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Sample records for isotope exchange reactions

  1. The Kinetics of Isotopic Exchange Reactions.

    ERIC Educational Resources Information Center

    Logan, S. R.

    1990-01-01

    Discussed are the kinetic interactions of these chemical processes and the determination of the actual order of such reactions. Included are multiple exchange, catalytic exchange with deuterium, and depletion of the original substrate. (CW)

  2. The Kinetics of Isotopic Exchange Reactions.

    ERIC Educational Resources Information Center

    Logan, S. R.

    1990-01-01

    Discussed are the kinetic interactions of these chemical processes and the determination of the actual order of such reactions. Included are multiple exchange, catalytic exchange with deuterium, and depletion of the original substrate. (CW)

  3. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, Frank P.; Herbst, Ronald S.

    1995-01-01

    The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

  4. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, F.P.; Herbst, R.S.

    1995-05-30

    The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

  5. Surface mediated isotope exchange reactions between water and gaseous deuterium

    NASA Astrophysics Data System (ADS)

    Roland, Teboh F.; Borysow, Jacek; Fink, Manfred

    2006-07-01

    Maintaining isotopic purity of hydrogen is one of the major tasks in tritium processing systems. The work with multiple isotopes and isotopomers is accompanied by isotope exchanges which is often accelerated by catalysts e.g. surfaces of various materials. In this work, densities of D 2O, HDO produced via isotope exchange reactions in the mixture of D 2, H 2, D 2O, H 2O, HD and HDO contained in a stainless steel (type SS304) vessel were measured as a function of time (40-36 000 s) and pressures near 3.5 × 10 2 Pa, using mass spectrometry. The derived rates of change of the isotopomers densities are described accurately by a postulated kinetic model.

  6. Isotope exchange reactions involving HCO+ with CO: A theoretical approach

    NASA Astrophysics Data System (ADS)

    Mladenović, M.; Roueff, E.

    2017-09-01

    Aims: We aim to investigate fractionation reactions involved in the 12C/13C, 16O/18O, and 17O balance. Methods: Full-dimensional rovibrational calculations were used to compute numerically exact rovibrational energies and thermal equilibrium conditions to derive the reaction rate coefficients. A nonlinear least-squares method was employed to represent the rate coefficients by analytic functions. Results: New exothermicities are derived for 30 isotopic exchange reactions of HCO+ with CO. For each of the reactions, we provide the analytic three-parameter Arrhenius-Kooij formula for both the forward reaction and backward reaction rate coefficients, that can further be used in astrochemical kinetic models. Rotational constants derived here for the 17O containing forms of HCO+ may assist detection of these cations in outer space.

  7. Analysis of the galactosyltransferase reaction by positional isotope exchange and secondary deuterium isotope effects

    SciTech Connect

    Kim, S.C.; Singh, A.N.; Raushel, F.M.

    1988-11-15

    The mechanism of the galactosyltransferase-catalyzed reaction was probed using positional isotope exchange, alpha-secondary deuterium isotope effects, and inhibition studies with potential transition state analogs. Incubation of (beta-18O2, alpha beta-18O)UDP-galactose and alpha-lactalbumin with galactosyltransferase from bovine milk did not result in any positional isotope exchange. The addition of 4-deoxy-4-fluoroglucose as a dead-end inhibitor did not induce any detectable positional isotope exchange. alpha-Secondary deuterium isotope effects of 1.21 +/- 0.04 on Vmax and 1.05 +/- 0.04 on Vmax/KM were observed for (1-2H)-UDP-galactose. D-Glucono-1,5-lactone, D-galactono-1,4-lactone, D-galactono-1,5-lactone, nojirimycin, and deoxynojirimycin, did not inhibit the galactosyl transfer reaction at concentrations less than 1.0 mM. The magnitude of the secondary deuterium isotope effect supports a mechanism in which the anomeric carbon of the galactosyl moiety has substantial sp2 character in the transition state. Therefore, the cleavage of the bond between the galactose and UDP moieties in the transition state has proceeded to a much greater extent than the formation of the bond between the galactose and the incoming glucose. The lack of a positional isotope exchange reaction indicates that the beta-phosphoryl group of the UDP is not free to rotate in the absence of an acceptor substrate.

  8. Positional isotope exchange analysis of the pantothenate synthetase reaction.

    PubMed

    Williams, LaKenya; Zheng, Renjian; Blanchard, John S; Raushel, Frank M

    2003-05-06

    Pantothenate synthetase from Mycobacterium tuberculosis catalyzes the formation of pantothenate from ATP, D-pantoate, and beta-alanine. The formation of a kinetically competent pantoyl-adenylate intermediate was established by the observation of a positional isotope exchange (PIX) reaction within (18)O-labeled ATP in the presence of d-pantoate. When [betagamma-(18)O(6)]-ATP was incubated with pantothenate synthetase in the presence of d-pantoate, an (18)O label gradually appeared in the alphabeta-bridge position from both the beta- and the gamma-nonbridge positions. The rates of these two PIX reactions were followed by (31)P NMR spectroscopy and found to be identical. These results are consistent with the formation of enzyme-bound pantoyl-adenylate and pyrophosphate upon the mixing of ATP, D-pantoate, and enzyme. In addition, these results require the complete torsional scrambling of the two phosphoryl groups of the labeled pyrophosphate product. The rate of the PIX reaction increased as the D-pantoate concentration was elevated and then decreased to zero at saturating levels of D-pantoate. These inhibition results support the ordered binding of ATP and D-pantoate to the enzyme active site. The PIX reaction was abolished with the addition of pyrophosphatase; thus, PP(i) must be free to dissociate from the active site upon formation of the pantoyl-adenylate intermediate. The PIX reaction rate diminished when the concentrations of ATP and D-pantoate were held constant and the concentration of the third substrate, beta-alanine, was increased. This observation is consistent with a kinetic mechanism that requires the binding of beta-alanine after the release of pyrophosphate from the active site of pantothenate synthetase. Positional isotope exchange reactions have therefore demonstrated that pantothenate synthetase catalyzes the formation of a pantoyl-adenylate intermediate upon the ordered addition of ATP and pantoate.

  9. On the interaction of isotopic exchange processes with photochemical reactions in atmospheric oxides of nitrogen

    SciTech Connect

    Freyer, H.D.; Kley, D.; Volz-Thomas, A.; Kobel, K.

    1993-08-20

    The authors study the isotopic composition of nitic oxide and nitrogen dioxide in the atmosphere. They model the observed results for {sup 15}N/{sup 14}N ratios in terms of isotopic exchange reactions with ozone and photolytic reactions on the oxides. They find there has to be an interaction of these two reactions, in conjunction with seasonl variations of nitrogen oxide/ozone ratios, to account for observed isotopic ratios of the nitrogen isotopes.

  10. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

    PubMed

    Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi

    2015-04-28

    The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

  11. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields.

    PubMed

    Tomza, Michał

    2015-08-07

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products.

  12. Fast chemical and isotopic exchange of nitrogen during reaction with hot molybdenum

    NASA Astrophysics Data System (ADS)

    Yokochi, Reika; Marty, Bernard

    2006-07-01

    Molybdenum crucibles are commonly used to extract nitrogen from geological samples by induction heating. Because nitrogen is known to be reactive with certain metals (e.g., Ti and Fe), we have tested the reactivity of gaseous nitrogen with a Mo crucible held at 1800°C. The consumption of nitrogen, determined by monitoring the N2/40Ar ratio of the gas phase, varied between 25 and 100%, depending on the reaction duration. Nitrogen of the reacted gas was found to be systematically enriched in 15N relative to 14N by 10‰ compared to the initial isotopic composition, without any correlation with nitrogen consumption. We propose that a rapid isotopic exchange occurs between nitrogen originally trapped in the crucible and nitrogen from the gas phase, which modifies the isotopic composition of the reacted gas. This process can significantly bias the isotopic determination of nitrogen in rocks and minerals when a Mo furnace is used for gas extraction. Meanwhile, the rate of N-Mo chemical bonding may be controlled by the formation of nitride (rather than solid solution), a process slower than the isotopic exchange. The use of a Mo furnace for the extraction of trace nitrogen from rocks and minerals should therefore be avoided.

  13. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  14. Positional isotope exchange analysis of the uridine-diphosphoglucose pyrophosphorylase reaction

    SciTech Connect

    Hester, L.; Hilscher, L.; Raushel, F.M.

    1986-05-01

    The enzyme uridine-diphosphoglucose pyrophosphorylase catalyzes the reversible formation of pyrophosphate and UDP-glucose from UTP and glc-1P. The positional isotope exchange reaction was measured using oxygen-18 labelled UTP. The synthesis of (..beta..-/sup 18/O/sub 2/, ..beta gamma..-/sup 18/O, ..gamma..-/sup 18/O/sub 3/)UTP was accomplished by the coupled activities of carbamate kinase, nucleoside diphosphate kinase, and nucleoside monophosphate kinase. The exchange of an oxygen-18 from a ..beta..-nonbridge position of the labelled UTP to the ..cap alpha beta..-bridge position was measured with /sup 31/P NMR. The ratio of the rate of net substrate turnover and the positional isotope exchange rate was measured as a function of the initial glc-1P concentration. This ratio was found to increase with an increasing concentration of glc-1P. The intercept at low glc-1P was found to be 1.2 and the slope was 4.5 mM/sup -1/. These results have been interpreted to mean that this enzyme has an ordered addition of substrates. The lower limit for the release of pyrophosphate from E-UDPG-PP/sub i/ relative to V/sub 2/ is 1.2. The rate constant for the release of UTP from E-UTP relative to V/sub 1/ is 9.

  15. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    PubMed

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions.

  16. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.

    PubMed

    Rustad, James R; Casey, William H

    2012-01-10

    Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface.

  17. State-to-state quantum dynamics of O + O2 isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions.

    PubMed

    Sun, Zhigang; Liu, Lan; Lin, Shi Ying; Schinke, Reinhard; Guo, Hua; Zhang, Dong H

    2010-01-12

    The O + O(2) exchange reaction is a prerequisite for the formation of ozone in Earth's atmosphere. We report here state-to-state differential and integral cross sections for several O + O(2) isotope-exchange reactions obtained by dynamically exact quantum scattering calculations at collision energies relevant to atmospheric conditions. These reactions are shown to be highly nonstatistical, evidenced by dominant forward scattering and deviation of the integral cross section from the statistical limit. Mechanistic analyses revealed that the nonstatistical channel is facilitated by short-lived osculating resonances. The theoretical results provided an in-depth interpretation of a recent molecular beam experiment of the exchange reaction and shed light on the initial step of ozone recombination.

  18. Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

    NASA Astrophysics Data System (ADS)

    Wortmann, Ulrich G.; Chernyavsky, Boris; Bernasconi, Stefano M.; Brunner, Benjamin; Böttcher, Michael E.; Swart, Peter K.

    2007-09-01

    Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the δ18O composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report δ18O values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our δ18O data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m 3 of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed δ18O data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.

  19. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO2 surface: The case of terminal oxygen atom exchange

    NASA Astrophysics Data System (ADS)

    Kevorkyants, Ruslan; Sboev, Mikhail. N.; Chizhov, Yuri V.

    2017-05-01

    Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between 16O18O and terminal oxygen atom of a defect TiO2 surface, which is modeled by amorphous Ti8O16 nanocluster in excited S1 electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O3- chemisorption species match well EPR data on O2 adsorption on UV-irradiated nanocrystalline TiO2. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction's mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VOx/TiO2 reported earlier.

  20. Measurements of 18O18O and 17O18O in the atmosphere and the role of isotope-exchange reactions

    NASA Astrophysics Data System (ADS)

    Yeung, Laurence Y.; Young, Edward D.; Schauble, Edwin A.

    2012-09-01

    Of the six stable isotopic variants of O2, only three are measured routinely. Observations of natural variations in 16O18O/16O16O and 16O17O/16O16O ratios have led to insights in atmospheric, oceanographic, and paleoclimate research. Complementary measurements of the exceedingly rare 18O18O and 17O18O isotopic variants might therefore broaden our understanding of oxygen cycling. Here we describe a method to measure natural variations in these multiply substituted isotopologues of O2. Its accuracy is demonstrated by measuring isotopic effects for Knudsen diffusion and O2 electrolysis in the laboratory that are consistent with theoretical predictions. We then report the first measurements of 18O18O and 17O18O proportions relative to the stochastic distribution of isotopes (i.e., Δ36 and Δ35 values, respectively) in tropospheric air. Measured enrichments in 18O18O and 17O18O yield Δ36 = 2.05 ± 0.24‰ and Δ35 = 1.4 ± 0.5‰ (2σ). Based on the results of our electrolysis experiment, we suggest that autocatalytic O(3P) + O2 isotope exchange reactions play an important role in regulating the distribution of 18O18O and 17O18O in air. We constructed a box model of the atmosphere and biosphere that includes the effects of these isotope exchange reactions, and we find that the biosphere exerts only a minor influence on atmospheric Δ36 and Δ35 values. O(3P) + O2 isotope exchange in the stratosphere and troposphere is therefore expected to govern atmospheric Δ36 and Δ35 values on decadal timescales. These results suggest that the `clumped' isotopic composition of atmospheric O2in ice core records is sensitive to past variations in atmospheric dynamics and free-radical chemistry.

  1. Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

    NASA Astrophysics Data System (ADS)

    Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

    2017-08-01

    Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

  2. Evidence for o-atom exchange in the O(1D) + N2O reaction as the source of mass-independent isotopic fractionation in atmospheric N2O.

    SciTech Connect

    Miller, Charles E.; Liang, Mao-Chang; Blake, Geoffrey A.; Muller, Richard Partain; Yung, Yuk L.

    2004-07-01

    Recent experiments have shown that in the oxygen isotopic exchange reaction for O({sup 1}D) + CO{sub 2} the elastic channel is approximately 50% that of the inelastic channel [Perri et al., 2003]. We propose an analogous oxygen atom exchange reaction for the isoelectronic O({sup 1}D) + N{sub 2}O system to explain the mass-independent isotopic fractionation (MIF) in atmospheric N{sub 2}O. We apply quantum chemical methods to compute the energetics of the potential energy surfaces on which the O({sup 1}D) + N{sub 2}O reaction occurs. Preliminary modeling results indicate that oxygen isotopic exchange via O({sup 1}D) + N{sub 2}O can account for the MIF oxygen anomaly if the oxygen atom isotopic exchange rate is 30-50% that of the total rate for the reactive channels.

  3. An algorithm for the deconvolution of mass spectroscopic patterns in isotope labeling studies. Evaluation for the hydrogen-deuterium exchange reaction in ketones.

    PubMed

    Gruber, Christian C; Oberdorfer, Gustav; Voss, Constance V; Kremsner, Jennifer M; Kappe, C Oliver; Kroutil, Wolfgang

    2007-07-20

    An easy to use computerized algorithm for the determination of the amount of each labeled species differing in the number of incorporated isotope labels based on mass spectroscopic data is described and evaluated. Employing this algorithm, the microwave-assisted synthesis of various alpha-labeled deuterium ketones via hydrogen-deuterium exchange with deuterium oxide was optimized with respect to time, temperature, and degree of labeling. For thermally stable ketones the exchange of alpha-protons was achieved at 180 degrees C within 40-200 min. Compared to reflux conditions, the microwave-assisted protocol led to a reduction of the required reaction time from 75-94 h to 40-200 min. The alpha-labeled deuterium ketones were reduced by biocatalytic hydrogen transfer to the corresponding enantiopure chiral alcohols and the deconvolution algorithm validated by regression analysis of a mixture of labeled and unlabeled ketones/alcohols.

  4. Quasiclassical trajectory studies of 18O(3P) + NO2 isotope exchange and reaction to O2 + NO on D0 and D1 potentials

    NASA Astrophysics Data System (ADS)

    Fu, Bina; Zhang, Dong H.; Bowman, Joel M.

    2013-07-01

    We report quasiclassical trajectory calculations for the bimolecular reaction 18O(3P) + NO2 on the recent potential energy surfaces of the ground (D0) and first excited (D1) states of NO3 [B. Fu, J. M. Bowman, H. Xiao, S. Maeda, and K. Morokuma, J. Chem. Theory. Comput. 9, 893 (2013)], 10.1021/ct3009792. The branching ratio of isotope exchange versus O2 + NO formation, as well as the product angular distributions and energy and rovibrational state distributions are presented. The calculations are done at the collision energy of relevance to recent crossed beam experiments [K. A. Mar, A. L. Van Wyngarden, C.-W. Liang, Y. T. Lee, J. J. Lin, and K. A. Boering, J. Chem. Phys. 137, 044302 (2012)], 10.1063/1.4736567. Very good agreement is achieved between the current calculations and these experiments for the branching ratio and final translational energy and angular distributions of isotope exchange products 16O(3P) + NO2 and O2 + NO formation products. The reactant 18O atom results in 18O16O but not N18O for the O2 + NO formation product channel, consistent with the experiment. In addition, the detailed vibrational and rotational state information of diatomic molecules calculated currently for the 34O2 + NO formation channel on D0 and D1 states are in qualitative agreement with the previous experimental and theoretical results of the photodissociation of NO3 and are consistent with older thermal bimolecular kinetics measurements.

  5. Investigation of hydrogen isotope exchange reaction rate in mixed gas (H{sub 2} and D{sub 2}) at pressure up to 200 MPa using Raman spectroscopy

    SciTech Connect

    Tikhonov, V.V.; Yukhimchuk, A.A.; Musyayev, R.K.; Gurkin, A.I.

    2015-03-15

    Raman spectroscopy is a relevant method for obtaining objective data on isotopic exchange rate in a gaseous mix of hydrogen isotopes, since it allows one to determine a gaseous mix composition in real time without sampling. We have developed a high-pressure fiber-optic probe to be used for obtaining protium Raman spectra under pressures up to 400 MPa and we have recorded spectral line broadening induced by molecule collisions starting from ∼ 40 MPa. Using this fiber-optic probe we have performed experiments to study isotopic exchange kinetics in a gaseous mix of hydrogen isotopes (protium-deuterium) at pressures up to 200 MPa. Preliminary results show that the dependence of the average isotopic exchange rate related to pressure take unexpected values at the very beginning of the time evolution. More work is required to understand this inconsistency.

  6. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    HEUNG, LEUNGK.

    2004-08-18

    Porous solids such as activated alumina, silica and molecular sieves generally contain significant amounts of hydrogen atoms in the form of H2O or OH even at high temperature and low humidity environment. A significant amount of this hydrogen is available for reversible isotopic exchange. This exchange reaction is slow under normal conditions and does not render itself to practical applications. But if the exchange kinetics is improved this reaction has the potential to be used for tritium removal from gas streams or for hydrogen isotopic separation.The use of catalysts to improve the exchange kinetics between hydrogen isotope in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum or palladium as the catalyst. The granules were packed in a 2-cm diameter column for isotope exchange tests. Gas streams containing different concentrations of deuterium in nitrogen or argon were fed through the protium saturated column. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  7. Rate of oxygen isotope exchange between selenate and water.

    PubMed

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

    The rate of oxygen isotope exchange between selenate and water was investigated at conditions of 10 to 80 °C and pH -0.6 to 4.4. Oxygen isotope exchange proceeds as a first-order reaction, and the exchange rate is strongly affected by reaction temperature and pH, with increased rates of isotope exchange at higher temperature and lower pH. Selenate speciation (HSeO(4)(-) vs SeO(4)(2-)) also has a significant effect on the rate of isotope exchange. The half-life for isotope exchange at example natural conditions (25 °C and pH 7) is estimated to be significantly in excess of 10(6) years. The very slow rate of oxygen isotope exchange between selenate and water under most environmental conditions demonstrates that selenate-δ(18)O signatures produced by biogeochemical processes will be preserved and hence that it will be possible to use the value of selenate-δ(18)O to investigate the biogeochemical behavior of selenate, in an analogous fashion to the use of sulfate-δ(18)O to study the biogeochemical behavior of sulfate.

  8. Photonuclear reactions on titanium isotopes

    SciTech Connect

    Belyshev, S. S.; Dzhilavyan, L. Z.; Ishkhanov, B. S.; Kapitonov, I. M.; Kuznetsov, A. A. Orlin, V. N.; Stopani, K. A.

    2015-03-15

    The photodisintegration of titanium isotopes in the giant-dipole-resonance energy region is studied by the photon-activation method. Bremsstrahlung photons whose spectrum has the endpoint energy of 55 MeV is used. The yields and integrated cross sections are determined for photoproton reactions on the titanium isotopes {sup 47,48,49,50}Ti. The respective experimental results are compared with their counterparts calculated on the basis of the TALYS code and a combined photonucleon-reaction model. The TALYS code disregards the isospin structure of the giant dipole resonance and is therefore unable to describe the yield of photoproton reactions on the heavy titanium isotopes {sup 49,50}Ti.

  9. Thermal decomposition of methanol in the sonolysis of methanol-water mixtures. Spin-trapping evidence for isotope exchange reactions

    SciTech Connect

    Krishna, C.M.; Lion, Y.; Kondo, T.; Riesz, P.

    1987-11-05

    The spin trap 3,5-dibromo-4-nitrosobenzenesulfonate was used to monitor the yield of free radicals produced during sonolysis of water-methanol mixtures. Methyl radicals and CH/sub 2/OH radicals were observed as well as the isotopically mixed radicals CH/sub 2/D and CHD/sub 2/ when CH/sub 3/OD:D/sub 2/O mixtures were studied. The results clearly show that thermal decomposition of methanol to methyl radicals occurs in the gas phase. The methyl radical yield rises sharply at very low concentrations of methanol, reaches a maximum at 5 mol dm/sup -3/ in water and decreases to a smaller value in methanol. The yield of methyl radicals as a function of methanol concentration is discussed in terms of the different factors influencing the sonochemistry.

  10. Calculation of individual isotope equilibrium constants for geochemical reactions

    USGS Publications Warehouse

    Thorstenson, D.C.; Parkhurst, D.L.

    2004-01-01

    Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation

  11. Catalytic gasification: Isotopic labeling and transient reaction

    SciTech Connect

    Saber, J.M.; Falconer, J.L.; Brown, L.F.

    1985-01-01

    Temperature-programmed reaction was used with labeled isotopes (/sup 13/C and /sup 18/O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO/sub 2//90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 K and 950 K, and in the presence of gaseous carbon dioxide, the complexes promoted carbon and oxygen exchange between the gas-phase CO/sub 2/ and the surface. Oxygen exchanged between the surface complexes; but carbon did not exchange between the carbonate and the carbon black. As the temperature rose, the complexes decomposed to produce carbon dioxide, and catalytic gasification then began. Elemental potassium formed, and the active catalyst appears to alternate between potassium metal and a potassium-oxygen-carbon complex.

  12. Heavy atom isotope effects on enzymatic reactions

    NASA Astrophysics Data System (ADS)

    Paneth, Piotr

    1994-05-01

    The theory of isotope effects, which has proved to be extremely useful in providing geometrical details of transition states in a variety of chemical reactions, has recently found an application in studies of enzyme-catalyzed reactions. These reactions are multistep in nature with few steps being partially rate-limiting, thus interpretation of these isotope effects is more complex. The theoretical framework of heavy-atom isotope effects on enzymatic reactions is critically analyzed on the basis of recent results of: carbon kinetic isotope effects on carbonic anhydrase and catalytic antibodies; multiple carbon, deuterium isotope effects on reactions catalyzed by formate decarboxylase; oxygen isotope effects on binding processes in reactions catalyzed by pyruvate kinase; and equilibrium oxygen isotope effect on binding an inhibitor to lactate dehydrogenase. The advantages and disadvantages of reaction complexity in learning details of formal and molecular mechanisms are discussed in the examples of reactions catalyzed by phosphoenolpyruvate carboxylase, orotidine decarboxylase and glutamine synthetase.

  13. Isotope exchange in oxide-containing catalyst

    NASA Technical Reports Server (NTRS)

    Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

    1989-01-01

    A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

  14. The non-statistical dynamics of the {sup 18}O + {sup 32}O{sub 2} isotope exchange reaction at two energies

    SciTech Connect

    Van Wyngarden, Annalise L.; Mar, Kathleen A.; Wiegel, Aaron A.; Quach, Jim; Nguyen, Anh P. Q.; Lin, Shi-Ying; Lendvay, Gyorgy; Guo, Hua; Lin, Jim J.; Lee, Yuan T.; Boering, Kristie A.

    2014-08-14

    The dynamics of the {sup 18}O({sup 3}P) + {sup 32}O{sub 2} isotope exchange reaction were studied using crossed atomic and molecular beams at collision energies (E{sub coll}) of 5.7 and 7.3 kcal/mol, and experimental results were compared with quantum statistical (QS) and quasi-classical trajectory (QCT) calculations on the O{sub 3}(X{sup 1}A’) potential energy surface (PES) of Babikov et al. [D. Babikov, B. K. Kendrick, R. B. Walker, R. T. Pack, P. Fleurat-Lesard, and R. Schinke, J. Chem. Phys. 118, 6298 (2003)]. In both QS and QCT calculations, agreement with experiment was markedly improved by performing calculations with the experimental distribution of collision energies instead of fixed at the average collision energy. At both collision energies, the scattering displayed a forward bias, with a smaller bias at the lower E{sub coll}. Comparisons with the QS calculations suggest that {sup 34}O{sub 2} is produced with a non-statistical rovibrational distribution that is hotter than predicted, and the discrepancy is larger at the lower E{sub coll}. If this underprediction of rovibrational excitation by the QS method is not due to PES errors and/or to non-adiabatic effects not included in the calculations, then this collision energy dependence is opposite to what might be expected based on collision complex lifetime arguments and opposite to that measured for the forward bias. While the QCT calculations captured the experimental product vibrational energy distribution better than the QS method, the QCT results underpredicted rotationally excited products, overpredicted forward-bias and predicted a trend in the strength of forward-bias with collision energy opposite to that measured, indicating that it does not completely capture the dynamic behavior measured in the experiment. Thus, these results further underscore the need for improvement in theoretical treatments of dynamics on the O{sub 3}(X{sup 1}A’) PES and perhaps of the PES itself in order to better

  15. Highly tritiated water processing by isotopic exchange

    SciTech Connect

    Shu, W.M.; Willms, R.S.; Glugla, M.; Cristescu, I.; Michling, R.; Demange, D.

    2015-03-15

    Highly tritiated water (HTW) is produced in fusion machines and one of the promising technologies to process it is isotopic exchange. 3 kinds of Pt-catalyzed zeolite (13X-APG, CBV-100-CY and HiSiv-1000) were tested as candidates for isotopic exchange of highly tritiated water (HTW), and CBV-100-CY (Na-Y type with a SiO{sub 2}/Al{sub 2}O{sub 3} ratio of ∼ 5.0) shows the best performance. Small-scale tritium testing indicates that this method is efficient for reaching an exchange factor (EF) of 100. Full-scale non-tritium testing implies that an EF of 300 can be achieved in 24 hours of operation if a temperature gradient is applied along the column. For the isotopic exchange, deuterium recycled from the Isotope Separation System (deuterium with 1% T and/or 200 ppm T) should be employed, and the tritiated water regenerated from the Pt-catalyzed zeolite bed after isotopic exchange should be transferred to Water Detritiation System (WDS) for further processing.

  16. Isotopic Exchange in Porous and Dense Magnesium Borohydride.

    PubMed

    Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

    2015-09-01

    Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2.

  17. Kinetic theory of oxygen isotopic exchange between minerals and water

    USGS Publications Warehouse

    Criss, R.E.; Gregory, R.T.; Taylor, H.P.

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  18. Modeling the isotope effect in Walden inversion reactions

    NASA Astrophysics Data System (ADS)

    Schechter, Israel

    1991-05-01

    A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH 3T and CH 2TF from the reaction T + CH 3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

  19. Carbon isotopic exchange between dissolved inorganic and organic carbon

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Freeman, K. H.; House, C. H.; Arthur, M. A.

    2009-12-01

    The pools of inorganic and organic carbon are often considered to be separate and distinct. Isotopic exchange between the inorganic and organic carbon pools in natural waters is rarely considered plausible at low temperatures owing to kinetic barriers to exchange. In certain circumstances, however carboxyl carbon of dissolved organic matter (DOM) may be subject to exchange with the dissolved inorganic carbon (DIC) pool. We report results from an isotopic labeling experiment that resulted in rapid methanogen-catalyzed isotopic exchange between DIC and the carboxyl carbon of acetate. This exchange rapidly mixes the isotopic composition of the DIC pool into the dissolved organic carbon (DOC) acetate pool. This exchange is likely associated with the reversible nature of the carbon monoxide dehydrogenase enzyme. In nature, many decarboxylase enzymes are also reversible and some can be shown to facilitate similar exchange reactions. Those decarboxylase enzymes that are important in lignin decomposition and other organic carbon (OC) transformations may help to mask the isotopic composition of the precursor DOC with as much as 15% contribution from DIC. Though this dilution is unlikely to matter in soils where DOC and DIC are similar in composition, this exchange may be extremely important in systems where the stable or radioisotope composition of DOC and DIC differ significantly. As an example of the importance of this effect, we demonstrate that the stable and radiocarbon isotopic composition of fluvial DOC could be altered by mixing with marine DIC to produce a DOC composition similar to those observed in the deep marine DOC pool. We hypothesize that this exchange resolves the conundrum of apparently old (>5 kyr) marine-derived DOC. If most of the carboxyl carbon of pre-aged, terrestrial-derived DOC (15% of total carbon) is subject to exchange with marine DIC, the resulting carbon isotopic composition of deep DOC will be similar to that observed in deep marine studies

  20. Unbiased isotope equilibrium factors from partial isotope exchange experiments in 3-exchange site systems

    NASA Astrophysics Data System (ADS)

    Agrinier, Pierre; Javoy, Marc

    2016-09-01

    Two methods are available in order to evaluate the equilibrium isotope fractionation factors between exchange sites or phases from partial isotope exchange experiments. The first one developed by Northrop and Clayton (1966) is designed for isotope exchanges between two exchange sites (hereafter, the N&C method), the second one from Zheng et al. (1994) is a refinement of the first one to account for a third isotope exchanging site (hereafter, the Z method). In this paper, we use a simple model of isotope kinetic exchange for a 3-exchange site system (such as hydroxysilicates where oxygen occurs as OH and non-OH groups like in muscovite, chlorite, serpentine, or water or calcite) to explore the behavior of the N&C and Z methods. We show that these two methods lead to significant biases that cannot be detected with the usual graphical tests proposed by the authors. Our model shows that biases originate because isotopes are fractionated between all these exchanging sites. Actually, we point out that the variable mobility (or exchangeability) of isotopes in and between the exchange sites only controls the amplitude of the bias, but is not essential to the production of this bias as previously suggested. Setting a priori two of the three exchange sites at isotopic equilibrium remove the bias and thus is required for future partial exchange experiments to produce accurate and unbiased extrapolated equilibrium fractionation factors. Our modeling applied to published partial oxygen isotope exchange experiments for 3-exchange site systems (the muscovite-calcite (Chacko et al., 1996), the chlorite-water (Cole and Ripley, 1998) and the serpentine-water (Saccocia et al., 2009)) shows that the extrapolated equilibrium fractionation factors (reported as 1000 ln(α)) using either the N&C or the Z methods lead to bias that may reach several δ per mil in a few cases. These problematic cases, may be because experiments were conducted at low temperature and did not reach high

  1. Double charge exchange on Te isotopes in the generalized seniority scheme

    SciTech Connect

    Wu, H.C. |; Ginocchio, J.N.; Dieperink, A.E.; Scholten, O.

    1996-09-01

    The pion double-charge-exchange reactions on the Te isotopes are discussed in the generalized seniority scheme. The elementary process of charge exchange is described in a double scattering process within the plane wave limit. The transition rates are calculated for double-isobaric-analog state as well as for ground-state reactions. {copyright} {ital 1996 The American Physical Society.}

  2. Separation of uranium isotopes by chemical exchange

    DOEpatents

    Ogle, P.R. Jr.

    1974-02-26

    A chemical exchange method is provided for separating /sup 235/U from / sup 238/U comprising contacting a first phase containing UF/sub 6/ with a second phase containing a compound selected from the group consisting of NOUF/sub 6/, NOUF/sub 7/, and NO/sub 2/UF/sub 7/ until the U Fsub 6/ in the first phase becomes enriched in the /sup 235/U isotope. (Official Gazette)

  3. Rapid biologically mediated oxygen isotope exchange between water and phosphate

    NASA Astrophysics Data System (ADS)

    Paytan, Adina; Kolodny, Yehoshua; Neori, Amir; Luz, Boaz

    2002-03-01

    In order to better constrain the rate of oxygen isotope exchange between water and phosphate via biochemical reactions a set of controlled experiments were conducted in 1988 at the Aquaculture Plant in Elat, Israel. Different species of algae and other organisms were grown in seawater tanks under controlled conditions, and the water temperature and oxygen isotopic composition (δ18Ow) were monitored. The oxygen isotopic composition of phosphate (δ18Op) in the organisms' food source, tissues, and the δ18Op of dissolved inorganic phosphate (DIP) were measured at different stages of the experiments. Results indicate that intracellular oxygen isotope exchange between phosphorus compounds and water is very rapid and occurs at all levels of the food chain. Through these reactions the soft tissue δ18Op values become 23-26‰ higher than δ18Ow, and δ18Op values of DIP become ~20‰ higher than δ18Ow. No correlation between δ18Op values and either temperature or P concentrations in these experiments was observed. Our data imply that biogenic recycling and intracellular phosphorus turnover, which involves kinetic fractionation effects, are the major parameters controlling the δ18Op values of P compounds dissolved in aquatic systems. This information is fundamental to any application of δ18Op of dissolved organic or inorganic phosphate to quantify the dynamics of phosphorus cycling in aquatic systems.

  4. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  5. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange.

    PubMed

    Zheng, Yong-Fei

    2016-01-01

    Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4 and BiPO4 are enriched in (18)O relative to AgPO4, and the three phosphates are consistently depleted in (18)O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of (18)O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the (18)O/(16)O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4-H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite-water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate-water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates.

  6. Oxygen-isotope exchange rates for three isostructural polyoxometalate ions.

    PubMed

    Villa, Eric M; Ohlin, C André; Casey, William H

    2010-04-14

    We compare oxygen-isotope exchange rates for all structural oxygens in three polyoxoniobate ions that differ by systematic metal substitutions of Ti(IV) --> Nb(V). The [H(x)Nb(10)O(28)]((6-x)-), [H(x)TiNb(9)O(28)]((7-x)-), and [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ions are all isostructural yet have different Brønsted properties. Rates for sites within a particular molecule in the series differ by at least approximately 10(4), but the relative reactivities of the oxygen sites rank in nearly the same relative order for all ions in the series. Within a single ion, most structural oxygens exhibit rates of isotopic exchange that vary similarly with pH, indicating that each structure responds as a whole to changes in pH. Across the series of molecules, however, the pH dependencies for isotope exchanges and dissociation are distinctly different, reflecting different contributions from proton- or base-enhanced pathways. The proton-enhanced pathway for isotope exchange dominates at most pH conditions for the [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ion, but the base-enhanced pathways are increasingly important for the [H(x)TiNb(9)O(28)]((7-x)-) and [H(x)Nb(10)O(28)]((6-x)-) structures at higher pH. The local effect of Ti(IV) substitution could be assessed by comparing rates for structurally similar oxygens on each side of the [H(x)TiNb(9)O(28)]((7-x)-) ion and is surprisingly small. Interestingly, these nanometer-size structures seem to manifest the same general averaged amphoteric chemistry that is familiar for other reactions affecting oxides in water, including interface dissolution by proton- and hydroxyl-enhanced pathways.

  7. Reaction Kinetics of HBr with HO2: A New Channel for Isotope Scrambling Reactions.

    PubMed

    Church, Jonathan R; Skodje, Rex T

    2016-11-03

    The gas phase reaction kinetics of HBr with the HO2 radical are investigated over the temperature range of T = 200-1500 K using a theoretical approach based on transition state theory. The parameters for the potential energy surface are computed using density functional theory with the M11 exchange functional. The rate coefficient for the HBr + HO2 → Br + H2O2 abstraction channel is found to be somewhat larger than previous estimates at low temperatures due to quantum tunneling. The present study reveals the existence of a novel exchange pathway, HBr + H'O2 → H'Br + HO2, which exhibits a much lower reaction barrier than does the abstraction route. The transition state for this process is a symmetrical planar five-membered-ring-shaped structure. At low temperatures, this concerted double hydrogen transfer reaction is several orders of magnitude faster than the abstraction channel. The exchange process may be observed using isotope scrambling reactions; such reactions may contribute to observed isotope abundances in the atmosphere. The rate coefficients for the isotopically labeled reactions are computed.

  8. Diffusional exchange of isotopes in a metal hydride sphere.

    SciTech Connect

    Wolfer, Wilhelm G.; Hamilton, John C.; James, Scott Carlton

    2011-04-01

    This report describes the Spherical Particle Exchange Model (SPEM), which simulates exchange of one hydrogen isotope by another hydrogen isotope in a spherical metal hydride particle. This is one of the fundamental physical processes during isotope exchange in a bed of spherical metal particles and is thus one of the key components in any comprehensive physics-based model of exchange. There are two important physical processes in the model. One is the entropy of mixing between the two isotopes; the entropy of mixing is increased by having both isotopes randomly placed at interstitial sites on the lattice and thus impedes the exchange process. The other physical process is the elastic interaction between isotope atoms on the lattice. The elastic interaction is the cause for {beta}-phase formation and is independent of the isotope species. In this report the coupled diffusion equations for two isotopes in the {beta}-phase hydride are solved. A key concept is that the diffusion of one isotope depends not only on its concentration gradient, but also on the concentration gradient of the other isotope. Diffusion rate constants and the chemical potentials for deuterium and hydrogen in the {beta}-phase hydride are reviewed because these quantities are essential for an accurate model of the diffusion process. Finally, a summary of some of the predictions from the SPEM model are provided.

