs to the CNT/PPy film electrode. The optimum amperometric response for nitrate was obtained in 0.1 M phosphate buffer solution (PBS), pH 7.5 including 0.1 M lithium chloride and 7 mM potassium ferricyanide with an applied potential of 0.13 V (vs. Ag/AgCl, 3 M NaCl). Sensitivity was found to be 300 nA/mM in a linear range of 0.44–1.45 mM with a regression coefficient of 0.97. The biosensor response showed a higher linear range in comparison to standard nitrate analysis methods which were tested in this study and NADH based nitrate biosensors. A minimum detectable concentration of 0.17 mM (S/N = 3) with a relative standard deviation (RSD) of 5.4% (n = 7) was obtained for the biosensor. Phenol and glucose inhibit the electrochemical reaction strictly at a concentration of 1 μg/L and 20 mg/L, respectively. The biosensor response retained 70% of its initial response over 10 day usage period when used everyday. - Highlights: ► K 3 Fe(CN) 6 has been used for the first time as mediator for nitrate reductase. ► Better performance was obtained in comparison to other nitrate biosensor studies operated with various mediators. ► Analytical parameters were better than standard nitrate analysis methods.

  7. Sulfate and nitrate levels in aqueous, atmospheric aerosols

    International Nuclear Information System (INIS)

    Peterson, T.W.; Seinfeld, J.H.

    1979-01-01

    The formation of sulfates and nitrates in marine aerosol particles is investigated. A simulation of the growth and chemical reactions of an aerosol particle composed initially of an equilibrium mixture of NaCl and MgCl 2 and exposed to SO 2 , NO, NO 2 , NH 3 and H 2 SO 4 vapor is used to predict the relative compositions of sulfates, nitrates and ammonium, assuming gas-phase sulfur dioxide oxidation and liquid-phase nitrate formation. Results indicate an increase in nitrate concentration and a decrease in sulfate and ammonium concentrations with increasing particle radius and a near-stoichiometric ratio of nitrate and sulfate to ammonium. The noted deviations of this ratio from those observed experimentally are considered to indicate the relative importances of liquid-phase sulfur dioxide oxidation at various locations

  8. Solid-phase molecular recognition of cytosine based on proton-transfer reaction. Part II. supramolecular architecture in the cocrystals of cytosine and its 5-Fluoroderivative with 5-Nitrouracil

    Directory of Open Access Journals (Sweden)

    Portalone Gustavo

    2011-09-01

    Full Text Available Abstract Background Cytosine is a biologically important compound owing to its natural occurrence as a component of nucleic acids. Cytosine plays a crucial role in DNA/RNA base pairing, through several hydrogen-bonding patterns, and controls the essential features of life as it is involved in genetic codon of 17 amino acids. The molecular recognition among cytosines, and the molecular heterosynthons of molecular salts fabricated through proton-transfer reactions, might be used to investigate the theoretical sites of cytosine-specific DNA-binding proteins and the design for molecular imprint. Results Reaction of cytosine (Cyt and 5-fluorocytosine (5Fcyt with 5-nitrouracil (Nit in aqueous solution yielded two new products, which have been characterized by single-crystal X-ray diffraction. The products include a dihydrated molecular salt (CytNit having both ionic and neutral hydrogen-bonded species, and a dihydrated cocrystal of neutral species (5FcytNit. In CytNit a protonated and an unprotonated cytosine form a triply hydrogen-bonded aggregate in a self-recognition ion-pair complex, and this dimer is then hydrogen bonded to one neutral and one anionic 5-nitrouracil molecule. In 5FcytNit the two neutral nucleobase derivatives are hydrogen bonded in pairs. In both structures conventional N-H...O, O-H...O, N-H+...N and N-H...N- intermolecular interactions are most significant in the structural assembly. Conclusion The supramolecular structure of the molecular adducts formed by cytosine and 5-fluorocytosine with 5-nitrouracil, CytNit and 5FcytNit, respectively, have been investigated in detail. CytNit and 5FcytNit exhibit widely differing hydrogen-bonding patterns, though both possess layered structures. The crystal structures of CytNit (Dpka = -0.7, molecular salt and 5FcytNit (Dpka = -2.0, cocrystal confirm that, at the present level of knowledge about the nature of proton-transfer process, there is not a strict correlation between the Dpka values

  9. Energy-Storage Applications for a pH Gradient between Two Benzimidazole-Ligated Ruthenium Complexes That Engage in Proton-Coupled Electron-Transfer Reactions in Solution.

    Science.gov (United States)

    Motoyama, Daisuke; Yoshikawa, Kai; Ozawa, Hiroaki; Tadokoro, Makoto; Haga, Masa-Aki

    2017-06-05

    The judicious selection of pairs of benzimidazole-ligated ruthenium complexes allowed the construction of a rechargeable proton-coupled electron-transfer (PCET)-type redox battery. A series of ruthenium(II) and -(III) complexes were synthesized that contain substituted benzimidazoles that engage in PCET reactions. The formation of intramolecular Ru-C cyclometalation bonds stabilized the resulting ruthenium(III) complexes, in which pK a values of the imino N-H protons on the benzimidazoles are usually lower than those for the corresponding ruthenium(II) complexes. As a proof-of-concept study for a solution redox battery based on such PCET reactions, the charging/discharging cycles of several pairs of ruthenium complexes were examined by chronopotentiometry in an H-type device with half-cells separated by a Nafion membrane in unbuffered CH 3 CN/H 2 O (1/1, v/v) containing 0.1 M NaCl. During the charging/discharging cycles, the pH value of the solution gradually changed accompanied by a change of the open-circuit potential (OCP). The changes for the OCP and pH value of the solution in the anodic and cathodic half-cells were in good agreement with the predicted values from the Pourbaix diagrams for the pairs of ruthenium complexes used. Accordingly, the careful selection of pairs of ruthenium complexes with a sufficient potential gradient and a suitably large pK a difference is crucial: the charge generated between the two ruthenium complexes changes the OCP and the pH difference between the two cells in an unbuffered solution, given that the PCET reactions occur at both electrodes and that discharging leads to the original state. Because the electric energy is stored as a pH gradient between the half-cells, new possibilities for PCET-type rocking-chair redox batteries arise.

  10. Electronic device for measuring the polarization parameter in the π-p → π0n charge exchange reaction on a polarized proton target

    International Nuclear Information System (INIS)

    Brehin, S.

    1967-12-01

    An electronic apparatus has been constructed to measure the polarization parameter P 0 (t) in π - p → π 0 n charge exchange scattering at 5.9 GeV/c and 11,2 GeV/c on polarized proton target. This device insures triggering of a heavy plate spark chamber, allowing visualisation of γ rays from the π 0 decays when the associated neutron offers suitable characteristics in direction and energy. The neutron is detected by an array of 32 counters and his energy is measured by a time of flight method. Electronic circuits of this apparatus are described as test and calibration methods used. (author) [fr

  11. Antimony doped tin oxides and their composites with tin pyrophosphates as catalyst supports for oxygen evolution reaction in proton exchange membrane water electrolysis

    DEFF Research Database (Denmark)

    Xu, Junyuan; Li, Qingfeng; Hansen, Martin Kalmar

    2012-01-01

    based on tin pyrophosphates as the catalyst support. The materials showed an overall conductivity of 0.57 S cm−1 at 130 °C under the water vapor atmosphere with a contribution of the proton conduction. Using this composite support, iridium oxide nanoparticle catalysts were prepared and characterized...... in sulfuric and phosphoric acid electrolytes, showing much enhanced catalytic activity. Electrolyzer tests were conducted at both 80 °C with an Aquivion™ membrane and at 130 °C with a phosphoric acid doped Aquivion™ membrane. Significant improvement in the anodic kinetics was achieved on the composite...

  12. Yttrium Nitrate mediated Nitration of Phenols at room temperature in ...

    Indian Academy of Sciences (India)

    Rapid nitration of electron rich phenols using Y(NO₃)₃.6H₂O in glacial acetic acid at room temperature was observed with good yield. The method allows nitration of phenols without oxidation, and isolation of nitration product in a rapid and simple way. The described method is selective for phenols.

  13. Yttrium Nitrate mediated Nitration of Phenols at room temperature in ...

    Indian Academy of Sciences (India)

    which resulted in many neurological disorders.1 Thus, the mechanism of nitration in biological system explains how environment and genetic factors induce neurological disorder. Conventional nitration involves use of concentrated H2SO4 and HNO3 mixture as the nitrating agent. Such a method suffers from drawbacks.

  14. Periplasmic nitrate reductase revisited: a sulfur atom completes the sixth coordination of the catalytic molybdenum.

    Science.gov (United States)

    Najmudin, Shabir; González, Pablo J; Trincão, José; Coelho, Catarina; Mukhopadhyay, Abhik; Cerqueira, Nuno M F S A; Romão, Carlos C; Moura, Isabel; Moura, José J G; Brondino, Carlos D; Romão, Maria J

    2008-06-01

    NapA samples. These studies indicate that this signal is not associated with a Mo(V)-nitrate adduct and that the hyperfine structure originates from two equivalent solvent-exchangeable protons. The new coordination sphere of molybdenum proposed on the basis of our studies led us to revise the currently accepted reaction mechanism for periplasmic nitrate reductases. Proposals for a new mechanism are discussed taking into account a molybdenum and ligand-based redox chemistry, rather than the currently accepted redox chemistry based solely on the molybdenum atom.

  15. Study of structures associated with the large angle production of π+-, K+-, P and antiP with high transverse momentum in proton-proton reactions at the CERN collision rings

    International Nuclear Information System (INIS)

    Villeneuve de Janti, Philippe.

    1980-10-01

    Data are analyzed from ISR-410/413 at 53 GeV energy in the center of mass. An attempt is made to find out wether correlations are present in the events and especially wether a jet structure can be associated with the production of triggering particle. A cluster particle structure is then investigated in the azimuthal hemisphere opposite the trigger by an original event-by-event analysis method. Certain properties of high longitudinal momentum particle systems (so-called 'spectator systems') are examined. Whenever possible the results obtained are compared with: a) predictions of hard collision models of components, b) effects already observed in low Psub(T) reactions, c) results of a Monte Carlo simulation of inelastic pp reactions containing no explicit dynamic mechanism and used to estimate the contribution of purely kinematic stresses of the effects observed [fr

  16. Nitrate Leaching Management

    Science.gov (United States)

    Nitrate (NO3) leaching is a significant nitrogen (N) loss process for agriculture that must be managed to minimize NO3 enrichment of groundwater and surface waters. Managing NO3 leaching should involve the application of basic principles of understanding the site’s hydrologic cycle, avoiding excess ...

  17. Identification of 100Sn and other proton drip-line nuclei in the reaction 112Sn + natNi at 63 MeV/nucleon

    International Nuclear Information System (INIS)

    Lewitowicz, M.; Anne, R.; Auger, G.; Bazin, D.; Corre, J.M.; Borcea, C.; Borrel, V.; Fomichov, A.; Grzywacz, R.; and others.

    1996-01-01

    The doubly-magic nucleus 100 Sn and six new neutron-deficient nuclei in the A∼100 region were identified in the reaction 112 Sn + nat Ni at 63 MeV/nucleon. The experiment was carried out using the high acceptance device SISSI and the Alpha and LISE3 spectrometers at GANIL. The identification of the reaction products (A, Z and Q) was made using the measurements of time-of-flight, energy-loss and kinetic energy. (author)

  18. Light-induced protein nitration and degradation with HONO emission

    Science.gov (United States)

    Meusel, Hannah; Elshorbany, Yasin; Kuhn, Uwe; Bartels-Rausch, Thorsten; Reinmuth-Selzle, Kathrin; Kampf, Christopher J.; Li, Guo; Wang, Xiaoxiang; Lelieveld, Jos; Pöschl, Ulrich; Hoffmann, Thorsten; Su, Hang; Ammann, Markus; Cheng, Yafang

    2017-10-01

    Proteins can be nitrated by air pollutants (NO2), enhancing their allergenic potential. This work provides insight into protein nitration and subsequent decomposition in the presence of solar radiation. We also investigated light-induced formation of nitrous acid (HONO) from protein surfaces that were nitrated either online with instantaneous gas-phase exposure to NO2 or offline by an efficient nitration agent (tetranitromethane, TNM). Bovine serum albumin (BSA) and ovalbumin (OVA) were used as model substances for proteins. Nitration degrees of about 1 % were derived applying NO2 concentrations of 100 ppb under VIS/UV illuminated conditions, while simultaneous decomposition of (nitrated) proteins was also found during long-term (20 h) irradiation exposure. Measurements of gas exchange on TNM-nitrated proteins revealed that HONO can be formed and released even without contribution of instantaneous heterogeneous NO2 conversion. NO2 exposure was found to increase HONO emissions substantially. In particular, a strong dependence of HONO emissions on light intensity, relative humidity, NO2 concentrations and the applied coating thickness was found. The 20 h long-term studies revealed sustained HONO formation, even when concentrations of the intact (nitrated) proteins were too low to be detected after the gas exchange measurements. A reaction mechanism for the NO2 conversion based on the Langmuir-Hinshelwood kinetics is proposed.

  19. On the isomers of pyridine-4-carboxaldoxime and its nitrate salt, X-ray crystal structure and quantum chemical calculations

    Science.gov (United States)

    Soliman, Saied M.; Albering, Jörg; Abu-Youssef, Morsy A. M.

    2017-07-01

    The reaction between nitric acid and pyridine-4-carboxaldoxime (P4A) afford the corresponding pyridinum nitrate salt (P4AN). Its X-ray structure is measured and compared with the related P4A salts. The DFT/B3LYP results showed that both the P4A and P4AN favored the Syn-I form which has the lowest energy among the other possible isomers. Transition state calculations predicted that the Syn-I form is the thermodynamically and kinetically most stable form. The X-ray solid state structure of the new nitrate salt (P4AN) indicated that the labile proton favored the N-atom of the pyridine ring. DFT studies showed that the same is true for its solution in polar solvents. In contrast, the pyridinium cation is not favored either in the gas phase or solution of P4AN in nonpolar solvent. In these cases, the proton favored to bond with one O-atom from the nitrate group. Second order interaction energies and Mayer bond order values revealed these results. The bond order of the Nsbnd H bond is higher in polar solvents as well as at the experimental structure than either in the gas phase or non polar solvents. The topology parameters obtained from the atoms in molecules (AIM) analysis were used to describe the nature of the Nsbnd H and Osbnd H bonds. The bond critical points (BCP) were found to be close to the H-atoms in case of stronger interaction.

  20. Double differential cross sections for (p,n) reactions of 18 and 25 MeV protons with isotopes of Cr, Fe, Co, Ni, Cu, Y, Zr, Mo, Pd and Tb

    International Nuclear Information System (INIS)

    Scobel, W.; Blann, M.; Komoto, T.; Trabandt, M.; Grimes, S.M.; Hansen, L.F.; Pohl, B.A.; Wong, C.

    1984-06-01

    Cross sections for the inclusive production of neutrons from reactions of 25 MeV protons with 50 52 53 Cr, 54 56 58 Fe, 59 Co, 60 Ni, 63 Cu, 89 Y, 90 91 92 94 Zr, 92 94 95 96 97 98 100 Mo, 110 Pd and 159 Tb and of 18 MeV protons with 90 91 92 94 Zr have been measured with time-of-flight techniques for 16 angles between 3.5 0 less than or equal to theta/sub lab/ less than or equal to 159.0 0 . After a short presentation of the motivations for these measurements, the experimental set up is discussed with emphasis on the systematic and statistical error sources pertinent to this work, in particular the question of background correction in the continuous parts of the spectra. The main purpose of this report is to make the experimental results of this work (angle integrated spectra, angular distributions) available for distribution, reducing thereby the data required in publication of the results of these experiments. 20 references

  1. Effects of air exchange, temperature and slurry management on odorant emissions from pig production units and slurry tanks studied by proton-transfer-reaction mass spectrometry (PTR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Feilberg, A.; Adamsen, A.P.S.; Liu, D.; Hansen, M.J.; Bildsoe, P. [Aarhus Univ., Tjele (Denmark). Dept. of Biosystems Engineering

    2010-07-01

    The factors affecting the variability of odorant emissions from intensive pig production facilities were examined using proton-transfer-reaction mass spectrometry (PTR-MS) to monitor emissions of odorants. Quantitative and time-resolved results for protonated ions representing hydrogen sulphide (H{sub 2}S), volatile organic sulphur compounds, organic amines, volatile carboxylic acids, carbonyls, phenols and indoles can be obtained. This study presented the results from PTRMS measurements of odorant emissions from finisher pig houses and finisher manure storage tanks. The measurements were performed at an experimental full-scale pig section with mechanical ventilation and at an experimental manure storage facility with controlled air exchange. Field measurements were taken during variable air exchange rates and temperatures, during finisher growth, and during emptying of the slurry pit. The results revealed a pronounced diurnal variation in emissions of odorants from the pig section with peaks in daytime coinciding with the highest ventilation rates and highest room temperatures. The highest emission rates were observed for H{sub 2}S and carboxylic acids. Based on odour threshold values, methanethiol and 4-methylphenol were estimated to contribute considerably to the odour nuisance. Discharging of the slurry pit led to reduced H{sub 2}S emissions, but peaks of H{sub 2}S were observed during manure handling.

  2. Studies of one- and two-proton transfer in {sup 12}C,{sup 16}O+{sup 154}Sm, and {sup 16}O+{sup 115}In reactions

    Energy Technology Data Exchange (ETDEWEB)

    Nayak, B.K.; Choudhury, R.K.; Biswas, D.C.; Pant, L.M.; Saxena, A.; Nadkarni, D.M.; Kapoor, S.S. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    1997-06-01

    Cross sections for quasielastic scattering and transfer reactions have been measured for {sup 12}C, {sup 16}O+{sup 154}Sm, and {sup 16}O+{sup 115}In systems at energies above the Coulomb barrier. The transfer probabilities for one- and two-proton stripping reactions show an exponential decrease with increasing distance of closest approach for all the systems and the measured decay constants are found to be smaller than those derived from binding-energy considerations on the basis of the semiclassical model using a Coulomb trajectory. These results on the observed enhancement of transfer probabilities were further analyzed within the framework of the semiclassical model using two different formalisms: (1) considering the contribution of both Coulomb and nuclear branches of distance of closest approach to transfer probability and (2) in terms of the quantum diffractional effect in the broadening of the transfer angular distribution. It is seen that both these formalisms are able to offer a consistent explanation for the observed enhancement in the transfer probabilities and account for the {open_quotes}slope anomaly{close_quotes} seen in the transfer reactions in these systems. {copyright} {ital 1997} {ital The American Physical Society}

  3. Measurement of conversion electrons with the $^{208}Pb(p,n)^{208}Bi$ reaction and derivation of the shell model proton neutron hole interaction from the properties of $^{208}Bi$

    CERN Document Server

    Maier, K H; Dracoulis, G D; Boutachkov, P; Aprahamian, A; Byrne, A P; Davidson, P M; Lane, G L; Marie-Jeanne, Mélanie; Nieminen, P; Watanabe, H

    2007-01-01

    Conversion electrons from 208Bi have been measured using singles and coincidence techniques with the 208Pb(p,n)208Bi reaction at 9 MeV. The new information on multipolarities and spins complements that available from recent gamma-gamma-coincidence studies with the same reaction [Boutachkov et al., Nucl. Phys. A768, 22 (2006)]. The results on electromagnetic decays taken together with information on spectroscopic factors from earlier single-particle transfer reaction measurements represent an extensive data set on the properties of the one-proton one-neutron-hole states below 3 MeV, a spectrum which is virtually complete. Comparison of the experimental observables, namely, energies, spectroscopic factors, and gamma-branching ratios, with those calculated within the shell model allows extraction of the matrix elements of the shell model residual interaction. More than 100 diagonal and nondiagonal elements can be determined in this way, through a least squares fit to the experimental data. This adjustment of the...

  4. Cross section measurement of residues produced in proton- and deuteron-induced spallation reactions on 93Zr at 105 MeV/u using the inverse kinematics method

    Directory of Open Access Journals (Sweden)

    Kawase Shoichiro

    2017-01-01

    Full Text Available Isotopic production cross sections in the proton- and deuteron-induced spallation reactions on 93Zr at an energy of 105 MeV/u were measured in inverse kinematics conditions for the development of realistic nuclear transmutation processes for long-lived fission products (LLFPs with neutron and light-ion beams. The experimental results were compared to the PHITS calculations describing the intra-nuclear cascade and evaporation processes. Although an overall agreement was obtained, a large overestimation of the production cross sections for the removal of a few nucleons was seen. A clear shell effect associated with the neutron magic number N = 50 was observed in the measured isotopic production yields of Zr and Y isotopes, which can be reproduced reasonably by the PHITS calculation.

  5. Towards mechanistic representations of SOA from BVOC + NO3 reactions

    Science.gov (United States)

    Monoterpene reaction with nitrate radicals is a significant source of organic aerosol in the southeast United States. This source of organic aerosol represents an anthropogenic control on biogenic organic aerosol since nitrate radicals result from NOx emissions and are generally ...

  6. Energizing porters by proton-motive force.

    Science.gov (United States)

    Nelson, N

    1994-11-01

    It is generally accepted that the chemistry of water was the most crucial determinant in shaping life on earth. Among the more important chemical features of water is its dissociation into protons and hydroxyl ions. The presence of relatively high proton concentrations in the ambient solution resulted in the evolution of proton pumps during the dawn of life on earth. These proton pumps maintained neutral pH inside the cells and generated electrochemical gradients of protons (proton-motive force) across their membranes. The existence of proton-motive force enabled the evolution of porters driven by it that are most probably among the more primitive porters in the world. The directionality of the substrate transport by the porters could be to both sides of the membranes because they can serve as proton symporters or antiporters. One of the most important subjects of this meeting is the mechanism by which proton-motive and other ion-motive forces drive the transport processes through porters. Is there a common mechanism of action for all proton-driven porters? Is there some common partial reaction by which we can identify the way that porters are energized by proton-motive force? Is there a common coupling between proton movement and uptake or secretion of certain molecules? Even a partial answer to one of these questions would advance our knowledge... or confusion. As my mentor Efraim Racker used to say: 'If you are not totally confused you do not understand the issue'.

  7. Thermodynamics and proton activities of protic ionic liquids with quantum cluster equilibrium theory

    Science.gov (United States)

    Ingenmey, Johannes; von Domaros, Michael; Perlt, Eva; Verevkin, Sergey P.; Kirchner, Barbara

    2018-05-01

    We applied the binary Quantum Cluster Equilibrium (bQCE) method to a number of alkylammonium-based protic ionic liquids in order to predict boiling points, vaporization enthalpies, and proton activities. The theory combines statistical thermodynamics of van-der-Waals-type clusters with ab initio quantum chemistry and yields the partition functions (and associated thermodynamic potentials) of binary mixtures over a wide range of thermodynamic phase points. Unlike conventional cluster approaches that are limited to the prediction of thermodynamic properties, dissociation reactions can be effortlessly included into the bQCE formalism, giving access to ionicities, as well. The method is open to quantum chemical methods at any level of theory, but combination with low-cost composite density functional theory methods and the proposed systematic approach to generate cluster sets provides a computationally inexpensive and mostly parameter-free way to predict such properties at good-to-excellent accuracy. Boiling points can be predicted within an accuracy of 50 K, reaching excellent accuracy for ethylammonium nitrate. Vaporization enthalpies are predicted within an accuracy of 20 kJ mol-1 and can be systematically interpreted on a molecular level. We present the first theoretical approach to predict proton activities in protic ionic liquids, with results fitting well into the experimentally observed correlation. Furthermore, enthalpies of vaporization were measured experimentally for some alkylammonium nitrates and an excellent linear correlation with vaporization enthalpies of their respective parent amines is observed.

  8. Refining method for bismuth nitrate

    International Nuclear Information System (INIS)

    Shibata, Shigeyuki.

    1997-01-01

    The present invention concerns a method of separating and removing α ray emitting nuclides present in an aqueous solution of bismuth nitrate by an industrially convenient method. A nitric acid concentration in the aqueous solution of bismuth nitrate in which α ray emitting nuclides are dissolved is lowered to coprecipitate the bismuth oxynitrate and the α ray emitting nuclides. The coprecipitation materials are separated from the aqueous solution of bismuth nitrate to separate the α ray emitting nuclides dissolved in the aqueous solution of bismuth nitrate thereby refining the aqueous solution of bismuth nitrate. (T.M.)

  9. Inter-hemispheric comparisons of SPE-associated Impulsive Nitrate Enhancements in Polar Ice

    Science.gov (United States)

    Kepko, L.; Spence, H. E.; Shea, M. A.; Smart, D. F.; Curran, M.; Dreschhoff, G. A.

    2006-05-01

    Several studies have suggested an association between impulsive nitrate enhancements observed in polar ice and solar proton events (SPEs). However, the validity of this association is still the subject of some controversy. One difficulty in addressing this controversy is the inherently high noise level of unconsolidated firn, which typically constitutes the top few tens of meters of ice cores. This high noise level hampers identification of impulsive nitrate enhancements during the space-age, when routine solar proton measurements are available. To overcome this difficulty we examine cores from both hemispheres, including Summit (Greenland), Windless Bight (Antarctica) and Law Dome (Antarctica). Cross-correlation of the cores reduces the effect of local noise and also provides a picture of the global response and insight into seasonal dependencies. We will compare our list of globally observed impulsive nitrate enhancements to the solar proton record.

  10. Nitrate in drinking water

    DEFF Research Database (Denmark)

    Schullehner, Jörg

    Annual nationwide exposure maps for nitrate in drinking water in Denmark from the 1970s until today will be presented based on the findings in Schullehner & Hansen (2014) and additional work on addressing the issue of private well users and estimating missing data. Drinking water supply in Denmark...... is highly decentralized and fully relying on simple treated groundwater. At the same time, Denmark has an intensive agriculture, making groundwater resources prone to nitrate pollution. Drinking water quality data covering the entire country for over 35 years are registered in the public database Jupiter....... In order to create annual maps of drinking water quality, these data had to be linked to 2,852 water supply areas, which were for the first time digitized, collected in one dataset and connected to the Jupiter database. Analyses of the drinking water quality maps showed that public water supplies...

  11. Nitrate in drinking water

    DEFF Research Database (Denmark)

    Schullehner, Jörg; Hansen, Birgitte; Sigsgaard, Torben

    is highly decentralized and fully relying on simple treated groundwater. At the same time, Denmark has an intensive agriculture, making groundwater resources prone to nitrate pollution. Drinking water quality data covering the entire country for over 35 years are registered in the public database Jupiter......Annual nationwide exposure maps for nitrate in drinking water in Denmark from the 1970s until today will be presented based on the findings in Schullehner & Hansen (2014) and additional work on addressing the issue of private well users and estimating missing data. Drinking water supply in Denmark....... In order to create annual maps of drinking water quality, these data had to be linked to 2,852 water supply areas, which were for the first time digitized, collected in one dataset and connected to the Jupiter database. Analyses of the drinking water quality maps showed that public water supplies...

  12. Study of the. gamma. rho. -->. n. pi. /sup +/ reaction with polarized protons and photons at E/sub. gamma. /=340 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Get' man, V.A.; Gorbenko, V.G.; Grushin, V.F.; Derkach, A.Y.; Zhebrovskii, Y.V.; Karnaukhov, I.M.; Kolesnikov, L.Y.; Lukhanin, A.A.; Rubashkin, A.L.; Sanin, V.M.; Sorokin, P.V.; Sporov, E.A.; Telegin, Y.N.

    1979-07-05

    A two-fold polarization experiment of the ''beam-target'' type is carried out for the first time for the reaction ..gamma..p..-->..n..pi../sup +/ for E/sub ..gamma../ =340 MeV, and the three polarization parameters, ..sigma.., T, and P are determined simultaneously.

  13. Phenomenological comparison of inelastic electron-proton scattering with reaction K+p→K0 + anything at 5, 8.2 and 16 GeV/c

    International Nuclear Information System (INIS)

    Chliapnikov, P.V.; Kubic, V.M.; Perevoztchikov, V.M.; Rubin, A.M.; Tchikilev, O.G.; Vorobjev, A.P.; Kinson, J.B.; Jobes, M.; Storr, K.M.; Watkins, D.

    1976-01-01

    An analysis is presented of the reaction K + p→K 0 + anything at incident momenta of 5, 8.2 and 16 GeV/c in terms of the Bjoerken variables ω and x. Assuming dominance of rho exchange, the structure function F 2 (x,y) is derived which is found similar to the one obtained in deep inelastic electroproduction. (Auth.)