  9. Method for isotope replenishment in an exchange liquid used in a laser induced isotope enrichment process

    SciTech Connect

    Keyser, G.M.; Mader, D.L.; O'Neill, J.A.

    1986-11-04

    A method is described for deuterium or tritium isotope replenishment of an exchange liquid in a process for concentrating deuterium or tritium by means of a laser induced selective photodissociation of a deuterium or tritium containing working compound mixed with its protiated or deuterated analog. The working compound is selected from the group consisting of a dueterated or tritiated analog of a dihalomethane, a trihalomethane, a 1,2-dihaloethylene, a trihaloethylene, a tetrahaloethane, and a pentahaloethane. The method comprises: selectively laser photodissociating the working compound to give an isotope enriched compound and an isotope depleted working compound; contacting the isotope depleted working compound mixture countercurrently with an exchange liquid having approximately the isotope concentration of an external source feed stream of water of D/sub 2/O in a first contacting column. The countercurrent contacting provides an isotope replenishment of the working compound as it moves up the column and an isotope depletion of the exchange liquid as it moves down the column. The exchange liquid consists essentially of a mixture of water of D/sub 2/O and a strong base catalyst; removing isotope deplated exchange liquid from the bottom of the first column; contacting the isotope depleted exchange liquid countercurrently with the feed stream in a second contacting apparatus thereby providing isotope replenishment of the exchange liquid and isotope depletion of the feed stream without causing salting out of the base catalyst; and removing the isotope replenished exchange liquid from one end of the second apparatus for use in the first column and removing isotope depleted water of D/sub 2/O steam from the other end of the second apparatus.

  10. Individual Differences in Reactions to Inequitable Exchanges.

    ERIC Educational Resources Information Center

    Ellis, Barbara B.; Penner, Louis A.

    1983-01-01

    Investigates the role of sociopathic tendencies in reactions to inequitable exchanges in 273 males and females classified as high or low in sociopathy. Subjects read narratives of inequitable exchanges and assumed the role of the exploiter and the role of the victim in each. (Author/RH)

  11. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    Heung, L.K.; Staack, G.C.

    2005-07-15

    The use of catalysts to improve the exchange kinetics between hydrogen isotopes in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum as the catalyst. The granules saturated with water at room humidity were packed in a 2-cm diameter column for isotope exchange tests. Deuterium and protium were alternately fed through the column at a constant rate. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  12. Process for exchanging hydrogen isotopes between gaseous hydrogen and water

    SciTech Connect

    Hindin, Saul G.; Roberts, George W.

    1980-08-12

    A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

  13. Isotopic fractionation in low temperature ion--molecule exchange reactions: Enrichment of sup 22 Ne in Ne sup + sub n clusters formed by association in an ionized free jet

    SciTech Connect

    DeLuca, M.J.; Cyr, D.M.; Chupka, W.A.; Johnson, M.A. )

    1990-06-15

    Cationic clusters of neon atoms (Ne{sup +}{sub {ital n}} ) formed by association of neutrals onto seed ions in an ionized supersonic expansion are found to favor incorporation of the heavier isotope ({sup 22}Ne) {ital by} {ital as} {ital much} {ital as} {ital a} {ital factor} {ital of} 15 (in the dimer and trimer ions) when compared to a simple statistical distribution based on natural abundances. This enrichment is attributed to the small difference in zero-point energies among species formed with the two major isotopes of neon ({sup 20}Ne and {sup 22}Ne), which is of the same order as the collisional energy of particles in the expanding jet. This enrichment is anticipated by current models of isotope exchange which are invoked to explain the anomalous isotope abundance patterns in interstellar clouds.

  14. Strangeness exchange reactions and hypernuclei

    SciTech Connect

    Dover, C.B.

    1982-01-01

    Recent progress in the spectroscopy of ..lambda.. and ..sigma.. hypernuclei is reviewed. Prospects for the production of doubly strange hypernuclei at a future kaon factory are assessed. It is suggested that the (K/sup -/,K/sup +/) reaction on a nuclear target may afford an optimal way of producing the H dibaryon, a stable six quark object with J/sup ..pi../ = O/sup +/, S = -2.

  15. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    SciTech Connect

    Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.; Scherer, Michelle M.; Spicuzza, Michael J.; Valley, John W.; Johnson, Clark M.

    2015-07-01

    solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸OGth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II)aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.

  16. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography

    PubMed Central

    Ismail, Ibrahim; Fawzy, Ahmed S.; Ahmad, Mohammad I.; Aly, Hisham F.; Nomura, Masao; Fujii, Yasuhiko

    2012-01-01

    The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ε’s, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ε’s, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated. PMID:25685410

  17. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography.

    PubMed

    Ismail, Ibrahim; Fawzy, Ahmed S; Ahmad, Mohammad I; Aly, Hisham F; Nomura, Masao; Fujii, Yasuhiko

    2013-03-01

    The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ε's, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ε's, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated.

  18. Experimental observations on carbon isotope exchange in carbonate-water systems

    NASA Astrophysics Data System (ADS)

    Mozeto, A. A.; Fritz, P.; Reardon, E. J.

    1984-03-01

    This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 10 11 reaction sites per cm 2, following a second order rate law with respect to 13C concentration in solution ( constant kex ⋍ 10 6 cm 5 mole -1 s -1 and half-life t 1/2 = 700 s). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10 -8 s -1 and a t 1/2 of 10 7 s. Negative isotopic gradient experiments and runs with calcite crystals in Mg 2+ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.

  19. Iron isotope fractionation between aqueous Fe(II) and goethite revisited: New insights based on a multi-direction approach to equilibrium and isotopic exchange rate modification

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Reddy, Thiruchelvi R.; Scherer, Michelle M.; Johnson, Clark M.

    2014-08-01

    The Fe isotope compositions of naturally occurring Fe oxide minerals provide insights into biogeochemical processes that occur in modern and ancient environments. Key to understanding isotopic variations in such minerals is knowledge of the equilibrium Fe isotope fractionation factors between common minerals and aqueous Fe species. Because experimental measurements of isotopic fractionation may reflect a combination of kinetic and equilibrium fractionations during rapid dissolution and precipitation, even in experiments that employ the three-isotope method, assessment of the attainment of equilibrium is often difficult. Here, we re-examine Fe isotope exchange, via a 57Fe tracer, and natural mass-dependent fractionation, through changes in initial 56Fe/54Fe ratios, between aqueous Fe(II) (Fe(II)aq) and goethite. This approach uses the three-isotope method, but is distinct in its evaluation of kinetic isotope fractionation and the attainment of equilibrium by: (i) employing a multi-direction approach to equilibrium at 22 °C via reaction of three Fe(II)aq solutions that had different initial 56Fe/54Fe ratios, (ii) conducting isotopic exchange experiments at elevated temperature (50 °C), and (iii) modifying the rate of isotopic exchange through a combination of trace-element substitutions and particle coarsening to evaluate corresponding temporal changes in fractionation trajectories that may reflect changing instantaneous fractionation factors. We find that rapid isotopic exchange produces kinetic isotope effects between Fe(II)aq and goethite, which shifts the 56Fe/54Fe ratios of Fe(II)aq early in reactions toward that of goethite, indicating that the instantaneous Fe(II)aq-goethite fractionation factor under kinetic conditions is small. Importantly, however, this kinetic fractionation is “erased” with continued reaction, and this is evident by the congruence for multiple-exchange trajectories of distinct initial Fe(II)aq solutions toward the same final value

  20. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    SciTech Connect

    Rosenberg, R.M.; O'Leary, M.H.

    1985-03-26

    The authors have measured the /sup 13/C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D/sub 2/O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D/sub 2/O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The /sup 13/C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the /sup 13/C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier.

  1. Forging Colloidal Nanostructures via Cation Exchange Reactions

    PubMed Central

    2016-01-01

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

  2. Kinetic isotope effects for fast deuterium and proton exchange rates

    PubMed Central

    Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey

    2016-01-01

    By monitoring the effect of deuterium decoupling on the decay of transverse 15N magnetization in D–15N spin pairs during multiple-refocusing echo sequences, we have determined fast D–D exchange rates k D and compared them with fast H–H exchange rates k H in tryptophan to determine the kinetic isotope effect as a function of pH and temperature. PMID:27009684

  3. Kinetic isotope effects for fast deuterium and proton exchange rates.

    PubMed

    Canet, Estel; Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey

    2016-04-21

    By monitoring the effect of deuterium decoupling on the decay of transverse (15)N magnetization in D-(15)N spin pairs during multiple-refocusing echo sequences, we have determined fast D-D exchange rates kD and compared them with fast H-H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.

  4. Nuclear Reaction Data on Titanium Isotopes

    SciTech Connect

    Oh, S. Y.; Kawano, T.; Kahler, S.; Cowell, S.; Dashdorj, D.

    2008-04-17

    We evaluated the nuclear data on titanium isotopes, {sup 46-50}Ti. We used GNASH, a Hauser-Feshbach reaction model code, for the threshold reactions and CoH for the total and capture cross sections. While we calculated the transmission coefficients using well-known optical potentials for the GNASH calculation, we adjusted the level density and the pre-equilibrium parameters by taking into account the LANSCE/GEANIE experiment on {sup 48}Ti reaction cross sections as well as other experiments available for (n,p), (n,{alpha}), etc. The direct inelastic scattering was also included by using the coupled-channel calculation and the DWBA method. The coupled-channels potential was assumed to be similar to the spherical potential of Koning and Delaroche with proper deformation parameters. Meanwhile we investigated the resolved resonance parameters in the energy region below several hundred keV. In essence, we adopted the parameters from the Mughabghab's 2006 compilation, making some adjustments to mainly reproduce the reference thermal cross sections. This new evaluation was validated with the MCNP calculations of k-eff's on seven hard-spectrum criticality experiments that involve Ti as a reflector or moderator.

  5. Production of medical 99 m Tc isotope via photonuclear reaction

    NASA Astrophysics Data System (ADS)

    Fujiwara, M.; Nakai, K.; Takahashi, N.; Hayakawa, T.; Shizuma, T.; Miyamoto, S.; Fan, G. T.; Takemoto, A.; Yamaguchi, M.; Nishimura, M.

    2017-01-01

    99 m Tc with a 6 hour half-life is one of the most important medical isotopes used for the Single-Photon Emission Computed Tomography (SPECT) inspection in hospitals of US, Canada, Europe and Japan. 99 m Tc isotopes are extracted by the milking method from parent 99Mo isotopes with a 66 hour half-life. The supply of 99Mo isotopes now encounters a serious crisis. Hospitals may not suitably receive 99Mo medical isotopes in near future, due to difficulties in production by research nuclear reactors. Many countries are now looking for alternative ways to generate 99Mo isotopes other than those with research reactors. We discuss a sustained availability of 99 m Tc isotopes via the nat Mo(γ, n) photonuclear reaction, and discuss to solve technical problems for extracting pure 99 m Tc isotopes from other output materials of photonuclear reactions.

  6. Chromatographic separation of neodymium isotopes by using chemical exchange process.

    PubMed

    Ismail, I M; Ibrahim, M; Aly, H F; Nomura, M; Fujii, Y

    2011-05-20

    The neodymium isotope effects were investigated in Nd-malate ligand exchange system using the highly porous cation exchange resin SQS-6. The temperature of the chromatographic columns was kept constant at 50°C by temperature controlled water passed through the columns jackets. The separation coefficient of neodymium isotopes, ɛ's, was calculated from the isotopic ratios precisely measured by means of an ICP mass spectrometer equipped with nine collectors as ion detectors. The separation coefficient, ɛ×10(5), were calculated and found to be 1.4, 4.8, 5.4, 10.6, 16.8 and 20.2 for (143)Nd, (144)Nd, (145)Nd, (146)Nd, (148)Nd and (150)Nd, respectively.

  7. Equilibrium isotopic fractionation and isotopic exchange kinetics between Cr(III) and Cr(VI)

    NASA Astrophysics Data System (ADS)

    Wang, Xiangli; Johnson, Thomas M.; Ellis, Andre S.

    2015-03-01

    We determined the equilibrium isotope fractionation between Cr(III) and Cr(VI), defined as Δ53CrVI-III = δ53Cr(VI) - δ53Cr(III), and the rates of isotopic exchange between the two redox species under different conditions. In high Cr concentration, low-pH experiments we determined the Δ53CrV-III between CrO42- and Cr(H2O)63+ to be 5.2 ± 0.3‰ and 5.5 ± 0.3‰ at 60 °C and 40 °C, respectively. At 25 °C, the system only progressed 25% toward isotopic equilibrium after 684 days. By extrapolating from the 60 °C and 40 °C experiments we estimated the Δ53CrVI-III between CrO42- and Cr(H2O)63+ to be 5.8 ± 0.5‰ at 25 °C. Isotope exchange rates between dissolved Cr(III) and dissolved Cr(VI) at 25 °C, 40 °C, and 60 °C were determined to be 3.13 × 10-5 M day-1, 6.83 × 10-4 M day-1, and 8.37 × 10-3 M day-1, respectively. In low concentration, neutral-pH experiments we determined the isotopic exchange rates between dissolved Cr(VI) and solid Cr(III) oxyhydroxide at 25 °C. In these experiments, significant isotopic exchange was found on time scales of months, though the magnitude of isotopic shifts was limited by the small mass of Cr(III) available for exchange on the surfaces of Cr(III) oxyhydroxide particles. Exchange rates were relatively fast, compared to rates obtained from high concentration, low-pH experiments. This faster isotopic exchange is attributed to adsorption of Cr(VI) to Cr(III) particle surfaces, which keeps Cr(III) and Cr(VI), and potentially intermediate species Cr(V), in close proximity long enough to allow multiple electron transfers. The isotopic exchange rate at neutral-pH was found to conform to the rate law R = k·[Cr(VI)]adsorbed, in which R is the isotopic exchange rate (M day-1); k is the rate constant, determined to be 0.00047 day-1; [CrO42-]adsorbed is the concentration of Cr(VI) adsorbed to Cr(III) oxyhydroxide (M). The impact of isotopic exchange on the 53Cr/52Cr ratio of the dissolved Cr(VI) depends on the relative masses

  8. Multiphysics Model of Palladium Hydride Isotope Exchange Accounting for Higher Dimensionality

    SciTech Connect

    Gharagozloo, Patricia E.; Eliassi, Mehdi; Bon, Bradley Luis

    2015-03-01

    This report summarizes computational model developm ent and simulations results for a series of isotope exchange dynamics experiments i ncluding long and thin isothermal beds similar to the Foltz and Melius beds and a lar ger non-isothermal experiment on the NENG7 test bed. The multiphysics 2D axi-symmetr ic model simulates the temperature and pressure dependent exchange reactio n kinetics, pressure and isotope dependent stoichiometry, heat generation from the r eaction, reacting gas flow through porous media, and non-uniformities in the bed perme ability. The new model is now able to replicate the curved reaction front and asy mmetry of the exit gas mass fractions over time. The improved understanding of the exchange process and its dependence on the non-uniform bed properties and te mperatures in these larger systems is critical to the future design of such sy stems.

  9. The fractionation of selenium isotopic exchange between Se (0) and Se (IV)

    NASA Astrophysics Data System (ADS)

    Can, T. D.; Jianming, Z.; Qin, H.; Xu, W.

    2016-12-01

    Selenium (Se) has six naturally stable isotopes, 74Se, 76Se, 77Se, 78Se, 80Se, and 82Se; with the relative abundance of 0.89%, 9.37%, 7.64%, 23.77%, 49.61%, and 8.73%, respectively. According to the previous work, the variations in δ82/76Se suggested that biogeochemical cycling in earth surface can lead to significant Se isotopic fractionation [1]. It was now believed that the abiotic and biotic reduction for Se (IV) and Se (VI) oxyanion was the main processes for Se isotope fractionation in natural systems. However, recently, the theoretical calculation by first-principles shows that equilibrium Se isotope fractionation between SeO32-and SeO42- can reach Δ82/76Se =13.3‰ at the 25 °, and have a trend of heavy Se isotopes enrichment as SeO42- > SeO3 2- > HSeO3- > SeO2 > selenoamino acids > alkylselenides > Se (0) or H2Se >HSe-[2]. So we take a new idea that the significant isotopic fractionation of Se may be caused by the combined role of Se reduction and isotopic exchange. In the past years, the study of the mechanism of Se isotope fractionation was mainly focused on the reduction of Se oxyanion, but for the fractionation by the isotope exchange between different Se speciation is poorly studied. Therefore, we take the isotope exchange between Se (0) and Se (IV) as an example, to compare the isotope fractionation of Se under the different reaction conditions. Experiment was conducted using 10 mg Se (0) particles mixed with 2 mg/L Se (IV) solution in different medium (MQ-water, 0.1mol/L and 1mol / L NaOH), and the time lasted for 96 days. The value of δ82/76Se in Se (IV) solution from the initial -1.20 ‰ to 2.22‰, 4.20‰ and 6.69‰, respectively. From this experiment we can know, with the increasement of alkalinity in medium solution, the rate for oxidation of Se (0) oxidized by the dissolved oxygen is gradually to increase, and can gain more free electrons for the reaction of the isotopic exchange between Se (0) and Se (IV), and make the rate of isotopic

  10. [Solid state isotope hydrogen exchange for deuterium and tritium in human gene-engineered insulin].

    PubMed

    Zolotarev, Yu A; Dadayan, A K; Kozik, V S; Gasanov, E V; Nazimov, I V; Ziganshin, R Kh; Vaskovsky, B V; Murashov, A N; Ksenofontov, A L; Haribin, O N; Nikolaev, E N; Myasoedov, N F

    2014-01-01

    The reaction of high temperature solid state catalytic isotope exchange in peptides and proteins under the action of catalyst-activated spillover hydrogen was studied. The reaction of human gene-engineered insulin with deuterium and tritium was conducted at 120-140° C to produce insulin samples containing 2-6 hydrogen isotope atoms. To determine the distribution of the isotope label over tritium-labeled insulin's amino acid residues, oxidation of the S-S bonds of insulin by performic acid was performed and polypeptide chains isolated; then their acid hydrolysis, amino acid analysis and liquid scintillation counts of tritium in the amino acids were conducted. The isotope label was shown to be incorporated in all amino acids of the protein, with the peptide fragment FVNQHLCGSHLVE of the insulin β-chain showing the largest incorporation. About 45% of the total protein isotope label was incorporated in His5 and His10 of this fragment. For the analysis of isotope label distribution in labeled insulin's peptide fragments, the recovery of the S-S bonds by mercaptoethanol, the enzymatic hydrolysis by glutamyl endopeptidase from Bacillus intermedius and HPLC division of the resulting peptides were carried out. Attribution of the peptide fragments formed due to hydrolysis at the Glu-X bond in the β-chain was accomplished by mass spectrometry. Mass spectrometry analysis data of the deuterium-labeled insulin samples' isotopomeric composition showed that the studied solid state isotope exchange reaction equally involved all the protein molecules. Biological studying of tritium-labeled insulin showed its physiological activity to be completely retained.

  11. Exchange of oxygen isotopes in carbon dioxide-phosphoric [correction of phosporic] acid systems.

    PubMed

    Wachter, E A; Hayes, J M

    1985-01-01

    The rate of exchange of isotopes of oxygen between solutions of concentrated phosphoric acid and CO2 was measured as a function of temperature, acid strength (pressure of water in equilibrium with the solution), pressure of CO2, and surface area of the reaction vessel. At 75 degrees C, significant exchange was found to occur even for the "anhydrous" phosphoric acids, those in which the nominal percentage of H3PO4 in solution is equal to or exceeds 100%. Exchange is much slower at 25 degrees C, but isotopic shifts as large as 0.1% can be observed in 95% H3PO4 at equilibration times approaching 1000 hr. Rates of exchange were found to be dependent upon the vapor pressure of water in equilibrium with the acid solutions. Exchange was found to occur primarily on the surface of the reaction vessel above the solution, with no dependence on total CO2 pressure. These observations indicate that phosphoric acids with nominal concentrations of H3PO4 approaching 105% are preferable for the minimization of exchange between CO2 samples and acid solutions during phosphorolyses of carbonate materials. Moreover, with such acids, significant time--temperature trade-offs are possible, allowing rapid preparation of CO2 at elevated temperatures.

  12. Practically convenient and industrially-aligned methods for iridium-catalysed hydrogen isotope exchange processes.

    PubMed

    Cochrane, A R; Idziak, C; Kerr, W J; Mondal, B; Paterson, L C; Tuttle, T; Andersson, S; Nilsson, G N

    2014-06-14

    The use of alternative solvents in the iridium-catalysed hydrogen isotope exchange reaction with developing phosphine/NHC Ir(I) complexes has identified reaction media which are more widely applicable and industrially acceptable than the commonly employed chlorinated solvent, dichloromethane. Deuterium incorporation into a variety of substrates has proceeded to deliver high levels of labelling (and regioselectivity) in the presence of low catalyst loadings and over short reaction times. The preparative outputs have been complemented by DFT studies to explore ligand orientation, as well as solvent and substrate binding energies within the catalyst system.

  13. Upper limit on the rate constant for isotope exchange between molecular oxygen and ozone at 298 K

    NASA Technical Reports Server (NTRS)

    Anderson, S. M.; Morton, J.; Mauersberger, K.

    1987-01-01

    The gas phase bimolecular isotope exchange reaction between molecular oxygen and ozone has been investigated directly for the first time. Its rate coefficient is found to be less than 2 x 10 to the -25th cu cm/sec at 298 K, over six orders of magnitude below recent estimates. Much faster exchange was observed over condensed ozone at 77 K, suggesting isotopic scrambling is catalyzed under these conditions. The low rate coefficient implies that homogeneous exchange between ground state oxygen and ozone molecules cannot play a significant role in heavy ozone chemistry.

  14. Isotope exchange kinetics in metal hydrides I : TPLUG model.

    SciTech Connect

    Larson, Rich; James, Scott Carlton; Nilson, Robert H.

    2011-05-01

    A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show

  15. Global simulation of the carbon isotope exchange of terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Ito, A.; Terao, Y.; Mukai, H.

    2009-12-01

    There remain large uncertainties in our quantification of global carbon cycle, which has close interactions with the climate system and is subject to human-induced global environmental change. Information on carbon isotopes is expected to reduce the uncertainty by providing additional constraints on net atmosphere-ecosystem exchange. This study attempted to simulate the dynamics of carbon isotopes at the global scale, using a process-based terrestrial ecosystem model: Vegetation Integrative SImulator for Trace gases (VISIT). The base-model of carbon cycle (Sim-CYCLE, Ito 2003) has already considered stable carbon isotope composition (13C/12C), and here radioactive carbon isotope (14C) was included. The isotope ratios characterize various aspects of terrestrial carbon cycle, which is difficult to be constrained by sole mass balance. For example, isotopic discrimination by photosynthetic assimilation is closely related with leaf stomatal conductance and composition of C3 and C4 plant in grasslands. Isotopic disequilibrium represents mean residence time of terrestrial carbon pools. In this study, global simulations (spatial resolution 0.5-deg, time-step 1-month) were conducted during the period 1901 to 2100 on the basis of observed and projected atmospheric CO2, climate, and land-use conditions. As anthropogenic CO2 accumulates in the atmosphere, heavier stable carbon isotope (13C) was diluted, while radioactive carbon isotope (14C) is strongly affected by atomic bomb experiments mainly in the 1950s and 1960s. The model simulated the decadal change in carbon isotope compositions. Leaf carbon with shorter mean residence time responded rapidly to the atmospheric change, while plant stems and soil humus showed substantial time-lag, leading to large isotopic disequilibrium. In the future, the isotopic disequilibrium was estimated to augment, due to accelerated rate of anthropogenic CO2 accumulation. Spatial distribution of stable isotope composition (12C/13C, or d13C) was

  16. A model of oxygen transport in Pt/ceria catalysts from isotope exchange

    SciTech Connect

    Holmgren, A.; Andersson, B.; Duprez, D.

    1999-03-10

    From isotope oxygen exchange reactions and simulations of these experiments, the important steps in oxygen transport in Pt/ceria were distinguished and their rates were estimated. A Pt/alumina sample was also experimentally investigated for comparison. Oxygen surface diffusion as well as oxygen spillover from Pt to ceria was found to be fast in comparison with adsorption/desorption of oxygen on the metal and oxygen bulk diffusion. The exchange rate was found to be higher on a very-low-Pt-dispersion sample than on a high-dispersion sample, which in the model was explained by the different adsorption properties of oxygen.

  17. Fractionation of strontium isotopes in cation-exchange chromatography

    SciTech Connect

    Oi, Takao; Ogino, Hideki; Kakihana, Hidetake ); Hosoe, Morikazu )

    1992-04-01

    Strontium isotope fractionation has been observed in cation-exchange chromatography of strontium salts. The heavier isotopes have been found enriched at the front parts of displacement-type chromatograms, which means that the heavier isotopes are preferentially fractionated into the solution phase. The average values of the single-stage separation factor (S) minus one per unit mass difference between isotopes have been 1.0 {times} 10{sup {minus}6} for the strontium chloride system, 2.9 {times} 10{sup {minus}6} for the strontium acetate system, and 3.1 {times} 10{sup {minus}6} for the strontium lactate system at 25C. No evidence of the odd-even anomalous isotope effects has been observed. The isotopic reduced partition function ratios (RPFRs) of the strontium species involved in the present study have been estimated; the RPFRs of the complex species have been found to be larger than that of simple hydrated strontium lactate and strontium acetate systems are larger than that of the strontium chloride system.

  18. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Reeves, Eoghan P.; Seewald, Jeffrey S.; Sylva, Sean P.

    2012-01-01

    To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1-C5n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323 °C and 35-36 MPa. Extensive and reversible incorporation of water-derived hydrogen into C2-C5n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3-C5n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkanes and their corresponding alkenes facilitates rapid 2H/1H exchange between water and alkyl-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.

  19. Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water

    SciTech Connect

    Butler, J.P.

    1980-04-01

    The discovery, at Chalk River Nuclear Laboratories, of a simple method of wetproofing platinum catalysts so that they retain their activity in liquid water stimulated a concentrated research program for the development of catalysts for the hydrogen-water isotopic exchange reaction. This paper reviews 10 years of study which have resulted in the development of highly active platinum catalysts which remain effective in water for periods greater than a year. The most efficient way to use these catalysts for the separation of hydrogen isotopes is in a trickle bed reactor which effects a continuous separation. The catalyst is packed in a column with hydrogen and water flowing countercurrently through the bed. The overall isotope transfer rate measured for the exchange reaction is influenced by various parameters, such as hydrogen and water flow rates, temperature, hydrogen pressure, and platinum metal loading. The effect of these parameters as well as the improved performance obtained by diluting the hydrophobic catalyst with inert hydrophilic packing are discussed. The hydrophobic catalysts can be effectively used in a variety of applications of particular interest in the nuclear industry. A Combined Electrolysis Catalytic Exchange - Heavy Water Process (CECE-HWP) is being developed at Chalk River with the ultimate aim of producing parasitic heavy water from electrolytic hydrogen streams. Other more immediate applications include the final enrichment of heavy water and the extraction of tritium from light and heavy water. Pilot plant studies on these latter processes are currently in progress.

  20. A Flow-through Reaction Cell that Couples Time-resolved X-ray Diffraction with Stable Isotope Analysis

    SciTech Connect

    Hanson, J.C.; Wall, A.J.; Heaney, P.J.; Mathur, R.; Post, J.E.; Eng, P.J.

    2011-04-01

    A non-metallic flow-through reaction cell is described, designed for in situ time-resolved X-ray diffraction coupled with stable isotope analysis. The experimental setup allows the correlation of Cu isotope fractionation with changes in crystal structure during copper sulfide dissolution. This flow-through cell can be applied to many classes of fluid-mineral reactions that involve dissolution or ion exchange.

  1. Positional isotope exchange studies on enzyme using NMR spectroscopy

    SciTech Connect

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, /sup 18/O-..beta..,..gamma..-ATP and /sup 18/O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field /sup 31/P NMR, we were able to differentiate between /sup 18/O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with /sup 18/O-..beta..,..gamma..-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the /sup 18/O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN/sub 1//sub P/) type of mechanism

  2. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  3. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  4. Surface Exchange and Bulk Diffusivity of LSCF as SOFC Cathode: Electrical Conductivity Relaxation and Isotope Exchange Characterizations

    SciTech Connect

    Li, Yihong; Gerdes, Kirk; Horita, Teruhisa; Liu, Xingbo

    2013-05-05

    The oxygen diffusion coefficient (D) and surface exchange coefficient (k) of a typical SOFC cathode material, La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-δ} (LSCF) were characterized by both electrical conductivity relaxation (ECR) and oxygen isotope exchange (IE) methods. Conductivity relaxation experiments were conducted at 800°C for small step changes in partial pressure of oxygen (P{sub O{sub 2}} ), both decreasing and increasing, from 0.02 atm to 0.20 atm. The results revealed P{sub O{sub 2}} dependent hysteresis with the reduction process requiring more equilibration time than oxidation. Analysis of the experimental data indicated that the surface exchange coefficient is a function of the final oxygen partial pressure in an isothermal system. In addition, both forward and backward oxygen reduction reaction constants, which are vital for the fundamental understanding of SOFC cathode reaction mechanisms, are investigated based on the relationship between surface exchange coefficient and P{sub O{sub 2}} . The direct comparisons between the results from both ECR and IE were presented and the possible experimental errors in both methods were discussed.

  5. Isotopic exchange in mineral-fluid systems: III. Rates and mechanisms of oxygen isotope exchange in the system granite-H sup 2 O + KCl at hydrothermal conditions

    SciTech Connect

    Cole, D.R.; Jacobs, G.K. ); Ohmoto, Hiroshi Tohuku Univ., Sendai )

    1992-01-01

    Variations with time in the alteration mineralogy and the oxygen isotopic composition of solutions, minerals, and rocks have been experimentally investigated at T = 170 to 300C, P = L/V to 0.3 kb, water/rock mass ratios (0.2 to 6), and grain sizes ({approximately} 0.1 mm to 2.5 mm) for periods up to 1,006 h. Alteration assemblages formed in the experiments are dominated by chlorite (after biotite), sericite-zeolite-albite (after K-feldspar and plagioclase), and hematite (after magnetite and pyrite). Reaction of rock and aqueous solution resulted in depletion of {sup 18}O in the solid and enrichment of {sup 18}O in the fluid. The magnitudes of change increase as temperature, time, salt concentration, and surface area increase. The trends in isotopic shifts are directly related to changes in the style and intensity of mineralogic alteration in the granite. The degree of isotope exchange in the experimental systems between granite (minerals) and solutions was computed from the comparison with calculated equilibrium fractionation factors and yield values of less than 5 to 50% exchange. The {delta}{sup 18}O changes of the rocks, minerals, and fluid were observed to follow closely with those expected from a first-order rate law. Based on a simple closed-system model with (W/S) mass ratios between 0.5 and 5, the authors estimate the minimum time required for granite-fluid isotopic equilibration to be roughly 200 years or less for grains 1 cm in radius or smaller (porous-media analog) reacted at 300C, and between 10{sup 4} and 10{sup 5} years for grains ranging from 0.1 to 1 m in radius (fractured-media analog) reacted at 300C.

  6. Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

    NASA Technical Reports Server (NTRS)

    Yung, Y. L.; Lee, A. Y.; Irion, F. W.; DeMore, W. B.; Wen, J.

    1997-01-01

    Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

  7. Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

    NASA Technical Reports Server (NTRS)

    Yung, Y. L.; Lee, A. Y.; Irion, F. W.; DeMore, W. B.; Wen, J.

    1997-01-01

    Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

  8. Deuterium retention in tungsten after heavy ion damage and hydrogen isotope exchange in PISCES

    NASA Astrophysics Data System (ADS)

    Barton, J. L.; Wang, Y. Q.; Dittmar, T.; Doerner, R. P.; Tynan, G. R.

    2014-08-01

    The effect of H isotope exchange and radiation damage on the retention of D in W was examined in the PISCES linear plasma device. W samples were treated with D plasma at low sample temperatures (473 K), with a fluence of 1026 ions/m2 and ion energies of 150 eV. Each sample was then exposed to varying doses of H plasma with similar sample temperature and plasma conditions to fluences ranging from 0 to 1026 ions/m2, to examine the effectiveness of isotope exchange as a means of tritium removal. The D(3He, p)4He nuclear reaction was used to measure D concentration profiles up to a depth of 7.7 μm. Thermal desorption spectroscopy (TDS) was used to determine the D retained throughout the bulk of the sample. Isotope exchange allows for a unique study of atomic migration by separately examining the diffusion of implanted atoms from those bombarding the surface. D atoms are exchanged out of traps as a result of H plasma bombardment and diffuse until either falling into another trap or reaching the surface to recombine and escape. Radiation damage at levels of 0.01, 0.1, and 1 displacements per atom (dpa) was carried out before plasma exposure on some samples with 2 MeV Cu ions as a surrogate for damage caused by fusion neutrons. The Cu ion damage was compared to damage induced by 6 MeV W ions to see if there is an effect of Cu contamination on retention. We saw little difference in Cu versus W ion damage at low dpa, but at 1 dpa, where Cu content reached 65 appm, contamination seems to be significant. Retention measurements showed that ion damage has little effectiveness on isotope removal at these sample temperatures; however, there is evidence to suggest that the trapping mechanisms in W change as damage is increased.

  9. Diffusion, trapping, and isotope exchange of plasma implanted deuterium in ion beam damaged tungsten

    NASA Astrophysics Data System (ADS)

    Barton, Joseph Lincoln

    Tritium accumulation in nuclear fusion reactor materials is a major concern for practical and safe fusion energy. This work examines hydrogen isotope exchange as a tritium removal technique, analyzes the effects of neutron damage using high energy copper ion beams, and introduces a diffusion coefficient that is a function of the concentration of trapped atoms. Tungsten samples were irradiated with high energy (0.5 - 5 MeV) copper ions for controlled levels of damage - 10-3 to 10-1 displacements per atom (dpa) - at room temperature. Samples were then exposed to deuterium plasma at constant temperature (˜ 380 K) to a high fluence of 1024 ions/m2, where retention is at is maximized (i.e. saturated). By then subsequently exposing these samples to fractions of this fluence with hydrogen plasma, isotope exchange rates were observed. The resulting deuterium still trapped in the tungsten is then measured post mortem. Nuclear reaction analysis (NRA) gives the depth resolved deuterium retention profile with the 3He(D,p) 4He reaction, and thermal desorption spectroscopy (TDS) gives the total amount of deuterium trapped in the tungsten by heating a sample in vacuum up to 1200 K and measuring the evaporated gas molecules with a residual gas analyzer. Isotope exchange data show that hydrogen atoms can displace trapped deuterium atoms efficiently only up to the first few microns, but does not affect the atoms trapped at greater depths. In ion damaged tungsten, measurements showed a significant increase in retention in the damage region proportional to dpa 0.66, which results in a significant spike in total retention, and isotope exchange in damaged samples is still ineffective at depths greater than a few microns. Thus, isotope exchange is not an affective tritium removal technique; however, these experiments have shown that trapping in material defects greatly affects diffusion. These experiments lead to a simplified diffusion model with defect densities as the only free

  10. Isotopic effects of fragment-yields in proton induced reactions on Sn isotopes

    NASA Astrophysics Data System (ADS)

    Balabekyan, A. R.; Danagulyan, A. S.; Drnoyan, J. R.; Demekhina, N. A.; Adam, J.; Kalinnikov, V. G.; Musulmanbekov, G.

    2004-04-01

    Analysis of isotopic characteristics of products related to the inclusive data measured using activation method in proton reactions at the energies 0.66, 1.0 and 8.1 GeV with separated tin isotopes is presented. Experimental results are systematized in form of cross section ratios for two targets of different isotope composition. Scaling behavior is observed for reactions with heavy residuals in the same manner as in light fragment production processes. These results are discussed in the light of relevant recent data. Finally, dependence of scaling parameters on the target neutron excess is observed.

  11. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    ERIC Educational Resources Information Center

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  12. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    ERIC Educational Resources Information Center

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  13. Extracting Spectroscopic Factors of Argon Isotopes from Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Manfredi, Juan; Tsang, Betty; Lynch, Bill; Barney, Jon; Estee, Justin; Sweany, Sean; Cerizza, Giordano; Iwasaki, Hironori; Loelius, Charles; Ayyad, Yassid; Anderson, Corinne; Xiao, Zhigang; Li, Zihuang; Lee, Jenny; Xu, Zhengyu; Rogers, Andrew; Brown, Kyle; Pruitt, Cole; Sobotka, Lee; Charity, Robert; Langer, Christoph; Chajecki, Zbigniew; Jones, Kate; Smith, Karl; Winkelbauer, Jack

    2016-09-01

    There is a discrepancy of spectroscopic factors (SFs) of argon isotopes depending on the use of transfer reactions or knockout reactions. Understanding how the SFs of these isotopes change across the isotopic chain is important for understanding how single particle structure changes with neutron number. The transfer reactions 34Ar(p,d) and 46Ar(p,d) were measured at the National Superconducting Cyclotron Laboratory using the High Resolution Array (HiRA) to detect the outgoing deuterons and the S800 Spectrometer to detect the heavy recoil. SFs can be extracted from these angular distributions via DWBA calculations. Preliminary findings on the data will be presented. National Nuclear Security Administration Stewardship Science Graduate Fellowship.

  14. Extracting Spectroscopic Factors of Argon Isotopes from Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Manfredi, Juan; Lee, J.; Tsang, M. B.; Lynch, W. G.; Barney, J.; Estee, J.; Sweany, S.; Brown, K. W.; Cerizza, G.; Anderson, C.; Setiawan, H.; Loelius, C.; Xu, Z.; Rogers, A. M.; Pruitt, C.; Sobotka, L. G.; Elson, J. M.; Langer, C.; Chajecki, Z.; Chen, G.; Jones, K. L.; Smith, K.; Xiao, Z.; Li, Z.; Winkelbauer, J. R.