  14. Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration.

    Science.gov (United States)

    Sun, Yan; Lu, Wenchao; Liu, Jianbo

    2017-02-09

    8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a 1 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H] + , deprotonated [8-oxoG - H] - , and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (E col ) on reaction cross sections over a center-of-mass E col range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H] - was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H] - was captured as the main oxidation product. Reaction cross section for [8-oxoG - H] - ·W + 1 O 2 decreases with increasing E col and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H] + ·W 0,1 and [8-oxoG - H] - ·W 0

  15. Proton therapy

    International Nuclear Information System (INIS)

    Jongen, Y.

    1995-01-01

    Ideal radiotherapy deposits a large amount of energy in the tumour volume, and none in the surrounding healthy tissues. Proton therapy comes closer to this goal because of a greater concentration of dose, well defined proton ranges and points of energy release which are precisely known - the Bragg peak1. In the past, the development of clinical proton therapy has been hampered by complexity, size, and cost. To be clinically effective, energies of several hundred MeV are required; these were previously unavailable for hospital installations, and pioneering institutions had to work with complex, inadequate equipment originally intended for nuclear physics research. Recently a number of specialist organizations and commercial companies have been working on dedicated systems for proton therapy. One, IBA of Belgium, has equipment for inhouse hospital operation which encompasses a complete therapy centre, delivered as a turnkey package and incorporating a compact, automated, higher energy cyclotron with isocentric gantries. Their system will be installed at Massachusetts General Hospital, Boston. The proton therapy system comprises: - a 235 MeV isochronous cyclotron to deliver beams of up to 1.5 microamps, but with a hardware limitation to restrict the maximum possible dose; - variable energy beam (235 to 70 MeV ) with energy spread and emittance verification; - a beam transport and switching system to connect the exit of the energy selection system to the entrances of a number of gantries and fixed beamlines. Along the beam transport system, the beam characteristics are monitored with non-interceptive multiwire ionization chambers for automatic tuning; - gantries fitted with nozzles and beamline elements for beam control; both beam scattering and beam wobbling techniques are available for shaping the beam;

  16. A quantum-rovibrational-state-selected study of the proton-transfer reaction H2+(X2Σ: v+ = 1-3; N+ = 0-3) + Ne → NeH+ + H using the pulsed field ionization-photoion method: observation of the rotational effect near the reaction threshold.

    Science.gov (United States)

    Xiong, Bo; Chang, Yih-Chung; Ng, Cheuk-Yiu

    2017-07-19

    Using the sequential electric field pulsing scheme for vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection, we have successfully prepared H 2 + (X 2 Σ: v + = 1-3; N + = 0-5) ions in the form of an ion beam in single quantum-rovibrational-states with high purity, high intensity, and narrow laboratory kinetic energy spread (ΔE lab ≈ 0.05 eV). This VUV-PFI-PI ion source, when coupled with the double-quadrupole double-octupole ion-molecule reaction apparatus, has made possible a systematic examination of the vibrational- as well as rotational-state effects on the proton transfer reaction of H 2 + (X 2 Σ: v + ; N + ) + Ne. Here, we present the integral cross sections [σ(v + ; N + )'s] for the H 2 + (v + = 1-3; N + = 0-3) + Ne → NeH + + H reaction observed in the center-of-mass kinetic energy (E cm ) range of 0.05-2.00 eV. The σ(v + = 1, N + = 1) exhibits a distinct E cm onset, which is found to agree with the endothermicity of 0.27 eV for the proton transfer process after taking into account of experimental uncertainties. Strong v + -vibrational enhancements are observed for σ(v + = 1-3, N + ) in the E cm range of 0.05-2.00 eV. While rotational excitations appear to have little effect on σ(v + = 3, N + ), a careful search leads to the observation of moderate N + -rotational enhancements at v + = 2: σ(v + = 2; N + = 0) quantum dynamics predictions. We hope that these new experimental results would further motivate more rigorous theoretical calculations on the dynamics of this prototypical ion-molecule reaction.

  17. New determination of proton spectroscopic factors and reduced widths for 8Be states in the 16.5-18.0 MeV excitation energy region via the study of the 7Li(3He,d )8Be transfer reaction at Elab=20 MeV: Implication for the 7Li(p ,α )4He hydrogen burning reaction

    Science.gov (United States)

    Belhout, A.; Ouichaoui, S.; Beaumevieille, H.; Bouchemha, A.; Bogaert, G.; Fortier, S.; Kiener, J.; Lefebvre-Schuhl, A.; Maison, J. M.; Rosier, L.; Rotbard, J.; Tatischeff, V.; Thibaud, J. P.; Vernotte, J.

    2017-11-01

    The angular distributions of 8Be states in the excitation energy region Ex˜(16.5 -18.2 ) MeV produced in the 7Li(3He,d )8Be proton transfer reaction have been measured at the Orsay 14.8 -MV tandem accelerator for 2+3He ion bombarding energy, Elab=20 MeV, and forward angular range, θlab=5 ∘-50 ∘ . A high energy resolution detection system composed of a split-pole magnetic spectrometer and a Δ E -E , position-sensitive drift chamber was used to record the energy spectra of outgoing deuterons. The measured cross section data for the direct reaction component have been separated from the compound nucleus one, then analyzed in the framework of the nonlocal, finite-range (FR)-distorted-wave Born approximation (DWBA) theory. New values of the C2S and (Sp 1 /2,Sp 3 /2) proton absolute and partial spectroscopic factors and related γp2(a ) proton reduced widths versus the p +7Li channel radius have been extracted for the 2+(16.626 ) and 2+(16.922 ) ,T =0 +1 isospin-mixed loosely bound states of astrophysical interest and the 1+(17.640 ) , T =1 unbound state of 8Be. They are compared to sparse earlier experimental values and to shell-model-predicted ones from the literature, and are discussed. In particular, the status of the spectroscopic information on the 2+ isospin-mixed doublet is reviewed and updated. The application in nuclear astrophysics of the DWBA derived results is emphasized.

  18. Experiments on iron shield transmission of quasi-monoenergetic neutrons generated by 43- and 68-MeV protons via the {sup 7}Li(p,n) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Hiroshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Tanaka, Shun-ichi; Nakao, Noriaki [and others

    1996-03-01

    In order to provide benchmark data of neutrons transmitted through iron shields in the intermediate-energy region, spatial distributions of neutron energy spectra and reaction rates behind and inside the iron shields of thickness up to 130 cm were measured for 43- and 68-MeVp-{sup 7}Li neutrons using a quasi-monoenergetic neutron beam source at the 90-MV AVF cyclotron facility of the TLARA facility in JAERI. The measured data by five kinds of detectors: the BC501A detector, the Bonner ball counter, {sup 238}U and {sup 232}Th fission counters, {sup 7}LiF and {sup nat}LiF TLDs and solid state nuclear track detector, are numerically provided in this report in the energy region between 10{sup -4} eV and the energy of peak neutrons generated by the {sup 7}Li(p,n) reaction. (author).

  19. Experiments on iron shield transmission of quasi-monoenergetic neutrons generated by 43- and 68-MeV protons via the 7Li(p,n) reaction

    International Nuclear Information System (INIS)

    Nakashima, Hiroshi; Tanaka, Shun-ichi; Nakao, Noriaki

    1996-03-01

    In order to provide benchmark data of neutrons transmitted through iron shields in the intermediate-energy region, spatial distributions of neutron energy spectra and reaction rates behind and inside the iron shields of thickness up to 130 cm were measured for 43- and 68-MeVp- 7 Li neutrons using a quasi-monoenergetic neutron beam source at the 90-MV AVF cyclotron facility of the TLARA facility in JAERI. The measured data by five kinds of detectors: the BC501A detector, the Bonner ball counter, 238 U and 232 Th fission counters, 7 LiF and nat LiF TLDs and solid state nuclear track detector, are numerically provided in this report in the energy region between 10 -4 eV and the energy of peak neutrons generated by the 7 Li(p,n) reaction. (author)

  20. COGEMA Experience in Uranous Nitrate Preparation

    International Nuclear Information System (INIS)

    Tison, E.; Bretault, Ph.

    2006-01-01

    yield of the operation and its simplicity were the main reasons for this choice. Nowadays, our catalytic hydrogenation process is used in all the commercial reprocessing plants worldwide: THORP at Sellafield, UP3 and UP2 800 at La Hague, and RRP at Rokkasho-Mura. In this process, uranyl nitrate is reduced to uranous nitrate by hydrogen in presence of a platinum based catalyst. Most of the plants implement the reaction in the same kind of reactor: 'co-current, up-flow and fixed-bed reactor'. For UP2 800 at La Hague, started in 1994, a new kind of reactor allowing a higher capacity has been developed. In this reactor, the catalyst bed is not fixed but circulating (fluidized bed). The aim of the paper is to describe both reactor technology implemented in La Hague (fixed bed and fluidized bed), to show their performance in terms of capacity and yield and to compare their operating and maintenance principles. (authors)

  1. Asymptotic normalization coefficients from proton transfer reactions and astrophysical S factors for the (CNOC)-C-13(p, gamma)N-14 radiative capture process

    Czech Academy of Sciences Publication Activity Database

    Mukhamedzhanov, A. M.; Azhari, A.; Burjan, Václav; Gagliardi, C. A.; Kroha, Václav; Sattarov, A.; Tang, X.; Trache, L.; Tribble, R. E.

    2003-01-01

    Roč. 725, č. 22 (2003), s. 279-294 ISSN 0375-9474 R&D Projects: GA ČR GA202/01/0709; GA MŠk ME 385 Institutional research plan: CEZ:AV0Z1048901 Keywords : radiative capture reaction * asymptotic normalization coefficient Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.761, year: 2003

  2. Formation and de-excitation of hot nuclei in reactions induced by proton beams (475 MeV and 2 GeV) and 3He beam (2 GeV)

    International Nuclear Information System (INIS)

    Ledoux, X.

    1995-04-01

    We are studying the formation and the de-excitation of hot nuclei created in reactions induced by light high energy projectiles. These reactions, described in a two step model: an intranuclear cascade followed by an evaporation phase, produce nuclei in which the collective modes (compression, rotation, deformation) are weakly excited. By measuring the neutron multiplicities, event by event with ORION, and the light charged particle energies and multiplicities one can evaluate the excitation energy distribution of the nuclei. At the same time, theoretical simulations are carried out using the intranuclear cascade code developed by J. Cugnon and the statistical de-excitation code GEMINI. The good agreement with experimental results indicate that 10% of the p-nucleus interactions lead to temperatures greater than 5 MeV. The observation of the fission of a nucleus with a temperature close to 5 MeV shows that the nucleus behaves as a set of bound nucleons and, that the temperature stability limit is not yet reached. The observed decline of fission probability at high excitation energies is most likely to be correlated to the appearance of an other de-excitation process (evaporation residues emission or multifragmentation) which could not be experimentally detected. Finally, in the last chapter, we briefly present the principle of transmutation for long-lived nuclear waste with a proton accelerator and underline the interest of the present work in such studies. (author). 54 refs., 80 figs., 13 tabs

  3. Nitrate biosensors and biological methods for nitrate determination.

    Science.gov (United States)

    Sohail, Manzar; Adeloju, Samuel B

    2016-06-01

    The inorganic nitrate (NO3‾) anion is present under a variety of both natural and artificial environmental conditions. Nitrate is ubiquitous within the environment, food, industrial and physiological systems and is mostly present as hydrated anion of a corresponding dissolved salt. Due to the significant environmental and toxicological effects of nitrate, its determination and monitoring in environmental and industrial waters are often necessary. A wide range of analytical techniques are available for nitrate determination in various sample matrices. This review discusses biosensors available for nitrate determination using the enzyme nitrate reductase (NaR). We conclude that nitrate determination using biosensors is an excellent non-toxic alternative to all other available analytical methods. Over the last fifteen years biosensing technology for nitrate analysis has progressed very well, however, there is a need to expedite the development of nitrate biosensors as a suitable alternative to non-enzymatic techniques through the use of different polymers, nanostructures, mediators and strategies to overcome oxygen interference. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Proton radiography to improve proton therapy treatment

    NARCIS (Netherlands)

    Takatsu, J.; van der Graaf, E. R.; van Goethem, Marc-Jan; van Beuzekom, M.; Klaver, T.; Visser, Jan; Brandenburg, S.; Biegun, A. K.

    The quality of cancer treatment with protons critically depends on an accurate prediction of the proton stopping powers for the tissues traversed by the protons. Today, treatment planning in proton radiotherapy is based on stopping power calculations from densities of X-ray Computed Tomography (CT)

  5. Asymmetries from the 4He(p,2p)3H reaction at 250 and 500 MeV using polarized protons

    International Nuclear Information System (INIS)

    Margaziotis, D.J.; Epstein, M.B.; van Oers, W.T.H.; Hasell, D.K.; Abegg, R.; Moss, G.A.; Greeniaus, L.G.; Cameron, J.M.; Stetz, A.W.

    1982-01-01

    Analyzing powers for the 4 He(p,2p) 3 H reaction have been measured at 250 and 500 MeV for three pairs of quasifree angles, i.e., 55 0 -25 0 , 50 0 -30 0 , and 45 0 -35 0 . The range of recoil momenta covered is from zero to 150 MeV/c. The data have been compared with distorted-wave impulse approximation predictions. In general only reasonable agreement is obtained, pointing to deficiencies in the distorted wave impulse approximation even at low recoil momenta

  6. Mutational analysis of the respiratory nitrate transporter NarK2 of Mycobacterium tuberculosis.

    Directory of Open Access Journals (Sweden)

    Michelle M Giffin

    Full Text Available Mycobacterium tuberculosis induces nitrate reductase activity in response to decreasing oxygen levels. This is due to regulation of both the transcription and the activity of the nitrate transporter NarK2. A model of NarK2 structure is proposed containing 12 membrane spanning regions consistent with other members of the major facilitator superfamily. The role of the proton gradient was determined by exposing M. tuberculosis to uncouplers. Nitrite production decreased indicating that the importation of nitrate involved an H(+/nitrate symporter. The addition of nitrite before nitrate had no effect, suggesting no role for a nitrate/nitrite antiporter. In addition the NarK2 knockout mutant showed no defect in nitrite export. NarK2 is proposed to be a Type I H(+/nitrate symporter. Site directed mutagenesis was performed changing 23 amino acids of NarK2. This allowed the identification of important regions and amino acids of this transporter. Five of these mutants were inactive for nitrate transport, seven produced reduced activity and eleven mutants retained wild type activity. NarK2 is inactivated in the presence of oxygen by an unknown mechanism. However none of the mutants, including those with mutated cysteines, were altered in their response to oxygen levels. The assimilatory nitrate transporter NasA of Bacillus subtilis was expressed in the M. tuberculosis NarK2 mutant. It remained active during aerobic incubation showing that the point of oxygen control is NarK2.

  7. Leading proton production in deep inelastic scattering at HERA

    NARCIS (Netherlands)

    Chekanov, S.; Derrick, M.; Magill, S.; Musgrave, B.; Nicholass, D.; Repond, J.; Yoshida, R.; Mattingly, M. C. K.; Antonioli, P.; Bari, G.; Bellagamba, L.; Boscherini, D.; Bruni, A.; Bruni, G.; Cindolo, G. Cara Romeo F.; Corradi, M.; Giusti, P.; Iacobucci, G.; Margotti, A.; Massam, T.; Nania, R.; Polini, A.; Antonelli, S.; Basile, M.; Bindi, M.; Cifarelli, L.; Contin, A.; Palmonari, F.; De Pasquale, S.; Sartorelli, G.; Zichichi, A.; Bartsch, D.; Brock, I.; Hartmann, H.; Hilger, E.; Jakob, H. -P.; Juengst, M.; Nuncio-Quiroz, A. E.; Samson, U.; Schoenberg, V.; Shehzadi, R.; Wlasenko, M.; Brook, N. H.; Heath, G. P.; Kaur, M.; Kaur, P.; Singh, I.; Capua, M.; Fazio, S.; Pellegrino, A.

    The semi-inclusive reaction e(+)p -> e(+) Xp was studied with the ZEUS detector at HERA with an integrated luminosity of 12.8 pb(-1). The final-state proton, which was detected with the ZEUS leading proton spectrometer, carried a large fraction of the incoming proton energy, x(L) > 0.32, and its

  8. Accurate accelerator energy calibration using selected resonances in proton elastic scattering and in (p,γ) and (p,p‧γ) reactions

    Science.gov (United States)

    Paneta, V.; Kokkoris, M.; Lagoyannis, A.; Preketes-Sigalas, K.

    2017-09-01

    The present work aims at contributing to the field of Ion Beam Analysis by providing a set of standard, high-accuracy nuclear resonance reaction data points to be used for accelerator energy calibration up to 4.6 MeV, more specifically with the use of the 27Al(p,γ), 13C(p,γ), 12C(p,p0) and 32S(p,p‧γ) resonant reactions, as a result of a comprehensive investigation in two different laboratories. The use of resonances at higher energies, namely up to 6 MeV, is also discussed. The measurements have been performed at two different electrostatic accelerators, namely at the 5.5 MV HV TN-11 of NCSR "Demokritos", Greece, and at the 5 MV 15SDH-2 Pelletron Tandem accelerator at Uppsala University in Uppsala, Sweden. Common points were used to normalize and validate the data. The possible use of the 16O(p,p0) resonance at 3.47 MeV is also discussed and analyzed.

  9. Laboratory studies of nitrate radical chemistry - application to atmospheric processes

    Energy Technology Data Exchange (ETDEWEB)

    Noremsaune, Ingse

    1997-12-31

    This thesis studies atmospheric chemistry and tries in particular to fill gaps in the data base of atmospheric reactions. It studies the nitrate radical reactions with chloroethenes and with but-2-yne (2-butyne). The mechanisms and rate coefficients for the NO{sub 3}-initiated degradation of the chloroethenes and 2-butyne were investigated by means of the static reaction chamber and the fast flow-discharge technique. The reactions between the nitrate radical and the chloroethenes were studied at atmospheric pressure in a reaction chamber with synthetic air as bath gas. FTIR (Fourier Transform InfraRed spectroscopy) spectroscopy was used to follow the reactions and to identify the products. Products were observed for the reactions with (E)-1,2-dichloroethene and tetrachloroethene, although the absorption bands are weak. The alkyl peroxynitrate and nitrate compounds form very strong and characteristic absorption bands. The rate coefficients for the reactions between NO{sub 3} and the chloroethenes were investigated at room temperature by three different methods. The results are given in tables. 132 refs., 44 figs., 21 tabs.

  10. Sigmatropic proton shifts: a quantum chemical study.

    Science.gov (United States)

    Wang, Yi; Yu, Zhi-Xiang

    2017-09-13

    A quantum chemical study of [1,j] sigmatropic proton shifts in polyenyl anions and related conjugated systems has been performed. We found that the Woodward-Hoffmann rules can be applied to understand the stereochemical outcome of these sigmatropic rearrangements, showing that [1,j] sigmatropic proton shift occurs antarafacially when j = 4n + 2, while suprafacial proton shift is symmetry-allowed when j = 4n. The activation barriers for [1,j] proton shifts in polyenyl anions C j H j+3 - are 48.2 (j = 2), 32.8 (j = 4), 21.0 (j = 6), 40.5 (j = 8), and 49.1 (j = 10) kcal mol -1 , respectively. This trend can be explained by the trade-off between stereoelectronic requirement and ring strain in the proton shift transition structure. Among these reactions, only the [1,6] proton shift with the lowest activation barrier can occur intramolecularly under mild reaction conditions. The others are unlikely to take place in a direct manner. Consequently, proton shuttles are generally required to facilitate these sigmatropic proton shifts through a protonation/deprotonation mechanism.

  11. Influence of Nitrate on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

    International Nuclear Information System (INIS)

    Szecsody, Jim E.; Phillips, Jerry L.; Vermeul, Vince R.; Fruchter, Jonathan S.; Williams, Mark D.

    2005-01-01

    The purpose of this laboratory study is to determine the influence of nitrate on the Hanford 100D Area in situ redox manipulation (ISRM) barrier longevity. There is a wide spread groundwater plume of 60 mg/L nitrate upgradient of the ISRM barrier with lower nitrate concentrations downgradient, suggestive of nitrate reduction occurring. Batch and 1-D column experiments showed that nitrate is being slowly reduced to nitrite and ammonia. These nitrate reduction reactions are predominantly abiotic, as experiments with and without bactericides present showed no difference in nitrate degradation rates. Nitrogen species transformation rates determined in experiments covered a range of ferrous iron/nitrate ratios such that the data can be used to predict rates in field scale conditions. Field scale reaction rate estimates for 100% reduced sediment (16 C) are: (a) nitrate degradation = 202 ± 50 h (half-life), (b) nitrite production = 850 ± 300 h, and (c) ammonia production = 650 ± 300 h. Calculation of the influence of nitrate reduction on the 100D Area reductive capacity requires consideration of mass balance and reaction rate effects. While dissolved oxygen and chromate reduction rates are rapid and essentially at equilibrium in the aquifer, nitrate transformation reactions are slow (100s of hours). In the limited (20-40 day) residence time in the ISRM barrier, only a portion of the nitrate will be reduced, whereas dissolved oxygen and chromate are reduced to completion. Assuming a groundwater flow rate of 1 ft/day, it is estimated that the ISRM barrier reductive capacity is 160 pore volumes (with no nitrate), and 85 pore volumes if 60 mg/L nitrate is present (i.e., a 47% decrease in the ISRM barrier longevity). Zones with more rapid groundwater flow will be less influenced by nitrate reduction. For example, a zone with a groundwater flow rate of 3 ft/day and 60 mg/L nitrate will have a reductive capacity of 130 pore volumes. Finally, long-term column experiments

  12. Structure of the bacterial deacetylase LpxC bound to the nucleotide reaction product reveals mechanisms of oxyanion stabilization and proton transfer.

    Science.gov (United States)

    Clayton, Gina M; Klein, Daniel J; Rickert, Keith W; Patel, Sangita B; Kornienko, Maria; Zugay-Murphy, Joan; Reid, John C; Tummala, Srivanya; Sharma, Sujata; Singh, Sheo B; Miesel, Lynn; Lumb, Kevin J; Soisson, Stephen M

    2013-11-22

    The emergence of antibiotic-resistant strains of pathogenic bacteria is an increasing threat to global health that underscores an urgent need for an expanded antibacterial armamentarium. Gram-negative bacteria, such as Escherichia coli, have become increasingly important clinical pathogens with limited treatment options. This is due in part to their lipopolysaccharide (LPS) outer membrane components, which dually serve as endotoxins while also protecting Gram-negative bacteria from antibiotic entry. The LpxC enzyme catalyzes the committed step of LPS biosynthesis, making LpxC a promising target for new antibacterials. Here, we present the first structure of an LpxC enzyme in complex with the deacetylation reaction product, UDP-(3-O-(R-3-hydroxymyristoyl))-glucosamine. These studies provide valuable insight into recognition of substrates and products by LpxC and a platform for structure-guided drug discovery of broad spectrum Gram-negative antibiotics.

  13. dl-Asparaginium nitrate

    Directory of Open Access Journals (Sweden)

    Nabila Moussa Slimane

    2009-09-01

    Full Text Available In the title compound, C4H9N2O3+·NO3−, alternatively called (1RS-2-carbamoyl-1-carboxyethanaminium nitrate, the asymmetric unit comprises one asparaginium cation and one nitrate anion. The strongest cation–cation O—H...O hydrogen bond in the structure, together with other strong cation–cation N—H...O hydrogen bonds, generates a succession of infinite chains of R22(8 rings along the b axis. Additional cation–cation C—H...O hydrogen bonds link these chains into two-dimensional layers formed by alternating R44(24 and R42(12 rings. Connections between these layers are provided by the strong cation–anion N—H...O hydrogen bonds, as well as by one weak C—H...O interaction, thus forming a three-dimensional network. Some of the cation–anion N—H...O hydrogen bonds are bifurcated of the type D—H...(A1,A2.

  14. Particle multiplicity in proton-proton collisions with ALICE

    CERN Document Server

    Monteno, Marco

    2005-01-01

    Proton-proton collisions at the LHC will be studied with the ALICE detector, not only as a benchmark for the comparison with heavy-ion reactions, but also as a mean to study important aspects of pp physics in the new energy domain probed by the LHC. A report will be given here on the potentialities of ALICE in the study of the global properties of pp events, and especially of their multiplicity. This will be one of the main issues in pp physics where, because of the special features of its design, ALICE will be competitive with the other LHC experiments.

  15. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

    Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

  16. The purified ATPase from chromaffin granule membranes is an anion-dependent proton pump.

    Science.gov (United States)

    Moriyama, Y; Nelson, N

    1987-07-05

    The proton-ATPase of chromaffin granules was purified so as to maintain its proton-pumping activity when reconstituted into phospholipid vesicles. The purification procedure involved solubilization with polyoxyethylene 9 lauryl ether, hydroxylapatite column, precipitation by ammonium sulfate, and glycerol gradient centrifugation. The protease inhibitor mixture used in previous studies inhibited the proton-pumping activity of the enzyme; therefore, the protein was stabilized by pepstatin A and leupeptin. The enzyme was purified at least 50-fold with respect to both ATPase and proton-pumping activity. The ATP-dependent proton uptake activity of the reconstituted enzyme was absolutely dependent on the presence of Cl- or Br- outside the vesicles, whereas sulfate, acetate, formate, nitrate, and thiocyanate were inhibitory. Sulfate inhibition seems to be due to competition with Cl- on the anion-binding site outside the vesicles, whereas nitrate and thiocyanate inhibited only from the internal side. As with the inhibition by N-ethylmaleimide, the proton-pumping activity was much more sensitive to nitrate than the ATPase activity. About 20 mM nitrate were sufficient for 90% inhibition of the proton-pumping activity while 100 mM inhibited only 50% of the ATPase activity both in situ and in the reconstituted enzyme. The possible regulatory effect of anions on the ATP-dependent proton uptake in secretory granules is discussed.

  17. Nitrate storage and dissimilatory nitrate reduction by eukaryotic microbes

    DEFF Research Database (Denmark)

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly...... and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate...... storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described...

  18. Neutrinos from the primary proton-proton fusion process in the Sun.

    Science.gov (United States)

    2014-08-28

    In the core of the Sun, energy is released through sequences of nuclear reactions that convert hydrogen into helium. The primary reaction is thought to be the fusion of two protons with the emission of a low-energy neutrino. These so-called pp neutrinos constitute nearly the entirety of the solar neutrino flux, vastly outnumbering those emitted in the reactions that follow. Although solar neutrinos from secondary processes have been observed, proving the nuclear origin of the Sun's energy and contributing to the discovery of neutrino oscillations, those from proton-proton fusion have hitherto eluded direct detection. Here we report spectral observations of pp neutrinos, demonstrating that about 99 per cent of the power of the Sun, 3.84 × 10(33) ergs per second, is generated by the proton-proton fusion process.

  19. Extraction of NOx and Determination of Nitrate by Acid Reduction in ...

    African Journals Online (AJOL)

    Nitrite is determined by Griess reaction, and removed from samples by urea treatment to obviate any interference by nitrite in nitrate determination. Nitrate is determined by acid reduction method with minimum detection limit 0.5 ppm as N. The methods have been applied to selected environmental samples including food ...

  20. Nitrate and drinking water from private wells: Will there be an ...

    African Journals Online (AJOL)

    Conclusion: High nitrate levels drinking water is dangerous to health and can cause methemoglobinemia in children. It may also increase cancer risk in adults because nitrate is endogenously reduced to nitrite and subsequent nitrosation reactions give rise to N‑nitroso compounds (NOCs), which are highly carcinogenic ...

  1. Formation of genotoxic compounds by medium pressure ultra violet treatment of nitrate rich water

    NARCIS (Netherlands)

    Martijn, A.J.; Boersma, M.G.; Vervoort, Jacques; Rietjens, I.; Kruithof, J.C.

    2014-01-01

    Genotoxic compounds were produced by full-scale medium pressure (MP) ultraviolet hydrogen peroxide (UV/H2O2) treatment of nitrate-rich pretreated surface water. It was hypothesized that this formation was caused by the reaction of nitrate photolysis intermediates with natural organic matter (NOM).