    2017-01-01

    A spectroscopic factor (SF) quantifies the single particle occupancy of a given state in a nucleus. For the argon isotopes, there is a discrepancy of the SF between studies that use transfer reactions and knockout reactions. Understanding the SFs of these isotopes, and in particular how the SF changes across the isotopic chain, is important for understanding how single particle structure changes with neutron number. The transfer reactions 34Ar(p,d) and 46Ar(p,d) were measured at the National Superconducting Cyclotron Laboratory (NSCL) using the same beam energy (70 MeV/u) as from the previous knockout measurement. Spectroscopic factors were extracted from measured angular distributions via ADWA calculations. Preliminary findings will be presented. The National Superconducting Cyclotron Laboratory is supported by the NSF (PHY 1102511), and Juan Manfredi is supported by the DOE NNSA Stewardship Science Graduate Fellowship.

  15. High-Temperature Oxygen Isotope Exchange Between Meteorite Sample and Water Vapor: Preliminary Experimental Results

    NASA Astrophysics Data System (ADS)

    Yu, Y.; Hewins, R. H.; Clayton, R. N.; Mayeda, T. K.

    1993-07-01

    Chondrules in carbonaceous and ordinary chondrites show slope-1 mixing lines on the oxygen three-isotope diagram, suggestive of a gas-melt exchange process during chondrule formation. In order to test this conjecture and to extend our existing knowledge of chondrule thermal history and the kinetics of reaction of interstellar dust with solar nebula gas, an experiment involving high- temperature oxygen isotope exchange between a 16O-rich sample (meteorite) and water vapor (terrestrial) has been designed. The experiment was conducted with a DELTECH vertical tube furnace with ceramic parts shielded with metal foil. The starting meteorite powder (one of two C3 carbonaceous chondrites--bulk Allende and Ornans) was pressed into a pellet and suspended at the hot spot inside the furnace. The furnace gas was a mixture of H2O vapor and H2 (1 atm total pressure, fO2 = IW-0.5) [1]. The preliminary experiments were performed at 1400 degrees C for durations from 5 minutes to 36 hours, and were terminated by quenching the samples into liquid nitrogen. The meteorite charges and the water samples collected were later analyzed for their oxygen isotope compositions. The experimental results (Fig.1) show that the exchange process has greatly modified delta-18O and delta-17O for both meteorites, which move towards the projected equilibrium point as the heating time increases. For Allende samples, the exchange proceeds quickly in the first 5 minutes, which accounts for most of the isotope exchange (~84% of total change in delta-18O(sub)A-W, and ~57% of total change in delta-17O). Then the exchange is dramatically slowed down, and takes at least 12 hours to finally reach equilibrium with the ambient water vapor. The approach to equilibrium is not a straight line on the three-isotope graph, possibly due to the presence of residual 16O-rich solids in the molten sample. A similar exchange profile is observed for Ornans samples. However, it takes longer for the Ornans sample to reach

  16. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    NASA Astrophysics Data System (ADS)

    Babikov, Dmitri

    2017-03-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital ΔΔ values obtained within this model for 33S and 36S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  17. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    PubMed Central

    Babikov, Dmitri

    2017-01-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital Δ values obtained within this model for 33S and 36S is −1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth. PMID:28258172

  18. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth.

    PubMed

    Babikov, Dmitri

    2017-03-21

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: (33)S, (34)S, and (36)S. Interestingly, the ratio of capital [Formula: see text] values obtained within this model for (33)S and (36)S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  19. Unusual origins of isotope effects in enzyme-catalysed reactions

    PubMed Central

    Northrop, Dexter B

    2006-01-01

    High hydrostatic pressure is a neglected tool for probing the origins of isotope effects. In chemical reactions, normal primary deuterium isotope effects (DIEs) arising solely from differences in zero point energies are unaffected by pressure; but some anomalous isotope effects in which hydrogen tunnelling is suspected are partially suppressed. In some enzymatic reactions, high pressure completely suppresses the DIE. We have now measured the effects of high pressure on the parallel 13C heavy atom isotope effect of yeast alcohol dehydrogenase and found that it is also suppressed by high pressure and, similarly, suppressed in its entirety. Moreover, the volume changes associated with the suppression of both deuterium and heavy atom isotope effects are virtually identical. The equivalent decrease in activation volumes for hydride transfer, when one mass unit is added to the carbon end of a scissile C–H bond as when one mass unit is added to the hydrogen end, suggests a common origin. Given that carbon is highly unlikely to undergo tunnelling, it follows that hydrogen is not doing so either. The origin of these isotope effects must lie elsewhere. We offer protein domain motions as a possibility. PMID:16873122

  20. Direct Measurement of Biosphere-Atmosphere Isotopic Exchange Using the Eddy Covariance Technique

    USDA-ARS?s Scientific Manuscript database

    Quantifying isotopic CO2 exchange between the biosphere and atmosphere presents a significant measurement challenge, but has the potential to provide important constraints on local, regional, and global carbon cycling. Past approaches have indirectly estimated isotopic CO2 exchange using relaxed edd...

  1. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  2. Preparation of radioactive acetyl-l-carnitine by an enzymatic exchange reaction

    SciTech Connect

    Emaus, R.; Bieber, L.L.

    1982-01-15

    A rapid method for the preparation of (1-/sup 14/C)acetyl-L-carnitine is described. The method involves exchange of (1-/sup 14/C)acetic acid into a pool of unlabeled acetyl-L-carnitine using the enzymes acetyl-CoA synthetase and carnitine acetyltransferase. After isotopic equilibrium is attained, radioactive acetylcarnitine is separated from the other reaction components by chromatography on Dowex 1 (C1/sup -/) anion exchange resin. One of the procedures used to verify the product (1-/sup 14/C)acetyl-L-carnitine can be used to synthesize (3S)-(5-/sup 14/C)citric acid.

  3. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates

    NASA Astrophysics Data System (ADS)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.

    2012-02-01

    Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H 2O) 63+), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen) 2(H 2O) 2] 3+ [ 1] and [Rh(phen) 2(H 2O)Cl] 2+ [ 2] where (phen) = 1,10-phenanthroline. Complex [ 1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [ 2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of 18O and 16O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k0298 = 5 × 10 -8(±0.5 × 10 -8) s -1 for [ 1] and k0298 = 2.5 × 10 -9(±1 × 10 -9) for [ 2]. Enthalpy and entropy activation parameters (Δ H‡ and Δ S‡) were measured to be 119(±3) kJ mol -1, and 14(±1) J mol -1 K -1, respectively for [ 1]. The corresponding parameters for the mono-aquo complex, [ 2], are 132(±3) kJ mol -1 and 41.5(±2) J mol -1 K -1. Rates increase by many orders of magnitude

  4. Putrescine metabolism: enzymatic formation and non-enzymatic isotope exchange of delta1-pyrroline.

    PubMed

    Callery, P S; Nayar, M S; Geelhaar, L A

    1984-03-01

    The deamination of putrescine catalysed by diamine oxidase was carried out in deuterium oxide and deuterated buffers. Enamine and alpha, beta-unsaturated intermediates were excluded, based on the observation that deuterium was not incorporated into delta 1-pyrroline during its enzymatic formation in deuterium oxide. When the reaction mixture was buffered with phosphate, isolated delta 1-pyrroline contained two deuterium atoms at C-3, indicating that a phosphate-promoted, non-enzymatic isotope exchange had occurred. Using 5,5-dimethyl-delta 1-pyrroline as a model compound, the nature of the non-enzymatic deuterium exchange was studied and a bifunctional catalysis mechanism proposed. The results suggest that the choice of buffer could alter the conclusions drawn from enzyme mechanism studies involving imine-enamine tautomerism .

  5. Water Vapor Isotopic Fractionation and Strat/trop Exchange

    NASA Astrophysics Data System (ADS)

    Jucks, K. W.; Johnson, D. G.; Traub, W. A.; Chance, K. V.

    We will present atmospheric observations of the isotopic fractionation for water vapor as observed by the Smithsonian Astrophysical Observatory far-infrared spectrometer (FIRS-2). The stratospheric observations are corrected with a photochemical model to account for methane oxidation to determine the "entry level" isotopic fractionation of water in the stratosphere. These values are then compared to a simple Rayleigh frac- tionation model that includes estimations of convection, radiative heating, and mixing to infer relative contributions to stratosphere/troposphere exchange. The observations of water vapor fractionation are most consistent with a model that mixes air uplifted from roughly 11 km with significantly more air that has been dehydrated by convec- tion to an effective temperature that is much cooler than the tropopause temperature. The water vapor mixing ratio in the stratosphere results from a combination of radia- tive heating, recirculation of stratospheric air, and deep convection that supplies the air to the upper tropical troposphere. We believe that these types of observations could be a powerful tool for constraining circulation models.

  6. An Exchange-Only Qubit in Isotopically Enriched 28Si

    NASA Astrophysics Data System (ADS)

    Gyure, Mark

    2015-03-01

    We demonstrate coherent manipulation and universal control of a qubit composed of a triple quantum dot implemented in an isotopically enhanced Si/SiGe heterostructure, which requires no local AC or DC magnetic fields for operation. Strong control over tunnel rates is enabled by a dopantless, accumulation-only device design, and an integrated measurement dot enables single-shot measurement. Reduction of magnetic noise is achieved via isotopic purification of the silicon quantum well. We demonstrate universal control using composite pulses and employ these pulses for spin-echo-type sequences to measure both magnetic noise and charge noise. The noise measured is sufficiently low to enable the long pulse sequences required for exchange-only quantum information processing. Sponsored by United States Department of Defense. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressly or implied, of the United States Department of Defense or the U.S. Government. Approved for public release, distribution unlimited.

  7. Modeling Large Zinc Isotope Fractionations Associated with Reaction Kinetics

    NASA Astrophysics Data System (ADS)

    Black, J. R.; John, S.; Kavner, A.

    2009-12-01

    Often multiple processes govern isotope fractionation during a chemical reaction, such as the mass-transport, equilibrium and reaction kinetics between reactants and products. Here we use experimental electrochemical techniques to control the mass-transport and reaction kinetics of the electrodeposition reaction: Zn2+ + 2e- = Zn(s); and model the isotopic fractionation measured to resolve the underlying mechanisms of fractionation. Zn was plated on a rotating disc electrode at various applied overpotentials, rotation rates and temperatures. Electroplated Zn was recovered in acid for analysis of the stable isotope composition by multi-collector ICP-MS. The isotopic composition (66Zn/64Zn) of plated metal is reported relative to the stock solution. A large range of Δ66Znsample-stock is observed, with increasing fractionation at higher rotation rates (Fig. 1A), and lower overpotentials (Fig. 1B). Models of electrochemical kinetics, show that these variables control the relative rates of precipitation and diffusion, as defined by the Koutecky-Levich equation [Bard and Faulkner (2001), Electrochemical Methods, John Wiley & Sons]. Using this equation to interpret our data shows that all the data fall along a systematic trend (Fig. 1C) with smaller fractionations in the mass-transport limited regime and larger fractionations produced under electrochemical kinetic control. We extend the Koutecky-Levich model to predict isotope fractionation during electrochemical processes as a function of mass-dependent diffusion (Fig. 2A); standard rate constant (Fig. 2B); and transfer coefficient, describing reaction barrier symmetry (Fig. 2C). A comparison of the model and our data shows that diffusive and equilibrium fractionation alone (Fig. 2A-B) cannot reproduce the trends in our data, but a mass-dependence in α can explain our observations. However, the predicted fractionation is very sensitive to the magnitude of k0 (Fig. 2C). This model predicts how isotope fractionation

  8. Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

    USGS Publications Warehouse

    Stoffregen, R.E.; Rye, R.O.; Wasserman, M.D.

    1994-01-01

    Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400??C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from -6.25 moles alkali m-2s-1 at 400??C to - 11.7 moles alkali m-2s-1 at 200??C. The variation in these rates with temperature is given by the equation log k* = -8.17(1000/T(K)) + 5.54 (r2 = 0.987) which yields an activation energy of 37.4 ?? 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ?? 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100??C. Computed hydrogen diffusion coefficients range from -15.7 to -17.3 cm2s-1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause

  9. Samarium Ion Exchanged Montmorillonite for High Temperature Cumene Cracking Reaction

    NASA Astrophysics Data System (ADS)

    Binitha, N. N.; Silija, P. P.; Suraj, V.; Yaakob, Z.; Sugunan, S.

    2011-02-01

    Montmorillonite clay is cation exchanged with samarium and its catalytic influence in cumene cracking reaction is investigated. Effect of exchange with sodium ions on further exchange with samarium ions is also noted. Acidity measurements are done using Temperature Programmed Desorption (TPD) of ammonia. The retention of basic structure is proved from FTIR spectra and XRD patterns. Elemental analysis result shows that samarium exchange has occurred, which is responsible for the higher catalytic activity. Surface area and pore volume remains more or less unaffected upon exchange. Thermogravimetric analysis indicates the enhanced thermal stability on exchanging. Cumene cracking reaction is carried out at atmospheric pressure in a fixed bed glass reactor at 673 K. The predominance of Brønsted acidity is confirmed from high selectivity to benzene.

  10. Using reactive artificial muscles to determine water exchange during reactions

    NASA Astrophysics Data System (ADS)

    Otero, T. F.; Martínez, J. G.; Zaifoglu, B.

    2013-10-01

    Artificial muscles based on films of conducting polymers translate film volume variations, driven by electrochemical reactions (Faradaic motors), into macroscopic movements with generation of mechanical energy. The reaction promotes exchange of counterions (anions here) and solvent molecules with the electrolyte. Attributing here both the film volume variation and the movement originated by these exchanges of ions and solvent, the described angles can be used to quantify the exchanged solvent. Different angles described by bending muscles consuming equal driving charges in electrolytes having the same cation and different anions were measured. The number of exchanged counterions is given by the consumed charge and the ion valence: this is a Faradaic reaction. The described angle fraction due to the exchanged anions is given by the number of anions and the crystallographic radius. Taking as reference the anion giving the shorter angle, whatever the consumed charge, the relative number of solvent molecules exchanged by the polymeric membrane during a reversible reaction was determined. Actuators and artificial muscles can be used as useful tools for, at least, an initial study of the solvent exchange during reactions in reactive gels.

  11. Symmetry and the geometric phase in ultracold hydrogen-exchange reactions

    NASA Astrophysics Data System (ADS)

    Croft, J. F. E.; Hazra, J.; Balakrishnan, N.; Kendrick, B. K.

    2017-08-01

    Quantum reactive scattering calculations are reported for the ultracold hydrogen-exchange reaction and its non-reactive atom-exchange isotopic counterparts, proceeding from excited rotational states. It is shown that while the geometric phase (GP) does not necessarily control the reaction to all final states, one can always find final states where it does. For the isotopic counterpart reactions, these states can be used to make a measurement of the GP effect by separately measuring the even and odd symmetry contributions, which experimentally requires nuclear-spin final-state resolution. This follows from symmetry considerations that make the even and odd identical-particle exchange symmetry wavefunctions which include the GP locally equivalent to the opposite symmetry wavefunctions which do not. It is shown how this equivalence can be used to define a constant which quantifies the GP effect and can be obtained solely from experimentally observable rates. This equivalence reflects the important role that discrete symmetries play in ultracold chemistry and highlights the key role that ultracold reactions can play in understanding fundamental aspects of chemical reactivity more generally.

  12. Iridium(I)-catalyzed regioselective C-H activation and hydrogen-isotope exchange of non-aromatic unsaturated functionality.

    PubMed

    Kerr, William J; Mudd, Richard J; Paterson, Laura C; Brown, Jack A

    2014-11-03

    Isotopic labelling is a key technology of increasing importance for the investigation of new CH activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium-catalyzed CH activation and hydrogen-isotope exchange at the β-position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3 )][PF6 ] (cod=1,5-cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β-activation and labelling of a range of α,β-unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals

    PubMed Central

    2015-01-01

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn2+ and Cd2+) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu2–xSe) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core–shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu+ ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu2–xSe samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  14. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

    PubMed

    Lesnyak, Vladimir; Brescia, Rosaria; Messina, Gabriele C; Manna, Liberato

    2015-07-29

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature.

  15. Continuous Consecutive Reactions with Inter‐Reaction Solvent Exchange by Membrane Separation

    PubMed Central

    Peeva, Ludmila; Da Silva Burgal, Joao; Heckenast, Zsofia; Brazy, Florine; Cazenave, Florian

    2016-01-01

    Abstract Pharmaceutical production typically involves multiple reaction steps with separations between successive reactions. Two processes which complicate the transition from batch to continuous operation in multistep synthesis are solvent exchange (especially high‐boiling‐ to low‐boiling‐point solvent), and catalyst separation. Demonstrated here is membrane separation as an enabling platform for undertaking these processes during continuous operation. Two consecutive reactions are performed in different solvents, with catalyst separation and inter‐reaction solvent exchange achieved by continuous flow membrane units. A Heck coupling reaction is performed in N,N‐dimethylformamide (DMF) in a continuous membrane reactor which retains the catalyst. The Heck reaction product undergoes solvent exchange in a counter‐current membrane system where DMF is continuously replaced by ethanol. After exchange the product dissolved in ethanol passes through a column packed with an iron catalyst, and undergoes reduction (>99 % yield). PMID:27669675

  16. Continuous Consecutive Reactions with Inter-Reaction Solvent Exchange by Membrane Separation.

    PubMed

    Peeva, Ludmila; Da Silva Burgal, Joao; Heckenast, Zsofia; Brazy, Florine; Cazenave, Florian; Livingston, Andrew

    2016-10-17

    Pharmaceutical production typically involves multiple reaction steps with separations between successive reactions. Two processes which complicate the transition from batch to continuous operation in multistep synthesis are solvent exchange (especially high-boiling- to low-boiling-point solvent), and catalyst separation. Demonstrated here is membrane separation as an enabling platform for undertaking these processes during continuous operation. Two consecutive reactions are performed in different solvents, with catalyst separation and inter-reaction solvent exchange achieved by continuous flow membrane units. A Heck coupling reaction is performed in N,N-dimethylformamide (DMF) in a continuous membrane reactor which retains the catalyst. The Heck reaction product undergoes solvent exchange in a counter-current membrane system where DMF is continuously replaced by ethanol. After exchange the product dissolved in ethanol passes through a column packed with an iron catalyst, and undergoes reduction (>99 % yield). © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  17. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    SciTech Connect

    Draayer, Jerry P.

    2014-09-28

    We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

  18. Concentrating low-level tritiated water through isotope exchange

    SciTech Connect

    Jorgensen, B.S.; Dye, R.C.; Pratt, L.R.; Gomez, M.A.; Meadows, J.E.

    2000-03-01

    Trapping of tritium on polymers with specific functional groups was investigated as a means of treating waste streams containing low levels of tritium. Chemical exchange of tritium with hydrogen on the functional group was used as the mechanism for trapping. The polymers tested include Aurorez polybenzimidazole resin beads, Chelex 100 resin beads, Duolite GT-73, microcrystalline cellulose, and polyethylenimine. The tests were performed under simulated operating conditions on water obtained from the Radioactive Liquid Waste Treatment Facility at Los Alamos National Laboratory, Tritiated water from the Tritium Systems Test Assembly is discharged to this plant. Polyethylenimine is a water-soluble polymer that was tested using a stirred membrane cell with an ultrafiltration membrane. All of the polymers except polyethylenimine took up tritium from the water. Polybenzimidazole demonstrated the highest tritium uptake. The results are explained on the basis of the type of functional group, hydrogen bonding, and rigidity of the molecular structure of the polymer. The theoretical calculations indicate that significant isotope discrimination requires high-frequency modes with hydrogen bonding contribution and support the experimental findings. Modeling suggested trends that may lead to structures that are more efficient in trapping tritium.

  19. A pore scale description of calcium isotope exchange and equilibration with calcite

    NASA Astrophysics Data System (ADS)

    Druhan, J. L.; Huber, C.; Parmigiani, A.

    2014-12-01

    The distribution of stable isotope ratios between dissolved and solid phases are commonly used to assess processes of mineral formation, alteration and dissolution in a variety of low temperature systems. In order to model this partitioning, a description of isotopic exchange occurring at the fluid-solid surface is required. The use of continuum scale reactive transport models to describe heterogeneous isotopic fractionation is thus hindered by the ability to discretize isotopic gradients within a solid phase. Here we present a multi-component pore scale model for the partitioning of calcium isotopes between dissolved Ca2+ and calcite using a lattice Boltzmann method capable of describing the isotopic composition of an evolving mineral surface distinct from the bulk calcite composition. A key feature of our model is the ability to simultaneously track isotopic exchange at the fluid-solid surface as well as the isotopic composition of both bulk fluid and bulk calcite. This is significant in that the surface exchange dictates the evolution of isotopic compositions through time, while the bulk isotope ratios represent the actual measured values of samples collected in the field. Using this approach, we reexamine the distribution of calcium isotope ratios in pore fluids and carbonates reported for deep-sea core profiles with particular emphasis on interpretation of the equilibrium fractionation factor. Based on simulations of an initially supersaturated fluid surrounding a calcite crystal at a range of porosities, we show that the fluid can achieve both chemical and isotopic equilibrium with the solid surface while maintaining the appearance of disequilibrium with the bulk solid. The extent to which the final equilibrated calcium isotope ratio of the bulk fluid and bulk solid agree is therefore a function of the depth into the mineral surface that is exchangeable with the fluid.

  20. Computation of kinetic isotope effects for enzymatic reactions

    PubMed Central

    GAO, JiaLi

    2013-01-01

    We describe a computational approach, incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects. Two aspects are highlighted: (1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical (QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory, and (2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects (KIEs). In this approach, which is called the PI-FEP/UM method, a light (heavy) isotope is mutated into a heavy (light) counterpart in centroid path integral simulations. The method is illustrated in the study of primary and secondary KIEs in two enzyme systems. In the case of nitroalkane oxidase, the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water. In the dopa delarboxylase reaction, there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions. These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions. PMID:23976893

  1. Computation of kinetic isotope effects for enzymatic reactions.

    PubMed

    Gao, Jiali

    2012-12-01

    We describe a computational approach, incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects. Two aspects are highlighted: (1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical (QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory, and (2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects (KIEs). In this approach, which is called the PI-FEP/UM method, a light (heavy) isotope is mutated into a heavy (light) counterpart in centroid path integral simulations. The method is illustrated in the study of primary and secondary KIEs in two enzyme systems. In the case of nitroalkane oxidase, the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water. In the dopa delarboxylase reaction, there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions. These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions.

  2. Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

    NASA Astrophysics Data System (ADS)

    Cole, David R.

    2000-03-01

    Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order

  3. Hydrogen isotope exchange in tungsten: Discussion as removal method for tritium

    NASA Astrophysics Data System (ADS)

    Roth, J.; Schwarz-Selinger, T.; Alimov, V. Kh.; Markina, E.

    2013-01-01

    Hydrogen isotope exchange in re-crystallized polycrystalline tungsten was investigated at 320 and 450 K. In a first step the tungsten samples were loaded with deuterium to a fluence of 1024 D/m2 from a low-temperature plasma at 200 eV/D particle energy. In a second step, H was implanted at the same particle energy and similar target temperature with a mass-separated ion beam at different ion fluences ranging from 2 × 1020 to 7.5 × 1023 H/m2. The analytic methods used were nuclear reaction analysis with D(3He,p)α reaction and elastic recoil detection analysis with 4He. In order to determine the D concentration at depths of up to 7.4 μm the 3He energy was varied from 0.5 to 4.5 MeV. It was found that already at an H fluence of 2 × 1020 H/m2, i.e. at 1/5000 of the initial D fluence, about 30% of the retained D was released. Depth profiling of D without and with subsequent H implantation shows strong replacement close to the surface at 320 K, but extending to all analyzable depths at 450 K especially at high fluences, leading to higher release efficiency. The reverse sequence of hydrogen isotopes allowed the analysis of the replacing isotope and showed that the release of D is balanced by the uptake of H. It also shows that hydrogen does not diffuse through a region of filled traps into a region were unfilled traps can be encounter but transport is rather a dynamic process of trapping and de-trapping even at 320 K. Initial D retention in H loaded W is an order of magnitude higher than in pristine W, indicating that every H-containing trap is a potential trap for D. In consequence, hydrogen isotope exchange is not a viable method to significantly enhance the operation time before the tritium inventory limit is reached but should be considered an option to reduce the tritium inventory in ITER before major interventions at the end of an operation period.

  4. Stereochemistry of the acyl dihydroxyacetone phosphate acyl exchange reaction.

    PubMed

    Friedberg, S J; Satsangi, N; Weintraub, S T

    1991-02-01

    The fatty acid of acyl dihydroxyacetone phosphate can be exchanged enzymatically for another fatty acid. It has been shown that this reaction proceeds by cleavage of the oxygen bound to C-1 of the dihydroxyacetone phosphate (DHAP) moiety rather than by the more common cleavage at the acyl to oxygen bond. In the present study, the stereochemistry of this reaction was defined further; using deuterated substrates and fast atom bombardment-mass spectrometry, it was shown that the fatty acid exchange involves the stereospecific labilization of the pro-R hydrogen at C-1 of the DHAP moiety of acyl DHAP. The mechanism of ether bond formation, in which acyl DHAP is converted to O-alkyl DHAP, also proceeds via labilization of the pro-R hydrogen and cleavage of the fatty acid at the C-1 to oxygen bond. In addition, other workers have provided evidence that the enzyme responsible for the exchange reaction is O-alkyl DHAP synthetase. Therefore, the present results support the hypothesis that the acyl exchange is the reverse reaction of the first step in O-alkyl DHAP synthesis; in both of these reactions the pro-R hydrogen of C-1 of the DHAP moiety of acyl DHAP and the fatty acid moiety are labilized with cleavage of the fatty acid at the DHAP C-1 to oxygen bond.

  5. Lock-exchange experiments with an autocatalytic reaction front

    NASA Astrophysics Data System (ADS)

    Malham, I. Bou; Jarrige, N.; Martin, J.; Rakotomalala, N.; Talon, L.; Salin, D.

    2010-12-01

    A viscous lock-exchange gravity current corresponds to the reciprocal exchange of two fluids of different densities in a horizontal channel. The resulting front between the two fluids spreads as the square root of time, with a diffusion coefficient reflecting the buoyancy, viscosity, and geometrical configuration of the current. On the other hand, an autocatalytic reaction front between a reactant and a product may propagate as a solitary wave, namely, at a constant velocity and with a stationary concentration profile, resulting from the balance between molecular diffusion and chemical reaction. In most systems, the fluid left behind the front has a different density leading to a lock-exchange configuration. We revisit, with a chemical reaction, the classical situation of lock-exchange. We present an experimental analysis of buoyancy effects on the shape and the velocity of the iodate arsenous acid autocatalytic reaction fronts, propagating in horizontal rectangular channels and for a wide range of aspect ratios (1/3 to 20) and cylindrical tubes. We do observe stationary-shaped fronts, spanning the height of the cell and propagating along the cell axis. Our data support the contention that the front velocity and its extension are linked to each other and that their variations scale with a single variable involving the diffusion coefficient of the lock-exchange in the absence of chemical reaction. This analysis is supported by results obtained with lattice Bathnagar-Gross-Krook (BGK) simulations Jarrige et al. [Phys. Rev. E 81, 06631 (2010)], in other geometries (like in 2D simulations by Rongy et al. [J. Chem. Phys. 127, 114710 (2007)] and experiments in cylindrical tubes by Pojman et al. [J. Phys. Chem. 95, 1299 (1991)]), and for another chemical reaction Schuszter et al. [Phys. Rev. E 79, 016216 (2009)].

  6. THE EXCHANGE REACTION OF ACETYL FLUORIDE AND ACETYL HEXAFLUOROARSENATE,

    DTIC Science & Technology

    From the temperature dependence of the exchange rate of the methyl protons between acetyl fluoride and acetyl hexafluoroarsenate an Arrhenius...the reaction was found to be one-half order in acetyl hexafluoroarsenate and zero order in acetyl fluoride. (Author)

  7. Wavelength-selective light-triggered strand exchange reaction.

    PubMed

    Morihiro, K; Kodama, T; Mori, S; Tsunoda, S; Obika, S

    2016-02-07

    We prepared an oligodeoxynucleotide (ODN) bearing two 4-hydroxy-2-mercaptobenzimidazole nucleobase analogues (SB(NV) and SB(NB)) modified with different photolabile groups. This ODN enabled a light-triggered strand exchange reaction in a wavelength-selective manner.

  8. Low temperature equilibrium isotope fractionation and isotope exchange kinetics between U(IV) and U(VI)

    NASA Astrophysics Data System (ADS)

    Wang, Xiangli; Johnson, Thomas M.; Lundstrom, Craig C.

    2015-06-01

    Measurements of the uranium (U) isotope ratio 238U/235U provide an emerging redox proxy in environmental and paleoredox studies, but many key parameters concerning U isotope fractionation are still poorly constrained. Here we report the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI), and rates of isotope exchange between solid-phase U(IV) and dissolved U(VI). We conducted one experiment at high concentration [35 mM U(IV) and 32 mM U(VI)] and low pH (0.2) in hydrochloric acid media at room temperature to determine the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI). Isotopic equilibrium was reached in about 19 days under such experimental conditions. The equilibrium isotope fractionation was determined to be 1.64 ± 0.16‰, with U(IV) being enriched in 238U relative to U(VI). Applicability of the determined equilibrium fractionation is discussed. We also conducted a set of experiments to determine isotopic exchange rates between dissolved U(VI) and nanouraninite U(IV) under conditions closer to those in natural system, with lower concentrations and neutral pH. The exchange rate was found to conform to the rate law R = k[U(VI)]adsorbed, in which R is the isotopic exchange rate (μM day-1); k is the rate constant determined to be 0.21 day-1; and [U(VI)]adsorbed is the concentration of U(VI) adsorbed to nanouraninite (μM). Our results, combined with consideration of the variables controlling U(VI)-U(IV) contact in natural settings, indicate that the timescale for significant isotope equilibration varies depending on environmental conditions, mostly uranium concentrations. In natural uncontaminated sediments with low uranium concentrations, equilibration is expected to occur on a timescale of hundreds to thousands of years. In contrast, in U-contaminated aquifers with high U concentrations, significant equilibration could occur on timescales of weeks to years.

  9. Studies of the reactivity of the ferrihydrite surface by iron isotopic exchange and Mossbauer spectroscopy

    USGS Publications Warehouse

    Rea, B.A.; Davis, J.A.; Waychunas, G.A.

    1994-01-01

    A combination of chemical and spectroscopic techniques were employed to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Labile sites are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population population of surface sites. -from Authors

  10. Reaction cross sections of carbon isotopes incident on a proton

    SciTech Connect

    Abu-Ibrahim, B.; Horiuchi, W.; Kohama, A.; Suzuki, Y.

    2008-03-15

    We systematically study total reaction cross sections of carbon isotopes with N=6-16 on a proton target for wide range of incident energies. An emphasis is put on the difference from the case of a carbon target. The calculations include the reaction cross sections of {sup 19,20,22}C at 40A MeV, the data of which have recently been measured at RIKEN. The Glauber theory is used to calculate the reaction cross sections. To describe the intrinsic structure of the carbon isotopes, we use a Slater determinant generated from a phenomenological mean-field potential, and construct the density distributions. To go beyond the simple mean-field model, we adopt two types of dynamical models: One is a core+n model for odd-neutron nuclei, and the other is a core+n+n model for {sup 16}C and {sup 22}C. We propose empirical formulas which are useful in predicting unknown cross sections.

  11. Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

    PubMed

    Yurimoto; Ito; Nagasawa

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  12. Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

    PubMed

    Yurimoto, H; Ito, M; Nagasawa, H

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  13. Geometric phase effects in ultracold hydrogen exchange reaction

    NASA Astrophysics Data System (ADS)

    Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, N.

    2016-10-01

    The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H2 product or in the D+H2 (v=4,j=0) \\to HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. Experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.

  14. Geometric phase effects in ultracold hydrogen exchange reaction

    SciTech Connect

    Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

    2016-10-14

    The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H2 product or in the D+H2 $(v=4,j=0)\\,\\to $ HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. In conclusion, experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.

  15. Geometric phase effects in ultracold hydrogen exchange reaction

    DOE PAGES

    Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

    2016-10-14

    The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H2 product or in the D+H2more » $$(v=4,j=0)\\,\\to $$ HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. In conclusion, experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.« less

  16. No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

    NASA Astrophysics Data System (ADS)

    Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming

    2012-10-01

    In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for

  17. Ammonium transport and reaction in contaminated groundwater: Application of isotope tracers and isotope fractionation studies

    USGS Publications Warehouse

    Böhlke, J.K.; Smith, R.L.; Miller, D.N.

    2006-01-01

    Ammonium (NH4+) is a major constituent of many contaminated groundwaters, but its movement through aquifers is complex and poorly documented. In this study, processes affecting NH4+ movement in a treated wastewater plume were studied by a combination of techniques including large-scale monitoring of NH4+ distribution; isotopic analyses of coexisting aqueous NH4+, NO3-, N2, and sorbed NH 4+; and in situ natural gradient 15NH 4+ tracer tests with numerical simulations of 15NH4+, 15NO3-, and 15N2 breakthrough data. Combined results indicate that the main mass of NH4+ was moving downgradient at a rate about 0.25 times the groundwater velocity. Retardation factors and groundwater ages indicate that much of the NH4+ in the plume was recharged early in the history of the wastewater disposal. NO3- and excess N2 gas, which were related to each other by denitrification near the plume source, were moving downgradient more rapidly and were largely unrelated to coexisting NH 4+. The ??15N data indicate areas of the plume affected by nitrification (substantial isotope fractionation) and sorption (no isotope fractionation). There was no conclusive evidence for NH 4+-consuming reactions (nitrification or anammox) in the anoxic core of the plume. Nitrification occurred along the upper boundary of the plume but was limited by a low rate of transverse dispersive mixing of wastewater NH4+ and O2 from overlying uncontaminated groundwater. Without induced vertical mixing or displacement of plume water with oxic groundwater from upgradient sources, the main mass of NH4+ could reach a discharge area without substantial reaction long after the more mobile wastewater constituents are gone. Multiple approaches including in situ isotopic tracers and fractionation studies provided critical information about processes affecting NH4+ movement and N speciation.

  18. Comparison of [82Br]4-bromoantipyrine and [125I]4-iodoantipyrine: the kinetics of exchange reaction and biodistribution in rats.

    PubMed

    Liu, B L; Kung, H F; Billings, J; Blau, M

    1987-01-01

    Kinetics and mechanism of isotope exchange reaction between [82Br]bromide anion and 4-bromoantipyrine (BrAP), and the iodine-bromine exchange reaction between [125I]iodide anion and BrAP were studied. The preparation of [82Br]BrAP followed by exponential exchange law, the kinetics of the exchange reaction is a second-order reaction with an activation energy of 23.3 kcal/mol. The optimal exchange condition for halogen exchange between [125I]iodide and BrAP was by a hydrothermal melt method at 110 degrees C and 5 min reaction time. The partition coefficient at pH 7.0 for IAP and BrAP was 20.9 and 13.5, respectively. However, BrAP, which displayed the lower partition coefficient, showed higher brain uptake in rats than that for IAP (2.0% dose/organ vs 1.74% dose/organ), at 2 min after an i.v. injection.

  19. Towards improved quantification of internal diffusion resistances and CO2 isotope exchange in leaves

    NASA Astrophysics Data System (ADS)

    West, J. B.; Ogee, J.; Burlett, R.; Gimeno, T.; Genty, B.; Jones, S.; Wohl, S.; Bosc, A.; Cochet, Y.; Domec, J. C.; Wingate, L.

    2016-12-01

    The oxygen isotopic composition (δ18O) of atmospheric CO2 can constrain the C cycle at a range of scales, in particular partitioning net CO2 exchanges into their component gross fluxes and providing insights to linked C and water fluxes. There are significant limitations to utilizing the δ18O of CO2 in this way, however, because of uncertainties associated with the isotopic exchange of CO2 with terrestrial water pools. Leaf water represents a critical pool with ongoing debates about its enrichment in heavy isotopes during transpiration and the hydration of CO2 and the resulting oxygen isotope exchange. Isotopic heterogeneity of the leaf water, the spatial distribution and activity of carbonic anhydrase (CA) within leaves, and resistance to diffusion of CO2 from the substomatal cavity to chloroplasts are all key components with important uncertainties. Better constraints on these would significantly improve our ability to understand and model the global C budget as well as yield insights to fundamental aspects of leaf physiology. We report results using a new measurement system that permits the simultaneous measurement of the 13C and 18O composition of CO2 and the 18O isotopic composition of leaf transpiration. As this new approach permits rapid alteration of the isotopic composition of gases interacting with the leaf, key model parameters can be derived directly and simultaneously. Hence, our approach dos not rely on separate measurements shifted in time from the gas exchange measurements or that may not quantify the relevant scale of heterogeneity (e.g., CA enzyme assays or bulk leaf water extraction and analysis). In particular, this new method explicitly distinguishes the leaf mesophyll resistance to CO2 transport relevant for photosynthesis from the resistance required for interpreting the d18O of CO2. This new measurement system and modeling approach allows a thorough assessment of key elements of our current understanding of CO2-H2O oxygen isotope exchange

  20. Rapid carbon-carbon bond formation and cleavage revealed by carbon isotope exchange between the carboxyl carbon and inorganic carbon in hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Glein, C. R.; Cody, G. D.