  2. Nitration of Phenols Using Cu(NO[subscript 3])[subscript 2]: Green Chemistry Laboratory Experiment

    Science.gov (United States)

    Yadav, Urvashi; Mande, Hemant; Ghalsasi, Prasanna

    2012-01-01

    An easy-to-complete, microwave-assisted, green chemistry, electrophilic nitration method for phenol using Cu(NO[subscript 3])[subscript 2] in acetic acid is discussed. With this experiment, students clearly understand the mechanism underlying the nitration reaction in one laboratory session. (Contains 4 schemes.)

  3. Homolytic iodination and nitration of some benzene derivatives in the gas phase

    International Nuclear Information System (INIS)

    Vonk, W.F.M.

    1980-01-01

    Two gas phase reactions, involving the iodination and nitration of benzene derivatives, are described. The experimental techniques of the apparatus and the methods used are outlined. The kinetic H/D isotope effect in the gas phase nitration of benzene with NO 2 is determined. (C.F.)

  4. Palladium-Catalyzed Synthesis of Δ(2)-Isoxazoline from Toluene Derivatives Enabled by the Triple Role of Silver Nitrate.

    Science.gov (United States)

    Li, Chengliang; Deng, Hongmei; Li, Chunju; Jia, Xueshun; Li, Jian

    2015-11-20

    A palladium-catalyzed direct synthesis of Δ(2)-isoxazoline from toluene derivatives has been established. The present reaction proceeds through nondirected Csp(3)-H activation, benzylic nitration, dehydration, and cycloaddition. This protocol also features the unusual triple role of silver nitrate in a one-pot reaction.

  5. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Science.gov (United States)

    2010-07-01

    ..., combustible liquids, corrosive liquids, chlorates, permanganates, finely divided metals, caustic soda... molten ammonium nitrate if a fire occurred (and thus become potential detonators for the storage piles...

  6. Molecular mechanisms for generating transmembrane proton gradients

    Science.gov (United States)

    Gunner, M.R.; Amin, Muhamed; Zhu, Xuyu; Lu, Jianxun

    2013-01-01

    Membrane proteins use the energy of light or high energy substrates to build a transmembrane proton gradient through a series of reactions leading to proton release into the lower pH compartment (P-side) and proton uptake from the higher pH compartment (N-side). This review considers how the proton affinity of the substrates, cofactors and amino acids are modified in four proteins to drive proton transfers. Bacterial reaction centers (RCs) and photosystem II (PSII) carry out redox chemistry with the species to be oxidized on the P-side while reduction occurs on the N-side of the membrane. Terminal redox cofactors are used which have pKas that are strongly dependent on their redox state, so that protons are lost on oxidation and gained on reduction. Bacteriorhodopsin is a true proton pump. Light activation triggers trans to cis isomerization of a bound retinal. Strong electrostatic interactions within clusters of amino acids are modified by the conformational changes initiated by retinal motion leading to changes in proton affinity, driving transmembrane proton transfer. Cytochrome c oxidase (CcO) catalyzes the reduction of O2 to water. The protons needed for chemistry are bound from the N-side. The reduction chemistry also drives proton pumping from N- to P-side. Overall, in CcO the uptake of 4 electrons to reduce O2 transports 8 charges across the membrane, with each reduction fully coupled to removal of two protons from the N-side, the delivery of one for chemistry and transport of the other to the P-side. PMID:23507617

  7. Evaluation of ferrocyanide/nitrate explosive hazard

    International Nuclear Information System (INIS)

    Cady, H.H.

    1992-06-01

    Los Alamos National Laboratory agreed to assist Pacific Northwest Laboratory in the Ferrocyanide Safety Evaluation Program by helping to evaluate the explosive hazard of several mixtures of simulated ferrocyanide waste-tank sludge containing sodium nitrite and sodium nitrate. This report is an evaluation of the small-scale safety tests used to assess the safety of these materials from an explosive point of view. These tests show that these materials are not initiated by mechanical insult, and they require an external heat source before any exothermic chemical reaction can be observed

  8. Activated carbon from orange peels as supercapacitor electrode and catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell

    Directory of Open Access Journals (Sweden)

    M. Dhelipan

    2017-05-01

    Full Text Available Activated carbon is synthesized using orange peel as precursor through chemical activation using H3PO4 and its ability as electrocatalyst support for ORR reaction is examined. The prepared material was subjected to various structural, compositional, morphological and electrochemical studies. For ORR activity, the platinum loaded on activated carbon (Pt/OP-AC was investigated by cyclic voltammograms (CVs recorded in N2 and O2 saturated 0.1 M aqueous HClO4. For supercapacitor performance, three electrode systems was tested in aqueous H2SO4 for feasibility determination and showed electrochemical double layer capacitance (EDLC behaviour which is expected for activated carbon like materials. Electrochemical surface area (ECSA of the activated carbon from orange peel is measured using CV. The physical properties of the prepared carbon are studied using SEM (scanning electron microscope, XRD (X-ray diffraction, Fourier transform infrared (FT-IR spectroscopy and Raman spectroscopy. The AC derived from orange peels delivered a high specific capacitance of 275 F g−1 at 10 mV s-1 scan rate. Hence, this study suggested that orange peels may be considered not only as a potential alternative source for synthesizing carbon supported catalyst for fuel cell application but also highlight the production of low-cost carbon for further applications like supercapacitors.

  9. Decomposition of metal nitrate solutions

    International Nuclear Information System (INIS)

    Haas, P.A.; Stines, W.B.

    1982-01-01

    Oxides in powder form are obtained from aqueous solutions of one or more heavy metal nitrates (e.g. U, Pu, Th, Ce) by thermal decomposition at 300 to 800 deg C in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal. (author)

  10. Evaluation of nitrate destruction methods

    International Nuclear Information System (INIS)

    Taylor, P.A.; Kurath, D.E.; Guenther, R.

    1993-01-01

    A wide variety of high nitrate-concentration aqueous mixed [radioactive and Resource Conservation and Recovery Act (RCRA) hazardous] wastes are stored at various US Department of Energy (DOE) facilities. These wastes will ultimately be solidified for final disposal, although the waste acceptance criteria for the final waste form is still being determined. Because the nitrates in the wastes will normally increase the volume or reduce the integrity of all of the waste forms under consideration for final disposal, nitrate destruction before solidification of the waste will generally be beneficial. This report describes and evaluates various technologies that could be used to destroy the nitrates in the stored wastes. This work was funded by the Department of Energy's Office of Technology Development, through the Chemical/Physical Technology Support Group of the Mixed Waste Integrated Program. All the nitrate destruction technologies will require further development work before a facility could be designed and built to treat the majority of the stored wastes. Several of the technologies have particularly attractive features: the nitrate to ammonia and ceramic (NAC) process produces an insoluble waste form with a significant volume reduction, electrochemical reduction destroys nitrates without any chemical addition, and the hydrothermal process can simultaneously treat nitrates and organics in both acidic and alkaline wastes. These three technologies have been tested using lab-scale equipment and surrogate solutions. At their current state of development, it is not possible to predict which process will be the most beneficial for a particular waste stream

  11. Optimum conditions for cotton nitrate reductase extraction and ...

    African Journals Online (AJOL)

    Conditions of nitrate reductase extraction and activity measurement should be adapted to plant species, and to the organs of the same plant, because of extreme weaknesses and instabilities of the enzyme. Different extraction and reaction media have been compared in order to define the best conditions for cotton callus ...

  12. Toluene nitration in irradiated nitric acid and nitrite solutions

    Energy Technology Data Exchange (ETDEWEB)

    Elias, Gracy, E-mail: gracy.elias@inl.go [Idaho National Laboratory, Chemical and Radiation Measurement Department, P.O. Box 1625, Idaho Falls, ID 83415-2213 (United States); Mincher, Bruce J. [Idaho National Laboratory, Aqueous Separations and Radiochemistry Department, P.O. Box 1625, Idaho Falls, ID 83415-6180 (United States); Mezyk, Stephen P. [California State University-Long Beach, Department of Chemistry and Biochemistry, 1250 Bellflower Boulevard, Long Beach, CA 90840-3903 (United States); Muller, Jim [University of Utah, Department of Chemistry, Salt Lake City, UT 84112-0850 (United States); Martin, Leigh R. [Idaho National Laboratory, Aqueous Separations and Radiochemistry Department, P.O. Box 1625, Idaho Falls, ID 83415-6180 (United States)

    2011-04-15

    The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using {gamma} and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO{sub 3}, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the {sup {center_dot}N}O{sub 2} radical.

  13. Toluene nitration in irradiated nitric acid and nitrite solutions

    Science.gov (United States)

    Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

    2011-04-01

    The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.

  14. Toluene nitration in irradiated nitric acid and nitrite solutions

    International Nuclear Information System (INIS)

    Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

    2011-01-01

    The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO 3 , ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the · NO 2 radical.

  15. Ceric ammonium nitrate catalysed three component one-pot efficient ...

    Indian Academy of Sciences (India)

    Wintec

    Abstract. Ceric ammonium nitrate (CAN) is used as an efficient catalyst for the synthesis of 2,4,5- triaryl-1H-imidazoles via condensation of benzoin/benzil, ammonium acetate, and aromatic aldehydes. The easy work-up, higher yields and shorter reaction time are the advantages of the method presented here. Keywords.

  16. Incorporation of fluorophosphate into zinc–aluminium–nitrate ...

    Indian Academy of Sciences (India)

    The intercalation of fluorophosphate (PO3F2-, FP) in the [Zn–Al] layered double hydroxides (LDHs) was investigated. A nitrate precursor was prepared by coprecipitaion at pH 9. An attempt to intercalate FP by direct coprecipitation reaction led to a poorly crystalline LDH phase. The effects of pH, aging time and anion ...

  17. Ceric ammonium nitrate catalysed three component one-pot efficient ...

    Indian Academy of Sciences (India)

    Ceric ammonium nitrate (CAN) is used as an efficient catalyst for the synthesis of 2,4,5-triaryl-1H-imidazoles via condensation of benzoin/benzil, ammonium acetate, and aromatic aldehydes. The easy work-up, higher yields and shorter reaction time are the advantages of the method presented here.

  18. Nitrate to ammonia and ceramic (NAC) process during batch and continuous operation

    International Nuclear Information System (INIS)

    Muguercia, I.; Solomon, S.; Ebadian, M.A.

    1996-01-01

    The nitrate to ammonia and ceramic (NAC) process is an innovative technology for the denitration of radioactive sodium nitrate-based liquid waste found throughout Department of Energy (DOE) facilities in the United States. In the present investigation, two reaction systems were studied. The first utilized only sodium nitrate as the substrate for the aluminum. The second consisted of the multication composition of waste forms located at the Hanford facility. Studies were carried out on the batch reaction at three different starting nitrate ion concentrations, each at three different temperatures. For each of these conditions, the rate of nitrate depletion was determined, and rate constants were calculated. The reaction did not demonstrate simple kinetics; rather, it appeared to involve two zero order reactions. Certain generalities were obtained in both the batch reaction and in the continuous process, nonetheless. It was found that the conversion of nitrate to ammonia seemed to be most efficient at the lowest temperature studied, 50 degrees C. This behavior was more obvious in the case of the unadulterated nitrate solution than with the Hanford simulant. To elaborate a practical, marketable product, it was necessary to develop a process that could be carried out in a continuous matter, whereby reactants were continuously fed into a reactor while the products of the reaction were simultaneously removed. Thus, the objective has been to develop the prototype procedures for carrying out this continuous reaction. As a corollary of this research, it was first necessary to define the characteristics of the reaction with respect to rate, conversion efficiency, and safety. To achieve this end, reactions were run under various batch conditions, and an attempt was made to measure the rates of the depletion of nitrate and the production of ammonia and hydrogen as well as pH and temperature changes

  19. Laboratory investigation of microbiologically influenced corrosion of C1018 carbon steel by nitrate reducing bacterium Bacillus licheniformis

    International Nuclear Information System (INIS)

    Xu, Dake; Li, Yingchao; Song, Fengmei; Gu, Tingyue

    2013-01-01

    Nitrate injection is used to suppress reservoir souring in oil and gas fields caused by Sulfate Reducing Bacteria (SRB) through promotion of nitrate respiration by Nitrate Reducing Bacteria (NRB). However, it is not well publicized that nitrate reduction by NRB can cause Microbiologically Influenced Corrosion (MIC) because nitrate reduction coupled with iron oxidation is thermodynamically favorable. NRB benefits bioenergetically from this redox reaction under biocatalysis. This work showed that the Bacillus licheniformis biofilm, when grown as an NRB biofilm, caused a 14.5 μm maximum pit depth and 0.89 mg/cm 2 normalized weight loss against C1018 carbon steel in one-week lab tests

  20. A new method to produce nanoscale iron for nitrate removal

    International Nuclear Information System (INIS)

    Chen, S.-S.; Hsu, H.-D.; Li, C.-W.

    2004-01-01

    This article proposes a novel technology combining electrochemical and ultrasonic methods to produce nanoscale zero valent iron (NZVI). With platinum placed in the cathode and the presence of the dispersion agent, 0.2g/l cetylpyridinium chloride (CPC), a cation surfactant, in the solution, the nanoscale iron particle was successfully produced with diameter of 1-20 nm and specific surface area of 25.4m 2 /g. The produced NZVI was tested in batch experiments for nitrate removal. The results showed that the nitrate reduction was affected by pH. Al low pH, nitrate was shown faster decline and more reduction in term of g NO 3 - -N/g NZVI. The reaction was first order and kinetic coefficients for the four pHs were directly related to pH with R 2 >0.95. Comparing with microscale zero-valent iron (45μm, 0.183m 2 /g), microscale zero-valent iron converted nitrate to ammonia completely, but NZVI converted nitrate to ammonia partially from 36.2 to 45.3% dependent on pH. For mass balance of iron species, since the dissolved iron in the solution was very low ( 2 O 3 was recognized. Thus the reaction mechanisms can be determined

  1. Proton transport in a membrane protein channel: two-dimensional infrared spectrum modeling.

    NARCIS (Netherlands)

    Liang, C.; Knoester, J.; Jansen, T.L.Th.A.

    2012-01-01

    We model the two-dimensional infrared (2DIR) spectrum of a proton channel to investigate its applicability as a spectroscopy tool to study the proton transport process in biological systems. Proton transport processes in proton channels are involved in numerous fundamental biochemical reactions.

  2. The effects of essential oil, povidone-iodine, and chlorhexidine mouthwash on salivary nitrate/nitrite and nitrate-reducing bacteria.

    Science.gov (United States)

    Mitsui, Takahiro; Harasawa, Ryô

    2017-12-27

    Dietary nitrate is reduced to nitrite and nitric oxide by microbial flora, and this activity is beneficial to vascular health. It has been reported that this bacterial process is inhibited by chlorhexidine mouthwash, although the effects of other products are largely unknown. This study examined the effects of several treatments on salivary nitrate/nitrite and nitrate-reducing bacteria. Twelve university staff and students performed mouth-washing with water (control), essential oil, 0.35% povidone-iodine, or 0.0025% chlorhexidine and then ate 100 g lettuce (110 mg nitrate content), followed by collection of saliva and tongue bacteria at the baseline, and 1, 5, and 10 h thereafter. The individual treatments were separated by an interval of one week. Salivary nitrate/nitrite was measured by the calorimetric method, and a representative nitrate-reducing bacterial species, Veillonella dispar, was detected and semi-quantified using a polymerase chain reaction (PCR) assay. Significant increases in salivary nitrate/nitrite were observed for all treatments (all P mouthwash had little effect, whereas V. dispar DNA bands were markedly inhibited after washing with chlorhexidine. These results suggest that essential oil and povidone-iodine mouthwash have little effect on oral nitrate-reducing activity. Salivary nitrite production was not reduced by chlorhexidine, but the fainter band of V. dispar DNA suggests that longer daily use might blunt this nitrate-reducing activity.

  3. Studying solubility of praseodymium(3) nitrate with nitrates of aniline, guanidine in aqueous solution

    International Nuclear Information System (INIS)

    Kuznetsova, L.S.; Zhuravlev, E.F.

    1977-01-01

    The solubility in the systems praseodymium nitrate-aniline nitrate-water(1) and praseodymium nitrate-guanidine nitrate-water(2) has been studied at 20 and 40 deg C. In the given temperature range the state diagrams of the systems correspond to the isotherms of the simple eutonic type. Aniline nitrate and hexahydrate of praseodymium nitrate in the first system and guanidine nitrate and hexahydrate of praseodymium nitrate in the second system are equilibrium solid phases. The most developed crystallization fields are those of amine nitrates; eutonics are enriched with praseodymium nitrate

  4. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  5. Proton imaging apparatus for proton therapy application

    International Nuclear Information System (INIS)

    Sipala, V.; Lo Presti, D.; Brianzi, M.; Civinini, C.; Bruzzi, M.; Scaringella, M.; Talamonti, C.; Bucciolini, M.; Cirrone, G.A.P.; Cuttone, G.; Randazzo, N.; Stancampiano, C.; Tesi, M.

    2011-01-01

    Radiotherapy with protons, due to the physical properties of these particles, offers several advantages for cancer therapy as compared to the traditional radiotherapy and photons. In the clinical use of proton beams, a p CT (Proton Computer Tomography) apparatus can contribute to improve the accuracy of the patient positioning and dose distribution calculation. In this paper a p CT apparatus built by the Prima (Proton Imaging) Italian Collaboration will be presented and the preliminary results will be discussed.

  6. Proton radioactivity from proton-rich nuclei

    International Nuclear Information System (INIS)

    Guzman, F.; Goncalves, M.; Tavares, O.A.P.; Duarte, S.B.; Garcia, F.; Rodriguez, O.

    1999-03-01

    Half-lives for proton emission from proton-rich nuclei have been calculated by using the effective liquid drop model of heavy-particle decay of nuclei. It is shown that this model is able to offer results or spontaneous proton-emission half-life-values in excellent agreement with the existing experimental data. Predictions of half-life-values for other possible proton-emission cases are present for null orbital angular momentum. (author)

  7. Nitrate, NO and haemoglobin in plant adaptation to hypoxia: an alternative to classic fermentation pathways.

    Science.gov (United States)

    Igamberdiev, Abir U; Hill, Robert D

    2004-12-01

    The role of nitrate reduction to produce nitric oxide (NO) and its subsequent oxidation by oxyhaemoglobin as a mechanism to maintain plant cell energetics during hypoxia is examined. Nitrate reduction in hypoxic conditions can be considered as an alternative respiratory pathway, with nitrate as an intermediate electron acceptor, contributing to the oxidation of NADH. NO, produced in the reaction, does not accumulate due to the induction of hypoxia-induced (class 1) haemoglobins. These haemoglobins remain in the oxyhaemoglobin form, even at oxygen tensions two orders of magnitude lower than necessary to saturate cytochrome c oxidase. They act, probably in conjunction with a flavoprotein, as NO dioxygenases converting NO back to nitrate, consuming NAD(P)H in the process. The overall system oxidizes 2.5 moles of NADH per one mole of nitrate recycled during the reaction, leading to the maintenance of redox and energy status during hypoxia and resulting in the reduced production of ethanol and lactic acid.

  8. Transformation of Nitrate and Toluene in Groundwater by Sulfur Modified Iron(SMI-III)

    Science.gov (United States)

    Lee, W.; Park, S.; Lim, J.; Hong, U.; Kwon, S.; Kim, Y.

    2009-12-01

    In Korea, nitrate and benzene, toluene, ethylbenzene, and xylene isomers (BTEX) are frequently detected together as ground water contaminants. Therefore, a system simultaneously treating both nitrate (inorganic compound) and BTEX (organic compounds) is required to utilize groundwater as a water resource. In this study, we investigated the efficiency of Sulfur Modified Iron (SMI-III) in treating both nitrate and BTEX contaminated groundwater. Based on XRD (X-Ray Diffraction) analysis, the SMI-III is mainly composed of Fe3O4, S, and Fe. A series of column tests were conducted at three different empty bed contact times (EBCTs) for each compound. During the experiments, removal efficiency for both nitrate and toluene were linearly correlated with EBCT, suggesting that SMI-III have an ability to transform both nitrate and toluene. The concentration of SO42- and oxidation/reduction potential (ORP) were also measured. After exposed to nitrate contaminated groundwater, the composition of SMI-III was changed to Fe2O3, Fe3O4, Fe, and Fe0.95S1.05. The trends of effluent sulfate concentrations were inversely correlated with effluent nitrate concentrations, while the trends of ORP values, having the minimum values of -480 mV, were highly correlated with effluent nitrate concentrations. XRD analysis before and after exposed to nitrate contaminated groundwater, sulfate production, and nitrite detection as a reductive transformation by-product of nitrate suggest that nitrate is reductively transformed by SMI-III. Interestingly, in the toluene experiments, the trends of ORP values were inversely correlated with effluent toluene concentrations, suggesting that probably degrade through oxidation reaction. Consequently, nitrate and toluene probably degrade through reduction and oxidation reaction, respectively and SMI-III could serve as both electron donor and acceptor.

  9. In Situ Calibration for Proton Particle Telescope

    Science.gov (United States)

    Stillman, Collin; Padalino, Stephen; Polsin, Danae; Russ, Megan; Krieger, Michael; Bienstock, Mollie; Ellison, Drew; Simone, Angela; Yuly, Mark; Mann, Keith; Reynolds, Tyler; Sangster, Craig

    2012-10-01

    Neutrons produced via the 3H(2H,n)4He reaction at the Ohio University Accelerator Lab were used to activate a graphite sample via the ^12C(n,2n)^11C reaction in an attempt to measure the (n,2n) reaction cross section. Before striking the graphite, the neutrons struck a thin polyethylene foil and elastically scattered protons in to a surface barrier detector telescope. The recoiling protons were used to determine the energy and number of neutrons which struck the ^12C activation sample. To verify that the particle telescope's predicted response function for 15 to 27 MeV protons was correct a calibration of the detector telescope was performed in air on the SUNY Geneseo tandem Pelletron accelerator. High energy protons were created via the ^2H(^3He, p)^4He reaction by bombarding a deuterated polyethylene target with 4.5 MeV ^3He ions. The high-energy protons then pass through a Kapton window from vacuum into air where they were detected by the particle telescope. The dependence of the detector response on various proton energies was then investigated for various detector geometries. This data was extremely useful when performing the graphite activation experiment at the Ohio University accelerator lab. Funded in part by a grant from the DOE through the Laboratory for Laser Energetics.

  10. Variability of nitrate and phosphate

    Digital Repository Service at National Institute of Oceanography (India)

    Sardessai, S.; Sundar, D.

    and the high-nitrate waters farther upstream led to a sharp increase in nitrates in the first few kilometres from the mouth of the Mandovi. Thus, at the end of the summer monsoon, the channels of the Mandovi and Zuari have nitrate concentrations of the order... in June. Throughout this period, the properties of the waters at the mouth migrate upstream owing to horizontal mixing. One consequence of this mixing is a steady rise in salinity in the channels of the Mandovi and Zuari. Since the concentration June 13...

  11. Scandium extraction by methyltrialkylammonium nitrate from nitrate solutions

    International Nuclear Information System (INIS)

    Stepanov, S.I.; Kiyatkina, N.G.; Fedotov, O.N.

    1987-01-01

    Chemistry of scandium extraction by methyltrialkylammonium (MTAA) nitrate in toluene from nitrate solutions is studied. Methods of saturation, equilibrium shift, physicochemical analysis, isomolar series and UV-spectroscopy are used to determine the composition of extracted complexes. It is shown that with low saturation degrees of extractant (R 4 N) 6 Sc(NO 3 ) 9 complex is formed in organic phase and with saturation - (R 4 N) 3 xSc(NO 3 ) 6 complex

  12. Rare earth(3) nitrates extraction with trialkylmethylammonium nitrate in toluene

    International Nuclear Information System (INIS)

    Pyartman, A.K.; Kovalev, S.V.; Keskinov, V.A.; Khokhlova, N.V.

    1997-01-01

    Extraction of rare earth(3) nitrates [praseodymium(3)-lutetium(3)] with trialkylmethylammonium nitrate in toluene at T = 298.15 K and pH 2 is studied. Extraction isotherms are described with regard to formation of compounds of (R 4 N) i [Ln(NO 3 ) 3+i ] composition (i = 2, 3) in organic phase. Values of extraction constants are calculated, they are decreasing in the praseodymium(3) - lutetium(3) series

  13. A new route to copper nitrate hydroxide microcrystals

    International Nuclear Information System (INIS)

    Niu Haixia; Yang Qing; Tang Kaibin

    2006-01-01

    A solution evaporation route has been successfully developed for the growth of copper nitrate hydroxide microcrystals using copper nitrate solution as the starting material in the absence of any surfactants or templates. The products were characterized by X-ray diffraction (XRD), infrared (IR) spectrum, scanning electron microscopy (SEM) and thermogravimetric (TG) analysis measurements. Controlled experiments suggested that the reaction temperature and solution concentration played an important role on the formation of the products. A possible formation mechanism of the products was also proposed

  14. Measurement of the space- and angle-dependent spectra of fast neutrons and secondary charged particles from spallation-reactions of 590 MeV protons in thick uranium targets

    International Nuclear Information System (INIS)

    Raupp, F.

    1983-04-01

    At SIN time-of-flight measurements have been performed to determine the yields of neutrons and charged particles emitted from a 10 cm x 10 cm x 40 cm long uranium target bombared with 590 MeV protons from the SIN cyclotron. Measurements were made at angles of 30 0 , 90 0 and 150 0 relative to the incident proton beams for different penetration depths of protons into the target. The detector was a NE213 liquid scintillator. Beside the measurement of the yields of leakage neutrons the used time-of-flight method permitted also to determine the yields of emitted charged particles. Differential spectra of secondary protons, deuterons and pions have also been measured and analysed at 6 penetration depths of the proton beam into the target and at 3 angles (30 0 , 90 0 and 150 0 ). (orig.) [de

  15. Measurements of gas and volatile element production rates from an irradiated molten lead and lead-bismuth spallation target with proton beams of 1 and 1.4 GeV; Mesures de taux de production d'elements gazeux et volatiles lors de reactions induites par des protons de 1 et 1,4 GeV sur des cibles epaisses de plomb et plomb-bismuth liquides

    Energy Technology Data Exchange (ETDEWEB)

    Tall, Y

    2008-03-15

    The integrated project EUROTRANS (European Research Programme for the Transmutation of High Level Nuclear Waste in an Accelerator Driven System) of the 6. EURATOM Framework Programme aims to demonstrate the transmutation of radioactive waste in ADS (Accelerator Driven Sub-critical system). It will carry out a first advanced design of an experimental facility to demonstrate the technical feasibility of transmutation, and will produce a conceptual design of an industrial facility dedicated to transmutation. An ADS consists of three fundamental elements: the accelerator of protons, the sub-critical core and the spallation target. SUBATECH (physique Sub-Atomique et des Technologies associees) laboratory is involved to the study of the chosen liquid lead-bismuth as a spallation ADS target. The irradiation of liquid lead-bismuth target with energetic proton beam generates in addition to neutrons, volatile and radioactive residues. In order to determine experimentally the production rates of gas and volatile elements following a spallation reaction in a lead-bismuth target, the experiment IS419 was performed at the ISOLDE facility at CERN (Centre Europeen de la Recherche Nucleaire). This experiment constitutes the frame of the thesis whose main objective is to assess and study the production and release rates of many gas and volatile element from the irradiated lead-bismuth target with an energetic proton beam. The obtained data are compared to Monte Carlo simulation code (MCNPX) results in order to test the intranuclear cascade model of Bertini and of Cugnon, and the evaporation options of Dresner and Schmidt. (author)

  16. A model for proton-induced SEU

    International Nuclear Information System (INIS)

    Bion, T.; Bourrieau, J.

    1989-01-01

    This paper presents a method for predicting proton-induced single event effect (SEE) rates in devices exposed to given proton fluxes, within a particular spacecraft shielding. The approach uses heavy-ion cross section experimental data, combined with nuclear reaction calculations, in order to determine proton-induced SEE cross section versus proton energy relationship. Calculations for two devices, the Fairchild 932422 RAM and the Intel 2164A dRAM, for which heavy-ion test data was available, are presented and compared with the results of Bendel and with ground based experimental data. Available on-orbit SEE data are used and compared with the authors predictions. A comparison of predicted SEE rates for both protons and cosmic rays at various 60 degrees circular orbits is discussed. Good agreement is found in all cases

  17. Proton conducting ceramic membranes for hydrogen separation

    Science.gov (United States)

    Elangovan, S [South Jordan, UT; Nair, Balakrishnan G [Sandy, UT; Small, Troy [Midvale, UT; Heck, Brian [Salt Lake City, UT

    2011-09-06

    A multi-phase proton conducting material comprising a proton-conducting ceramic phase and a stabilizing ceramic phase. Under the presence of a partial pressure gradient of hydrogen across the membrane or under the influence of an electrical potential, a membrane fabricated with this material selectively transports hydrogen ions through the proton conducting phase, which results in ultrahigh purity hydrogen permeation through the membrane. The stabilizing ceramic phase may be substantially structurally and chemically identical to at least one product of a reaction between the proton conducting phase and at least one expected gas under operating conditions of a membrane fabricated using the material. In a barium cerate-based proton conducting membrane, one stabilizing phase is ceria.