    2013-12-01

    The carbon isotopic composition of organic compounds in water-rock systems (e.g., hydrothermal vents, sedimentary basins, and carbonaceous meteorites) is generally interpreted in terms of the isotopic composition of the sources of such molecules, and the kinetic isotope effects of metabolic or abiotic reactions that generate or transform such molecules. This hinges on the expectation that the carbon isotopic composition of many organic compounds is conserved under geochemical conditions. This expectation is reasonable in light of the strength of carbon-carbon bonds (ca. 81 kcal/mol); in general, environmental conditions conducive to carbon-carbon bond cleavage typically lead to transformations of organic molecules (decarboxylation is a notable example). Geochemically relevant reactions that involve isotopic exchange between carbon atoms in organic molecules and inorganic forms of carbon with no change in molecular structure appear to be rare. Notwithstanding such rarity, there have been preliminary reports of relatively rapid carbon isotope exchange between the carboxyl group in carboxylic acids and carbon dioxide in hot water [1,2]. We have performed laboratory hydrothermal experiments to gain insights into the mechanism of this surprising reaction, using phenylacetate as a model structure. By mass spectrometry, we confirm that the carboxyl carbon undergoes facile isotopic exchange with 13C-labeled bicarbonate at moderate temperatures (i.e., 230 C). Detailed kinetic analysis reveals that the reaction rate is proportional to the concentrations of both reactants. Further experiments demonstrate that the exchange reaction only occurs if the carbon atom adjacent to the carboxyl carbon is bonded to a hydrogen atom. As an example, no carbon isotope exchange was observed for benzoate in experiments lasting up to one month. The requirement of an alpha C-H bond suggests that enolization (i.e., deprotonation of the H) is a critical step in the mechanism of the exchange

  1. Reaction mechanism and isotope effects derived from centroid transition state theory in intramolecular proton transfer reactions

    NASA Astrophysics Data System (ADS)

    Iftimie, Radu; Schofield, Jeremy

    2001-10-01

    In this article the tautomerization reaction of the enol form of malonaldehyde is used to investigate the magnitude and origin of changes in centroid transition state theory proton transfer reaction rate predictions caused by the quantum dispersion of heavy nuclei. Using an empirical valence bond method to construct the potential energy surface, it is found that quantization of the nuclear degrees of freedom of the carbon atoms significantly influences the centroid potential of mean force used to describe the proton transfer reaction. In contrast, an ab initio simulation carried out using a recently developed molecular mechanics based importance sampling method [J. Chem. Phys. 114, 6763 (2001)] in combination with an accurate density functional theory evaluation of the electronic energies shows a substantially smaller influence of the quantum nuclear degrees of freedom of the secondary atoms on the centroid potential of mean force. A detailed analysis of the different influence of quantization of the nuclear degrees of freedom of secondary atoms observed in the ab initio and empirical valence bond centroid potential of mean force was carried out. It is shown that for the empirical valence bond potential, a significant decrease of the centroid potential of mean force arises through the quantum tunneling of carbon atoms in the molecular backbone. Furthermore, it is demonstrated that in molecular mechanics potentials aimed to describe intramolecular proton transfer reactions, the functional form of the potential energy terms coupling the primary and secondary atom motions as the reaction proceeds as well as the mass of the primary particle can significantly influence the centroid transition state theory predictions of secondary kinetic isotope effects. Finally, the dependence of the reaction rate predictions and isotope effects on the choice of reaction coordinate is investigated and the validity of calculating kinetic isotope effects using the centroid transition

  2. Use of micrometeorological techniques to study the isotopic exchange in ecosystems

    NASA Astrophysics Data System (ADS)

    Santos, E.; Wagner-Riddle, C.; Brown, S. E.; Stropes, K.

    2015-12-01

    The combination of micrometeorological techniques with high frequency concentration measurements of stable isotopes are a powerful tool to study the temporal dynamics of isotope signatures at the ecosystem level. The objective of this study was to study the isotopic composition of the net CO2 exchange (NEE) above and with corn and tall grass canopies. Profiles of stable isotopes of CO2 (12C-CO2, 13C-CO2 and 18O-CO2) were measured using tunable diode laser trace gas analyzers and multiport sampling systems in corn (12C-CO2 and 13C-CO2, only) and tall grass canopies. These measurements were combined with the flux gradient method and Lagrangian dispersion analysis to estimate the isotopic signatures of the net CO2 flux. The use of a gradient of a concentration threshold to screen half hourly period improved the estimates of flux signatures by the isotope flux ratio approach. The Langrangian dispersion analysis and the isotope flux ratio method estimates showed good agreement above the corn canopy, indicating that the former method can be a viable alternative to study the isotopic exchange within plant canopies. The 13CO2 composition of NEE showed a downward trend near the end of the growing season, which may be related to a reduction of autotrophic respiration in the soil.

  3. Cross-ligation and exchange reactions catalyzed by hairpin ribozymes.

    PubMed Central

    Komatsu, Y; Koizumi, M; Sekiguchi, A; Ohtsuka, E

    1993-01-01

    The negative strand of the satellite RNA of tobacco ringspot virus (sTobRV(-)) contains a hairpin catalytic domain that shows self-cleavage and self-ligation activities in the presence of magnesium ions. We describe here that the minimal catalytic domain can catalyze a cross-ligation reaction between two kinds of substrates in trans. The cross-ligated product increased when the reaction temperature was decreased during the reaction from 37 degrees C to 4 degrees C. A two-stranded hairpin ribozyme, divided into two fragments between G45 and U46 in a hairpin loop, showed higher ligation activity than the nondivided ribozyme. The two stranded ribozyme also catalyzed an exchange reaction of the 3'-portion of the cleavage site. Images PMID:8441626

  4. Guest exchange in an encapsulation complex: A supramolecular substitution reaction

    PubMed Central

    Santamaría, Javier; Martín, Tomás; Hilmersson, Göran; Craig, Stephen L.; Rebek, Julius

    1999-01-01

    Encapsulation complexes are reversibly formed assemblies in which small molecule guests are completely surrounded by large molecule hosts. The assemblies are held together by weak intermolecular forces and are dynamic: they form and dissipate on time scales ranging from milliseconds to days—long enough for many interactions, even reactions, to take place within them. Little information is available on the exchange process, how guests get in and out of these complexes. Here we report that these events can be slow enough for conventional kinetic studies, and reactive intermediates can be detected. Guest exchange has much in common with familiar chemical substitution reactions, but differs in some respects: no covalent bonds are made or broken, the substrate is an assembly rather than a single molecule, and at least four molecules are involved in multiple rate-determining steps. PMID:10411877

  5. Momentum transfer in relativistic heavy ion charge-exchange reactions

    NASA Technical Reports Server (NTRS)

    Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

    1991-01-01

    Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

  6. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  7. [Exchange reactions in brain tissue under chronic ethanol intoxication].

    PubMed

    Gil'miiarova, F N; Radomskaia, V M; Vinogradova, L N

    1982-01-01

    The paper deals with characterization of systems utilizing ethanol and reactions conjugated with its exchange in the brain tissue under chronic alcohol intoxication. The following is established: the absence of the alcoholdehydrogenase pathway of ethanol oxidation in rabbits, unbalanced splitting of carbohydrates under two-months ethanol load, disturbance of oxidative processes in the tricarboxylic acids cycle, a decrease in the pool of oxidized nicotin amide coenzymes.

  8. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  9. Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A 1H NMR and isotopic exchange study.

    PubMed

    De la Fuente, Julio R; Jullian, Carolina; Saitz, Claudio; Neira, Verónica; Poblete, Oscar; Sobarzo-Sánchez, Eduardo

    2005-10-28

    [reaction: see text] Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by (1)H NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D(2)O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion.

  10. Hydrogen isotope exchange in a metal hydride tube

    SciTech Connect

    Robinson, David B.

    2014-09-01

    This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

  11. First observation of a mass independent isotopic fractionation in a condensation reaction

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

    1994-01-01

    Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

  12. Nitrogen isotope exchange between NO and NO2 and its implications for δ15N variations in tropospheric NOx and atmospheric nitrate

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Simonini, Damian S.; Michalski, Greg

    2016-01-01

    The nitrogen (N) isotope exchange between nitric oxide (NO) and nitrogen dioxide (NO2) has been previously suggested to influence N stable isotope compositions (δ15N) of these molecules. However, there is disagreement in the magnitude of the N isotopic fractionation (αNO2>/NO) resulting from this exchange process between previous experimental and theoretical studies. To this end, we measured αNO2>/NO associated with this exchange reaction at various temperatures. Our results indicate αNO2>/NO to be 1.0403 ± 0.0015, 1.0356 ± 0.0015, and 1.0336 ± 0.0014 at 278 K, 297 K, and 310 K, respectively. These measured values are within experimental error of the values we calculated using a modified version of the Bigeleisen-Mayer equation corrected for accurate zero-point energies, indicating an agreement between experiment and theory. Modeling of this exchange reaction demonstrates that δ15N-NO2 may exhibit a diurnal and seasonal profile if N isotopic equilibrium is achieved.

  13. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase.

    PubMed

    Esaki, N; Nakayama, T; Sawada, S; Tanaka, H; Soda, K

    1985-07-16

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the following straight-chain L-amino acids which are not susceptible to elimination: norleucine, norvaline, alpha-aminobutyrate, and alanine. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. One beta-hydrogen of S-methyl-L-cysteine was exchanged faster than the other, although both the beta-hydrogens were exchanged completely with deuterium ultimately. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically. None of the following amino acids were susceptible to the enzymatic hydrogen exchange: D isomers of the above amino acids, branched chain L-amino acids, acidic L-amino acids, and basic L-amino acids.(ABSTRACT TRUNCATED AT 250 WORDS)

  14. Measurements of Forest-Atmosphere Isotopic CO2 Exchange by Eddy Covariance

    NASA Astrophysics Data System (ADS)

    Wehr, R. A.; Munger, J. W.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Saleska, S. R.

    2010-12-01

    Isotopic CO2 flux measurements are a promising means for partitioning the net ecosystem exchange of CO2 into photosynthetic and respiratory components. This approach to partitioning is possible in principle because of the distinct isotopic signatures of respired and photosynthesized CO2, but has been infeasible in practice—especially in forests—because of the difficulty of measuring isotopic ratios with sufficient precision and time response for use in eddy covariance (EC) flux calculations. Recent advances in laser spectroscopic instrumentation have changed that. We report measurements of isotopic (13C and 18O) CO2 exchange made by eddy covariance at Harvard Forest between April and December, 2010. The measurements were made using a continuous-wave quantum cascade laser spectrometer (Aerodyne Research Inc.) sampling at 4 Hz and are, to our knowledge, the first EC isotopic flux measurements at a forest site. The spectrometer can measure δ13C and δ18O with internal precisions (standard deviation of 1-minute averages) of 0.03 ‰, and [CO2] with an internal precision of 15 ppb; the instrumental accuracy, calibration, and long-term stability are discussed in detail. The isotopic data are considered in relation to environmental variables (PAR, temperature, humidity, soil temperature and moisture), and a first attempt at flux partitioning using the isotopic fluxes is presented.

  15. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, Marcus Johannes Jacobus

    1992-11-01

    The hydrogen exchange reaction H + H2 → H2 + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a `perfect experiment`, measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H2 reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H2 molecules. DH molecules formed in the D + H2 reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 103 molecules/cc. This thesis does not contain experimental results for the D + H2 reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  16. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H[sub 2] [yields] H[sub 2] + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a 'perfect experiment', measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H[sub 2] reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H[sub 2] molecules. DH molecules formed in the D + H[sub 2] reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10[sup 3] molecules/cc. This thesis does not contain experimental results for the D + H[sub 2] reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  17. Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

    PubMed

    Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

    2015-09-15

    Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Theoretical evaluation of isotopic fractionation factors in oxidation reactions of benzene, phenol and chlorophenols.

    PubMed

    Adamczyk, Paweł; Paneth, Piotr

    2011-09-01

    We have studied theoretically the rate determining steps of reactions of benzene with permanganate, perchlorate, ozone and dioxygen in the gas phase and aqueous solution as well as phenol and dichlorophenol in protonated and unprotonated forms in aqueous solution. Kinetic isotope effects were then calculated for all carbon atoms and based on their values isotopic fractionation factors corresponding to compound specific isotopic analysis have been evaluated. The influence of the oxidant, substituents, environment and protonation on the isotopic fractionation factors has been analyzed.

  19. Grain boundary diffusion of Si, Mg, and O in enstatite reaction rims: a SIMS study using isotopically doped reactants

    NASA Astrophysics Data System (ADS)

    Milke, R.; Wiedenbeck, M.; Heinrich, W.

    2001-07-01

    Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in 18O and 29Si were used as reactants. The relative mobility of18O and 29Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg2SiO4=0.5 Mg2Si2O6+MgO at the forsterite-enstatite, and MgO+SiO2=0.5 Mg2Si2O6 at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using DSi,EnVol at dry conditions from the literature, results a D'Si,En δ value of 3×10-24 m3 s-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to 18O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and Ox,Enδ cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity MgOδ of MgO in iron-free enstatite is 8×10-22 m3 s-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo92) as reactant reveal lower rates

  20. Nitroxyl Radical plus Hydroxylamine Pseudo Self-Exchange Reactions: Tunneling in Hydrogen Atom Transfer

    PubMed Central

    Wu, Adam; Mader, Elizabeth A.; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Mayer, James M.

    2009-01-01

    Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO• (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO• (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl (tBu2NO•), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and tBu2NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of nitroxyl radicals. The HAT reactions all have |ΔGo| ≤ 1.4 kcal mol−1 and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO• + TEMPO-H → 4-oxo-TEMPO-H + TEMPO• occurs with k2H,MeCN = 10 ± 1 M−1 s−1 in MeCN at 298 K (K2H,MeCN = 4.5 ± 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k2D,MeCN = 0.44 ± 0.05 M−1 s−1 with k2H,MeCN/k2D,MeCN = 23 ± 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH2Cl2, 23 ± 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO• with 4-MeO-TEMPO-H(D) also has a large KIE, k3H/k3D = 21 ± 3 in MeCN. For these three reactions, the EaD – EaH values, between 0.3 ± 0.6 and 1.3 ± 0.6 kcal mol−1, and the log(AH/AD) values, between 0.5 ± 0.7 and 1.1 ± 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of tBu2NO• + TEMPO-H(D) in MeCN has a large KIE, 16 ± 3 in MeCN, and very unusual isotopic activation parameters, EaD – EaH = −2.6 ± 0.4 and log(AH/AD) = 3.1 ± 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH3)2NO• + (CH3)2NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO(•/H), tBu2NO(•/H), and Ph2NO(•/H) self-exchange reactions reveal why the

  1. Characterising the exchangeability of phenanthrene associated with naturally occurring soil colloids using an isotopic dilution technique.

    PubMed

    Tavakkoli, Ehsan; Juhasz, Albert; Donner, Erica; Lombi, Enzo

    2015-04-01

    The association of polycyclic aromatic hydrocarbons (PAHs) with inorganic and organic colloids is an important factor influencing their bioavailability, mobility and degradation in the environment. Despite this, our understanding of the exchangeability and potential bioavailability of PAHs associated with colloids is limited. The objective of this study was to use phenanthrene as a model PAH compound and develop a technique using (14)C phenanthrene to quantify the isotopically exchangeable and non-exchangeable forms of phenanthrene in filtered soil water or sodium tetraborate extracts. The study was also designed to investigate the exchangeability of colloidal phenanthrene as a function of particle size. Our findings suggest that the exchangeability of phenanthrene in sodium tetraborate is controlled by both inorganic and organic colloids, while in aqueous solutions inorganic colloids play the dominant role (even though coating of these by organic matter cannot be excluded). Filter pore size did not have a significant effect on phenanthrene exchangeability. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. EXPERIMENTAL RESULTS FOR THE ISOTOPIC EXCHANGE OF A 1600 LITER TITANIUM HYDRIDE STORAGE VESSEL

    SciTech Connect

    Klein, J.

    2010-12-14

    Titanium is used as a low pressure tritium storage material. The absorption/desorption rates and temperature rise during air passivation have been reported previously for a 4400 gram prototype titanium hydride storage vessel (HSV). A desorption limit of roughly 0.25 Q/M was obtained when heating to 700 C which represents a significant residual tritium process vessel inventory. To prepare an HSV for disposal, batchwise isotopic exchange has been proposed to reduce the tritium content to acceptable levels. A prototype HSV was loaded with deuterium and exchanged with protium to determine the effectiveness of a batch-wise isotopic exchange process. A total of seven exchange cycles were performed. Gas samples were taken nominally at the beginning, middle, and end of each desorption cycle. Sample analyses showed the isotopic exchange process does not follow the standard dilution model commonly reported. Samples taken at the start of the desorption process were lower in deuterium (the gas to be removed) than those taken later in the desorption cycle. The results are explained in terms of incomplete mixing of the exchange gas in the low pressure hydride.

  3. Dual pressure-dual temperature isotope exchange process

    DOEpatents

    Babcock, D.F.

    1974-02-12

    A liquid and a gas stream, each containing a desired isotope, flow countercurrently through two liquid-gas contacting towers maintained at different temperatures and pressures. The liquid is enriched in the isotope in one tower while the gas is enriched within the other and a portion of at least one of the enriched streams is withdrawn from the system for use or further enrichment. The tower operated at the lower temperature is also maintained at the lower pressure to prevent formation of solid solvates. Gas flow between the towers passes through an expander-compressor apparatas to recover work from the expansion of gas to the lower pressure and thereby compress the gas returning to the tower of higher pressure. (Official Gazette)

  4. Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction

    PubMed Central

    Rossi, Federico; Rustici, Mauro; Rossi, Claudio; Tiezzi, Enzo

    2007-01-01

    In this work we present results about the deuterium isotope effect on the global kinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependence of the Induction Period upon the percentage of deuterated reactants was found. The isotopic effect on the bromination reaction of malonic acid was evaluated.

  5. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    PubMed

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

    2012-09-30

    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  6. Hydrogen recycle and isotope exchange from dense carbon films

    SciTech Connect

    Clausing, R.E.; Heatherly, L.

    1987-03-01

    Dense carbon films were prepared by deposition from hydrogen plasmas to which methane was added. The initial hydrogen recycle coefficient from the films ranges from more than two to less than one. The films contain large amounts of hydrogen (up to 50 at. %). They adjust themselves to provide recycling coefficients near unity. Isotope changeover times tend to be long. The reservoir of hydrogen instantly available to the plasma to maintain or stabilize the recycle coefficient and isotopic composition of the plasma is 10/sup 15/ cm/sup -2/ or greater depending on film preparation, temperature, and prior plasma exposure conditions. Simulator observations tend to support and improve the understanding of the observations in TEXTOR and JET; however, they also point out the need for control of film deposition and operating parameters to provide desirable and reproducible properties. The films and the hydrogen isotopes they contain can be removed easily by plasma processes. Since the hydrogen in these films is relatively immobile except in the zone reached by energetic particles, or at temperatures above 400/sup 0/C, dense carbon films may be useful in managing the tritium recovery from near-term fusion experiments.

  7. The CH + CO reaction: Rate coefficient for carbon atom exchange at 294 K

    SciTech Connect

    Anderson, S.M.; McCurdy, K.E.; Kolb, C.E. )

    1989-02-09

    A fast-flow reactor equipped with isotope-specific laser-excited fluorescence detection of CH radicals has been used to study carbon atom exchange in the reaction between CH and CO at 294 K and 2 Torr of total pressure. The rate coefficient for exchange, k{sub 3} = (2.1 {times} 0.3) {times} 10{sup {minus}12} cm{sup 3} s{sup {minus}1}, is about an order of magnitude larger than the bimolecular rate for the addition reaction, k{sub 2} = (2.7 {plus minus} 0.4) {times} 10{sup {minus}13}. High-pressure limiting bimolecular and low-pressure termolecular recombination rate coefficients of 1.1 {times} 10{sup {minus}10} cm{sup 3} s{sup {minus}1} and 4.9 {times} 10{sup {minus}30} cm{sup 6} s{sup {minus}1} are derived. The results are discussed in the context of previous work on the title reaction and on the chemistry of singlet CH{sub 2}.

  8. EXFOR systems manual: Nuclear reaction data exchange format

    SciTech Connect

    McLane, V.

    1996-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. In addition to storing the data and its bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine).

  9. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions: implications for abiotic and thermogenic hydrocarbons in vent fluids

    NASA Astrophysics Data System (ADS)

    Reeves, E. P.; Seewald, J.; Sylva, S.

    2010-12-01

    Stable isotopes are extensively utilized in studies of hydrocarbons in naturals fluids. However, factors controlling the hydrogen isotope (2H/1H) composition of dissolved hydrocarbons in hydrothermal fluids are still poorly understood despite interest in their 2H/1H signatures as indicators of abiogenesis. Due to its high activation energy for exchange, alkyl-bound hydrogen (H) is typically considered to be isotopically conservative. Incorporation of water-derived H under hydrothermal conditions may, however, obscure any primary signatures associated with abiotic polymerization. To examine this process, we conducted experiments to investigate 2H/1H exchange between aqueous n-alkanes and water using a Au-TiO2 flexible cell hydrothermal apparatus. C1-C5 n-alkanes were heated at 325°C and 350 bar in aqueous solutions of varying initial 2H/1H ratios (δ2H) in the presence of a pyrite-pyrrhotite-magnetite (PPM) mineral redox buffer. Extensive incorporation of water-derived H into C2-C5 n-alkanes was observed on timescales of months. In contrast, relatively minor incorporation was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding alkenes by the reaction: CnH2n+2(aq) = CnH2n(aq) + H2(aq) Where H2(aq) is derived from water. The lack of substantial n-alkane decomposition on the timescale of observation, combined with an approach to steady-state isotopic compositions, indicate that n-alkane δD values likely reflect an approach to isotopic equilibrium rather than kinetically-controlled fractionation effects associated with degradation reactions. Substantially lower amounts of exchange were observed for ethane relative to C3-C5 n-alkanes, which suggests that alkene isomerization reactions may enhance incorporation of water-derived H in these compounds. Thus, reaction mechanisms exist in hydrothermal fluids that allow rapid 2H/1H exchange of alkyl-H with water on timescales comparable to crustal residence times

  10. Synthesis of layered sodium lanthanum selenide through ion exchange reactions

    SciTech Connect

    Butts, Laura J.; Strickland, Nicholas; Martin, Benjamin R.

    2009-04-02

    Layered hexagonal KLaSe2 ({alpha}-NaFeO{sub 2}-type) was synthesized using the reactive flux method and analyzed by powder XRD to determine its lattice constants (space group R-3m, a = 4.40508(5) A, c = 22.7838(5) A). NaLaSe{sub 2}, which normally crystallizes as a disordered rock salt structure with mixed Na+/La + 3 sites, was synthesized through a solid state ion exchange reaction at 585 deg. C from a 1:3 molar ratio mixture of KLaSe{sub 2}:NaI. The product of this reaction was hexagonally layered NaLaSe{sub 2} (space group R-3m, a = 4.3497(3) A, c = 20.808(2) A) isostructural to KLaSe{sub 2}. This product was analyzed by comparison with members of the set of solid solutions Na{sub (1-x)}K{sub (x)}LaSe{sub 2} to confirm that the extent ion exchange in this reaction was complete. Cubic (disordered) NaLaSe{sub 2} was also reacted with KI to yield the poorly crystalline hexagonally layered product with the approximate formula Na{sub 0.79}K{sub 0.21}LaSe{sub 2}.

  11. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    NASA Astrophysics Data System (ADS)

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H.

    2017-02-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  12. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism.

    PubMed

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H

    2017-02-22

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  13. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    PubMed Central

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H

    2017-01-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode. PMID:28224993

  14. Isotope Fractionation of chlorine in Aqueous System: One Study on Anion-Exchange Chromatography.

    NASA Astrophysics Data System (ADS)

    Musashi, M.; Oi, T.; Eggenkamp, H.; Van Cappellen, P.

    2001-05-01

    Stable chlorine isotopes such as 37Cl and 35Cl have been paid attention as useful tool identifying the source, and monitoring the transport process and natural fate of chlorinated organic pollutants in air and groundwater. However, it is not established yet whether any isotope effects accompany biodegradation or reductive dehalogenation of the pollutants (Clark and Fritz, 1997). Here we first present an experimental determination of isotope fractionation factor of chlorine in aqueous system by using anion-exchange chromatographic technique. Into the Cl-free anion exchange resin (Muromac, OH- form) packed in a 30 cm long pyrex glass column and controlled temperature at 25 oC, hydrochloric solution was fed with controlling the flow rate constant. Effluent from the column was recovered by an automatic fraction collector and prepared for Cl isotope analysis. The Cl isotope ratio (δ 37Cl vs. SMOC) was measured by IR-MS at the Utrecht University with precision of 0.06 per-mil. Magnitude of the factor obtained was 1.00035 at 25 oC. The result indicates that the lighter isotope (35Cl) was preferably fractionated into the resin phase, while the heavier one (37Cl) was enriched into the aqueous phase. This trend suggests that molecular structure of hydrolysis with Cl in aqueous phase may be more stable than that of Cl ionically bonding with the resin. This result may offer physico-chemical insights into behavior and fate of the pollutants.

  15. D/H Exchange Reactions in Salts Extracted from LEW 85320

    NASA Astrophysics Data System (ADS)

    Socki, R. A.; Romanek, C. S.; Gibson, E. K., Jr.

    1993-07-01

    ). Mass balance calculations reveal that absorption of the spiked water is stoichiometric with respect to the formation of CaSO4.2H2O, while within limits of sampling error no net change of weight was observed for the nesquehonite. Assuming that the change in deltaDnesq. is due entirely to exchange (i.e., no absorption), mass balance constraints dictate that less than 5 wt% of water exchanged. These data suggest that nesquehonite retains its original deltaD composition even under conditions of relatively high temperature and humidity. Hydrogen isotope data of water extracted from three generations of nesquehonite on LEW85320 are plotted as a function of the theoretical delta18O composition of water in equilibrium with the carbonate at 0 degrees C (where delta18Onesq. is derived by phosphoric acid digestion of the carbonate, assuming a calcite-CO2 fractionation factor of 1.01012). Our data plot very near the meteoric water line indicating formation from slightly enriched Antarctic meltwater. Water extracted from generations II (,99), salts consisting mostly of hydromagnesite (Mg5(CO3)4(OH)2.4H2O) (Gooding, 1993, personal communication), and III (,102), with mineralogy as yet unknown, is enriched in D (deltaD = -55 and -75 permil, respectively) and plot above the meteoric water line. Both generations precipitated in the Houston curatorial facility. Data suggest either that hydrogen isotopes have exchanged at least partially with local (i.e., Houston) water, or that the exchange reactions differ between structural sites within or among the various generations of efflorescent salts. Hydrogen isotopes extracted from hydrous weathering products can reveal information about the environment of crystal growth. However, hydrogen isotope exchange systematics could be complicated if water within the crystal structure of the mineral is located in multiple sites. Furthermore, these results could have profound implications for curation and long-term storage strategies in curatorial

  16. Pyrogen reactions to human serum albumin during plasma exchange.

    PubMed

    Pool, M; McLeod, B C

    1995-01-01

    Reactions to human serum albumin (HSA) in therapeutic plasma exchange (TPE) are rare. Nevertheless, older literature describes possible adverse effects, including specific immune responses to albumin or other proteins, and reactions due to contaminating organisms or pyrogen. During an eight day period three patients in our unit had unusual reactions after infusion of 1.5-2 L of HSA. Patient 1 had trembling that persisted for 20 min. Patient 2 had shaking for 40 min despite calcium gluconate infusion, and fever to 100.8 degrees F. Patient 3 had severe rigors that subsided after 90 min when meperidine was finally given, and fever to 103.5 degrees F. Record reviews revealed that all three patients had received HSA from the same lot, and that only one other TPE patient had received HSA from that lot. Neither our pharmacy nor the manufacturer was aware of other reactions associated with that lot. Material from a bottle only partially infused to patient 3 was negative in culture and was negative for pyrogen when retested by the manufacturer. Nevertheless, because patients 1 and 2 had each had multiple previous uneventful TPEs and because all three patients tolerated subsequent TPEs without incident when another brand of HSA was used, we conclude that these patients had pyrogen reactions to the implicated HSA lot. This experience illustrates the value of cluster recognition in arousing suspicion of unusual reactions to HSA and the value of recorded lot numbers in pursuing such suspicions. Apheresis personnel should be aware of the potential for pyrogen reactions with HSA and should record lot numbers of all fluids infused during TPE.

  17. Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange

    USGS Publications Warehouse

    Sharp, Z.D.; O'Neil, J.R.; Essene, E.J.

    1988-01-01

    The oxygen isotope ratios of various minerals were measured in a granulite-grade iron formation in the Wind River Range, Wyoming. Estimates of temperature and pressure for the terrane using well calibrated geothermometers and geobarometers are 730??50?? C and 5.5??0.5 kbar. The mineral constraints on fluid compositions in the iron formation during retrogression require either very CO2-rich fluids or no fluid at all. In the iron formation, isotopic temperature estimates from quartz-magnetite fractionations are controlled by the proximity to the enclosing granitic gneiss, and range from 500?? C (??qz - mt=10.0???) within 2-3 meters of the orthogneiss contact to 600?? C (??qz - mt=8.0???) farther from the contact. Temperature estimates from other isotopic thermometers are in good agreement with those derived from the quartz-magnetite fractionations. During prograde metamorphism, the isotopic composition of the iron formation was lowered by the infiltration of an external fluid. Equilibrium was achieved over tens of meters. Closed-system retrograde exchange is consistent with the nearly constant whole-rock ??18Owr value of 8.0??0.6???. The greater ??qz-mt values in the iron formation near the orthogneiss contact are most likely due to a lower oxygen blocking temperature related to greater exchange-ability of deformed minerals at the contact. Cooling rates required to preserve the quartz-magnetite fractionations in the central portion of the iron formation are unreasonably high (???800?? C/Ma). In order to preserve the 600?? C isotopic temperature, the diffusion coefficient D (for ??-quartz) should be two orders of magnitude lower than the experimentally determined value of 2.5??10-16 cm2/s at 833 K. There are no values for the activation energy (Q) and pre-exponential diffusion coefficient (D0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the diffusion

  18. Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; O'Neil, J. R.; Essene, E. J.

    1988-04-01

    The oxygen isotope ratios of various minerals were measured in a granulite-grade iron formation in the Wind River Range, Wyoming. Estimates of temperature and pressure for the terrane using well calibrated geothermometers and geobarometers are 730±50° C and 5.5±0.5 kbar. The mineral constraints on fluid compositions in the iron formation during retrogression require either very CO2-rich fluids or no fluid at all. In the iron formation, isotopic temperature estimates from quartz-magnetite fractionations are controlled by the proximity to the enclosing granitic gneiss, and range from 500° C ( Δ qz - mt=10.0‰) within 2 3 meters of the orthogneiss contact to 600° C ( Δ qz - mt=8.0‰) farther from the contact. Temperature estimates from other isotopic thermometers are in good agreement with those derived from the quartz-magnetite fractionations. During prograde metamorphism, the isotopic composition of the iron formation was lowered by the infiltration of an external fluid. Equilibrium was achieved over tens of meters. Closed-system retrograde exchange is consistent with the nearly constant whole-rock δ 18Owr value of 8.0±0.6‰. The greater Δ qz-mt values in the iron formation near the orthogneiss contact are most likely due to a lower oxygen blocking temperature related to greater exchange-ability of deformed minerals at the contact. Cooling rates required to preserve the quartz-magnetite fractionations in the central portion of the iron formation are unreasonably high (˜800° C/Ma). In order to preserve the 600° C isotopic temperature, the diffusion coefficient D (for α-quartz) should be two orders of magnitude lower than the experimentally determined value of 2.5×10-16 cm2/s at 833 K. There are no values for the activation energy ( Q) and pre-exponential diffusion coefficient ( D 0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the

  19. Positional isotope exchange analysis of the Mycobacterium smegmatis cysteine ligase (MshC).

    PubMed

    Williams, LaKenya; Fan, Fan; Blanchard, John S; Raushel, Frank M

    2008-04-22

    MshC catalyzes the ATP-dependent condensation of GlcN-Ins and cysteine to form Cys-GlcN-Ins, which is an intermediate in the biosynthetic pathway of mycothiol, i.e., 1-D-myo-inosityl-2-(N-acetyl-L-cysteinyl)amido-2-deoxy-alpha-D-glucopyranoside (MSH or AcCys-GlcN-Ins). MSH is produced by Mycobacterium tuberculosis, members of the Actinomycetes family, to maintain an intracellular reducing environment and protect against oxidative and antibiotic induced stress. The biosynthesis of MSH is essential for cell growth, and therefore, the MSH biosynthetic enzymes present potential targets for inhibitor design. The formation of kinetically competent adenylated intermediates was suggested by the observation of positional isotope exchange (PIX) reaction using [betagamma-(18)O6]-ATP in the presence of cysteine. The PIX rate depends on the presence of cysteine and increases with concentrations of cysteine. The loss of PIX activity upon the addition of small concentrations of pyrophosphatase suggests that the PP(i) is free to dissociate from the active site of cysteine ligase into the bulk solution. The PIX activity is also eliminated at high concentrations of GlcN-Ins, consistent with the mechanism in which GlcN-Ins binds after cysteine-adenylate formation. This PIX analysis confirms that MshC catalyzes the formation of a kinetically competent cysteinyl-adenylate intermediate after the addition of ATP and cysteine.

  20. Retention, isotope exchange, and thermal release of hydrogen in candidate materials for TFTR

    SciTech Connect

    Wampler, W. R.; Doyle, B. L.; Brice, D. K.; Picraux, S. T.

    1980-08-01

    The materials studied included TiC, TiB/sub 2/, VB/sub 2/, B/sub 4/C, B, Si, graphite, and the metals Ti, V, and 304L stainless steel. The TiC and TiB/sub 2/ were formed by chemical vapor deposition on a graphite substrate. The C/Ti ratio of the TiC was measured to be 1.0 +- .05 by ion backscattering analysis. The Ti and V were explosively bonded to copper substrates, and the VB/sub 2/ was made by borodizing vanadium. Carbon (compression annealed pyrolytic graphite from Union Carbide and Papyex graphite ribbon from Le Carbone) and single crystal silicon samples were included in the study as reference materials. The hydrogen retention and isotope exchange behavior for these materials were studied by measuring the amount of H or D retained as a function of incident fluence using the D(/sup 3/He,P)/sup 4/He nuclear reaction analysis techniques for D and H(/sup 15/N,..cap alpha gamma..) profiling for H.

  1. Charge-exchange reactions with a radioactive triton beam

    SciTech Connect

    Jaenecke, J.

    1998-12-21

    A high-resolution (t, {sup 3}He) test experiment has been performed recently by making use of a secondary triton beam produced by fragmentation of {alpha}-particles. The purpose of this charge-exchange experiment was to achieve good energy resolution in an (n,p)-type reaction at intermediate bombarding energies. The experiment was carried out with the K1200 cyclotron at the National Superconducting Cyclotron Laboratory using the A1200 beam-analysis system and the S800 magnetic spectrometer. The beam-analysis system was used to transport the energy-dispersed radioactive triton beam from the production target to the target position, and the magnetic spectrometer was used to focus the dispersion-matched {sup 3}He particles from the (t, {sup 3}He) reaction at 0 degree sign onto the focal plane of the spectrometer. An energy resolution of 200-250 keV was achieved.

  2. Chapter 18 – Tracing of Weathering Reactions and Water Flowpaths: A Multi-isotope Approach

    USGS Publications Warehouse

    Bullen, Tomas D.; Kendall, Carol

    1998-01-01

    This chapter discusses the importance of using isotopes in a complementary manner, primarily to constrain and enrich models developed from hydrologic and chemical data. Isotopes are viewed as tools for testing rather than developing hypotheses, particularly in studies operating under tight budgetary constraints. Water isotopes are very useful tools for determining water sources in catchments. Chemical tracers are very useful for understanding the reactions along flowpaths. The potential application of Fe isotopes to catchment studies lies in the assumption that Fe mobilized inorganically from minerals under either reducing or low-pH conditions will have a different isotopic composition than microbially-reduced Fe. To the extent that certain zones or flowpaths in the catchment can be characterized by microbial cycling of labile Fe, the Fe isotopes may provide an effective tracer of contributions from these pathways. The solute isotopes, for example, strontium, carbon, and lead are as yet under-utilized in catchment research compared to the water isotopes.

  3. Mechanism of the Exchange Reaction in HRAS from Multiscale Modeling

    PubMed Central

    Kapoor, Abhijeet; Travesset, Alex

    2014-01-01

    HRAS regulates cell growth promoting signaling processes by cycling between active (GTP-bound) and inactive (GDP-bound) states. Understanding the transition mechanism is central for the design of small molecules to inhibit the formation of RAS-driven tumors. Using a multiscale approach involving coarse-grained (CG) simulations, all-atom classical molecular dynamics (CMD; total of 3.02 µs), and steered molecular dynamics (SMD) in combination with Principal Component Analysis (PCA), we identified the structural features that determine the nucleotide (GDP) exchange reaction. We show that weakening the coupling between the SwitchI (residues 25–40) and SwitchII (residues 59–75) accelerates the opening of SwitchI; however, an open conformation of SwitchI is unstable in the absence of guanine nucleotide exchange factors (GEFs) and rises up towards the bound nucleotide to close the nucleotide pocket. Both I21 and Y32, play a crucial role in SwitchI transition. We show that an open SwitchI conformation is not necessary for GDP destabilization but is required for GDP/Mg escape from the HRAS. Further, we present the first simulation study showing displacement of GDP/Mg away from the nucleotide pocket. Both SwitchI and SwitchII, delays the escape of displaced GDP/Mg in the absence of GEF. Based on these results, a model for the mechanism of GEF in accelerating the exchange process is hypothesized. PMID:25272152

  4. Reactive Resonances in N+N2 Exchange Reaction

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Stallcop, James R.

    2003-01-01

    Rich reactive resonances are found in a 3D quantum dynamics study of the N + N2 exchange reaction using a recently developed ab initio potential energy surface. This surface is characterized by a feature in the interaction region called Lake Eyring , that is, two symmetric transition states with a shallow minimum between them. An L2 analysis of the quasibound states associated with the shallow minimum confirms that the quasibound states associated with oscillations in all three degrees of freedom in Lake Eyring are responsible for the reactive resonances in the state-to-state reaction probabilities. The quasibound states, mostly the bending motions, give rise to strong reasonance peaks, whereas other motions contribute to the bumps and shoulders in the resonance structure. The initial state reaction probability further proves that the bending motions are the dominating factors of the reaction probability and have longer life times than the stretching motions. This is the first observation of reactive resonances from a "Lake Eyring" feature in a potential energy surface.