  18. Nitrate augmented myocardial viability assessment

    International Nuclear Information System (INIS)

    Wadhwa, S.; Mansberb, R.; Fernandes, V.B.

    1997-01-01

    Full text: 24 hour 201 TI reinjection imaging improves myocardial viability detection when compared to standard 3-4 hour redistribution imaging, however, it is a time-consuming approach and some images do not provide adequate quality due to high background activity on the delayed scan. We tested whether sensitivity of redistribution and same day reinjection imaging could be improved by giving short-acting nitrates immediately prior to redistribution and reinjection imaging. Eighteen patients underwent a stress test (exercise or pharmacological) and 4 hour redistribution 201 TI SPECT study. Immediately after redistribution imaging, each patient was given 600 μg of sublingual glyceryl trinitrate and reimaged 15-20 minutes later (nitrate augmented image). Immediately following nitrate augmentation imaging, each patient was reinjected with 30 MBq of 201 TI and reimaged 20 minutes later (nitrate augmented reinjection images). Each patient returned 24 hours later and was reinjected with 40 MBq of 201 TI and imaged 20 minutes later (24 hour reinjection images). In all, each patient had five SPECT images as follows: stress/redistribution/ nitrate augmented redistribution/nitrate augmented same day reinjection/ 24 hour reinjection. The myocardium was divided into 11 segments and perfusion to each segment was scored by consensus method (2 blinded assessors) on a 4 point graded scale (0 = no perfusion, 1 = minimal perfusion, 2 = moderate perfusion, 3 = normal perfusion). Perfusion scores were analysed on a segment by segment basis; as well, each patient was given an overall perfusion score equal to the sum of the perfusion score for each segment. 150 segments with reduced perfusion were identified, of these 23 (15.3%) showed improvement in the redistribution images, 60 (40%) segments improved in the nitrate augmented images, 49 (32.7%) improved in the nitrate augmented reinjection images and 52 (34.7%) improved in the 24 hour reinjection images. To assess overall cardiac

  19. Proton movies

    CERN Multimedia

    2009-01-01

    A humorous short film made by three secondary school students received an award at a Geneva film festival. Even without millions of dollars or Hollywood stars at your disposal, it is still possible to make a good science fiction film about CERN. That is what three students from the Collège Madame de Staël in Carouge, near Geneva, demonstrated. For their amateur short film on the LHC, they were commended by the jury of the video and multimedia festival for schools organised by the "Media in education" service of the Canton of Geneva’s Public Education Department. The film is a spoof of a television news report on the LHC start-up. In sequences full of humour and imagination, the reporter conducts interviews with a very serious "Professor Sairne", some protons preparing for their voyage and even the neutrons that were rejected by the LHC. "We got the idea of making a film about CERN at the end of the summer," explains Lucinda Päsche, one of the three students. "We did o...

  20. Proton Transfer Reaction Time-of-Flight Mass Spectrometric (PTR-TOF-MS) determination of volatile organic compounds (VOCs) emitted from a biomass fire developed under stable nocturnal conditions

    Science.gov (United States)

    Brilli, Federico; Gioli, Beniamino; Ciccioli, Paolo; Zona, Donatella; Loreto, Francesco; Janssens, Ivan A.; Ceulemans, Reinhart

    2014-11-01

    Combustion of solid and liquid fuels is the largest source of potentially toxic volatile organic compounds (VOCs), which can strongly affect health and the physical and chemical properties of the atmosphere. Among combustion processes, biomass burning is one of the largest at global scale. We used a Proton Transfer Reaction “Time-of-Flight” Mass Spectrometer (PTR-TOF-MS), which couples high sensitivity with high mass resolution, for real-time detection of multiple VOCs emitted by burned hay and straw in a barn located near our measuring station. We detected 132 different organic ions directly attributable to VOCs emitted from the fire. Methanol, acetaldehyde, acetone, methyl vinyl ether (MVE), acetic acid and glycolaldehyde dominated the VOC mixture composition. The time-course of the 25 most abundant VOCs, representing ∼85% of the whole mixture of VOCs, was associated with that of carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4) emissions. The strong linear relationship between the concentrations of pyrogenic VOC and of a reference species (i.e. CO) allowed us to compile a list of emission ratios (ERs) and emission factors (EFs), but values of ER (and EF) were overestimated due to the limited mixing of the gases under the stable (non-turbulent) nocturnal conditions. In addition to the 25 most abundant VOCs, chemical formula and concentrations of the residual, less abundant VOCs in the emitted mixture were also estimated by PTR-TOF-MS. Furthermore, the evolution of the complex combustion process was described on the basis of the diverse types of pyrogenic gases recorded.

  1. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d`Exploitation du Retraitement et de Demantelement

    1995-12-20

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

  2. Proton loss by nuclear inelastic interactions in germanium

    International Nuclear Information System (INIS)

    Carlson, R.F.; Cox, A.J.; Abegg, R.; Davison, N.E.; Hasell, D.K.; McCamis, R.H.; Nasr, T.N.; Van Oers, W.T.H.; Manitoba Univ., Winnipeg

    1981-01-01

    The probability of protons undergoing nuclear inelastic interactions while stopping in germanium has been measured in a direct counting experiment using protons with energies between 25 and 49 MeV incident on a germanium detector. These values have been determined to an accuracy of approximately +-2%. Calculatins of the proton reaction probability over the incident energy range 20-150 MeV have also been made, using previously reported proton total reaction cross sections. The experimental and calculated results agree to within +-1.8%. (orig.)

  3. Proton Therapy - Accelerating Protons to Save Lives

    Energy Technology Data Exchange (ETDEWEB)

    Keppel, Cynthia [Hampton Univ. Proton Therapy Inst., Hampton, VA (United States)

    2011-10-25

    In 1946, physicist Robert Wilson first suggested that protons could be used as a form of radiation therapy in the treatment of cancer because of the sharp drop-off that occurs on the distal edge of the radiation dose. Research soon confirmed that high-energy protons were particularly suitable for treating tumors near critical structures, such as the heart and spinal column. The precision with which protons can be delivered means that more radiation can be deposited into the tumor while the surrounding healthy tissue receives substantially less or, in some cases, no radiation. Since these times, particle accelerators have continuously been used in cancer therapy and today new facilities specifically designed for proton therapy are being built in many countries. Proton therapy has been hailed as a revolutionary cancer treatment, with higher cure rates and fewer side effects than traditional X-ray photon radiation therapy. Proton therapy is the modality of choice for treating certain small tumors of the eye, head or neck. Because it exposes less of the tissue surrounding a tumor to the dosage, proton therapy lowers the risk of secondary cancers later in life - especially important for young children. To date, over 80,000 patients worldwide have been treated with protons. Currently, there are nine proton radiation therapy facilities operating in the United States, one at the Hampton University Proton Therapy Institute. An overview of the treatment technology and this new center will be presented.

  4. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F{sup −} + CH{sub 3}F S{sub N}2 and proton-abstraction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor, E-mail: czako@chem.elte.hu [Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University, H-1518 Budapest 112, P.O. Box 32 (Hungary)

    2015-06-28

    We develop a full-dimensional global analytical potential energy surface (PES) for the F{sup −} + CH{sub 3}F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller–Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are −0.45(−0.61), 46.07(45.16), and 29.18(26.07) kcal mol{sup −1}, respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol{sup −1}, respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol{sup −1}. Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F{sup −} + CH{sub 3}F(v = 0) reaction using the new PES. Apart from low collision energies (E{sub coll}), the S{sub N}2 excitation function is nearly constant, the abstraction cross sections rapidly increase with E{sub coll} from a threshold of ∼40 kcal mol{sup −1}, and retention trajectories via double inversion are found above E{sub coll} = ∼ 30 kcal mol{sup −1}, and at E{sub coll} =

  5. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    Science.gov (United States)

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  6. Nitrate reduction in water by aluminum alloys particles.

    Science.gov (United States)

    Bao, Zunsheng; Hu, Qing; Qi, Weikang; Tang, Yang; Wang, Wei; Wan, Pingyu; Chao, Jingbo; Yang, Xiao Jin

    2017-07-01

    Nano zero-valent iron (NZVI) particles have been extensively investigated for nitrate reduction in water. However, the reduction by NZVI requires acidic pH conditions and the final product is exclusively ammonium, leading to secondary contamination. In addition, nanomaterials have potential threats to environment and the transport and storage of nanomaterials are of safety concerns. Aluminum, the most abundant metal element in the earth's crust, is able to reduce nitrate, but the passivation of aluminum limits its application. Here we report Al alloys (85% Al) with Fe, Cu or Si for aqueous nitrate reduction. The Al alloys particles of 0.85-0.08 mm were inactivate under ambient conditions and a simple treatment with warm water (45 °C) quickly activated the alloy particles for rapid reduction of nitrate. The Al-Fe alloy particles at a dosage of 5 g/L rapidly reduced 50 mg-N/L nitrate at a reaction rate constant (k) of 3.2 ± 0.1 (mg-N/L) 1.5 /min between pH 5-6 and at 4.0 ± 0.1 (mg-N/L) 1.5 /min between pH 9-11. Dopping Cu in the Al-Fe alloy enhanced the rates of reduction whereas dopping Si reduced the reactivity of the Al-Fe alloy. The Al alloys converted nitrate to 20% nitrogen and 80% ammonium. Al in the alloy particles provided electrons for the reduction and the intermetallic compounds in the alloys were likely to catalyze nitrate reduction to nitrogen. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Geopolymerization at moderate temperatures in the presence of nitrate anion

    International Nuclear Information System (INIS)

    Ofer-Rozovsky, E.; Katz, A.; Borojovich, E.J.C.; Nikolski, A.; Binyamini, A.; Arbel-Haddad, M.; Bar-Nes, G.

    2015-01-01

    In recent years, geo-polymers generated by alkali-activation of amorphous aluminosilicate sources are considered as an alternative immobilizing matrix for low-level radioactive wastes. Although such waste streams contain low concentration of radioactive species, they are often highly saline. The aim of the research project presented here was to study the effect of the high salt content on the formation and evolution of meta-kaolin-based geo-polymeric systems cured at moderate temperatures, i.e. at 40 Celsius degrees. Meta-kaolin was alkali-activated using NaOH solutions of varying concentrations, yielding H 2 O:OH - ratios of 5.5, 9.15, 13.75 and 27.5. Sodium nitrate, which is often found at high concentrations in radioactive waste streams, was added to the activation solutions. The geo-polymeric mixtures were designed so that the Na 2 O:Al 2 O 3 ratio obtained was 1.00 in nitrate-free systems, and 1.25 in nitrate-containing systems. The ratio between nitrate and hydroxide ions, [NO 3 - ]: [OH - ], was adjusted to 0.25. The samples were cured in sealed containers at 40 C. degrees for periods ranging from one week to 3 months. The products were characterized by X-Ray diffractometry and Fourier Transform Mid-Infrared spectroscopy (FTIR). Leaching tests were performed according to the American Nuclear Society procedure ANS-16.1. Ion Chromatography was used to determine the concentration of leached Na + and NO 3 - ions. The results demonstrate the influence of composition and curing times on the mineralogy of the geo-polymeric matrix. Various crystalline phases such as zeolite A, faujasite, and nitrate bearing phases, nitrate sodalite and nitrate cancrinite, were identified among the reaction products. The sequence of phase evolution in these geo-polymeric systems was elucidated. The fraction of sodium ions released from samples containing sodium nitrate during the leaching test was found to be lower than that from reference samples prepared without the nitrate salt

  8. Sodium nitrate ingestion increases skeletal muscle nitrate content in humans.

    Science.gov (United States)

    Nyakayiru, Jean; Kouw, Imre W K; Cermak, Naomi M; Senden, Joan M; van Loon, Luc J C; Verdijk, Lex B

    2017-09-01

    Nitrate ([Formula: see text]) ingestion has been shown to have vasoactive and ergogenic effects that have been attributed to increased nitric oxide (NO) production. Recent observations in rodents suggest that skeletal muscle tissue serves as an endogenous [Formula: see text] "reservoir." The present study determined [Formula: see text] contents in human skeletal muscle tissue in a postabsorptive state and following ingestion of a sodium nitrate bolus (NaNO 3 ). Seventeen male, type 2 diabetes patients (age 72 ± 1 yr; body mass index 26.5 ± 0.5 kg/m 2 ; means ± SE) were randomized to ingest a dose of NaNO 3 (NIT; 9.3 mg [Formula: see text]/kg body wt) or placebo (PLA; 8.8 mg NaCl/kg body wt). Blood and muscle biopsy samples were taken before and up to 7 h following [Formula: see text] or placebo ingestion to assess [Formula: see text] [and plasma nitrite ([Formula: see text])] concentrations. Additionally, basal plasma and muscle [Formula: see text] concentrations were assessed in 10 healthy young (CON-Y; age 21 ± 1 yr) and 10 healthy older (CON-O; age 75 ± 1 yr) control subjects. In all groups, baseline [Formula: see text] concentrations were higher in muscle (NIT, 57 ± 7; PLA, 61 ± 7; CON-Y, 80 ± 10; CON-O, 54 ± 6 µmol/l) than in plasma (NIT, 35 ± 3; PLA, 32 ± 3; CON-Y, 38 ± 3; CON-O, 33 ± 3 µmol/l; P ≤ 0.011). Ingestion of NaNO 3 resulted in a sustained increase in plasma [Formula: see text], plasma [Formula: see text], and muscle [Formula: see text] concentrations (up to 185 ± 25 µmol/l) in the NIT group (time effect P nitrate ingestion is usually limited to the changes observed in plasma nitrate and nitrite concentrations. The present investigation assessed the skeletal muscle nitrate content in humans during the postabsorptive state, as well as following dietary nitrate ingestion. We show that basal nitrate content is higher in skeletal muscle tissue than in plasma and that ingestion of a dietary nitrate bolus strongly increases both plasma

  9. The effects of nitrate on the heterogeneous uptake of sulfur dioxide on hematite

    Science.gov (United States)

    Kong, L. D.; Zhao, X.; Sun, Z. Y.; Yang, Y. W.; Fu, H. B.; Zhang, S. C.; Cheng, T. T.; Yang, X.; Wang, L.; Chen, J. M.

    2014-09-01

    Nitrate is often found to be associated with atmospheric particles. Surface nitrate can change the hygroscopicity of these particles, and thus impact their chemical reactivity. However, the influence of nitrate on heterogeneous reactions of atmospheric trace gases is poorly understood. In this work, the effects of nitrate on heterogeneous conversion of SO2 with hematite at 298 K are investigated using an in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a White cell coupled with Fourier transform infrared spectroscopy (White cell-FTIR). It is found that nitrate participates in heterogeneous reactions of SO2, accelerates the formation rate of sulfate, and leads to the formation of surface-adsorbed HNO3 and gas-phase N2O and HONO. The results indicate that low to moderate amounts of nitrate significantly enhance the reactivity of hematite-nitrate mixtures, the uptake of SO2, and the formation of sulfate on hematite. For mixtures, the sample containing 24% nitrate exhibits the highest sulfate formation rate, and its corresponding uptake coefficient calculated by geometric surface area is about 5.5 times higher than that of hematite alone. The sample containing 48% nitrate presents the highest Brunauer-Emmett-Teller (BET) uptake coefficient, and the value is about 8 times higher than that of pure hematite. No uptake of SO2 and formation of sulfate are observed on pure nitrate. Evidence presented herein implies a significant contribution of the unreleased HNO3 and HONO in the particles for the conversion of SO2 and the enhanced formation of sulfate in the atmosphere. A possible mechanism for the influence of nitrate on the heterogeneous conversion of SO2 on hematite is proposed, and atmospheric implications based on these results are discussed.

  10. Proton-air and proton-proton cross sections

    Directory of Open Access Journals (Sweden)

    Ulrich Ralf

    2013-06-01

    Full Text Available Different attempts to measure hadronic cross sections with cosmic ray data are reviewed. The major results are compared to each other and the differences in the corresponding analyses are discussed. Besides some important differences, it is crucial to see that all analyses are based on the same fundamental relation of longitudinal air shower development to the observed fluctuation of experimental observables. Furthermore, the relation of the measured proton-air to the more fundamental proton-proton cross section is discussed. The current global picture combines hadronic proton-proton cross section data from accelerator and cosmic ray measurements and indicates a good consistency with predictions of models up to the highest energies.

  11. Cross section of 70-230 MeV proton production in the p + A → p + X reactions at 1-9 GeV/c, π+ + A → p + X at 1-6 GeV/c and in the π- + A → p + X at 1.4 and 5 GeV/c

    International Nuclear Information System (INIS)

    Bayukov, Yu.D.; Gavrilov, V.B.; Goryainov, N.A.

    1983-01-01

    The tables of cross sections of proton production with energies 70-230 KeV for reactions p+A→p+X at 1-9 GeV/c, π + +A→p+X at 1-6 GeV/c and π - +A→p+X at 1.4 and 5 GeV/c are presented. The dependences on initial particle momentum are measured (for protons at 1, 1.4, 2, 5, 6, 6.25, 6.5, 7, 7.5, 8.25, 8.5 and and 9 GeV/c, for π + at 1, 1.4, 2, 3, 4, 5 and 6 GeV/c and for π - at 1.4 and 5 GeV/c) for C, Cu, Pb and U targets at the angles of 59 deg, 89 deg, 119 deg and 160 deg. At these angles A-dependence was also measured in detail (for Be, C, Al, Ti, Fe, Cu, Nb, Cd, Sn, Ta, Pb and U targets) for initial protons with 7.5 GeV/c. Detailed angular dependences at the range from 10 deg to 177 deg are presented for C, Cu, Pb and U targets for initial protons of 7.5 GeV/c and π - mesons of 5 GeV/c

  12. Use of uranyl nitrate as a shift reagent in polar and inert solvents

    International Nuclear Information System (INIS)

    Nosov, B.P.

    1988-01-01

    This work examines the effect of uranyl nitrate as a shift reagent on the PMR spectra of different organic molecules in polar and inert solvents. In order to identify the coordination site of the uranyl ion, its effect on the spectra of amino acids and acetic or propionic acids in water was compared. It was found that the induced shifts of the protons in the corresponding positions of the different acids after addition of uranyl nitrate agreed to within ±0.01 ppm. When nitrogenous bases such as diethylamine and pyridine were added to solutions of the carboxylic acids with uranyl nitrate, an increase in the induced chemical shift of the resonance signals occurred. These facts suggest the coordination of the uranyl ion with the carboxyl oxygen both for acetic and propionic acids and for amino acids. The authors established that the addition of uranyl nitrate to solutions of organic compounds caused different downfield shifts of the resonance signals from the protons. In polar solvents shifts induced by uranyl nitrate in the PMR spectra of carboxylic acids occur only when nitrogenous bases are added

  13. Proton therapy device

    International Nuclear Information System (INIS)

    Tronc, D.

    1994-01-01

    The invention concerns a proton therapy device using a proton linear accelerator which produces a proton beam with high energies and intensities. The invention lies in actual fact that the proton beam which is produced by the linear accelerator is deflected from 270 deg in its plan by a deflecting magnetic device towards a patient support including a bed the longitudinal axis of which is parallel to the proton beam leaving the linear accelerator. The patient support and the deflecting device turn together around the proton beam axis while the bed stays in an horizontal position. The invention applies to radiotherapy. 6 refs., 5 figs

  14. Virtual Compton scattering off the proton at Jefferson Lab (experiment E93050): preliminary results of the cross-sections of the reaction (ep{yields}ep{gamma}) in order to find out the generalized polarizabilities (GPs) of the proton at Q{sup 2} = 1.9 GeV{sup 2}; Diffusion compton virtuelle a jefferson lab (experience E93050): resultat preliminaire des sections efficaces (ep{yields}ep{gamma}) en vue d'extraire les polarisabilites generalisees du proton a Q{sup 2} = 1.9 GEV{sup 2}

    Energy Technology Data Exchange (ETDEWEB)

    Jaminion, St

    2000-12-01

    Virtual Compton Scattering off the proton ({gamma}{sup *}p {yields} {gamma}p) at low energy is accessible via the reaction (ep {yields} ep{gamma}), and contains 6 new observables: Generalized Polarizabilities (GPs). Their extraction needs the measurement of absolute five fold differential cross sections for photon electroproduction off the proton. The determination of GPs will put new constraints on models of nucleon structure in the non-perturbative Quantum Chromodynamics region. Following the Mainz experiment realized at four momentum transfer Q{sup 2} = 0.33 GeV{sup 2}, the E93050 experiment which was performed in the Hall A of Jefferson Lab during march-april 1998, will allow the measurement of combinations of generalized polarizabilities at Q{sup 2}=1 and 1.9 GeV{sup 2}. The final electron and proton were detected in coincidence in the Hall A high resolution spectrometers. The final photon is reconstructed like a missing particle, and all its variables can be determined. We had to optimize optics tensor of each spectrometer in order to have the best reconstruction at vertex point. We created an acceptance function, which is included in the software simulating solid angle. We determined different cuts to substract our background dominating (ep {yields} ep{gamma}) reaction. This work allows to carry out our first photon electro-production cross section measurement at Q{sup 2}=1.9 GeV{sup 2}. The results seem to indicate a measurable effect of generalized polarizabilities, which remains however to be confirmed. (author)

  15. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

    International Nuclear Information System (INIS)

    Toulemonde, V.

    1995-01-01

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

  16. Observation of gaseous nitric acid production at a high-energy proton accelerator facility

    CERN Document Server

    Kanda, Y; Nakajima, H

    2005-01-01

    High-energy protons and neutrons produce a variety of radionuclides as well as noxious and oxidative gases, such as ozone and nitric acid, in the air mainly through the nuclear spallation of atmospheric elements. Samples were collected from the surfaces of magnets, walls, and floors in the neutrino beamline tunnel and the target station of the KEK 12-GeV proton synchrotron facility by wiping surfaces with filter paper. Considerably good correlations were found between the amounts of nitrate and tritium and between those of nitrate and /sup 7/Be. This finding gives evidence that at high-energy proton facilities, nitric acid is produced in the radiolysis of air in beam- loss regions. Also, the nitric acid on the surfaces was found to be desorbed and tended to be more uniform throughout the tunnel due to air circulation. The magnitude of diminishing from the surfaces was in the order of tritium>nitrate>/sup 7/Be1).

  17. Ions transfer modeling through monopolar and bipolar membranes: Treatment of wastewater containing ammonium nitrate by electrodialysis

    Directory of Open Access Journals (Sweden)

    Mohamed Amine Ben Ali

    2015-05-01

    Full Text Available In this study, a mathematical model was proposed to illustrate the different transport modes contributing in transfer of all involved species through anion, cation and bipolar membranes. This study was led on a wastewater containing ammonium nitrate treated by bipolar membrane electrodialysis (BPMED. In this electrodialysis, different species are involved, in particular, ammonium ions NH4+, nitrates NO3-, ammoniac NH3, water H2O and protons H+. Calculations led from the material balance sheets equations obtained in bath mode, allowed to validate the proposed transfer model and to check balance sheets material on all involved species during electrodialysis.

  18. Proton transfer reaction time-of-flight mass spectrometry: A high-throughput and innovative method to study the influence of dairy system and cow characteristics on the volatile compound fingerprint of cheeses.

    Science.gov (United States)

    Bergamaschi, M; Biasioli, F; Cappellin, L; Cecchinato, A; Cipolat-Gotet, C; Cornu, A; Gasperi, F; Martin, B; Bittante, G

    2015-12-01

    The aim of this work was to study the effect of dairy system and individual cow-related factors on the volatile fingerprint of a large number of individual model cheeses analyzed by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). A total of 1,075 model cheeses were produced using milk samples collected from individual Brown Swiss cows reared in 72 herds located in mountainous areas of Trento province (Italy). The herds belonged to 5 main dairy systems ranging from traditional to modern and the cows presented different daily milk yields (24.6±7.9kg × d(-1)), stages of lactation (199±138 d in milk), and parities (2.7±1.8). The PTR-ToF-MS revealed 619 peaks, of which the 240 most intense were analyzed, and 61 of these were tentatively attributed to relevant volatile organic compounds on the basis of their fragmentation patterns and data from the literature. Principal component analysis was used to convert the multiple responses characterizing the PTR-ToF-MS spectra into 5 synthetic variables representing 62% of the total information. These principal components were related to groups of volatile compounds tentatively attributed to different peaks and used to investigate the relationship of the volatile compound profile obtained by PTR-ToF-MS to animal and farm characteristics. Lactation stage is related to 4 principal components which brought together 52.9% of the total variance and 57.9% of the area of analyzed peaks. In particular, 2 principal components were positively related to peaks tentatively attributed to aldehydes and ketones and negatively related to alcohols, esters, and acids, which displayed a linear increase during lactation. The second principal component was affected by dairy system; it was higher in the modern system in which cows received total mixed rations. The third principal component was positively related to daily milk production. In summary, we report the first application of this innovative, high

  19. The stability and generation pattern of thermally formed isocyanic acid (ICA) in air - potential and limitations of proton transfer reaction-mass spectrometry (PTR-MS) for real-time workroom atmosphere measurements.

    Science.gov (United States)

    Jankowski, Mikolaj Jan; Olsen, Raymond; Thomassen, Yngvar; Molander, Paal

    2016-07-13

    Isocyanic acid (ICA) in vapour phase has been reported to be of unstable nature, making the occupational hygienic relevance of ICA questionable. The stability of pure ICA in clean air at different humidity conditions was investigated by Fourier transform-infrared spectrometric (FT-IR) measurements. Furthermore, the stability of ICA in a complex atmosphere representative thermal degradation hot-work procedures were examined by performing parallel measurements by proton transfer reaction-mass spectrometric (PTR-MS) instrumentation and off-line denuder air sampling using di-n-butylamine (as a derivatization agent prior to liquid chromatography mass spectrometric (LC-MS) determination). The apparent half-life of ICA in pure ICA atmospheres was 16 to 4 hours at absolute humidity (AH) in the range 4.2 to 14.6 g m(-3), respectively. In a complex atmosphere at an initial AH of 9.6 g m(-3) the apparent half-life of ICA was 8 hours, as measured with the denuder method. Thus, thermally formed ICA is to be considered as a potential occupational hazard with regard to inhalation. The generation pattern of ICA formed during controlled gradient (100-540 °C) thermal decomposition of different polymers in the presence of air was examined by parallel PTR-MS and denuder air sampling. According to measurement by denuder sampling ICA was the dominant aliphatic isocyanate formed during the thermal decomposition of all polymers. The real-time measurements of the decomposed polymers revealed different ICA generation patterns, with initial appearance of thermally released ICA in the temperature range 200-260 °C. The PTR-MS ICA measurements was however affected by mass overlap from other decomposition products at m/z 44, illustrated by a [ICA]Denuder/[ICA]PTR-MS ratio ranging from 0.04 to 0.90. These findings limits the potential use of PTR-MS for real time measurements of thermally released ICA in field, suggesting parallel sampling with short-term sequential off-line methodology.

  20. Thermal Decomposition of Nitrated Tributyl Phosphate

    International Nuclear Information System (INIS)

    Paddleford, D.F.; Hou, Y.; Barefield, E.K.; Tedder, D.W.; Abdel-Khalik, S.I.

    1995-01-01

    Contact between tributyl phosphate and aqueous solutions of nitric acid and/or heavy metal nitrate salts at elevated temperatures can lead to exothermic reactions of explosive violence. Even though such operations have been routinely performed safely for decades as an intrinsic part of the Purex separation processes, several so-called ''red oil'' explosions are known to have occurred in the United States, Canada, and the former Soviet Union. The most recent red oil explosion occurred at the Tomsk-7 separations facility in Siberia, in April 1993. That explosion destroyed part of the unreinforced masonry walls of the canyon-type building in which the process was housed, and allowed the release of a significant quantity of radioactive material