  5. Alloyed copper chalcogenide nanoplatelets via partial cation exchange reactions.

    PubMed

    Lesnyak, Vladimir; George, Chandramohan; Genovese, Alessandro; Prato, Mirko; Casu, Alberto; Ayyappan, S; Scarpellini, Alice; Manna, Liberato

    2014-08-26

    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide-sulfide (CZSeS), copper tin selenide-sulfide (CTSeS), and copper zinc tin selenide-sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide-sulfide (Cu2-xSeyS1-y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2-xSeyS1-y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV-vis-NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps.

  6. Alloyed Copper Chalcogenide Nanoplatelets via Partial Cation Exchange Reactions

    PubMed Central

    2014-01-01

    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide–sulfide (CZSeS), copper tin selenide–sulfide (CTSeS), and copper zinc tin selenide–sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide–sulfide (Cu2–xSeyS1–y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2–xSeyS1–y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV–vis–NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps. PMID:25050455

  7. Synthesis of temperature-responsive anion exchanger via click reaction.

    PubMed

    Murakami, Kenji; Yu, Xue; Kato, Takahiro; Inoue, Yukihiko; Sugawara, Katsuyasu

    2012-06-15

    The temperature-responsive anion exchanger was synthesized by immobilizing the poly(N-isopropylacrylamide) (PNIPAM), a kind of the temperature-responsive polymer, on the external surface of mesoporous silica via click reaction. The structure of this synthesized composite was characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), elemental analysis, and nitrogen adsorption experiment. The amount of PNIPAM immobilized on the external surface of mesoporous silica, which was calculated from the weight loss measured by thermogravimetry, increased from 5.3 wt.% to 12.9 wt.% (dry) depending on the amount of PNIPAM added in the click reaction. The adsorption-desorption behavior of methyl orange (MO) ions in this synthesized anion exchanger was affected by the temperature of aqueous solution: the MO ions were adsorbed and desorbed reversibly and repeatedly with changing the pH of the solution at 25 °C, while the amount of adsorbed MO ions remained nearly constant at about 0.05 mmol/g independent of the pH of the solution at 40 °C. Also, the amount of PNIPAM immobilized on the mesoporous silica influenced the adsorption rate of MO ions, suggesting that the adsorption rate in this composite is controlled by the diffusion of MO ions through the PNIPAM layer.

  8. A new approach to quantifying internal diffusion resistances and CO2 isotope exchange in leaves

    NASA Astrophysics Data System (ADS)

    West, Jason; Ogée, Jérôme; Burlett, Régis; Gimeno, Teresa; Genty, Bernard; Jones, Samuel; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    The oxygen isotopic composition (δ18O) of atmospheric CO2 can constrain the global CO2 budget at a range of scales, offering the potential to partition net CO2 exchanges into their component gross fluxes and provide insights to linkages between C and water cycles. However, there are significant limitations to utilizing the δ18O of CO2 to constrain C budgets because of uncertainties associated with the isotopic exchange of CO2 with terrestrial water pools. Leaf water in particular represents a critical pool with ongoing debates about its enrichment in heavy isotopes during transpiration and the hydration of CO2 and its oxygen isotope exchange with this pool. Isotopic heterogeneity of the leaf water, the spatial distribution and activity of carbonic anhydrase (CA) within leaves, and resistance to diffusion of CO2 from the substomatal cavity to chloroplasts are all key components with important uncertainties. Better constraints on these would significantly improve our ability to understand and model the global C budget as well as yield insights to fundamental aspects of leaf physiology. We report results using a new measurement system that permits the simultaneous measurement of the 13C and 18O composition of CO2 and the 18O isotopic composition of leaf transpiration. As this new approach permits rapid alteration of the isotopic composition of gases interacting with the leaf, key model parameters can be derived directly and simultaneously. Hence, our approach dos not rely on separate measurements shifted in time from the gas exchange measurements or that may not quantify the relevant scale of heterogeneity (e.g., CA enzyme assays or bulk leaf water extraction and analysis). In particular, this new method explicitly distinguishes the leaf mesophyll resistance to CO2 transport relevant for photosynthesis from the resistance required for interpreting the δ18O of CO2 and allows us to derive other relevant parameters directly. This new measurement system and modeling

  9. Installations for separation of hydrogen isotopes by the method of chemical isotopic exchange in the `water-hydrogen` system

    SciTech Connect

    Andreev, B.M.; Sakharovsky, Y.A.; Rozenkevich, M.B.; Magomedbekov, E.P.; Park, Y.S.; Uborskiy, V.V.; Trenin, V.D.; Alekseev, I.A.; Fedorchenko, O.A.; Karpov, S.P.; Konoplev, K.A.

    1995-10-01

    The paper presents the results of more than a year of running a pilot setup for separation of hydrogen isotopes using catalytic isotopic exchange between hydrogen and liquid water. The setup is 5 m high, has the inner diameter of 28 mm, and is equipped with upper and lower reflux devices. The experimental values of HETP vary from 15 cm at T=333 K to 38 cm at T=293 K. The setup is capable of upgrading diluted heavy water with 85-90% deuterium content up to [D{sub 2}O] > 99.95 at.%, yielding daily 4 kg of the product. We also report on the progress in constructing a similar setup for eliminating tritium and an industrial setup, for which the one reported is a prototype. 10 refs., 1 fig., 3 tabs.

  10. Sulfite exchange dominates oxygen isotope compositions of sulfate produced from abiotic pyrite oxidation

    NASA Astrophysics Data System (ADS)

    Kohl, I. E.; Bao, H.

    2009-12-01

    The oxidation of reduced sulfur compounds (solid, liquid and gas phase) is of primary importance when attempting to understand the global sulfur and oxygen cycles as preserved in sulfate minerals. It has long been known that O2, H2O, and Fe3+ all play an important role during this oxidation process, especially during the oxidation of sulfide minerals. The exact role of each oxidant and/or oxygen source has yet to be experimentally determined for oxidation in aqueous solutions over a range of pH values. In addition, the reported air O2 signal being incorporated in product sulfate appears to be highly variable (9-60%), which could be due to the presence of multiple oxidation pathways or the inability of the traditional δ18O label to differentiate kinetic effects on the degree of oxygen exchange. Here we test the affect of pH dependent sulfite-water oxygen exchange rate and precipitation of ferric hydroxides on the produced sulfate’s O2/H2O ratio. Our experiments utilize a Δ17O isotope label in the solutions, enabling a quantitative determination of oxygen source ratios (O2 vs. H2O) in the produced sulfate. We oxidized crushed pyrite grains aerobically in sterile, buffered solutions at pH=2,7,9,10, and 11. A duplicate set was spiked with Fe3+. The results from the reactors indicate that despite the pH dependency of sulfite-water exchange rate, fast at low pH and slow at high pH, the stability of intermediates, thiosulfate and especially sulfite, in alkaline solutions allows the exchange to proceed to equilibrium. This resulted in sulfate produced above pH=9 to contain 21-24% air O2 signal, indicating the last oxidation step, producing sulfate from sulfite, proceeded with direct incorporation of dissolved air O2 as represented by equation (1). The role of Fe3+ under alkaline conditions was observed to be negligible. SO32- + 1/2O2 → SO42- (1) In the pH=2 reactor, the O2% in the produced sulfate was 21% with the addition of Fe3+, but was 28-29% without the Fe3

  11. Charge-exchange reaction by Reggeon exchange and W{sup +}W{sup −}-fusion

    SciTech Connect

    Schicker, R.

    2015-04-10

    Charge-exchange reactions at high energies are examined. The existing cross section data on the Reggeon induced reaction pp → n + Δ{sup ++} taken at the ZGS and ISR accelerators are extrapolated to the energies of the RHIC and LHC colliders. The interest in the charge-exchange reaction induced by W{sup ±}-fusion is presented, and the corresponding QCD-background is examined.

  12. HYDROGEN ISOTOPE RECOVERY USING PROTON EXCHANGE MEMBRANE ELECTROLYSIS OF WATER

    SciTech Connect

    Fox, E; Scott Greenway, S; Amy Ekechukwu, A

    2007-08-27

    A critical component of tritium glovebox operations is the recovery of high value tritium from the water vapor in the glove box atmosphere. One proposed method to improve existing tritium recovery systems is to replace the disposable hot magnesium beds used to separate the hydrogen and oxygen in water with continuous use Proton Exchange Membrane Electrolyzers (PEMEs). This study examines radiation exposure to the membrane of a PEME and examines the sizing difference that would be needed if the electrolyzer were operated with a cathode water vapor feed instead of an anode liquid water feed.

  13. Determination of uranium isotopes in environmental samples by anion exchange in sulfuric and hydrochloric acid media.

    PubMed

    Popov, L

    2016-09-01

    Method for determination of uranium isotopes in various environmental samples is presented. The major advantages of the method are the low cost of the analysis, high radiochemical yields and good decontamination factors from the matrix elements, natural and man-made radionuclides. The separation and purification of uranium is attained by adsorption with strong base anion exchange resin in sulfuric and hydrochloric acid media. Uranium is electrodeposited on a stainless steel disk and measured by alpha spectrometry. The analytical method has been applied for the determination of concentrations of uranium isotopes in mineral, spring and tap waters from Bulgaria. The analytical quality was checked by analyzing reference materials.

  14. Nuclear orientation of radon isotopes by spin-exchange optical pumping

    SciTech Connect

    Kitano, M.; Calaprice, F.P.; Pitt, M.L.; Clayhold, J.; Happer, W.; Kadar-Kallen, M.; Musolf, M.; Ulm, G.; Wendt, K.; Chupp, T.

    1988-05-23

    This paper reports the first demonstration of nuclear orientation of radon atoms. The method employed was spin exchange with potassium atoms polarized by optical pumping. The radon isotopes were produced at the ISOLDE isotope separator of CERN. The nuclear alignment of /sup 209/Rn and /sup 223/Rn has been measured by observation of ..gamma..-ray anisotropies and the magnetic dipole moment for /sup 209/Rn has been measured by the nuclear-magnetic-resonance method to be chemically bond..mu..chemically bond = 0.838 81(39)..mu../sub N/.

  15. Isotopic exchange between carbon dioxide and ozone via O((sup 1)D) in the stratosphere

    SciTech Connect

    Yung, Y.L.; DeMore, W.B.; Pinto, J.P.

    1991-01-01

    The authors propose a novel mechanism for isotopic exchange between CO{sub 2} and O{sub 3} via O ((1)D) + CO{sub 2} {minus}> CO{sub 3} followed by CO{sub 3} {minus}> CO{sub 2} + O((3)P). A one-dimensional model calculation shows that the mechanism can account for the enrichment in 18O in the stratospheric CO{sub 23} observed by Gamo et al. (1989), using the heavy O3 profile observed by Mauersberger (1981). The implication of the mechanism for other stratospheric species and as a source of isotopically heavy CO{sub 2} in the troposphere are briefly discussed.

  16. The purification of ITER project technology water from tritium in catalytic isotope exchange column using hydrophobic catalyzer

    SciTech Connect

    Andreev, M.I.; Sakharovskij, Y.A.; Rozenkevich, M.B.

    1994-12-31

    The new universal technological scheme for purification of ITER project tritium containing waste water has been proposed. The purification process as a whole has two technological parts. The starting concentrate of tritium up to about 100-300 Cu/l by the method of catalytic isotope exchange between hydrogen and liquid water and the final concentrate of tritium up to practically pure tritium by the isotope exchange in the system hydrogen-palladium. This report contains the experimental data about the effectiveness of the column for the isotope exchange between hydrogen and water.

  17. A universal empirical expression for the isotope surface exchange coefficients (k*) of acceptor-doped perovskite and fluorite oxides.

    PubMed

    De Souza, R A

    2006-02-21

    The isotope surface exchange coefficient k* determined in an 18O/16O exchange experiment characterises the exchange flux of the dynamic equilibrium between oxygen in the gas phase and oxygen in a solid oxide. At present there is no atomistic expression that relates measured exchange coefficients to materials' parameters. In this study an empirical, atomistic expression is developed that describes the exchange kinetics of gaseous oxygen with diverse acceptor-doped perovskite and fluorite oxides at temperatures above T approximately 900 K. The expression is used to explain the observed correlations between surface exchange coefficients k* and oxygen tracer diffusion coefficients D* and to identify compounds that exhibit high surface exchange coefficients.

  18. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    PubMed

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

  19. Population of 13Be with a Nucleon-Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Marks, Bradon; Deyoung, Paul; Smith, Jenna; Thoennessen, Michael; MoNA Collaboration

    2015-10-01

    Neutron-unbound nuclei are traditionally formed by the removal of one or more nucleons from a fast beam of ions. This method often results in a background, which is difficult to separate from the particle of interest. Nucleon-removal entrance-channels also require the ion beam to be more massive than the particle of interest, which presents the additional challenges of the beam being difficult to make. The present work was done with a nucleon-exchange entrance channel. At the National Superconducting Cyclotron Laboratory, a 71 MeV/u 13B beam impinged on a 47 mg/cm2 thick target of 9Be. As a result numerous reactions occurred, including the population of 13Be through the nucleon-exchange entrance-channel. The 13Be nuclei decayed to 12Be and one neutron in approximately 10-21 seconds. The resulting neutrons were detected by either the Modular Neutron Array (MoNA) or the Large multi-Institution Scintillator Array (LISA), while the 12Be nuclei were directed through an array of charged particle detectors by a 4T superconducting sweeper magnet. The four-momentum vectors of the fragment nucleus and the neutron were calculated to determine the decay energy of 13Be. Monte-Carlo simulations consistent with results from previous analyses of 13Be were satisfactorily fit to the decay-energy spectrum. Additionally, the cross-section for the nucleon-exchange entrance-channel is consistent with a theoretical prediction. This material is based upon work supported by the National Science Foundation under Grant No. PHY-1306074.

  20. Study of the dynamics and isotopic effects in the D + MgD reaction using the quasi-classical trajectory method

    NASA Astrophysics Data System (ADS)

    Huang, Zhuoyao; Li, Rui; Ge, Meihua; Zheng, Yujun; Meng, Xiangjia; Yang, Huan

    2017-10-01

    The dynamics of the D + MgD reaction at low collision energies are conducted in quasi-classical trajectory method (QCT) on three reaction channels, namely nonreactive, D abstraction, and D exchange. Isotopic effects between D + MgD and H + MgH reactions are included mainly in the exchange channel involving both direct and roaming mechanisms. The integral cross sections (ICSs), differential cross sections (DCSs) and state distributions at collision energies ranging from 1 to 9 kcal/mol are presented to show the dynamics and isotopic effects. Important difference can be found in the ro-vibrational state distributions between MgD2 and MgH2 systems.

  1. Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

    NASA Astrophysics Data System (ADS)

    Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

    2016-11-01

    Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

  2. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    PubMed

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment.

  3. Racing Carbon Atoms. Atomic Motion Reaction Coordinates and Structural Effects on Newtonian Kinetic Isotope Effects

    PubMed Central

    Andujar-De Sanctis, Ivonne L.

    2012-01-01

    Intramolecular 13C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton’s second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity. PMID:23025278

  4. Racing carbon atoms. Atomic motion reaction coordinates and structural effects on Newtonian kinetic isotope effects.

    PubMed

    Andujar-De Sanctis, Ivonne L; Singleton, Daniel A

    2012-10-19

    Intramolecular (13)C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton's second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity.

  5. Spin-Isospin responses via charge exchange reactions of RI beams at SHARAQ

    SciTech Connect

    Shimoura, Susumu

    2012-11-12

    Nuclear spectroscopy via direct reactions of RI beams is discussed focusing on characteristics of charge-exchange reactions of RI beams. Recent experiments using the SHARAQ spectrometer at the RIBF are presented, where isovector spin monopole and spin-non-flip monopole responses are studied by charge exchange reaction of RI beams. Some experimental plans and perspectives are also presented.

  6. Separation of selected stable isotopes by liquid-phase thermal diffusion and by chemical exchange

    NASA Astrophysics Data System (ADS)

    Rutherford, W. M.; Jepson, B. E.; Michaels, E. D.

    Useful applications of enriched stable nuclides are unduly restricted by high cost and limited availability. Recent research on liquid phase thermal diffusion (LTD) has resulted in practical processes for separating S34, CL35, and CL37 in significant quantities (100 to 500 g/yr) at costs much lower than those associated with the electromagnetic (Calutron) process. The separation of the isotopes of bromine by LTD is now in progress and BR79 is being produced in relatively simple equivalent at a rate on the order of 0.5 g/day. The results of recent measurements show that the isotopes of Zn can be separated by LTD of zinc alkyls. The isotopes of calcium can be separated by LTD and by chemical exchange. The LTD process is based on the use of aqueous Ca(NO3)2 as a working fluid.

  7. Pigment exchange of photosystem II reaction center by chlorophyll d.

    PubMed

    Tomo, Tatsuya; Hirano, Emi; Nagata, Junko; Nakazato, Katsuyoshi

    2005-06-01

    Pigment exchanges among photosystem reaction centers (RCs) are useful for the identification and functional analysis of chromophores in photosynthetic organisms. Pigment replacement within the spinach Photosystem II RC was performed with Chl d derived from the oxygenic alga Acaryochloris marina, using a protocol similar to that reported previously [Gall et al. (1998) FEBS Lett 434: 88-92] based on the incubation of reaction centers with an excess of other pigments. In this study, we analyzed Chl d-modified monomeric RC which was separated from Chl d-modified dimeric RC by size-exclusion chromatography. Based on the assumption of a constant ratio of two Pheo a molecules per RC, the number of Chl a molecules in Chl d-modified monomeric RCs was found to decrease from six to four. The absorption spectrum of the Chl d-modified monomeric RC at room temperature showed a large peak at 699.5 nm originating from Chl d and a small peak at 672.5 nm orignating from Chl a. Photoaccumulation of the Pheo a- in Chl d-modified monomeric RC, in the presence of sodium dithionate and methyl viologen, did not differ significantly from that in control RC, showing that the Chl d-modified monomeric RC retains its charge separation activity and photochemically active Pheo a.

  8. Charge-exchange reactions and electron-capture rates for presupernova stellar evolution

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but

  9. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    DOE PAGES

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times highermore » than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

  10. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    SciTech Connect

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times higher than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

  11. High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes

    NASA Astrophysics Data System (ADS)

    Sadat-Noori, Mahmood; Santos, Isaac R.; Tait, Douglas R.; Reading, Michael J.; Sanders, Christian J.

    2017-10-01

    We hypothesise that mangroves play an important role in groundwater exchange processes in sub-tropical and tropical estuarine waters. To investigate this, multiple high resolution time series measurements of radium across a tidal estuary (Coffs Creek, NSW, Australia) were performed as well as a spatial survey in both bottom and surface layers. Results from the spatial survey revealed increasing radium concentrations in parts of the estuary surrounded by mangroves. The average radium concentration in estuary areas lined with mangroves was 2.5 times higher than the average concentration at the mouth of the estuary and 6.5-fold higher than upstream freshwater areas. Additionally, the area enriched in radium coincided with low dissolved oxygen concentrations, implying that porewater exchange may drive anoxia. A radium mass balance model based on 223Ra and 224Ra isotopes at different sections of the estuary confirmed higher porewater exchange rates from areas fringed with mangrove vegetation. Estimated porewater exchange rates were 27.8 ± 5.3 and 13.6 ± 2.1 cm d-1 (0.8 ± 0.1 and 0.4 ± 0.1 m3 s-1) based on 223Ra and 224Ra isotopes, respectively. The average saline porewater exchange was ∼ 10-fold larger than the upstream surface freshwater inputs to the estuary. We suggest that mangrove environments within subtropical estuaries are hotspots for porewater exchange due to the complex belowground structure of crab burrows and the effect of tidal pumping. Because porewater exchange releases carbon and nitrogen from coastal sediments, development and modification of mangrove areas in subtropical estuaries have a significant effect on coastal biogeochemical cycles.

  12. OXYGEN ISOTOPIC COMPOSITIONS OF THE ALLENDE TYPE C CAIs: EVIDENCE FOR ISOTOPIC EXCHANGE DURING NEBULAR MELTING AND ASTEROIDAL THERMAL METAMORPHISM

    SciTech Connect

    Krot, A N; Chaussidon, M; Yurimoto, H; Sakamoto, N; Nagashima, K; Hutcheon, I D; MacPherson, G J

    2008-02-21

    that CAIs 100, 160 and CG5 experienced melting in an {sup 16}O-rich ({Delta}{sup 17}O < -20{per_thousand}) nebular gas in the CAI-forming region. The Type C and Type-B-like portions of CAI 6-1-72 experienced melting in an {sup 16}O-depleted ({Delta}{sup 17}O {ge} -13{per_thousand}) nebular gas. CAIs ABC, TS26 and 93 experienced isotopic exchange during re-melting in the presence of an {sup 16}O-poor ({Delta}{sup 17}O {ge} -10{per_thousand}) nebular gas in the chondrule-forming region(s). Subsequently, Allende Type C CAIs experienced post-crystallization isotopic exchange with an {sup 16}O-poor reservoir that affected largely melilite and anorthite. Because pseudomorphic replacement of lacy melilite by grossular, monticellite and forsterite occurred during thermal metamorphism, some oxygen isotopic exchange of melilite and anorthite must have continued after formation of these secondary minerals. We suggest that some or all oxygen isotopic exchange in melilite and anorthite occurred during fluid-assisted thermal metamorphism on the CV parent asteroid. Similar processes may have also affected melilite and anorthite of CAIs in metamorphosed CO chondrites.

  13. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways.

    PubMed

    Jin, Biao; Rolle, Massimo

    2016-03-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.

  14. Tropical tropopause water isotopes in a GCM: Sensitivity to cloud processes and stratosphere-troposphere exchange

    NASA Astrophysics Data System (ADS)

    Schmidt, G. A.; Hoffmann, G.; Hu, Y.

    2004-05-01

    Water isotopes ratios (δ 18O, δ D) are very sensitive tracers of the history of the water in the atmosphere. For example, depletion of heavy isotopes in convective plumes can be extreme and thus isotope ratios can be used to discriminate between upwelled and in-situ condensation. We present results with state-of-the-art GCMs that include water isotopes in every aspect of the modelled water cycle, including the relatively sophisticated prognostic cloud water scheme. These models also have reasonable representations of the stratospheric circulation and so can be used to look at the processes involved in stratosphere-troposphere exchange. We demonstrate that the models show a similar range of variability near the tropical tropopause to that seen in recent data, and that the zonal mean values are less depleted than a simple Rayleigh distillation column would suggest. Importantly, we show that the isotopes can be sensitive to uncertain details of the cloud parameterizations and thus may help in improving and validating cloud schemes in models.

  15. Observation of new neutron-deficient isotopes with Z ≥ 92 in multinucleon transfer reactions

    NASA Astrophysics Data System (ADS)

    Devaraja, H. M.; Heinz, S.; Beliuskina, O.; Comas, V.; Hofmann, S.; Hornung, C.; Münzenberg, G.; Nishio, K.; Ackermann, D.; Gambhir, Y. K.; Gupta, M.; Henderson, R. A.; Heßberger, F. P.; Khuyagbaatar, J.; Kindler, B.; Lommel, B.; Moody, K. J.; Maurer, J.; Mann, R.; Popeko, A. G.; Shaughnessy, D. A.; Stoyer, M. A.; Yeremin, A. V.

    2015-09-01

    In deep inelastic multinucleon transfer reactions of 48Ca + 248Cm we observed about 100 residual nuclei with proton numbers between Z = 82 and Z = 100. Among them, there are five new neutron-deficient isotopes: 216U, 219Np, 223Am, 229Am and 233Bk. As separator for the transfer products we used the velocity filter SHIP of GSI while the isotope identification was performed via the α decay chains of the nuclei. These first results reveal that multinucleon transfer reactions together with here applied fast and sensitive separation and detection techniques are promising for the synthesis of new isotopes in the region of heaviest nuclei.

  16. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    NASA Astrophysics Data System (ADS)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  17. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  18. Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.

    1989-01-01

    A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

  19. The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

    PubMed

    Jambrina, P G; Menéndez, M; Aoiz, F J

    2017-06-28

    In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I2, angular distributions in the laboratory frame for Hg + Br2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

  20. Isotope exchange, fluid-rock interaction and thermomechanics of detachments: Raft River, NW Utah

    NASA Astrophysics Data System (ADS)

    Gottardi, R.; Teyssier, C.; Valley, J. W.; Spicuzza, M. J.; Nachlas, W. O.; Quilichini, A.; Vennemann, T. W.

    2011-12-01

    The Raft River metamorphic core complex in NW Utah is bounded to the east by a Miocene detachment that localized in a Proterozoic quartzite which rests unconformably on Archean crystalline basement. In the Clear Creek Canyon, well-exposed sections of this quartz + white mica quartzite allow detailed sampling of the approximately 100 m thick quartzite mylonite. Stable isotope thermometry using quartz-muscovite pairs yields a relatively large (140°C) and smooth temperature variation over the 100 m section (485°C at the base to 345°C at the top, Gottardi et al., 2011, Geology). White mica δD values are as low as -120% indicating a composition for the fluid present during hydrogen isotopic exchange comprised between -70 and -100% (Suzuoki and Epstein, 1976, Geochimica et Cosmochimica Acta), which correlates well with fluid-inclusion analyses that yield δD values between -82 and -94%. Such negative fluid δD values indicate that mica interacted with a surface fluid at high temperature. New stable isotope analyses from a more closely spaced (~2m spacing over 50 m) section shed new light on the stable isotope exchange processes during mylonitization. Quartz δ18O values concentrate between 12 and 13.5 % while muscovite δ18O values range from 9.4 to 12 %. Fractionation coefficients in many samples yield the same range of temperatures (375-575°C); however 5 of 15 pairs are clearly out of equilibrium with apparent T's of 700-950°C. For those pairs, δ18O(quartz) vs. δ18O(muscovite) values suggest that isotopic exchange occurred in an open system, where muscovite exchanged while quartz was less affected. To evaluate this hypothesis, the chemical composition of muscovite is investigated by electron microprobe. Mapping of major elements (Si, Al, Fe, Mg, Ti) does not reveal any zoning or grain growth features. The chemical composition of quartz was investigated by cathodoluminescence images, which correlate well with microstructures; however, no significant features

  1. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    DOE PAGES

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO,more » and DTO) using D2 (or H2)« less

  2. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    SciTech Connect

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO, and DTO) using D2 (or H2)

  3. Evaluation of hydrogen isotope exchange methodology on adsorbents for tritium removal

    SciTech Connect

    Morgan, G.A.; Xin Xiao, S.

    2015-03-15

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H{sub 2} (when flowed through the molecular sieves) will exchange with the adsorbed water, D{sub 2}O, leaving H{sub 2}O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T{sub 2}O, HTO, and DTO) using D{sub 2} (or H{sub 2}). (authors)

  4. Isotopically exchangeable organic hydrogen in coal relates to thermal maturity and maceral composition

    USGS Publications Warehouse

    Mastalerz, Maria; Schimmelmann, A.

    2002-01-01

    Hydrogen isotopic exchangeability (Hex) and ??Dn values of non-exchangeable organic hydrogen were investigated in coal kerogens ranging in rank from lignite to graphite. The relative abundance of Hex is highest in lignite with about 18% of total hydrogen being exchangeable, and decreases to around 2.5% in coals with Ro of 1.7 to ca. 5.7%. At Still higher rank (Ro > 6%), Hex increases slightly, although the abundance of total hydrogen decreases. ??Dn is influenced by original biochemical D/H ratios and by thermal maturation in contact with water. Therefore, ??Dn does not show an overall consistent trend with maturity. ?? 2002 Elsevier Science Ltd. All rights reserved.

  5. Experimental investigation of rates and mechanisms of isotope exchange (O, H) between volcanic ash and isotopically-labeled water

    NASA Astrophysics Data System (ADS)

    Nolan, Gary S.; Bindeman, Ilya N.

    2013-06-01

    The hydrogen and oxygen isotope ratios in hydrous minerals and volcanic glass are routinely used as paleo-proxies to infer the isotopic values of meteoric waters and thus paleo-climatic conditions. We report a series of long-term exposure experiments of distal 7700 BP Mt. Mazama ash (-149‰ δ2H, +7‰ δ18O, 3.8 wt.% H2O) with isotopically-labeled water (+650‰ δ2H, +56‰ δ18O). Experiments were done at 70, 40 and 20 °C, and ranged in duration from 1 to 14454 h (˜20 months), to evaluate the rates of deuterium and 18O exchange, and investigate the relative role of exchange and diffusion. We also investigate the effect of drying on H2Otot and δ2H in native and reacted ash that can be used in defining the protocols for natural sample preparation. We employ Thermal Conversion Elemental Analyzer (TCEA) mass spectrometry, thermogravimetric analysis and a KBr pellet technique with infrared spectroscopy to measure the evolution of δ2H, total water, and OH water peaks in the course of exposure experiments, and in varying lengths of vacuum drying. Time series experiments aided by infrared measurements demonstrate the following new results: (i) It wasobserved that from 5 to >100‰ δ2H increases with time, with faster deuterium exchange at higher temperatures. Times at 15% of theoretical "full δ2H exchange" are: 15.8 years at 20 °C, 5.2 years at 40 °C, and 0.4 years at 70 °C. (ii) Even at extended exposure durations experiments show no net increase in water weight percent nor in δ18O in ash; water released from ash rapidly by thermal decomposition is not enriched in δ18O. This observation clearly suggests that it is hydrogen exchange, and not water addition or oxygen exchange that characterizes the process. (iii) Our time series drying, Fourier transform infrared (FTIR)-KBr and Thermogravimetric Analyzer (TGA) analyses collectively suggest a simple mechanistic view that there are three kinds of "water" in ash: water (mostly H2O) that is less strongly bonded

  6. A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

    USGS Publications Warehouse

    Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

    2011-01-01

    Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of

  7. Theoretical calculation of nitrogen isotope equilibrium exchange fractionation factors for various NOy molecules

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2015-09-01

    The nitrogen stable isotope ratio (15N/14N) of nitrogen oxides (NOx = NO + NO2) and its oxidation products (NOy = NOx + PAN (peroxyacetyl nitrate = C2H3NO5) + HNO3 + NO3 + HONO + N2O5 + ⋯ + particulate nitrates) has been suggested as a tool for partitioning NOx sources; however, the impact of nitrogen (N) equilibrium isotopic fractionation on 15N/14N ratios during the conversion of NOx to NOy must also be considered, but few fractionation factors for these processes have been determined. To address this limitation, computational quantum chemistry calculations of harmonic frequencies, reduced partition function ratios (15β), and N equilibrium isotope exchange fractionation factors (αA/B) were performed for various gaseous and aqueous NOy molecules in the rigid rotor and harmonic oscillator approximations using the B3LYP and EDF2 density functional methods for the mono-substitution of 15N. The calculated harmonic frequencies, 15β, and αA/B are in good agreement with available experimental measurements, suggesting the potential to use computational methods to calculate αA/B values for N isotope exchange processes that are difficult to measure experimentally. Additionally, the effects of solvation (water) on 15β and αA/B were evaluated using the IEF-PCM model, and resulted in lower 15β and αA/B values likely due to the stabilization of the NOy molecules from dispersion interactions with water. Overall, our calculated 15β and αA/B values are accurate in the rigid rotor and harmonic oscillator approximations and will allow for the estimation of αA/B involving various NOy molecules. These calculated αA/B values may help to explain the trends observed in the N stable isotope ratio of NOy molecules in the atmosphere.

  8. Real-time monitoring of the overall exchange of oxygen isotopes between aqueous CO32- and H2O by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Geisler, Thorsten; Perdikouri, Christina; Kasioptas, Argyrios; Dietzel, Martin

    2012-08-01

    In this contribution we demonstrate that in situ Raman spectroscopy is a powerful tool to study the exchange kinetics of oxygen isotopes between aqueous oxo-anions and water using the CO32--H2O system as an example. In situ exchange experiments have been carried out using a 1 M Na2CO3 solution at 45, 60, 75, and 100 °C in a closed system using an in-house-made Teflon©-based fluid cell. The solution was prepared with H2O enriched with 97 at.% 18O. At the given pH from 10.92 to 9.65 at 45-100 °C, respectively, CO32- is the dominant DIC species (>99% CO32-). At the beginning of the reaction the Raman spectrum of the solution is characterised by an intense band near 1067 cm-1 that has been assigned to the ν1(CO3) symmetric stretching vibration of the CO32- molecule. With increasing reaction time three, well-separated bands successively appear near 1046, 1026, and 1006 cm-1. These bands result from mass-related (isotopic) splitting of the ν1(CO3) mode and reflect the symmetric stretching vibration of the oxygen-related isotopologues C16O3-n18On2- (n = 1, 2, and 3). The relative integrated intensities of these bands are related to the amount of 18O present in the aqueous CO32- molecule, which allowed monitoring the time-dependent distribution of the four isotopologues at each temperature. The measured distributions as a function of time were found to agree well with those modelled on the basis of the overall reactions ΣC18O+3H18O⇌ΣC18O16O+3H16O, where the sum sign represents the sum of all carbonate species in solution and n = 0, 1, and 2. Moreover, the measured equilibrium fractions of 18O agree well with those expected from mass balance and published fractionation factors. After correcting the observed exchange rates for the dependence of the exchange kinetics on OH- and CO2(aq) activities, the observed overall logarithmic oxygen isotope exchange rates describe a linear relationship with the inverse temperature along with published exchange data that were

  9. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1978-01-01

    The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

  10. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    NASA Astrophysics Data System (ADS)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  11. The formation of Kuiper-belt binaries through exchange reactions.

    PubMed

    Funato, Yoko; Makino, Junichiro; Hut, Piet; Kokubo, Eiichiro; Kinoshita, Daisuke

    2004-02-05

    Recent observations have revealed that an unexpectedly high fraction--a few per cent--of the trans-Neptunian objects (TNOs) that inhabit the Kuiper belt are binaries. The components have roughly equal masses, with very eccentric orbits that are wider than a hundred times the radius of the primary. Standard theories of binary asteroid formation tend to produce close binaries with circular orbits, so two models have been proposed to explain the unique characteristics of the TNOs. Both models, however, require extreme assumptions regarding the size distribution of the TNOs. Here we report a mechanism that is capable of producing binary TNOs with the observed properties during the early stages of their formation and growth. The only required assumption is that the TNOs were initially formed through gravitational instabilities in the protoplanetary dust disk. The basis of the mechanism is an exchange reaction in which a binary whose primary component is much more massive than the secondary interacts with a third body, whose mass is comparable to that of the primary. The low-mass secondary component is ejected and replaced by the third body in a wide but eccentric orbit.

  12. Dynamics of the hydrogen exchange reaction using the photoloc technique

    NASA Astrophysics Data System (ADS)

    Fernandez-Alonso, Felix

    2000-08-01

    The dynamics of the H + D2 exchange reaction has been studied experimentally using laser, velocity- sensitive time-of-flight (TOF) methods. Chemical reaction is initiated by laser photolysis of a suitable HX precursor resulting in a collision energy spread of 50 MeV. HD(v ', J') products are detected via (2+1) resonance-enhanced multiphoton ionization (REMPI) inside a Wiley-McLaren time-of-flight spectrometer. Integral cross section measurements are performed by measuring the total ion yield into different product rovibrational states. In addition, core extraction of the ion packet prior to detection allows an unambiguous inversion of the laboratory product velocity distribution into a corresponding center-of-mass differential cross section with an angular resolution ranging from 3° for backward to 15° for forward scattering. The measured rotational distributions for the HD(v' = 1, 2, J) vibrational manifolds at collision energies ca. 1.6 eV agree closely with quasiclassical trajectory calculations. These distributions are colder than the ``prior'' limit indicating that other constraints besides energy conservation are dictating energy disposal into the rotational degree of Freedom of the diatomic product. Further insight into the dynamics of this reaction is given by the differential cross section measurements into particular HD(v' = 1, J') and HD(v' = 2, J') quantum states. In each vibrational manifold, the product angular distributions are completely back ward scattered for low- J' states, and they shift toward side scattering as the rotational excitation of the product increases. Experimental data at a lower angular resolution for HD(v' = 3, J' ) also show a similar trend in the angular distributions. The differential cross section data can be qualitatively explained by invoking a line- of-centers with nearly elastic specular scattering model which links the most probable scattering angle for a given HD(v', J') product state with initial impact parameter

  13. Controlled state-to-state atom-exchange reaction in an ultracold atom-dimer mixture

    NASA Astrophysics Data System (ADS)

    Rui, Jun; Yang, Huan; Liu, Lan; Zhang, De-Chao; Liu, Ya-Xiong; Nan, Jue; Chen, Yu-Ao; Zhao, Bo; Pan, Jian-Wei

    2017-07-01

    Ultracold molecules offer remarkable opportunities for the study of chemical reactions close to zero temperature. Although significant progress has been achieved in exploring ultracold bimolecular reactions, the investigations are usually limited to measurements of the overall loss rates of the reactants. Detection of the reaction products will improve our understanding of the reaction mechanism and provide a unique opportunity to study the state-to-state reaction dynamics. Here we report on the direct observation of an exoergic atom-exchange reaction in an ultracold atom-dimer mixture. Both the atom and molecule products are observed and the state-to-state reaction rate coefficient is measured. By changing the magnetic field, the reaction can be switched on or off, and the rate coefficient can be controlled. The observed atom-exchange reaction is an effective spin-exchange interaction between the dimer and the atom and may be exploited to study the Kondo effect with ultracold atoms.

  14. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  15. Low-Temperature Isotopic Exchange in Obsidian: Implications for Diffusive Mechanisms

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Cole, David R; Riciputi, Lee R

    2009-01-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more poorly understood. This paper presents the results of a series of isotopic exchange experiments aimed at further elucidating this process and determining the extent to which a point-by-point analysis of the D/H or 18O/18O isotopic composition across the hydrated rim on a geological or archaeological obsidian sample can be used as a paleoclimatic monitor. Experiments were performed by first hydrating the glass for five days in water of one isotopic composition, followed by five days in water of a second composition. Because waters of near end-member compositions were used (nearly pure 1H2 16O, 1H2 18O, and D2 16O), the relative migration of each species could be ascertained easily by depth-profiling using secondary ion mass spectrometry (SIMS). Results suggest that, during hydration, both the isotopic composition of the waters of hydration, as well as that of intrinsic water remaining from the initial formation of the glass vary dramatically, and a point-by-point analysis leading to paleoclimatic reconstruction is not feasible.

  16. Low-temperature isotopic exchange in obsidian: Implications for diffusive mechanisms.

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Cole, David R; Riciputi, Lee R

    2009-01-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more poorly understood. This paper presents the results of a series of isotopic exchange experiments aimed at further elucidating this process and determining the extent to which a point-by-point analysis of the D/H or 18O/18O isotopic composition across the hydrated rim on a geological or archaeological obsidian sample can be used as a paleoclimatic monitor. Experiments were performed by first hydrating the glass for 5 days in water of one isotopic composition, followed by 5 days in water of a second composition. Because waters of near end-member compositions were used (nearly pure 1H2 16O, 1H2 18O, and D2 16O), the relative migration of each species could be ascertained easily by depth-profiling using secondary ion mass spectrometry (SIMS). Results suggest that, during hydration, both the isotopic composition of the waters of hydration, as well as that of intrinsic water remaining from the initial formation of the glass vary dramatically, and a point-by-point analysis leading to paleoclimatic reconstruction is not feasible.

  17. An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

    PubMed

    Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

    2016-12-06

    In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (ENi(i)), (ii) assess their corresponding kinetic constants (k(i)), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k(i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

  18. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    SciTech Connect

    Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2014-10-15

    Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10{sup −2} s{sup −1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 °C.

  19. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

    PubMed

    Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

    2016-06-30

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

  20. Isotopic exchange between carbon dioxide and ozone via O( sup 1 D) in the stratosphere

    SciTech Connect

    Yung, Yuk L. ); DeMore, W.B. ); Pinto, J.P. )

    1991-01-01

    The authors propose a novel mechanism for isotopic exchange between CO{sub 2} and O{sub 3} via O({sup 1}D) + CO{sub 2} {yields} CO{sub 3} followed by CO{sub 3}* {yields} CO{sub 2} + O({sup 3}P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in {sup 18}O in the stratospheric CO{sub 2} observed by Gamo et al. (1989), using the heavy O{sub 3} profile observed by Mauersberger (1981). The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO{sub 2} in the troposphere are briefly discussed.

  1. Analysis of positional isotope exchange in ATP by cleavage of the. beta. P-O. gamma. P bond. Demonstration of negligible positional isotope exchange by myosin

    SciTech Connect

    Dale, M.P.; Hackney, D.D.

    1987-12-15

    A method for analysis of positional isotope exchange (PIX) during ATP in equilibrium HOH oxygen exchange is presented that uses a two-step degradation of ATP resulting in cleavage of the ..beta..P-O..gamma..P bond. This cleavage yields P/sub i/ derived from the ..gamma..-phosphoryl of ATP that contains all four of the ..gamma.. oxygens. Both PIX between the ..beta.., ..gamma..-bridge and ..beta..-nonbridge positions and washout of the ..gamma..-nonbridge oxygens can be simultaneously followed by using ATP labeled with /sup 17/O at the ..beta..-nonbridge positions and /sup 18/O at the ..beta..,..gamma..-bridge and ..gamma..-nonbridge positions. Application of this method to ATP in equilibrium HOH exchange during single turnovers of myosin indicates that the bulk of the ATP undergoes rapid washout of ..gamma..-nonbridge oxygens in the virtual absence of PIX. At 25/sup 0/C with subfragment 1 the scrambling rate is at the limit of detectability of approximately 0.001 s/sup -1/, which is 50-fold slower than the steady-state rate. This corresponds to a probability of scrambling for the ..beta..-oxygens of bound ADP of 1 in 10,000 for each cycle of reversible hydrolysis of bound ATP. A fraction of the ATP, however, does not undergo rapid washout. With myosin and stoichiometric ATP at 0/sup 0/C, this fraction correspond to 10% of the ATP remaining at 36 s, or 2% of the initial ATP, and an equivalent level of ATP is found that does not bind irreversibly to myosin in a cold chase experiment. A significant level of apparent PIX is observed with subfragment 1 in the fraction that resists washout, and this apparent PIX is shown to be due to contaminant adenylate kinase activity. This apparent PIX due to adenylate kinase provides a possible explanation for the PIX observed by Geeves et al. with subfragment 1.

  2. Isotopic air sampling in a tallgrass prairie to partition net ecosystem CO2 exchange

    NASA Astrophysics Data System (ADS)

    Lai, Chun-Ta; Schauer, Andrew J.; Owensby, Clenton; Ham, Jay M.; Ehleringer, James R.

    2003-09-01

    Stable isotope ratios of various ecosystem components and net ecosystem exchange (NEE) CO2 fluxes were measured in a C3-C4 mixture tallgrass prairie near Manhattan, Kansas. The July 2002 study period was chosen because of contrasting soil moisture contents, which allowed us to address the effects of drought on photosynthetic CO2 uptake and isotopic discrimination. Significantly higher NEE fluxes were observed for both daytime uptake and nighttime respiration during well-watered conditions when compared to a drought period. Given these differences, we investigated two carbon-flux partitioning questions: (1) What proportions of NEE were contributed by C3 versus C4 species? (2) What proportions of NEE fluxes resulted from canopy assimilation versus ecosystem respiration? To evaluate these questions, air samples were collected every 2 hours during daytime for 3 consecutive days at the same height as the eddy covariance system. These air samples were analyzed for both carbon isotope ratios and CO2 concentrations to establish an empirical relationship for isoflux calculations. An automated air sampling system was used to collect nighttime air samples to estimate the carbon isotope ratios of ecosystem respiration (δR) at weekly intervals for the entire growing season. Models of C3 and C4 photosynthesis were employed to estimate bulk canopy intercellular CO2 concentration in order to calculate photosynthetic discrimination against 13C. Our isotope/NEE results showed that for this grassland, C4 vegetation contributed ˜80% of the NEE fluxes during the drought period and later ˜100% of the NEE fluxes in response to an impulse of intense precipitation. For the entire growing season, the C4 contribution ranged from ˜68% early in the spring to nearly 100% in the late summer. Using an isotopic approach, the calculated partitioned respiratory fluxes were slightly greater than chamber-measured estimates during midday under well-watered conditions. In addition, time series

  3. Neutron Capture Reactions on lu Isotopes at Dance

    NASA Astrophysics Data System (ADS)

    Roig, O.; Meot, V.; Daugas, J.-M.; Morel, P.; Jandel, M.; Vieira, D. J.; Bond, E. M.; Bredeweg, T. A.; Couture, A. J.; Haight, R. C.; Keksis, A. L.; Rundberg, R. S.; Ullmann, J. L.; Wouters, J. M.

    2013-03-01

    The DANCE1 (Detector for Advanced Neutron Capture Experiments) array at LANSCE spallation neutron source in Los Alamos has been used to obtain the neutron radiative capture cross sections for 175Lu and 176Lu with neutron energies from thermal up to 100 keV. Both isotopes are of current interest for the nucleosynthesis s-process.2,3 Three targets were used to perform these measurements. One was natural Lu foil of 31 mg/cm2 and the other two were isotope-enriched targets of 175Lu and 176Lu. Firstly, the cross sections were obtained by normalizing yield to a well-known cross section at the thermal neutron energy. Now, we want to obtain absolute cross sections of radiative capture through a precise neutron flux determination, an accurate target mass measurement and an efficiency determination of the DANCE array.

  4. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  5. Isotopic exchange between carbon dioxide and ozone via O(1D) in the stratosphere

    NASA Technical Reports Server (NTRS)

    Yung, Yuk L.; Demore, W. B.; Pinto, Joseph P.

    1991-01-01

    A novel mechanism for isotropic exchange between CO2 and O3 via O(1D) + CO2 - CO3(asterisk) followed by CO3(asterisk) - CO2 + O(3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in O-18 in the stratospheric CO2 observed by Gamo et al. (1989), using the heavy O3 profile observed by Mauersberger (1981). The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO2 in the troposphere are briefly discussed.

  6. [Net CO2 exchange and carbon isotope flux in Acacia mangium plantation].

    PubMed

    Zou, Lu-Liu; Sun, Gu-Chou; Zhao, Ping; Cai, Xi-An; Zeng, Xiao-Ping; Wang, Quan

    2009-11-01

    By using stable carbon isotope technique, the leaf-level 13C discrimination was integrated to canopy-scale photosynthetic discrimination (Deltacanopy) through weighted the net CO2 assimilation (Anet) of sunlit and shaded leaves and the stand leaf area index (L) in an A. mangium plantation, and the carbon isotope fluxes from photosynthesis and respiration as well as their net exchange flux were obtained. There was an obvious diurnal variation in Deltacanopy, being lower at dawn and at noon time (18.47 per thousand and 19.87 per thousand, respectively) and the highest (21.21 per thousand) at dusk. From the end of November to next May, the Deltacanopy had an increasing trend, with an annual average of (20.37 +/- 0.29) per thousand. The carbon isotope ratios of CO2 from autotrophic respiration (excluding daytime foliar respiration) and heterotrophic respiration were respectively (- 28.70 +/- 0.75) per thousand and (- 26.75 +/- 1.3) per thousand in average. The delta13 C of nighttime ecosystem-respired CO2 in May was the lowest (-30.14 per thousand), while that in November was the highest (-28.01 per thousand). The carbon isotope flux of CO2 between A. mangium forest and atmosphere showed a midday peak of 178.5 and 217 micromol x m(-2) x s(-1) x per thousand in May and July, with the daily average of 638.4 and 873.2 micromol x m(-2) x s(-1) x per thousand, respectively. The carbon isotope flux of CO2 absorbed by canopy leaves was 1.6-2.5 times higher than that of CO2 emitted from respiration, suggesting that a large sum of CO2 was absorbed by A. mangium, which decreased the atmospheric CO2 concentration and improved the environment.

  7. RADIATION STABILITY OF NAFION MEMBRANES USED FOR ISOTOPE SEPARATION BY PROTON EXCHANGE MEMBRANE ELECTROLYSIS

    SciTech Connect

    Fox, E

    2009-05-15

    Proton Exchange Membrane Electrolyzers have potential interest for use for hydrogen isotope separation from water. In order for PEME to be fully utilized, more information is needed on the stability of Nafion when exposed to radiation. This work examines Nafion 117 under varying exposure conditions, including dose rate, total dosage and atmospheric condition. Analytical tools, such as FT-IR, ion exchange capacity, DMA and TIC-TOC were used to characterize the exposed membranes. Analysis of the water from saturated membranes can provide important data on the stability of the membranes during radiation exposure. It was found that the dose rate of exposure plays an important role in membrane degradation. Potential mechanisms for membrane degradation include peroxide formation by free radicals.

  8. Dual Studies on a Hydrogen–Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    PubMed Central

    2015-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen–deuterium (H–D) exchange of resorcinol by electrophilic aromatic substitution using D2O and a catalytic amount of H2SO4. The resulting labeled product is characterized by 1H NMR. Students also visualize a significant kinetic isotope effect (kH/kD ≈ 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the H–D exchange product. This method is highly adaptable to fit a target audience and has been successfully implemented in a pedagogical capacity with second-year introductory organic chemistry students as part of their laboratory curriculum. It was also adapted for students at the advanced high school level. PMID:25132687

  9. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect.

    PubMed

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-08-12

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D2O and a catalytic amount of H2SO4. The resulting labeled product is characterized by (1)H NMR. Students also visualize a significant kinetic isotope effect (kH/kD ≈ 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the H-D exchange product. This method is highly adaptable to fit a target audience and has been successfully implemented in a pedagogical capacity with second-year introductory organic chemistry students as part of their laboratory curriculum. It was also adapted for students at the advanced high school level.

  10. Synthesis of new transuranium isotopes in multinucleon transfer reactions using a velocity filter

    NASA Astrophysics Data System (ADS)

    Heinz, S.; Devaraja, H. M.; Beliuskina, O.; Comas, V.; Hofmann, S.; Hornung, C.; Münzenberg, G.; Ackermann, D.; Gupta, M.; Henderson, R. A.; Heßberger, F. P.; Kindler, B.; Lommel, B.; Mann, R.; Maurer, J.; Moody, K. J.; Nishio, K.; Popeko, A. G.; Shaughnessy, D. A.; Stoyer, M. A.; Yeremin, A. V.

    2016-09-01

    Recently, we reported the observation of several new isotopes with proton numbers Z ≥ 92 in low-energy collisions of 48Ca + 248Cm . The peculiarity is that the nuclei were produced in multinucleon transfer reactions, a method which is presently discussed as a possible new way to enter so far unknown regions in the upper part of the Chart of Nuclides. For separation of the transfer products we used a velocity filter, the Separator for Heavy Ion Reaction Products SHIP at GSI. The resulting strong background suppression allowed us to detect nuclei with cross-sections down to the sub-nanobarn scale. Beside the new isotopes we identified about 100 further target-like transfer products and determined their cross-sections. The results together with previous measurements strongly indicate that multinucleon transfer reactions are a viable pathway to the production of new transuranium isotopes.

  11. Massive sulfide deposits and hydrothermal solutions: incremental reaction modeling of mineral precipitation and sulfur isotopic evolution

    SciTech Connect

    Janecky, D.R.

    1986-01-01

    Incremental reaction path modeling of chemical and sulfur isotopic reactions occurring in active hydrothermal vents on the seafloor, in combination with chemical and petrographic data from sulfide samples from the seafloor and massive sulfide ore deposits, allows a detailed examination of the processes involved. This paper presents theoretical models of reactions of two types: (1) adiabatic mixing between hydrothermal solution and seawater, and (2) reaction of hydrothermal solution with sulfide deposit materials. In addition, reaction of hydrothermal solution with sulfide deposit minerals and basalt in feeder zones is discussed.

  12. Kinetic Isotope Effect on Transport Mediated by Clc-Type H+/CL- Exchangers

    NASA Astrophysics Data System (ADS)

    Picollo, Alessandra; Malvezzi, Mattia; Accardi, Alessio

    2013-01-01

    CLC transporters mediate the stoichiometric exchange of 2 Cl- ions for 1 H+ across the membranes of cellular compartments, mostly endosomes and lysosomes. Despite intense biophysical, structural and electrophysiological scrutiny the H+ transfer mechanism of these exchangers remains largely unknown. Previous work showed that two conserved Glutamates define the extremities of the H+ pathway in CLC exchangers. However, we don't know whether H+ transfer between these residues takes place along a series of protonatable moieties, via a Grotthuss mechanism and by diffusion of an H3+O cation and if at any step H+ tunneling plays a role. To differentiate between these possible mechanisms we measured the deuterium kinetic isotope effect on the transport rate of CLC-ec1 and CLC-5, respectively a prokaryotic and a eukaryotic CLC exchanger. We found that transport mediated by both proteins is slowed by ˜20-40% when H2O is replaced by D2O. This result suggests that the rate limiting step for H+ transport takes place along a hydrogen-bonded pathway, possibly formed by water molecules. However, we found that the voltage dependence of CLC-5 inhibition by extracellular H+ is eliminated by this substitution. This suggests that the voltage dependence of this process arises from a mechanism that is exquisitely sensitive to particle mass such as proton tunneling.

  13. Use of cation exchange chromatography for human C-peptide isotope dilution - mass spectrometric assay.

    PubMed

    Stoyanov, Alexander V; Rohlfing, Curt L; Connolly, Shawn; Roberts, Matthew L; Nauser, Christopher L; Little, Randie R

    2011-12-23

    An application of ion exchange chromatography for C-peptide analysis is described here. At the stage of C-peptide isolation, a strong cation exchanger (SP HP or MonoS) was used to purify the analyte from ballast proteins and peptides. The conditions of ion-exchange chromatographic separations were optimized using theoretical modeling of the net surface electric charge of the peptide as a function of pH. The purified and concentrated sample was further subjected to LC-MS/MS. In order to improve the reliability of analysis, two fragment ions were monitored simultaneously both for native C-peptide and internal standard, isotopically labeled C-peptides analogues (fragments with m/z of 927.7 and 147.2). Using ion-exchange chromatography, it became possible to process larger sample volumes, important for testing patients with very low C peptide levels, compared to currently used solid phase extraction methods. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Use of intermediate partitioning to calculate intrinsic isotope effects for the reaction catalyzed by malic enzyme

    SciTech Connect

    Grissom, C.B.; Cleland, W.W.

    1985-02-12

    For those enzymes that proceed via a stepwise reaction mechanism with a discrete chemical intermediate and where deuterium and /sup 13/C isotope effects are on separate steps, a new method has been developed to solve for the intrinsic deuterium and /sup 13/C kinetic isotope effects that relies on directly observing the partitioning of the intermediate between the forward and reverse directions. This observed partitioning ratio, along with the values of the primary deuterium, tritium, and /sup 13/C kinetic isotope effects on V/K for the substrate with the label being followed, allows an exact solution for the intrinsic deuterium and /sup 13/C isotope effects, the forward commitment for the deuterium-sensitive step, and the partition ratio for the intermediate in the reaction. This method allows portions of the reaction coordinate diagram to be defined precisely and the relative energy levels of certain activation barriers to be assigned exactly. With chicken liver triphosphopyridine nucleotide (TPN) malic enzyme activated by Mg/sup 2 +/, the partitioning of oxalacetate to pyruvate vs. malate in the presence of TPNH, 0.47, plus previously determined isotope effects gives an intrinsic deuterium isotope effect of 5.7 on hydride transfer and a /sup 13/C isotope effect of 1.044 on decarboxylation. Reverse hydride transfer is 10 times faster than decarboxylation, and the forward commitment for hydride transfer is 3.3. The /sup 13/C isotope effect is not significantly different with reduced acetylpyridine adenine dinucleotide phosphate replacing TPNH (although the pyruvate/malate partitioning ratio for oxalactate is now 9.9), but replacement of Mg/sup 2 +/ by Mn/sup 2 +/ raises the value to 1.065 (partition ratio 0.99).

  15. Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

  16. Hydrogen bonding induced proton exchange reactions in dense D2-NH3 and D2-CH4 mixtures.

    PubMed

    Borstad, Gustav M; Yoo, Choong-Shik

    2014-01-28

    We have investigated high-pressure behaviors of simple binary mixtures of NH3 and D2 to 50 GPa and CH4 and D2 to 30 GPa using confocal micro-Raman spectroscopy. The spectral data indicate strong proton exchange reactions occur in dense D2-NH3 mixture, producing different isotopes of ammonia such as NH3, NH2D, NHD2, and ND3. In contrast, the proton exchange process in dense D2-CH4 mixture is highly limited, and no vibration feature is apparent for deuterated methane. The vibrational modes of H2 isotopes in D2-NH3 are blue shifted from those of pure H2 isotopes, whereas the modes of D2-CH4 show overall agreement with those in pure D2 and CH4. In turn, this result advocates the presence of strong repulsion and thereby internal pressure in D2-NH3 mixture, which are absent in D2-CH4. In fact, the bond length of hydrogen molecules in D2-NH3, calculated from the present spectral data, is shorter than that observed in pure hydrogen - supporting the enhanced intermolecular interaction in the mixture. Comparing the present spectral results with those previously observed in D2-H2O mixtures further suggests that the strength of repulsive interaction or the magnitude of internal pressure in the mixtures is proportional to the strength of hydrogen bonding in H2O, NH3, and CH4 in decreasing order. Hence, we suggest that the proton exchange is assisted by hydrogen bonding in these molecules.

  17. Deformation effect on total reaction cross sections for neutron-rich Ne isotopes

    SciTech Connect

    Minomo, Kosho; Sumi, Takenori; Ogata, Kazuyuki; Shimizu, Yoshifumi R.; Yahiro, Masanobu; Kimura, Masaaki

    2011-09-15

    The isotope dependence of measured reaction cross sections in the scattering of {sup 28-32}Ne isotopes from a {sup 12}C target at 240 MeV/nucleon is analyzed by the double-folding model with the Melbourne g matrix. The density of the projectile is calculated by the mean-field model with the deformed Woods-Saxon potential. The deformation is evaluated by antisymmetrized molecular dynamics. The deformation of the projectile enhances calculated reaction cross sections to the measured values.

  18. The exchange of acetaldehyde between plants and the atmosphere: Stable carbon isotope and flux measurements

    NASA Astrophysics Data System (ADS)

    Jardine, Kolby Jeremiah

    The exchange of acetaldehyde between plant canopies and the atmosphere may significantly influence regional atmospheric chemistry and plant metabolism. While plants are known to both produce and consume acetaldehyde, the exchange of this compound with forested ecosystems is complicated by physical, biological, and chemical processes that range from being poorly understood to completely unknown. This precludes a quantitative understanding of acetaldehyde exchange rates between the atmosphere and the biosphere. In this study, the processes controlling the exchange of acetaldehyde with plant canopies was investigated using concentration, flux, and natural abundance 13C measurements of gas phase acetaldehyde from individual plants, soils, and entire ecosystems. Although previously only considered important in anoxic tissues, it was discovered that acetaldehyde is produced and consumed in leaves through ethanolic fermentation coupled to the pyruvate dehydrogenase bypass system under normal aerobic conditions. These coupled pathways determine the acetaldehyde compensation point, a major factor controlling its exchange with the atmosphere. Carbon isotope analysis suggests a new pathway for acetaldehyde production from plants under stress involving the peroxidation of membrane fatty acids. This pathway may be a major source of acetaldehyde to the atmosphere from plants under biotic and abiotic stresses. Plant stomata were found to be the dominant pathway for the exchange of acetaldehyde with the atmosphere with stomatal conductance influencing both emission and uptake fluxes. In addition, increasing temperature and solar radiation was found to increase the compensation point by increasing the rates of acetaldehyde production relative to consumption. Under ambient conditions, bare soil was neutral to the exchange of acetaldehyde while senescing and decaying leaves were found to be strong source of acetaldehyde to the atmosphere due to increased decomposition processes and

  19. Muonium Addition Reactions and Kinetic Isotope Effects in the Gas Phase: k∞ Rate Constants for Mu + C2H2.

    PubMed

    Arseneau, Donald J; Garner, David M; Reid, Ivan D; Fleming, Donald G

    2015-07-16

    The kinetics of the addition reaction of muonium (Mu) to acetylene have been studied in the gas phase at N2 moderator pressures mainly from ∼800 to 1000 Torr and over the temperature range from 168 to 446 K, but also down to 200 Torr at 168 K and over a much higher range of pressures, from 10 to 44 bar at 295 K, demonstrating pressure-independent rate constants, kMu(T). Even at 200 Torr moderator pressure, the kinetics for Mu + C2H2 addition behave as if effectively in the high-pressure limit, giving k∞ = kMu due to depolarization of the muon spin in the MuC2H2 radical formed in the addition step. The rate constants kMu(T) exhibit modest Arrhenius curvature over the range of measured temperatures. Comparisons with data and with calculations for the corresponding H(D) + C2H2 addition reactions reveal a much faster rate for the Mu reaction at the lowest temperatures, by 2 orders of magnitude, in accord with the propensity of Mu to undergo quantum tunneling. Moreover, isotopic atom exchange, which contributes in a major way to the analogous D atom reaction, forming C2HD + H, is expected to be unimportant in the case of Mu addition, a consequence of the much higher zero-point energy and hence weaker C-Mu bond that would form, meaning that the present report of the Mu + C2H2 reaction is effectively the only experimental study of kinetic isotope effects in the high-pressure limit for H-atom addition to acetylene.

  20. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    USGS Publications Warehouse

    Green, C.T.; Böhlke, J.K.; Bekins, B.A.; Phillips, S.P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field-scale (apparent) estimated reaction rates and isotopic fractionations and local-scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O 2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample-based estimates of "apparent" parameters with "true" (intrinsic) values. For this aquifer, non-Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2 threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport. ?? 2010 by the American Geophysical Union.

  1. Analysis of positional isotope exchange in ATP by cleavage of the beta P-O gamma P bond. Demonstration of negligible positional isotope exchange by myosin.

    PubMed

    Dale, M P; Hackney, D D

    1987-12-15

    A method for analysis of positional isotope exchange (PIX) during ATP in equilibrium with HOH oxygen exchange is presented that uses a two-step degradation of ATP resulting in cleavage of the beta P-O gamma P bond. This cleavage yields Pi derived from the gamma-phosphoryl of ATP that contains all four of the gamma oxygens. Both PIX between the beta,gamma-bridge and beta-nonbridge positions and washout of the gamma-nonbridge oxygens can be simultaneously followed by using ATP labeled with 17O at the beta-nonbridge positions and 18O at the beta,gamma-bridge and gamma-nonbridge positions. Application of this method to ATP in equilibrium with HOH exchange during single turnovers of myosin indicates that the bulk of the ATP undergoes rapid washout of gamma-nonbridge oxygens in the virtual absence of PIX. At 25 degrees C with subfragment 1 the scrambling rate is at the limit of detectability of approximately 0.001 s-1, which is 50-fold slower than the steady-state rate. This corresponds to a probability of scrambling for the beta-oxygens of bound ADP of 1 in 10,000 for each cycle of reversible hydrolysis of bound ATP. A fraction of the ATP, however, does not undergo rapid washout. With myosin and stoichiometric ATP at 0 degrees C, this fraction corresponds to 10% of the ATP remaining at 36 s, or 2% of the initial ATP, and an equivalent level of ATP is found that does not bind irreversibly to myosin in a cold chase experiment. A significant level of apparent PIX is observed with subfragment 1 in the fraction that resists washout, and this apparent PIX is shown to be due to contaminant adenylate kinase activity. This apparent PIX due to adenylate kinase provides a possible explanation for the PIX observed by Geeves et al. [Geeves, M. A., Webb, M. R., Midelfort, C. F., & Trentham, D. R. (1980) Biochemistry 19, 4748-4754] with subfragment 1.

  2. Isomeric Differentiation of Green Tea Catechins using Gas-Phase Hydrogen/Deuterium Exchange Reactions

    PubMed Central

    Niemeyer, Emily D.; Brodbelt, Jennifer S.

    2007-01-01

    Hydrogen/deuterium exchange reactions in a quadrupole ion trap mass spectrometer are used to differentiate galloylated catechin stereoisomers (catechin gallate and epicatechin gallate; gallocatechin gallate and epigallocatechin gallate) and the non-galloylated analogs (catechin and epicatechin, gallocatechin and epigallocatechin). Significant differences in the hydrogen/deuterium exchange behavior of the four pairs of deprotonated catechin stereoisomers are observed upon reaction with D2O. Interestingly, the non-galloylated catechins undergo H/D exchange to a much greater extent than the galloylated species, incorporating deuterium at both aromatic/allylic and active phenolic sites. Non-galloylated catechin isomers are virtually indistinguishable by their H/D exchange kinetics over a wide range of reaction times (0.05 to 10 s). Our experimental results are explained using high-level ab initio calculations to elucidate the subtle structural variations in the catechin stereoisomers that lead to their differing H/D exchange kinetics. PMID:17702600

  3. Platinum-gold cluster catalysts for D{sub 2}(gas)/H{sub 2}O(liquid) isotope exchange

    SciTech Connect

    Aubart, M.A.; Dor Koch, J.F.; Pignolet, L.H.

    1994-08-31

    The authors developed a homogeneous catalytic system for exchange of deuterium onto water. Platinum-gold phosphine cations catylze this exchange in pyridine. The authors probed these reactions kinetically and studied the catalysts by NMR allowing them to propose a reaction mechanism.

  4. Possibilities for synthesis of new isotopes of superheavy elements in fusion reactions

    NASA Astrophysics Data System (ADS)

    Zagrebaev, V. I.; Karpov, A. V.; Greiner, Walter

    2012-01-01

    Background. In the “cold” fusion reactions based on the use of lead and bismuth targets, the proton-rich isotopes of superheavy (SH) elements up to Z=113 have been produced. More neutron-rich isotopes of SH elements (up to Z=118) have been synthesized in “hotter” fusion reactions of 48Ca with actinide targets. α-decay half-lives of different isotopes of the same SH elements (for example, 112) were found to vary by several orders of magnitude. This indicates strong shell effects in this area of the nuclear map. The understanding of these effects and other properties of SH nuclei is strongly impeded by the absence of experimental data on decay properties of the not-yet-synthesized isotopes of SH elements located between those produced in the “cold” fusion reactions and those produced in the “hot” fusion reactions and also by the yet missing neutron-enriched isotopes of these elements.Purpose. In this paper we search for the optimal fusion reactions which may be used to fill this gap of the nuclear map and significantly extend the area of known SH nuclei.Method. For the calculation of the cross sections we use the same approach which was employed earlier for successful predictions of all 48Ca induced fusion reactions.Results. Several fusion reactions of the stable projectiles 40Ar, 44Ca, and 48Ca with different isotopes of actinides (lighter and heavier than those that have been already utilized in the Dubna experiments) could be used for synthesis of new SH nuclei. Predicted cross sections for the production of new isotopes of SH nuclei were found to be quite large, and the corresponding experiments can be easily performed at existing facilities. For the first time a “narrow pathway” to the middle of the island of stability was found owing to possible β+ decay of SH nuclei 291115 and 291114 which could be formed in ordinary fusion reactions.

  5. Application of neutral iridium(I) N-heterocyclic carbene complexes in ortho-directed hydrogen isotope exchange.

    PubMed

    Cochrane, Alison R; Irvine, Stephanie; Kerr, William J; Reid, Marc; Andersson, Shalini; Nilsson, Göran N

    2013-01-01

    Bench-stable complexes of the type [Ir(COD)(NHC)Cl] (NHC = N-heterocyclic carbene) have been investigated within the field of hydrogen isotope exchange. By employing a sterically encumbered NHC within such complexes and catalyst loadings of only 5 mol%, moderate to high deuterium incorporations were achieved across a range of aromatic ketones and nitrogen-based heterocycles. The simple and synthetically accessible catalysts reported herein present alternatives to phosphine-based species and increase the available labelling systems with respect to established iridium-based isotope exchange methodologies. Copyright © 2013 John Wiley & Sons, Ltd.

  6. [The isotope effect in the glycine dehydrogenase reaction is the cause of the intramolecular isotope inhomogeneity of glucose carbon of starch synthesized during photorespiration].

    PubMed

    Ivlev, A A

    2005-01-01

    The isotope distribution of glucose-6-phosphate in the main pathways of its biosynthesis (in the processes of CO2 assimilation and photorespiration in the Calvin cycle and during resynthesis from the degradation products of lipids and proteins) was analyzed. For reconstructing the isotope distribution of glucoso-6-phosphate synthesized in the Calvin cycle during photorespiration, the functioning of the cycle with regard to its coupling with the glycolate chain, which together constitute the photorespiration chain, was considered. In the glycine dehydrogenase reaction of the glycolate cycle, there arises an isotope effect, which determines the distribution of isotopes in the glucose-6-phosphate and other photorespiration products. The isotope effect of the glycine dehydrogenase reaction increases at the expense of the exhaustion of glucose resources feeding the photorespiration chain. As a result, atoms C-3 and C-4 of glucose become enriched with the heavy isotope, and subsequent mixing of atoms and the specificity of interactions in the photorespiration chain lead to an isotope weighting of the other atoms and an uneven distribution of carbon isotopes in glucose-6-phosphate and other photorespiration products. A comparison of the glucose-6-phosphate isotope patterns in different pathways of the synthesis with the experimental data on the distribution of carbon isotopes in starch glucose of storing plant organs led to the conclusion that the starch resources are predominantly formed at the expense of glucose-6-phosphate of photorespiration. This is consistent with the earlier observed enhancement of photorespiration at the stage of plant maturation.

  7. CO-laser-induced photochemical reaction of UF6 with HCl for the isotope separation of uranium hexafluoride

    NASA Astrophysics Data System (ADS)

    Ding, Hong-Bin; Shen, Z. Y.; Zhang, Cun H.

    1993-05-01

    In this paper, we report the results of CO-laser induced photochemical reaction of UF6 with HCl for the isotope separation of uranium hexafluoride, we also discussed that the molecular collision inducing V-T, V-V relaxation process affects on the selectivity of the isotope separation. The obtained quantum coefficiency of the reaction is about 0.34.

  8. Pion single- and double-charge-exchange reactions at low energies

    SciTech Connect

    Baer, H.W.

    1987-01-01

    The general features of pion charge-exchange reactions at energies of 20 to 80 MeV leading to nuclear isobaric-analog states (IAS) and double-isobaric-analog states (DIAS) are reviewed. The recent progress achieved in understanding the role of short-range N-N correlations in the double-charge-exchange reactions is presented. 36 refs., 21 figs., 2 tabs.

  9. Dithioacetal Exchange: A New Reversible Reaction for Dynamic Combinatorial Chemistry.

    PubMed

    Orrillo, A Gastón; Escalante, Andrea M; Furlan, Ricardo L E

    2016-05-10

    Reversibility of dithioacetal bond formation is reported under acidic mild conditions. Its utility for dynamic combinatorial chemistry was explored by combining it with orthogonal disulfide exchange. In such a setup, thiols are positioned at the intersection of both chemistries, constituting a connecting node between temporally separated networks.

  10. Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

    NASA Astrophysics Data System (ADS)

    Jin, Biao; Rolle, Massimo

    2016-04-01

    Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M

  11. Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.

    PubMed

    Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L

    2014-11-01

    This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Resolving isotopic fine structure to detect and quantify natural abundance- and hydrogen/deuterium exchange-derived isotopomers.

    PubMed

    Liu, Qian; Easterling, Michael L; Agar, Jeffrey N

    2014-01-07

    Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) is used for analyzing protein dynamics, protein folding/unfolding, and molecular interactions. Until this study, HDX MS experiments employed mass spectral resolving powers that afforded only one peak per nominal mass in a given peptide's isotope distribution, and HDX MS data analysis methods were developed accordingly. A level of complexity that is inherent to HDX MS remained unaddressed, namely, various combinations of natural abundance heavy isotopes and exchanged deuterium shared the same nominal mass and overlapped at previous resolving powers. For example, an A + 2 peak is comprised of (among other isotopomers) a two-(2)H-exchanged/zero-(13)C isotopomer, a one-(2)H-exchanged/one-(13)C isotopomer, and a zero-(2)H-exchanged/two-(13)C isotopomer. Notably, such isotopomers differ slightly in mass as a result of the ∼3 mDa mass defect between (2)H and (13)C atoms. Previous HDX MS methods did not resolve these isotopomers, requiring a natural-abundance-only (before HDX or "time zero") spectrum and data processing to remove its contribution. It is demonstrated here that high-resolution mass spectrometry can be used to detect isotopic fine structure, such as in the A + 2 profile example above, deconvolving the isotopomer species resulting from deuterium incorporation. Resolving isotopic fine structure during HDX MS therefore permits direct monitoring of HDX, which can be calculated as the sum of the fractional peak magnitudes of the deuterium-exchanged isotopomers. This obviates both the need for a time zero spectrum as well as data processing to account for natural abundance heavy isotopes, saving instrument and analysis time.

  13. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    NASA Astrophysics Data System (ADS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-12-01

    Oxygen exchange reactions performed on PuO2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO2. Previous CeO2 surrogate studies exhibit similar behavior, confirming that CeO2 is a good qualitative surrogate for PuO2, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here.

  14. Power law behavior of the isotope yield distributions in the multifragmentation regime of heavy ion reactions

    NASA Astrophysics Data System (ADS)

    Huang, M.; Wada, R.; Chen, Z.; Keutgen, T.; Kowalski, S.; Hagel, K.; Barbui, M.; Bonasera, A.; Bottosso, C.; Materna, T.; Natowitz, J. B.; Qin, L.; Rodrigues, M. R. D.; Sahu, P. K.; Schmidt, K. J.; Wang, J.

    2010-11-01

    Isotope yield distributions in the multifragmentation regime were studied with high-quality isotope identification, focusing on the intermediate mass fragments (IMFs) produced in semiviolent collisions. The yields were analyzed within the framework of a modified Fisher model. Using the ratio of the mass-dependent symmetry energy coefficient relative to the temperature, asym/T, extracted in previous work and that of the pairing term, ap/T, extracted from this work, and assuming that both reflect secondary decay processes, the experimentally observed isotope yields were corrected for these effects. For a given I=N-Z value, the corrected yields of isotopes relative to the yield of C12 show a power law distribution Y(N,Z)/Y(12C)~A-τ in the mass range 1⩽A⩽30, and the distributions are almost identical for the different reactions studied. The observed power law distributions change systematically when I of the isotopes changes and the extracted τ value decreases from 3.9 to 1.0 as I increases from -1 to 3. These observations are well reproduced by a simple deexcitation model, with which the power law distribution of the primary isotopes is determined to be τprim=2.4±0.2, suggesting that the disassembling system at the time of the fragment formation is indeed at, or very near, the critical point.

  15. Hydrogen isotope exchange and conditioning in graphite limiters used in TFTR

    SciTech Connect

    LaMarche, P.H.; Dylla, H.F.; McCarthy, P.J.; Ulrickson, M.

    1986-02-01

    Isotopic exchange experiments performed in TFTR are used to examine the outgassing and diffusive properties of graphite used as the plasma limiter. Changeover from hydrogen to deuterium for different periods ranges from approx.600 to 60 plasma discharges, which appears to be correlated to the limiter temperature. We present a simple analytical model that predicts a fast transient (approx.10 plasma discharges) changeover where the deuterium fueling dilutes the adsorbed and near-surface hydrogen, and a slowly changing term where bulk hydrogen diffuses to the surface. Using this model we can extract an activation energy for diffusion of 0.15 +- 0.02 eV. We hypothesize that interpore diffusion for this porous (approx.15%) material is consistent with our observations. 19 refs.

  16. Carbon mass-balance modeling and carbon isotope exchange processes in the Curonian Lagoon

    NASA Astrophysics Data System (ADS)

    Barisevičiūtė, Rūta; Žilius, Mindaugas; Ertürk, Ali; Petkuvienė, Jolita

    2016-04-01

    The Curonian lagoon one of the largest coastal lagoons in Europe is located in the southeastern part of the Baltic Sea and lies along the Baltic coast of Lithuania and the Kaliningrad region of Russia. It is influenced by a discharge of the Nemunas and other smaller rivers and saline water of the Baltic Sea. The narrow (width 0.4 km, deep 8-14 m) Klaipėda Strait is the only way for fresh water run-off and brackish water intrusions. This research is focused on carbon isotope fractionations related with air - water exchange, primary production and organic carbon sedimentation, mineralization and uptake from both marine and terrestrial sources.

  17. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    USGS Publications Warehouse

    Ball, J.W.; Bassett, R.L.

    2000-01-01

    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  18. Assay of low deuterium enrichment of water by isotopic exchange with [U-13C3]acetone and gas chromatography-mass spectrometry.

    PubMed

    Yang, D; Diraison, F; Beylot, M; Brunengraber, D Z; Samols, M A; Anderson, V E; Brunengraber, H

    1998-05-01

    A sensitive assay of the 2H-enrichment of water based on the isotopic exchange between the hydrogens of water and of acetone in alkaline medium is described and validated. For low 2H-enrichments (0.008 to 0.5%), the sample is spiked with [U-13C3]acetone and NaOH. After exchange, 2H-enriched [U-13C3]acetone is extracted with chloroform and assayed by gas chromatography-mass spectrometry. With some instruments, ion-molecule reactions, resulting in increased baseline enrichment, are minimized by lowering the electron ionization energy from the usual 70 to 10 eV. The 2H-enrichment of water is amplified nearly sixfold in the M4/M3 ratio of [U-13C3]acetone. For high 2H-enrichments (0.25 to 100%), the use of unlabeled acetone suffices. After exchange, the mass isotopomer distribution of acetone is analyzed, yielding the 2H-enrichment of water. The assay with [U-13C3]acetone allows measuring the 2H-enrichment of water even in biological samples containing acetone. This technique is more rapid and economical than the classical isotope ratio mass spectrometric assay of the enrichment of hydrogen gas derived from the reduction of water.

  19. Comparisons of phosphorothioate with phosphate transfer reactions for a monoester, diester, and triester: isotope effect studies.

    PubMed

    Catrina, Irina E; Hengge, Alvan C

    2003-06-25

    Phosphorothioate esters are sometimes used as surrogates for phosphate ester substrates in studies of enzymatic phosphoryl transfer reactions. To gain better understanding of the comparative inherent chemistry of the two types of esters, we have measured equilibrium and kinetic isotope effects for several phosphorothioate esters of p-nitrophenol (pNPPT) and compared the results with data from phosphate esters. The primary (18)O isotope effect at the phenolic group ((18)k(bridge)), the secondary nitrogen-15 isotope effect ((15)k) in the nitro group, and (for the monoester and diester) the secondary oxygen-18 isotope effect ((18)k(nonbridge)) in the phosphoryl oxygens were measured. The equilibrium isotope effect (EIE) (18)k(nonbridge) for the deprotonation of the monoanion of pNPPT is 1.015 +/- 0.002, very similar to values previously reported for phosphate monoesters. The EIEs for complexation of Zn(2+) and Cd(2+) with the dianion pNPPT(2-) were both unity. The mechanism of the aqueous hydrolysis of the monoanion and dianion of pNPPT, the diester ethyl pNPPT, and the triester dimethyl pNPPT was probed using heavy atom kinetic isotope effects. The results were compared with the data reported for analogous phosphate monoester, diester, and triester reactions. The results suggest that leaving group bond fission in the transition state of reactions of the monoester pNPPT is more advanced than for its phosphate counterpart pNPP, while alkaline hydrolysis of the phosphorothioate diester and triester exhibits somewhat less advanced bond fission than that of their phosphate ester counterparts.

  20. Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

    NASA Technical Reports Server (NTRS)

    King, C.-C.; Clayton, R. N.; Hayatsu, R.; Studier, M. H.

    1979-01-01

    Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

  1. Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

    NASA Technical Reports Server (NTRS)

    King, C.-C.; Clayton, R. N.; Hayatsu, R.; Studier, M. H.

    1979-01-01

    Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

  2. Process Model for Studying Regional 13C Stable Isotope Exchange between Vegetation and Atmosphere

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Chen, B.; Huang, L.; Tans, P.; Worthy, D.; Ishizawa, M.; Chan, D.

    2007-12-01

    The variation of the stable isotope 13CO2 in the air in exchange with land ecosystems results from fractionation processes in both plants and soil during photosynthesis and respiration. Its diurnal and seasonal variations therefore contain information on the carbon cycle. We developed a model (BEPS-iso) to simulate its exchange between vegetation and the atmosphere. To be useful for regional carbon cycle studies, the model has the following characteristics: (i) it considers the turbulent mixing in the vertical profile from the soil surface to the top of the planetary boundary layer (PBL); (ii) it scales individual leaf photosynthetic discrimination to the whole canopy through the separation of sunlit and shaded leaf groups; (iii) through simulating leaf-level photosynthetic processes, it has the capacity to mechanistically examine isotope discrimination resulting from meteorological forcings, such as radiation, precipitation and humidity; and (iv) through complete modeling of radiation, energy and water fluxes, it also simulates soil moisture and temperature needed for estimating ecosystem respiration and the 13C signal from the soil. After validation using flask data acquired at 20 m level on a tower near Fraserdale, Ontario, Canada, during intensive campaigns (1998-2000), the model has been used for several purposes: (i) to investigate the diurnal and seasonal variations in the disequilibrium in 13C fractionation between ecosystem respiration and photosynthesis, which is an important step in using 13C measurements to separate these carbon cycle components; (ii) to quantify the 13C rectification in the PBL, which differs significantly from CO2 rectification because of the diurnal and seasonal disequilibriums; and (iii) to model the 13C spatial and temporal variations over the global land surface for the purpose of CO2 inversion using 13C as an additional constraint.

  3. Active Target-Time Projection Chambers for Reactions Induced by Rare Isotope Beams: Physics and Technology

    NASA Astrophysics Data System (ADS)

    Mittig, Wolfgang

    2013-04-01

    Weakly bound nuclear systems can be considered to represent a good testing-ground of our understanding of non-perturbative quantum systems. Great progress in experimental sensitivity has been attained by increase in rare isotope beam intensities and by the development of new high efficiency detectors. It is now possible to study reactions leading to bound and unbound states in systems with very unbalanced neutron to proton ratios. Application of Active Target-Time Projection Chambers to this domain of physics will be illustrated by experiments performed with existing detectors. The NSCL is developing an Active Target-Time Projection Chamber (AT-TPC) to be used to study reactions induced by rare isotope beams at the National Superconducting Cyclotron Facility (NSCL) and at the future Facility for Rare Isotope Beams (FRIB). The AT-TPC counter gas acts as both a target and detector, allowing investigations of fusion, isobaric analog states, cluster structure of light nuclei and transfer reactions to be conducted without significant loss in resolution due to the thickness of the target. The high efficiency and low threshold of the AT-TPC will allow investigations of fission barriers and giant resonances with fast fragmentation rare isotope beams. This detector type needs typically a large number of electronic channels (order of magnitude 10,000) and a high speed DAQ. A reduced size prototype detector with prototype electronics has been realized and used in several experiments. A short description of other detectors of this type under development will be given.

  4. Isotope effects, dynamic matching, and solvent dynamics in a Wittig reaction. Betaines as bypassed intermediates.

    PubMed

    Chen, Zhuo; Nieves-Quinones, Yexenia; Waas, Jack R; Singleton, Daniel A

    2014-09-24

    The mechanism of the Wittig reaction of anisaldehyde with a stabilized ylide was studied by a combination of (13)C kinetic isotope effects, conventional calculations, and molecular dynamics calculations in a cluster of 53 THF molecules. The isotope effects support a cycloaddition mechanism involving two sequential transition states associated with separate C-C and P-O bond formations. However, the betaine structure in between the two transition states is bypassed as an equilibrated intermediate in most trajectories. The role of the dynamics of solvent equilibration in the nature of mechanistic intermediates is discussed.

  5. Isotope Effects, Dynamic Matching, and Solvent Dynamics in a Wittig Reaction. Betaines as Bypassed Intermediates

    PubMed Central

    2015-01-01

    The mechanism of the Wittig reaction of anisaldehyde with a stabilized ylide was studied by a combination of 13C kinetic isotope effects, conventional calculations, and molecular dynamics calculations in a cluster of 53 THF molecules. The isotope effects support a cycloaddition mechanism involving two sequential transition states associated with separate C–C and P–O bond formations. However, the betaine structure in between the two transition states is bypassed as an equilibrated intermediate in most trajectories. The role of the dynamics of solvent equilibration in the nature of mechanistic intermediates is discussed. PMID:25208686

  6. An Experimental Investigation of the Process of Isotope Exchange that Takes Place when Heavy Water Is Exposed to the Atmosphere

    ERIC Educational Resources Information Center

    Deeney, F. A.; O'Leary, J. P.

    2009-01-01

    We have used the recently developed method for rapid measurement of maximum density temperature to determine the rate at which hydrogen and deuterium isotope exchange takes place when a sample of heavy water is exposed to the atmosphere. We also provide a simple explanation for the observed linear rate of transition. (Contains 2 figures.)

  7. An Experimental Investigation of the Process of Isotope Exchange that Takes Place when Heavy Water Is Exposed to the Atmosphere

    ERIC Educational Resources Information Center

    Deeney, F. A.; O'Leary, J. P.

    2009-01-01

    We have used the recently developed method for rapid measurement of maximum density temperature to determine the rate at which hydrogen and deuterium isotope exchange takes place when a sample of heavy water is exposed to the atmosphere. We also provide a simple explanation for the observed linear rate of transition. (Contains 2 figures.)

  8. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1.

  9. Anion-exchange synthesis of nanoporous FeP nanosheets as electrocatalysts for hydrogen evolution reaction.

    PubMed

    Xu, You; Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Zhang, Bin

    2013-07-28

    Nanoporous FeP nanosheets are successfully synthesized via the anion-exchange reaction of inorganic-organic hybrid Fe18S25-TETAH (TETAH = protonated triethylenetetramine) nanosheets with P ions. The as-prepared nanoporous FeP nanosheets exhibit high electrochemical hydrogen evolution reaction activity in acidic medium.

  10. Inclusive measurement of (p,. pi. /sup -/xn) double charge exchange reactions on bismuth from threshold to 800 MeV

    SciTech Connect

    Dombsky, M.; D'Auria, J.M.; Kelson, I.; Yavin, A.I.; Ward, T.E.; Clark, J.L.; Ruth, T.; Sheffer, G.

    1985-07-01

    The energy dependence of the total angle-integrated cross section for the production of astatine isotopes from (p,..pi../sup -/xn) double charge exchange reactions on bismuth (/sup 209/Bi) was measured from 120 to 800 MeV using activation and radiochemical techniques. Chemical yields were estimated by direct radioassaying of /sup 211/At activity in thin (approx.1 mg/cm/sup 2/), irradiated bismuth targets. Calculations of the contributions of secondary (two-step) reactions to these measured astatine yields were performed, based partially upon the observed /sup 211/At activity although even at the highest energies, the contribution to products lighter than /sup 207/At was negligible. These data for products with as many as seven neutrons removed from the doubly coherent product (/sup 210/At) display nearly Gaussian shapes for the mass distributions of the astatine residues, with the maximum occurring for about /sup 204/At. The most probable momentum transfer deduced from these distributions for the initial ..pi../sup -/ production step was 335 MeV/c. The observed excitation functions display a behavior similar to that observed for the yield of /sup 210/Po from a (p,..pi../sup 0/) reaction on /sup 209/Bi, but radically different from that observed for inclusive ..pi../sup -/ reactions on a heavy nucleus. These data are discussed in terms of recent theoretical approaches to negative pion production from bismuth. In addition, a simple, schematic model is developed to treat the rapidly decreasing percentage of the total inclusive ..pi../sup -/ emission which is observed for this double charge exchange reaction. This model reflects the opacity of a nucleus to a source of internal energetic protons.

  11. Stable isotope fractionation during porous flow with fluid-solid reaction

    NASA Astrophysics Data System (ADS)

    Bohlin, Madeleine S.; Bickle, Mike J.

    2015-04-01

    Chemical weathering of the crust plays an important part in geochemical cycling by redistributing elements between Earth's surface reservoirs. On a geological time scale chemical weathering buffers Earth's climate as atmospheric CO2 is consumed during the breakdown of silicate minerals and eventually stored as carbonates in the ocean. However there are fundamental problems in estimating chemical weathering fluxes and their climatic impact. These include distinguishing between silicate and carbonate sources of riverine dissolved loads, understanding the nature of element cycling along groundwater and river flow paths, and understanding the couplings between climate and chemical weathering rates. An emerging field in studying chemical weathering is the use of light stable isotopes whose fractionations add additional constraints on weathering processes. Lithium isotopes have been highlighted in recent years as they almost exclusively reflect silicate weathering and have been shown to correlate with weathering intensity (e.g. Huh et al., 2001, Geochimica et Cosmochimica Acta). However, in order to understand the relationship between weathering intensity and lithium isotopic fractionation it is important to have appropriate physical models for the interaction of fluids and minerals in weathering environments. Weathering reactions likely take place continuously within catchments with water flowing through a range of shallow to deep paths as rock is progressively exhumed through these flow paths. To model this it is necessary to consider how kinetically-limited fluid-mineral reactions will evolve along individual water flow paths and to understand the range of inputs to river systems. We present a simple one-dimensional transport reaction model to calculate Li-isotopic fractionation in a plausible weathering setting. The modelling reveals the key controlling parameters and predicts the isotopic evolution along the water flow paths. The model shows that for such a one

  12. Selenium and sulfur in exchange reactions: a comparative study.

    PubMed

    Steinmann, Daniel; Nauser, Thomas; Koppenol, Willem H

    2010-10-01

    Cysteamine reduces selenocystamine to form hemiselenocystamine and then cystamine. The rate constants are k(1) = 1.3 × 10(5) M(-1) s(-1); k(-1) = 2.6 × 10(7) M(-1) s(-1); k(2) = 11 M(-1) s(-1); and k(-2) = 1.4 × 10(3) M(-1) s(-1), respectively. Rate constants for reactions of cysteine/selenocystine are similar. Reaction rates of selenium as a nucleophile and as an electrophile are 2-3 and 4 orders of magnitude higher, respectively, than those of sulfur. Sulfides and selenides are comparable as leaving groups.

  13. QUDeX-MS: hydrogen/deuterium exchange calculation for mass spectra with resolved isotopic fine structure.

    PubMed

    Salisbury, Joseph P; Liu, Qian; Agar, Jeffrey N

    2014-12-11

    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry permits analysis of structure, dynamics, and molecular interactions of proteins. HDX mass spectrometry is confounded by deuterium exchange-associated peaks overlapping with peaks of heavy, natural abundance isotopes, such as carbon-13. Recent studies demonstrated that high-performance mass spectrometers could resolve isotopic fine structure and eliminate this peak overlap, allowing direct detection and quantification of deuterium incorporation. Here, we present a graphical tool that allows for a rapid and automated estimation of deuterium incorporation from a spectrum with isotopic fine structure. Given a peptide sequence (or elemental formula) and charge state, the mass-to-charge ratios of deuterium-associated peaks of the specified ion is determined. Intensities of peaks in an experimental mass spectrum within bins corresponding to these values are used to determine the distribution of deuterium incorporated. A theoretical spectrum can then be calculated based on the estimated distribution of deuterium exchange to confirm interpretation of the spectrum. Deuterium incorporation can also be detected for ion signals without a priori specification of an elemental formula, permitting detection of exchange in complex samples of unidentified material such as natural organic matter. A tool is also incorporated into QUDeX-MS to help in assigning ion signals from peptides arising from enzymatic digestion of proteins. MATLAB-deployable and standalone versions are available for academic use at qudex-ms.sourceforge.net and agarlabs.com . Isotopic fine structure HDX-MS offers the potential to increase sequence coverage of proteins being analyzed through mass accuracy and deconvolution of overlapping ion signals. As previously demonstrated, however, the data analysis workflow for HDX-MS data with resolved isotopic fine structure is distinct. QUDeX-MS we hope will aid in the adoption of isotopic fine structure HDX

  14. Isotope exchange between natural and anthropogenic Pb in the coastal waters of Singapore: exchange experiment, Kd model, and implications for the interpretation of coastal 210Pb data

    NASA Astrophysics Data System (ADS)

    Boyle, E. A.; Chen, M.; Zurbrick, C.; Carrasco, G. G.

    2015-12-01

    Observations from annually-banded corals and seawater samples show that marine lead (Pb) in the coastal waters of Singapore has an isotopic composition that does not match that of the anthropogenic aerosols in this region, unlike what is seen in most parts of the open ocean. The 206Pb/207Pb composition of Singaporean marine Pb is 1.18-1.20 whereas the local aerosols are 1.14-1.16. In order to explore this discrepancy further, we collected a large volume water from the Johor River estuary (flowing from Malaysia to the northern border of Singapore), added a distinct isotope spike (NBS981, 206Pb/207Pb =1.093) to an unfiltered sample, and followed the dissolved isotope composition of the mixture during the following two months. The initial dissolved Pb concentration was 18.3 pmol/kg with 206Pb/207Pb of 1.200. "Total dissolvable" Pb released after acidification of the in the unfiltered sample was 373 pmol/kg with 206Pb/207Pb of 1.199, indicating that there is a large particulate Pb reservoir with an isotopic composition comparable to regional crustal natural Pb. The isotope spike should have brought the dissolved 206Pb/207Pb to 1.162, but less than a day after isotope spiking, the dissolved Pb had risen to 1.181 and continued a slow increase to 1.197 over the next two months. This experiment demonstrates that Johor estuary particulate matter contains a large reservoir of exchangeable Pb that will modify the isotopic composition of deposited aeolian aerosol anthropogenic Pb. We have modeled the evolution of Pb and Pb isotopes in this experiment with a single Kd -type model that assumes that there are two or three different Pb reservoirs with different exchange time constants. This observation has implications for isotope equilibrium between high Pb/210Pb continental particles and low Pb/210Pb ocean waters - what is merely isotope equilibration may appear to be 210Pb scavenging.

  15. Why Seemingly Trivial Events Sometimes Evoke Strong Emotional Reactions: The Role of Social Exchange Rule Violations

    PubMed Central

    Leary, Mark R.; Diebels, Kate J.; Jongman-Sereno, Katrina P.; Fernandez, Xuan Duong

    2015-01-01

    ABSTRACT People sometimes display strong emotional reactions to events that appear disproportionate to the tangible magnitude of the event. Although previous work has addressed the role that perceived disrespect and unfairness have on such reactions, this study examined the role of perceived social exchange rule violations more broadly. Participants (N = 179) rated the effects of another person’s behavior on important personal outcomes, the degree to which the other person had violated fundamental rules of social exchange, and their reactions to the event. Results showed that perceptions of social exchange rule violations accounted for more variance in participants’ reactions than the tangible consequences of the event. The findings support the hypothesis that responses that appear disproportionate to the seriousness of the eliciting event are often fueled by perceived rule violations that may not be obvious to others. PMID:26331429

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

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-06-01

    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-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.

  17. Use of radium isotopes to examine pore-water exchange in an estuary

    SciTech Connect

    Webster, I.T.; Hancock, G.J.; Murray, A.S.

    1994-12-01

    The measured distributions of four isotopes of Ra along the estuary of the Bega River are used to examine sediment-water columns exchange. Ra is created in estuarine sediments by the radioactive decay of insoluble Th parents residing close to or on the surfaces of the sediment grains. Ra desorbed into the pore water is continuously lost to the water column due to the cyclical draining and filling of the sediments by the tides. The distribution of Ra in the estuary is governed by its rate of loss from the sediments, its advection along the estuary resulting from river discharge into the estuary`s head, tidal mixing, and radioactive decay. These processes are all described in a model. Matching of model-predicted Ra concentrations with measurements allows an estimate of the effective depth in the sediments to which the pore water is exchanged every tidal cycle. This depth is large (15 cm), but it is shown to be reasonable for the Bega estuary. 19 refs., 11 figs., 1 tab.

  18. High temperature geospeedometry and oxygen isotopic exchange: an analytical point of view

    NASA Astrophysics Data System (ADS)

    Jaoul, O.; Bejina, F.

    2003-04-01

    The determination of cooling rates of rocks using classical geospeedometry often leads to results with uncertainties of several orders of magnitude, mainly because of the difficulty of choosing appropriate diffusion parameters D_0 and E. With a direct application to the 16O/18O isotopic study made by Edwards and Valley (1998, GCA 62, 2265-2277) in a marble (containing diopside (Di) grains imbedded in calcite (Cc)) from the Adirondacks, we have developed a purely analytical model that relates the isotopic partition between the two exchanging minerals as a function of the diopside grain size, d, the half thickness of flat grains (1-D calculation). In this example, diffusion is the slowest in diopside and thus controls the exchange. Calcite is an infinite isotopic reservoir with relatively rapid diffusion, and with no barrier to diffusion between Di / Cc grains. The system is supposed to be fully equilibrated at the initial temperature T_0 (˜675^oC) and the mean isotopic composition δ of diopside grains evolves during cooling, but less and less efficiently as diffusion slows down. Our analysis allows the determination of the initial cooling rate s of the rock: s=(0.40 RT^2_0 D(T_0)/(dexp_D)^2E)(δ_0-δ_1/δ_0-δexp_1)^2 with D(T_0) = D_0 exp(-E/RT_0). δ_0 and δ_1 are the isotopic values at respectively T_0, and T_1, the room temperature, and correspond to the thermometric equation δ = 21.98-1000A'/T^2, with A' = 2370 K^2. The parameter δ_1exp is to be determined experimentally by extrapolation of the δ data plotted against d toward d = 0. For large enough diopside grains with d > d_Dexp we demonstrate that δ-δ_0=(1.8095(δexp_1-δ_0)(ΔH/E)0.80dexp_D)\\cdot1/d with ΔH=2000 A' R/T_0(δ_0-δ_1exp) at the condition that ΔH/E < 0.20 (which is satisfied in E&V's study). We have derived similar relations for spherical grains. Experimental data δ plotted against 1/d give a straight line with slope p. Data depart from the straight line at the value 1/d >= 1/d

  19. Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

    USGS Publications Warehouse

    Baesman, S.M.; Miller, L.G.

    2005-01-01

    Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

  20. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    NASA Technical Reports Server (NTRS)

    Summers, David P.

    2003-01-01

    One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per

  1. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    NASA Technical Reports Server (NTRS)

    Summers, David P.

    2003-01-01

    One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per

  2. Biscysteine-Bearing Peptide Probes To Reveal Extracellular Thiol-Disulfide Exchange Reactions Promoting Cellular Uptake.

    PubMed

    Li, Tao; Gao, Wei; Liang, Jingjing; Zha, Mirao; Chen, Yaqi; Zhao, Yibing; Wu, Chuanliu

    2017-08-15

    In recent years, delivery systems based on the incorporation of thiols/disulfides have been extensively explored to promote the intracellular delivery of biological cargoes. However, it remains unclear about the detailed processes of thiol-disulfide exchanges taking place on the cell surface and how the exchange reactions promote the cellular uptake of cargoes bearing thiols or disulfide bonds. In this work, we report the rational design of biscysteine motif-containing peptide probes with substantially different ring-closing property and how these peptide probes were employed to explore the thiol-disulfide exchanges on the cell surface. Our results show that extensive thiol-disulfide exchanges between peptides and exofacial protein thiols/disulfides are involved in the cellular uptake of these peptide probes, and importantly glutathione (GSH) exported from the cytosols participates extensively in the exchange reactions. Cysteine-glycine-cysteine (CGC)-containing peptide probes can be more efficiently taken up by cells compared to other probes, and we suggested that the driving force for the superior cellular uptake arises from very likely the unique propensity of the CGC motif in forming doubly bridged disulfide bonds with exofacial proteins. Our probe-based strategy provides firsthand information on the detailed processes of the exchange reactions, which would be of great benefit to the development of delivery systems based on the extracellular thiol-disulfide exchanges for intracellular delivery of biologics.

  3. Measurement of (n, xnγ) reaction cross sections in W isotopes

    NASA Astrophysics Data System (ADS)

    Henning, Greg; Bacquias, Antoine; Borcea, Catalin; Capote, Roberto; Dessagne, Philippe; Drohé, Jean-Claude; Kawano, Toshihiko; Kerveno, Maëlle; Negret, Alexandru; Nyman, Markus; Olacel, Adina; Plompen, Arjan; Romain, Pascal; Scholtes, Pol; Rudolf, Gérard

    2017-09-01

    Evaluated nuclear data bases currently used for numerical simulation for the development of nuclear reactors still present large uncertainties. Their improvement is necessary, in particular through better reaction models and nuclear data. Among the reactions of interest, (n, xn) reactions are of great importance for the operation of a reactor as they modify the neutron spectrum, the neutron population, and produce radioactive species. Experimental data on (n, xnγ) reaction provide strong constraints on nuclear reaction mechanism theories. Tungsten isotopes - which are deformed like actinides but do not fission - are of interest to test the models. 182,184,186W(n, xnγ) cross sections are measured; results are compared with model calculations by TALYS, EMPIRE and CoH codes.

  4. Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

    NASA Astrophysics Data System (ADS)

    Manogaran, Lavaneesvari; Sek, Siok Kun

    2017-04-01

    Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

  5. Multiple isotope effects with alternative dinucleotide substrates as a probe of the malic enzyme reaction

    SciTech Connect

    Weiss, P.M.; Urbauer, J.L.; Cleland, W.W. ); Gavva, S.R.; Harris, B.G.; Cook, P.F. )

    1991-06-11

    Deuterium isotope effects and {sup 13}C isotope effects with deuterium- and protium-labeled malate have been obtained for both NAD- and NADP-malic enzymes by using a variety of alternative dinucleotide substrates. With nicotinamide-containing dinucleotides as the oxidizing substrate, the {sup 13}C effect decreases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data are consistent with a stepwise chemical mechanism in which hydride transfer precedes decarboxylation of the oxalacetate intermediate as previously proposed. When dinucleotide substrates such as thio-NAD, 3-nicotinamide rings are used, the {sup 13}C effect increases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data, at face value, are consistent with a change in mechanism from stepwise to concerted for the oxidative decarboxylation portion of the mechanism. However, the increase in the deuterium isotope effect from 1.5 to 3 with a concomitant decrease in the {sup 13}C isotope effect from 1.034 to 1.003 as the dinucleotide substrate is changed suggests that the reaction may still be stepwise with the non-nicotinamide dinucleotides. A more likely explanation is that a {beta}-secondary {sup 13}C isotope effect accompanies hydride transfer as a result of hyperconjugation of the {beta}-carboxyl of malate as the transition state for the hydride transfer step is approached.

  6. Stable carbon isotope fractionation during trichloroethene degradation in magnetite-catalyzed Fenton-like reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Liu, Cunfu; Yu, Tingting; Li, Xiaoqian

    2013-02-01

    Mineral-catalyzed Fenton-like oxidation of chlorinated ethylenes is an attractive technique for in situ soil and groundwater remediation. Stable carbon isotope enrichment factors associated with magnetite-catalyzed Fenton-like oxidation of trichloroethylene (TCE) have been determined, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by Fenton-like oxidation. The carbon enrichment factors (ɛ values) ranged from - 2.7‰ to - 3.6‰ with a mean value of - 3.3 ± 0.3‰, and only small differences were observed for different initial reactive conditions. The ɛ values were robust and reproducible, and were relatively insensitive to a number of environmental factors such as ratios of reactants and PCE co-contamination, which can reduce the uncertainty associated with application of isotope enrichment factors for quantification of in situ remediation by Fenton-like reaction. ɛ values for Fenton-like oxidation of TCE were intermediate in those previously reported for aerobic biological processes (ɛ = - 1.1 to - 20.7‰). Thus, field-derived ɛ values that are more negative than those for Fenton-like oxidation, may indicate the occurrence of aerobic biodegradation at contaminated sites undergoing in situ remediation with Fenton-like reaction. However, stable carbon isotope analysis is unable to determine whether there is the occurrence of biodegradation processes if field-derived ɛ values are less negative than those for Fenton-like oxidation.

  7. TORUS: Theory of Reactions for Unstable iSotopes - Year 1 Continuation and Progress Report

    SciTech Connect

    Arbanas, G; Elster, C; Escher, J; Mukhamedzhanov, A; Nunes, F; Thompson, I J

    2011-02-24

    The TORUS collaboration derives its name from the research it focuses on, namely the Theory of Reactions for Unstable iSotopes. It is a Topical Collaboration in Nuclear Theory, and funded by the Nuclear Theory Division of the Office of Nuclear Physics in the Office of Science of the Department of Energy. The funding started on June 1, 2010, it will have been running for nine months by the date of submission of this Annual Continuation and Progress Report on March 1, 2011. The extent of funding was reduced from the original application, and now supports one postdoctoral researcher for the years 1 through 3. The collaboration brings together as Principal Investigators a large fraction of the nuclear reaction theorists currently active within the USA. The mission of the TORUS Topical Collaboration is to develop new methods that will advance nuclear reaction theory for unstable isotopes by using three-body techniques to improve direct-reaction calculations, and, by using a new partial-fusion theory, to integrate descriptions of direct and compound-nucleus reactions. This multi-institution collaborative effort is directly relevant to three areas of interest: the properties of nuclei far from stability; microscopic studies of nuclear input parameters for astrophysics, and microscopic nuclear reaction theory.

  8. Explaining the isotope effect on heat transport in L-mode with the collisional electron-ion energy exchange

    NASA Astrophysics Data System (ADS)

    Schneider, P. A.; Bustos, A.; Hennequin, P.; Ryter, F.; Bernert, M.; Cavedon, M.; Dunne, M. G.; Fischer, R.; Görler, T.; Happel, T.; Igochine, V.; Kurzan, B.; Lebschy, A.; McDermott, R. M.; Morel, P.; Willensdorfer, M.; the ASDEX Upgrade Team; The EUROfusion MST1 Team

    2017-06-01

    In ASDEX Upgrade (AUG), the normalised gyroradius {ρ\\star} was varied via a hydrogen isotope scan while keeping other dimensionless parameters constant. This was done in L-mode, to minimise the impact of pedestal stability on confinement. Power balance and perturbative transport analyses reveal that the electron heat transport is unaffected by the differences in isotope mass. Nonlinear simulations with the Gene code suggest that these L-mode discharges are ion temperature gradient (ITG) dominated. The different gyroradii due to the isotope mass do not necessarily result in a change of the predicted heat fluxes. This result is used in simulations with the Astra transport code to match the experimental profiles. In these simulations the experimental profiles and confinement times are reproduced with the same transport coefficients for hydrogen and deuterium plasmas. The mass only enters in the energy exchange term between electrons and ions. These numerical observations are supported by additional experiments which show a lower ion energy confinement compared to that of the electrons. Additionally, hydrogen and deuterium plasmas have a similar confinement when the energy exchange time between electrons and ions is matched. This strongly suggests that the observed isotope dependence in L-mode is not dominated by a gyroradius effect, but a consequence of the mass dependence in the collisional energy exchange between electrons and ions.

  9. Homogeneous cationic substitution for two-dimensional layered metal oxide nanosheets via a galvanic exchange reaction.

    PubMed

    Lim, Joohyun; Lee, Jang Mee; Park, Boyeon; Jin, Xiaoyan; Hwang, Seong-Ju

    2017-01-05

    The galvanic exchange reaction of an exfoliated 2D layered metal oxide nanosheet (NS) with excess substituent metal cations enables the synthesis of a mixed metal oxide 2D NS with controllable cation compositions and physicochemical properties. The reaction of the exfoliated MnO2 NS with Fe(2+) or Sn(2+) ions at 90 °C induces the uniform galvanic replacement of Mn ions with these substituent ions, whereas the same reaction at 25 °C results in the intercalative restacking of the negatively-charged MnO2 NS with Fe(2+) or Sn(2+) cations. Upon the galvanic exchange reaction, the highly anisotropic MnO2 2D NS retains its original 2D morphology and layered structure, which is in stark contrast to 0D nanoparticles yielding hollow nanospheres via the galvanic exchange reaction. This observation is attributable to the thin thickness of the 2D NS allowing the simultaneous replacement of all the component surface-exposed metal ions. The resulting substitution of the MnO2 NS with Fe and Sn ions remarkably improves the electrode performance of the carbon-coated derivatives of the MnO2 NS for lithium ion batteries. The present study clearly demonstrates that the galvanic exchange reaction can provide an efficient method not only to tailor cation compositions but also to improve the functionalities of 2D metal oxide NSs and their carbon-coated derivatives.

  10. Stereospecificity of isotopic exchange of C-α-protons of glycine catalyzed by three PLP-dependent lyases: the unusual case of tyrosine phenol-lyase.

    PubMed

    Koulikova, Vitalia V; Zakomirdina, Lyudmila N; Gogoleva, Olga I; Tsvetikova, Marina A; Morozova, Elena A; Komissarov, Vsevolod V; Tkachev, Yaroslav V; Timofeev, Vladimir P; Demidkina, Tatyana V; Faleev, Nicolai G

    2011-11-01

    A comparative study of the kinetics and stereospecificity of isotopic exchange of the pro-2R- and pro-2S protons of glycine in (2)H(2)O under the action of tyrosine phenol-lyase (TPL), tryptophan indole-lyase (TIL) and methionine γ-lyase (MGL) was undertaken. The kinetics of exchange was monitored using both (1)H- and (13)C-NMR. In the three compared lyases the stereospecificities of the main reactions with natural substrates dictate orthogonal orientation of the pro-2R proton of glycine with respect to the cofactor pyridoxal 5'-phosphate (PLP) plane. Consequently, according to Dunathan's postulate with all the three enzymes pro-2R proton should exchange faster than does the pro-2S one. In fact the found ratios of 2R:2S reactivities are 1:20 for TPL, 108:1 for TIL, and 1,440:1 for MGL. Thus, TPL displays an unprecedented inversion of stereospecificity. A probable mechanism of the observed phenomenon is suggested, which is based on the X-ray data for the quinonoid intermediate, formed in the reaction of TPL with L-alanine. The mechanism implies different conformational changes in the active site upon binding of glycine and alanine. These changes can lead to relative stabilization of either the neutral amino group, accepting the α-proton, or the respective ammonium group, which is formed after the proton abstraction.

  11. Catalase reaction by myoglobin mutants and native catalase: mechanistic investigation by kinetic isotope effect.

    PubMed

    Kato, Shigeru; Ueno, Takafumi; Fukuzumi, Shunichi; Watanabe, Yoshihito

    2004-12-10

    The catalase reaction has been studied in detail by using myoglobin (Mb) mutants. Compound I of Mb mutants (Mb-I), a ferryl species (Fe(IV)=O) paired with a porphyrin radical cation, is readily prepared by the reaction with a nearly stoichiometric amount of m-chloroperbenzoic acid. Upon the addition of H2O2 to an Mb-I solution, Mb-I is reduced back to the ferric state without forming any intermediates. This indicates that Mb-I is capable of performing two-electron oxidation of H2O2 (catalatic reaction). Gas chromatography-mass spectroscopy analysis of the evolved O2 from a 50:50 mixture of H2(18)O2/H2(16)O2 solution containing H64D or F43H/H64L Mb showed the formation of 18O2 (m/e = 36) and 16O2 (m/e = 32) but not 16O18O (m/e = 34). This implies that O2 is formed by two-electron oxidation of H2O2 without breaking the O-O bond. Deuterium isotope effects on the catalatic reactions of Mb mutants and catalase suggest that the catalatic reactions of Micrococcus lysodeikticus catalase and F43H/H64L Mb proceed via an ionic mechanism with a small isotope effect of less than 4.0, since the distal histidine residue is located at a proper position to act as a general acid-base catalyst for the ionic reaction. In contrast, other Mb mutants such as H64X (X is Ala, Ser, and Asp) and L29H/H64L Mb oxidize H2O2 via a radical mechanism in which a hydrogen atom is abstracted by Mb-I with a large isotope effect in a range of 10-29, due to a lack of the general acid-base catalyst.

  12. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  13. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969. As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: that is machine-readable (for checking and indicating possible errors); that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  14. Deuterium in astrophysical ice analogues: Isotope exchange and IR detection sensitivity for HDO

    NASA Astrophysics Data System (ADS)

    Escribano, R. M.; Galvez, O.; Mate, B.; Herrero, V. J.

    2011-12-01

    Among D-bearing molecules, water is especially interesting from an astrophysical point of view. Although the deuterium content of water in astronomical environments is relatively small as compared with other molecules, it holds most valuable information, still largely undeciphered, on the dynamics of formation and evaporation of ice grain mantels in protostellar regions [1], and is crucial for the understanding of the formation of the Solar System and the Earth [2]. In this work, we have used the OD stretching bands of HDO and D2O molecules in various ice mixtures formed by vapor deposition on a cold substrate (see ref [3] for a description of the experimental set-up) to study the sensitivity of the IR technique for the detection of HDO in ice samples, and to monitor processes of H/D isotope exchange in these solids. It is found that the detection sensitivity is strongly dependent on the ice structure. The OD band is extremely broad and tends to disappear into the absorption continuum of H2O for low temperature amorphous samples. Detectable HDO/H2O ratios with this technique may range from a few per cent for amorphous samples to a few per thousand in crystalline ice. These relatively high upper limits and the appreciable dependence of the band shape on temperature, complicating the interpretation of data from many lines of sight, may question the usefulness of this technique. Isotopic H/D exchange in mixed ices of H2O/D2O is found to start at ~ 120 K and is greatly accelerated at 150 K, as crystallization proceeds in the ice. The process is mainly driven by proton transfer assisted by orientational defect mobility. Annealed amorphous samples are more favourable for isotope exchange than samples directly formed in the crystalline phase. The annealing process seems to lead to polycrystalline ice morphology with a higher defect activity. The present data emphasize the relevance of a depletion mechanism for D atoms in hydroxylic bonds in the solid state, recently

  15. An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

    NASA Astrophysics Data System (ADS)

    Uchikawa, J.; Zeebe, R. E.

    2011-12-01

    Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

  16. Methyl-coenzyme M reductase from methanogenic archaea: isotope effects on label exchange and ethane formation with the homologous substrate ethyl-coenzyme M.

    PubMed

    Scheller, Silvan; Goenrich, Meike; Thauer, Rudolf K; Jaun, Bernhard

    2013-10-09

    Ethyl-coenzyme M (CH3CH2-S-CH2CH2-SO3(-), Et-S-CoM) serves as a homologous substrate for the enzyme methyl-coenzyme M reductase (MCR) resulting in the product ethane instead of methane. The catalytic reaction proceeds via an intermediate that already contains all six C-H bonds of the product. Because product release occurs after a second, rate-limiting step, many cycles of intermediate formation and reconversion to substrate occur before a substantial amount of ethane is released. In deuterated buffer, the intermediate becomes labeled, and C-H activation in the back reaction rapidly leads to labeled Et-S-CoM, which enables intermediate formation to be detected. Here, we present a comprehensive analysis of this pre-equilibrium. (2)H- and (13)C-labeled isotopologues of Et-S-CoM were used as the substrates, and the time course of each isotopologue was followed by NMR spectroscopy. A kinetic simulation including kinetic isotope effects allowed determination of the primary and α- and β-secondary isotope effects for intermediate formation and for the C-H/C-D bond activation in the ethane-containing intermediate. The values obtained are in accordance with those found for the native substrate Me-S-CoM (see preceding publication, Scheller, S.; Goenrich, M.; Thauer, R. K.; Jaun, B. J. Am. Chem. Soc. 2013, 135, DOI: 10.1021/ja406485z) and thus imply the same catalytic mechanism for both substrates. The experiment by Floss and co-workers, demonstrating a net inversion of configuration to chiral ethane with CH3CDT-S-CoM as the substrate, is compatible with the observed rapid isotope exchange if the isotope effects measured here are taken into account.

  17. A molecular dynamics study of bond exchange reactions in covalent adaptable networks.

    PubMed

    Yang, Hua; Yu, Kai; Mu, Xiaoming; Shi, Xinghua; Wei, Yujie; Guo, Yafang; Qi, H Jerry

    2015-08-21

    Covalent adaptable networks are polymers that can alter the arrangement of network connections by bond exchange reactions where an active unit attaches to an existing bond then kicks off its pre-existing peer to form a new bond. When the polymer is stretched, bond exchange reactions lead to stress relaxation and plastic deformation, or the so-called reforming. In addition, two pieces of polymers can be rejoined together without introducing additional monomers or chemicals on the interface, enabling welding and reprocessing. Although covalent adaptable networks have been researched extensively in the past, knowledge about the macromolecular level network alternations is limited. In this study, molecular dynamics simulations are used to investigate the macromolecular details of bond exchange reactions in a recently reported epoxy system. An algorithm for bond exchange reactions is first developed and applied to study a crosslinking network formed by epoxy resin DGEBA with the crosslinking agent tricarballylic acid. The trace of the active units is tracked to show the migration of these units within the network. Network properties, such as the distance between two neighboring crosslink sites, the chain angle, and the initial modulus, are examined after each iteration of the bond exchange reactions to provide detailed information about how material behaviors and macromolecular structure evolve. Stress relaxation simulations are also conducted. It is found that even though bond exchange reactions change the macroscopic shape of the network, microscopic network characteristic features, such as the distance between two neighboring crosslink sites and the chain angle, relax back to the unstretched isotropic state. Comparison with a recent scaling theory also shows good agreement.

  18. Scaling Hydrologic Exchange Flows and Biogeochemical Reactions from Bedforms to Basins

    NASA Astrophysics Data System (ADS)

    Harvey, J. W.; Gomez-Velez, J. D.

    2015-12-01

    River water moves in and out of the main channel along pathways that are perpendicular to the channel's main axis that flow across or beneath the ground surface. These hydrologic exchange flows (HEFs) are difficult to measure, yet no less important than a river's downstream flow, or exchanges with the atmosphere and deeper groundwater (Harvey and Gooseff, 2015, WRR). There are very few comprehensive investigations of exchange fluxes to understand patterns with river size and relative importance of specific types of exchanges. We used the physically based model NEXSS to simulate multiple scales of hyporheic flow and their cumulative effects on solute reaction in large basins (on the order of Chesapeake Bay basin or larger). Our goal was to explain where and when particular types of hyporheic flow are important in enhancing key biogeochemical reactions, such as organic carbon respiration and denitrification. Results demonstrate that hyporheic flux (expressed per unit area of streambed) varies surprisingly little across the continuum of first-order streams to eighth-order rivers, and vertical exchange beneath small bedforms dominates in comparison with lateral flow beneath gravel bars and meanders. Also, the river's entire volume is exchanged many times with hyporheic flow within a basin, and the turnover length (after one entire river volume is exchanged) is strongly influenced by hydrogeomorphic differences between physiographic regions as well as by river size. The cumulative effects on biogeochemical reactions were assessed using a the reaction significance factor, RSF, which computes the cumulative potential for hyporheic reactions using a dimensionless index that balances reaction progress in a single hyporheic flow path against overall processing efficiency of river turnover through hyporheic flow paths of that type. Reaction significance appears to be strongly dominated by hydrologic factors rather than biogeochemical factors, and seems to be dominated by

  19. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    SciTech Connect

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  20. Astrophysical S factors for fusion reactions involving C, O, Ne, and Mg isotopes

    SciTech Connect

    Beard, M.; Afanasjev, A.V.; Chamon, L.C.; Gasques, L.R.; Wiescher, M.; Yakovlev, D.G.

    2010-09-15

    Using the Sao Paulo potential and the barrier penetration formalism we have calculated the astrophysical factor S(E) for 946 fusion reactions involving stable and neutron-rich isotopes of C, O, Ne, and Mg for center-of-mass energies E varying from 2 to {approx}18-30 MeV (covering the range below and above the Coulomb barrier). We have parameterized the energy dependence, S(E), by an accurate universal 9-parameter analytic expression and present tables of fit parameters for all the reactions. We also discuss the reduced 3-parameter version of our fit which is highly accurate at energies below the Coulomb barrier, and outline the procedure for calculating the reaction rates. The results can be easily converted to thermonuclear or pycnonuclear reaction rates to simulate various nuclear burning phenomena, in particular, stellar burning at high temperatures and nucleosynthesis in high density environments.

  1. Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

    NASA Technical Reports Server (NTRS)

    Tsuge, S.; Sagara, K.

    1978-01-01

    The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

  2. Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

    NASA Technical Reports Server (NTRS)

    Tsuge, S.; Sagara, K.

    1978-01-01

    The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

  3. Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

    SciTech Connect

    Jiang, Bin; Guo, Hua

    2013-12-14

    Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

  4. Carbon and Chlorine Isotope Fractionation Patterns Associated with Different Engineered Chloroform Transformation Reactions.

    PubMed

    Torrentó, Clara; Palau, Jordi; Rodríguez-Fernández, Diana; Heckel, Benjamin; Meyer, Armin; Domènech, Cristina; Rosell, Mònica; Soler, Albert; Elsner, Martin; Hunkeler, Daniel

    2017-06-06

    To use compound-specific isotope analysis for confidently assessing organic contaminant attenuation in the environment, isotope fractionation patterns associated with different transformation mechanisms must first be explored in laboratory experiments. To deliver this information for the common groundwater contaminant chloroform (CF), this study investigated for the first time both carbon and chlorine isotope fractionation for three different engineered reactions: oxidative C-H bond cleavage using heat-activated persulfate, transformation under alkaline conditions (pH ∼ 12) and reductive C-Cl bond cleavage by cast zerovalent iron, Fe(0). Carbon and chlorine isotope fractionation values were -8 ± 1‰ and -0.44 ± 0.06‰ for oxidation, -57 ± 5‰ and -4.4 ± 0.4‰ for alkaline hydrolysis (pH 11.84 ± 0.03), and -33 ± 11‰ and -3 ± 1‰ for dechlorination, respectively. Carbon and chlorine apparent kinetic isotope effects (AKIEs) were in general agreement with expected mechanisms (C-H bond cleavage in oxidation by persulfate, C-Cl bond cleavage in Fe(0)-mediated reductive dechlorination and E1CB elimination mechanism during alkaline hydrolysis) where a secondary AKIECl (1.00045 ± 0.00004) was observed for oxidation. The different dual carbon-chlorine (Δδ(13)C vs Δδ(37)Cl) isotope patterns for oxidation by thermally activated persulfate and alkaline hydrolysis (17 ± 2 and 13.0 ± 0.8, respectively) vs reductive dechlorination by Fe(0) (8 ± 2) establish a base to identify and quantify these CF degradation mechanisms in the field.

  5. IRiS—Exploring new frontiers in neutron-rich isotopes of the heaviest elements with a new Inelastic Reaction Isotope Separator

    NASA Astrophysics Data System (ADS)

    Dvorak, J.; Block, M.; Düllmann, Ch. E.; Heinz, S.; Herzberg, R.-D.; Schädel, M.

    2011-10-01

    A dedicated Inelastic Reaction Isotope Separator (IRiS) for multi-nucleon transfer products will be designed and installed at GSI. Research at IRiS will focus on the investigation of new neutron-rich isotopes of the heaviest elements, study of which will advance various research fields, such as nuclear chemistry, nuclear and atomic physics, as well as nuclear astrophysics. The scientific motivation for this project and the alternative design options for the separator and its main components are discussed.

  6. Possibilities of synthesis of unknown isotopes of superheavy nuclei with charge numbers Z > 108 in asymmetric actinide-based complete fusion reactions

    NASA Astrophysics Data System (ADS)

    Hong, Juhee; Adamian, G. G.; Antonenko, N. V.

    2016-10-01

    The possibilities of production of new isotopes of superheavy nuclei with charge numbers Z = 109-114 in various asymmetric hot fusion reactions are studied for the first time. The excitation functions of the formation of these isotopes in the xn evaporation channels are predicted and the optimal conditions for the synthesis are proposed. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of the heaviest nuclei obtained in cold and hot complete fusion reactions.

  7. Retention and selectivity of teicoplanin stationary phases after copper complexation and isotopic exchange.

    PubMed

    Berthod, A; Valleix, A; Tizon, V; Leonce, E; Caussignac, C; Armstrong, D W

    2001-11-15

    Teicoplanin is a macrocyclic glycopeptide that is highly effective as a chiral selector for LC enantiomeric separations. Two possible interaction paths were investigated and related to solute retention and selectivity: (1) interactions with the only teicoplanin amine group and (2) role of hydrogen bonding interactions. Mobile phases containing 0.5 and 5 mM copper ions were used to try to block the amine group. In the presence of copper ions, it was found that the teicoplanin stationary phase has a decreased ability to separate most underivatized racemic amino acids. However, it maintained its ability to separate enantiomers that were not alpha-amino acids. It is established that there is little copper-teicoplanin complex formation. The effect of Cu2+ on the enantioseparation of some alpha-amino acids appears to be due to the fact that these solutes are good bidentate ligands and form complexes with copper ions in the mobile phase. Isotopic exchange with deuterium oxide was performed using acetonitrile-heavy water mobile phases. It was found that the retention times of all amino acids were lower with deuterated mobile phases. The retention times of polar or apolar molecules without amine groups were higher with deuterated mobiles phases. In all cases, the enantioselectivity factors were unaffected by the deuterium exchange. It is proposed that the electrostatic interactions are decreased in the deuterated mobile phases and the solute-accessible stationary-phase volume is somewhat swollen by deuterium oxide. The balance of these effects is a decrease in the amino acid retention times and an increase in the apolar solute retention time. The enantioselectivity factors of all of the molecules remain unchanged because all of the interactions are changed equally. We propose a new global quality criterion (the E factor) for comparing and evaluating enantiomeric separations.

  8. Rates for neutron-capture reactions on tungsten isotopes in iron meteorites. [Abstract only

    NASA Technical Reports Server (NTRS)

    Masarik, J.; Reedy, R. C.

    1994-01-01

    High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.

  9. Chromatographic Separation of Cd from Plants via Anion-Exchange Resin for an Isotope Determination by Multiple Collector ICP-MS.

    PubMed

    Wei, Rongfei; Guo, Qingjun; Wen, Hanjie; Peters, Marc; Yang, Junxing; Tian, Liyan; Han, Xiaokun

    2017-01-01

    In this study, key factors affecting the chromatographic separation of Cd from plants, such as the resin column, digestion and purification procedures, were experimentally investigated. A technique for separating Cd from plant samples based on single ion-exchange chromatography has been developed, which is suitable for the high-precision analysis of Cd isotopes by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The robustness of the technique was assessed by replicate analyses of Cd standard solutions and plant samples. The Cd yields of the whole separation process were higher than 95%, and the (114/110)Cd values of three Cd second standard solutions (Münster Cd, Spex Cd, Spex-1 Cd solutions) relative to the NIST SRM 3108 were measured accurately, which enabled the comparisons of Cd isotope results obtained in other laboratories. Hence, stable Cd isotope analyses represent a powerful tool for fingerprinting specific Cd sources and/or examining biogeochemical reactions in ecological and environmental systems.

  10. Amide proton exchange rates of a bound pepsin inhibitor determined by isotope-edited proton NMR experiments

    SciTech Connect

    Fesik, S.W.; Luly, J.R.; Stein, H.H.; BaMaung, N.

    1987-09-30

    From a series of isotope-edited proton NMR spectra, amide proton exchange rates were measured at 20 C, 30 C, and 40/sup 0/C for a tightly bound /sup 15/N-labeled tripeptide inhibitor of porcine pepsin (IC50 = 1.7 X 10(-) M). Markedly different NH exchange rates were observed for the three amide protons of the bound inhibitor. The P1 NH exchanged much more slowly than the P2 NH and P3 NH. These results are discussed in terms of the relative solvent accessibility in the active site and the role of the NH protons of the inhibitor for hydrogen bonding to the enzyme. In this study a useful approach is demonstrated for obtaining NH exchange rates on ligands bound to biomacromolecules, the knowledge of which could be of potential utility in the design of therapeutically useful nonpeptide enzyme inhibitors from peptide leads.

  11. The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations.

    PubMed

    Becerra, Rosa; Cannady, J Pat; Dormer, Guy; Walsh, Robin

    2009-07-14

    Time-resolved kinetic studies of the reactions of silylene, SiH(2), and dideutero-silylene, SiD(2), generated by laser flash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH(3)C[triple bond, length as m-dash]CCH(3). The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF(6) bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(Infinity)/cm(3) molecule(-1) s(-1) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(1)/RTIn10log(k(D)(Infinity)/cm(3) molecule(-1) s(-1) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTIn10. Additionally, pressure-dependent rate coefficients for the reaction of SiH(2) with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC(4)H(8) reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH(2)C(CH(3))[double bond, length as m-dash]C(CH(3))-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH(3)CH[double bond, length as m-dash]C(CH(3))SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H-D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed

  12. State-to-state quantum dynamics of the H + HBr reaction: competition between the abstraction and exchange reactions.

    PubMed

    Xie, Changjian; Jiang, Bin; Xie, Daiqian

    2011-05-14

    Quantum state-to-state dynamics for the H + HBr(υ(i) = 0, j(i) =0) reaction was studied on an accurate ab intio potential energy surface for the electronic ground state of BrH(2). Both the H + HBr → H(2) + Br abstraction reaction and the H' + HBr → H'Br + H exchange reaction were investigated up to a collision energy of 2.0 eV. It was found that the abstraction channel is dominant at lower collision energies, while the exchange channel becomes dominant at higher collision energies. The total integral cross section of the abstraction reaction at a collision energy of 1.6 eV was found to be 1.37 Å(2), which is larger than a recent quantum mechanical result (1.06 Å(2)) and still significantly smaller than the experimental value (3 ± 1 Å(2)). Meanwhile, similar to the previous theoretical study, our calculations also predicted much hotter product rotational state distributions than those from the experimental study. This suggests that further experimental investigations are highly desirable to elucidate the dynamic properties of the title reactions.

  13. Possibility of production of neutron-rich Zn and Ge isotopes in multinucleon transfer reactions at low energies

    SciTech Connect

    Adamian, G. G.; Antonenko, N. V.; Sargsyan, V. V.; Scheid, W.

    2010-02-15

    The production cross sections of new neutron-rich {sup 84,86}Zn and {sup 90,92}Ge isotopes beyond N=50 are estimated for the first time in the multinucleon transfer reactions {sup 48}Ca + {sup 238}U and {sup 48}Ca + {sup 244}Pu. The production of new isotopes in reactions with a {sup 48}Ca beam is discussed for future experiments.

  14. Multi-Isotope Analysis as a Natural Reaction Probe of Biodegradation Mechanisms of 1,2- Dichloroethane

    NASA Astrophysics Data System (ADS)

    Hirschorn, S. K.; Dinglasan-Panlilio, M.; Edwards, E. A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2006-12-01

    1,2-Dichloroethane (1,2-DCA), a chlorinated aliphatic hydrocarbon, is an EPA priority pollutant and a widespread groundwater contaminant. Stable isotope fractionation during biodegradation of 1,2-DCA occurs due to differences in the reaction rates of heavy versus light atoms present at a reacting bond in the 1,2-DCA molecule. In general, light isotopic bonds react more quickly, producing a relative enrichment in the heavy isotope in the remaining contaminant pool. Compound specific isotope analysis has the potential to demonstrate the occurrence and extent of biodegradation at chlorinated solvent contaminated groundwater sites. In this study, stable carbon isotope fractionation was used as a novel reaction probe to provide information about the mechanism of 1,2-DCA biodegradation. Isotopic fractionation was measured during 1,2-DCA degradation by a microbial culture capable of degrading 1,2-DCA under O2-reducing and NO3-reducing conditions. The microbial culture produced isotopic enrichment values that are not only large and reproducible, but are the same whether O2 or NO3 was used as an electron acceptor. The mean isotopic enrichment value of -25.8 permil measured for the microbial culture during 1,2-DCA degradation under both O2 and NO3- reducing conditions can be converted into a kinetic isotope effect (KIE) value to relate the observed isotopic fractionation to the mechanism of degradation. This KIE value (1.05) is consistent with degradation via a hydrolysis (SN2) reaction under both electron-accepting conditions. Isotope analysis was able to provide a first line of evidence for the reaction mechanism of 1,2-DCA biodegradation by the microbial culture. Using a multi-isotope approach incorporating both carbon and hydrogen isotopic data, compound specific isotope analysis also has the potential to determine degradation mechanisms for 1,2-DCA under aerobic conditions where 1,2-DCA is known to be degraded by two distinct enzymatic pathways. Biodegradation of 1

  15. Use of H/D isotope effects to gather information about hydrogen bonding and hydrogen exchange rates.

    PubMed

    Takeda, Mitsuhiro; Miyanoiri, Yohei; Terauchi, Tsutomu; Yang, Chun-Jiun; Kainosho, Masatsune

    2014-04-01

    Polar side-chains in proteins play important roles in forming and maintaining three-dimensional structures, and thus participate in various biological functions. Until recently, most protein NMR studies have focused on the non-exchangeable protons of amino acid residues. The exchangeable protons attached to polar groups, such as hydroxyl (OH), sulfhydryl (SH), and amino (NH2) groups, have mostly been ignored, because in many cases these hydrogen atoms exchange too quickly with water protons, making NMR observations impractical. However, in certain environments, such as deep within the hydrophobic interior of a protein, or in a strong hydrogen bond to other polar groups or interacting ligands, the protons attached to polar groups may exhibit slow hydrogen exchange rates and thus become NMR accessible. To explore the structural and biological implications of the interactions involving polar side-chains, we have developed versatile NMR methods to detect such cases by observing the line shapes of (13)C NMR signals near the polar groups, which are affected by deuterium-proton isotope shifts in a mixture of H2O and D2O. These methods allow the detection of polar side-chains with slow hydrogen-deuterium exchange rates, and therefore provide opportunities to retrieve information about the polar side-chains, which might otherwise be overlooked by conventional NMR experiments. Future prospects of applications using deuterium-proton isotope shifts to retrieve missing structural and dynamic information of proteins are discussed.

  16. Energy-loss cross sections for inclusive charge-exchange reactions at intermediate energies

    NASA Technical Reports Server (NTRS)

    Cucinotta, Francis A.; Townsend, Lawrence W.; Dubey, Rajendra R.

    1993-01-01

    Charge-exchange reactions for scattering to the continuum are considered in a high-energy multiple scattering model. Calculations for (p,n) and (He-3,H-3) reactions are made and compared with experimental results for C-12, O-16, and Al-27 targets. Coherent effects are shown to lead to an important role for inelastic multiple scattering terms when light projectiles are considered.

  17. Preparation of functionalized cyclic enol phosphates by halogen-magnesium exchange and directed deprotonation reactions.

    PubMed

    Piller, Fabian M; Bresser, Tomke; Fischer, Markus K R; Knochel, Paul

    2010-07-02

    Cyclic enol phosphates were magnesiated by a halogen/magnesium exchange reaction or deprotonation using TMP-derived magnesium amide bases. The resulting magnesium reagents react readily with a wide range of electrophiles like allyl bromides and acid chlorides or can be used in Pd-catalyzed cross-coupling reactions. Several optically pure enol phosphates were prepared starting from readily available d-(+)-camphor derivatives.

  18. A Benchmark Study of Kinetic Isotope Effects and Barrier Heights for the Finkelstein Reaction.

    PubMed

    Żaczek, Szymon; Gelman, Faina; Dybala-Defratyka, Agnieszka

    2017-03-30

    Herein, we present a combined (experimental and computational) study of the Finkelstein reaction in condensed phase, where bromine is substituted by iodine in 2-bromoethylbenzene, in the presence of either acetone or acetonitrile as a solvent. Performance of various density functional theory and ab initio methods were tested for reaction barrier heights as well as for bromine and carbon kinetic isotope effects (KIEs). Two different implicit solvation models were examined (PCM and SMD). Theoretically predicted KIEs were compared with experimental values, while reaction barrier heights were assessed using the CCSD(T)-level and experimental energies as reference. In general, although the tested parameters (energies and KIEs) do not exhibit any substantial difference upon a change of the solvent, the different behavior of the theoretical methods was observed depending on the solvent. With respect to isotope effects, both PCM and SMD seem to perform very similarly, though results obtained with PCM are slightly closer to the experimental values. For predicting reaction barriers, utilization of either PCM or SMD solvation models yielded different results. Functionals from the ωB97 family: ωB97, ωB97X, and ωB97X-D provide the most accurate results for the studied system.

  19. Isotopic Effects on Stereodynamics of the C+ + H2 → CH+ + H Reaction

    NASA Astrophysics Data System (ADS)

    Guo, Lu; Yang, Yun-Fan; Fan, Xiao-Xing; Ma, Feng-Cai; Li, Yong-Qing

    2017-05-01

    The effects of isotope substitution on stereodynamic properties for the reactions {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T have been studied applying a quasi classical trajectory method occurring on the new ground state {{C H}}2+ potential energy surface [J. Chem. Phys. 142 (2015) 124302]. In the center of mass coordinates applying the quasi classical trajectory method to investigate the orientation and the alignment of the product molecule. Differential cross section and three angle distribution functions P(θr), P(ϕr), P( {θ }r,{φ }r ) on the potential energy surface that fixed the collision energy with a value is 40 kcal/mol have been studied. The isotope effect becomes more and more important with the reagent molecules H 2 changing into HD and HT. P({θ }r,{φ }r) as the joint probability density function of both polar angles θ r and ϕ r , which can illustrate more detailed dynamics information. The isotope effect is obvious influence on the properties of stereodynamics in the reactions of {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T. Supported by the National Natural Science Foundation of China under Grant Nos. 11474141, 11274149, 11544015, the Program for Liaoning Excellent Talents in University under Grant No. LJQ2015040, and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2014-1685)

  20. Tritium secondary kinetic isotope effect on phenylalanine ammonia-lyase-catalyzed reaction.

    PubMed

    Lewandowicz, A; Jemielity, J; Kańska, M; Zoń, J; Paneth, P

    1999-10-15

    The mechanism by which phenylalanine ammonia-lyase (PAL, EC 4.3.1.5) catalyzes the reversible elimination of ammonia from phenylalanine yielding (E)-cinnamic acid has gained much attention in the recent years. Dehydroalanine is essential for the catalysis. It was assumed that this prostetic group acts as the electrophile, leading to a covalently bonded enzyme-intermediate complex with quarternary nitrogen of phenylalanine. Recently, an alternative mechanism has been suggested in which the enzyme-intermediate complex is formed in a Friedel-Crafts reaction between dehydroalanine and orthocarbon of the aromatic ring. Using semiempirical calculations we have shown that these two alternative mechanisms can be distinguished on the basis of the hydrogen secondary kinetic isotope effect when tritium label is placed in the orthopositions. Our calculations indicated also that the kinetic isotope effect measured using ring-labeled d(5)-phenylalanine could not be used to differentiate these alternative mechanisms. Measured secondary tritium kinetic isotope effect shows strong dependence on the reaction progress, starting at the inverse value of k(H)/k(T) = 0.85 for 5% conversion and reaching the normal value of about 1.15 as the conversion increases to 20%. This dependence has been interpreted in terms of a complex mechanism with initial formation of the Friedel-Crafts type intermediate.

  1. Long-Term (4 mo) Oxygen Isotope Exchange Experiment between Zircon and Hydrothermal Fluid

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Schmitt, A. K.; Lundstrom, C.; Golledge, S.

    2013-12-01

    Knowing oxygen diffusivity in zircon has several critical applications: 1) establishing zircon stability and solubility in hot silica-saturated hydrothermal solutions; 2) deriving metamorphic and magmatic heating timescales from intra-crystal oxygen isotopic gradients; 3) assessing the survivability of oxygen isotopic signatures in Hadean zircons. We report results of a microanalytical investigation of an isotope exchange experiment using a cold-seal pressure apparatus at 850°C and 500 MPa over 4 months duration. Natural zircon, quartz and rutile were sealed with a silica-rich solution doped with 18-O, D, 7-Li and 10-B in a gold capsule. The diffusion length-scales were examined by depth profiling using time-of-flight (TOF) and high-sensitivity dynamic secondary ionization mass spectrometry (SIMS). Starting materials had distinct and homogeneous δ18O: zircon from Mesa Falls tuff of Yellowstone (+3.6‰), rutile from Karelia (-29‰), Bishop Tuff Quartz (+8.4‰), and δ18O doped water (+400‰). Starting material zircon showed invariant 18O/16O during depth profiling. After the 4 month experiment, rutile crystal surfaces displayed etching (100's of nm), while zircon exteriors lacked visible change. Quartz was completely dissolved and reprecipitated in a minor residue. Rutile developed ~2 μm long Fickian diffusion profiles largely consistent with the wet diffusion coefficients for rutile previously reported [1]. Surface U-Pb dating of zircon detected no significant Pb loss from the outermost ~300 nm of the crystal face and returned identical core-face ages. We performed δ18O depth profiling of zircon in two directions. First, forward profiles (crystal rim inwards) by dynamic SIMS (no surface treatment besides Au-coating; Cs+ beam of 20 kV impact energy) showed initially high and decreasing 18O/16O over ~130 nm; TOF-SIMS forward profiles using a 2 kV Cs+ sputter beam and 25 kV Bi3+ primary ions on uncoated zircon surfaces (cleaned for 2 min with HF) yielded

  2. Site-specific immobilization of proteins at zeolite L crystals by nitroxide exchange reactions.

    PubMed

    Becker, Maike; De Cola, Luisa; Studer, Armido

    2011-03-28

    Site-selective immobilization of dyes and different protein recognizing entities at the surface of zeolite L crystals using mild radical nitroxide exchange reactions is reported. Exposure of these crystals to aqueous protein solutions leads to site-selective immobilization of proteins onto the crystals.

  3. Analysis of longitudinal momentum distribution data of 26-29P isotopes in stripping reactions

    NASA Astrophysics Data System (ADS)

    Kumar, Ravinder; Singh, Pardeep; Kumar, Rajiv

    2017-02-01

    The orbital occupancy of the stripped proton in the phosphors isotopes with mass number 26-29 have been determined through the analysis of longitudinal momentum distributions (LMDs) of 25-28Si core fragments coming from 9Be(26-28P,25-27Si)X and 12C(29P,28Si)Y stripping reactions at high energies. It has been found that the probability of occupying d-orbital by the stripped proton is 40-60%, 30-50%, 30-50% and 0-20% in 26-29P isotopes, respectively. The effects of Coulomb barrier for the possibility of halo structure in proton-rich nuclei has also been examined and found that it decreases the chance of possessing halo structure in proton-rich nuclei.

  4. Interplay between single-particle and collective excitations in argon isotopes populated by transfer reactions

    SciTech Connect

    Szilner, S.; Jelavic-Malenica, D.; Soic, N.; Corradi, L.; Fioretto, E.; Sahin, E.; Silvestri, R.; Stefanini, A. M.; Valiente-Dobon, J. J.; Haas, F.; Lebhertz, D.; Bouhelal, M.; Caurier, E.; Courtin, S.; Goasduff, A.; Nowacki, F.; Ur, C. A.; Beghini, S.; Farnea, E.

    2011-07-15

    New {gamma} transitions have been identified in argon isotopes in {sup 40}Ar + {sup 208}Pb multiple transfer reactions by exploiting, in a fragment-{gamma} measurement, the new generation of magnetic spectrometers based on trajectory reconstruction coupled to large {gamma} arrays. The coupling of single-particle degrees of freedom to nuclear vibration quanta was discussed. The interpretation of the newly observed states within a particle-phonon coupling picture was used to consistently follow, via their excitation energies, the evolution of collectivity in odd Ar isotopes. The proposed level schemes are supported by the results of sd-pf shell-model calculations, which have been also employed to evaluate the strength functions of the populated states.

  5. Deuterium isotope effect on the induction period of the cerium catalyzed Belousov-Zhabotinsky reaction

    NASA Astrophysics Data System (ADS)

    Rossi, Federico; Simoncini, Eugenio; Marchettini, Nadia; Tiezzi, Enzo

    2009-02-01

    In this work we present results about the deuterium isotopic effect on the global kinetics of a cerium catalyzed Belousov-Zhabotinsky reaction. A nonlinear dependence of the induction period upon the percentage of deuterated reactants was found in batch conditions. In order to understand this result, we investigated two reaction pathways responsible for the length of the induction period, namely: (a) the reaction between the enolic form of the malonic acid with molecular bromine and (b) the oxidation of malonic acid by the Ce(IV) ion. In both cases we obtained a linear dependence of the kinetic constants on the percentage of deuterated reactants. Nevertheless, by inserting the experimental values in the MBM (Marburg-Budapest-Missoula) model, we were able to qualitatively simulate the observed trend of the induction period.

  6. Possibilities for synthesis of new isotopes of superheavy nuclei in cold fusion reactions

    NASA Astrophysics Data System (ADS)

    Bao, X. J.; Gao, Y.; Li, J. Q.; Zhang, H. F.

    2016-04-01

    In order to find a way to produce superheavy nuclei (SHN), which appear in the gap between the SHN synthesized by cold fusion and those by hot fusion, or those so far not yet been produced in the laboratory, we tried to make use of a set of projectile isotopic chains, to use a radioactive beam projectile, and to test symmetric fusion reactions for gaining more neutrons to synthesize neutron-richer SHN based on the dinuclear system (DNS) model via cold fusion reactions. It is found that the nuclei 265Mt,Ds,272268,273Rg, and 274,275,276Cn may be produced with the detectable evaporation residual cross sections. The intensities of radioactive beams are significantly less than those of the stable beams, therefore using a stable beam is predicted to be the most favorable method for producing SHN. From the symmetric reaction system 136Xe+136Xe , no fusion event was found.

  7. Mercury isotopes in a forested ecosystem: Implications for air-surface exchange dynamics and the global mercury cycle

    NASA Astrophysics Data System (ADS)

    Demers, Jason D.; Blum, Joel D.; Zak, Donald R.

    2013-01-01

    ABSTRACT Forests mediate the biogeochemical cycling of mercury (Hg) between the atmosphere and terrestrial ecosystems; however, there remain many gaps in our understanding of these processes. Our objectives in this study were to characterize Hg isotopic composition within forests, and use natural abundance stable Hg isotopes to track sources and reveal mechanisms underlying the cycling of Hg. We quantified the stable Hg isotopic composition of foliage, forest floor, mineral soil, precipitation, and total gaseous mercury (THg(g)) in the atmosphere and in evasion from soil, in 10-year-old aspen forests at the Rhinelander FACE experiment in northeastern Wisconsin, USA. The effect of increased atmospheric CO2 and O3 concentrations on Hg isotopic composition was small relative to differences among forest ecosystem components. Precipitation samples had δ202Hg values of -0.74 to 0.06‰ and ∆199Hg values of 0.16 to 0.82‰. Atmospheric THg(g) had δ202Hg values of 0.48 to 0.93‰ and ∆199Hg values of -0.21 to -0.15‰. Uptake of THg(g) by foliage resulted in a large (-2.89‰) shift in δ202Hg values; foliage displayed δ202Hg values of -2.53 to -1.89‰ and ∆199Hg values of -0.37 to -0.23‰. Forest floor samples had δ202Hg values of -1.88 to -1.22‰ and ∆199Hg values of -0.22 to -0.14‰. Mercury isotopes distinguished geogenic sources of Hg and atmospheric derived sources of Hg in soil, and showed that precipitation Hg only accounted for ~16% of atmospheric Hg inputs. The isotopic composition of Hg evasion from the forest floor was similar to atmospheric THg(g); however, there were systematic differences in δ202Hg values and MIF of even isotopes (∆200Hg and ∆204Hg). Mercury evasion from the forest floor may have arisen from air-surface exchange of atmospheric THg(g), but was not the emission of legacy Hg from soils, nor re-emission of wet-deposition. This implies that there was net atmospheric THg(g) deposition to the forest soils. Furthermore, MDF of

  8. Study for Nuclear Structures of 22-35Na Isotopes via Measurements of Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Suzuki, Shinji

    2014-09-01

    T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn., Kochi Univ. of Tech.) Reaction cross sections (σR) for 22-35Na isotopes have been measured at around 240 MeV/nucleon. The σR for 22-35Na were measured for the first time. Enhancement in cross sections is clearly observed from the systematics for stable nuclei, for isotopes with large mass numbers. These enhancement can be mainly ascribed to the nuclear deformation. We will discuss the nuclear structure (neutron skin, nuclear shell structure) for neutron-excess Na isotopes. T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn

  9. Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

    NASA Astrophysics Data System (ADS)

    Amini, M.; Holmden, C. E.; Francois, R. H.

    2009-12-01

    In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being

  10. Exchange-diffusion reactions in HfSiON during annealing studied by Rutherford backscattering spectrometry, nuclear reaction analysis and narrow resonant nuclear reaction profiling

    NASA Astrophysics Data System (ADS)

    Miotti, L.; Bastos, K. P.; Soares, G. V.; Driemeier, C.; Pezzi, R. P.; Morais, J.; Baumvol, I. J. R.; Rotondaro, A. L. P.; Visokay, M. R.; Chambers, J. J.; Quevedo-Lopez, M.; Colombo, L.

    2004-11-01

    HfSiON films deposited on Si (001) by reactive sputtering were submitted to rapid thermal annealing at 1000°C in vacuum, N2 and O2 atmospheres. The stability of the dielectric was evaluated by measuring the atomic transport and exchange of the chemical species, using Rutherford backscattering spectrometry, nuclear reaction analysis and narrow resonant nuclear reaction profiling. Annealing in O2 ambient reduced the N concentration mainly from near-surface regions where oxygen was incorporated in comparable amounts. Vacuum annealing, on the other hand, induced N loss preferentially from the Si/dielectric interface and O loss preferentially from near-surface regions. The results are explained in terms of exchange-diffusion reactions occurring in the HfSiON.

  11. Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Benzylic Ethers with Isotopically-Labeled Grignard Reagents

    PubMed Central

    2015-01-01

    In this manuscript we highlight the potential of stereospecific nickel-catalyzed cross-coupling reactions for applications in the pharmaceutical industry. Using an inexpensive and sustainable nickel catalyst, we report a gram-scale Kumada cross-coupling reaction. Reactions are highly stereospecific and proceed with inversion at the benzylic position. We also expand the scope of our reaction to incorporate isotopically labeled substituents. PMID:27458328

  12. Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

    PubMed

    Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

    2016-01-01

    Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

  13. Radiometric analysis of oxidative reactions in aromatization by placental microsomes. Presence of differential isotope effects.

    PubMed

    Miyairi, S; Fishman, J

    1985-01-10

    In order to study the initial as well as the final steps in the aromatization of androgens to estrogens, high-specific activity [19-C3H3]androstenedione and testosterone were synthesized. Incubations of [19-C3H3]androstenedione with human placental microsomes resulted in the generation of [3H]water, as a result of the dual hydroxylation at C-19, and [3H]formic acid reflecting final aromatization. After an initial lag in the production of [3H]formic acid, the two radiolabeled products were formed linearly with time at a ratio of 2 to 1 under subsaturating conditions and 2.2 to 1 when saturating levels of substrate were present. Incubation of a mixture of [19-C3H3]- and [4-14C]androstenedione with human placental microsomes yielded 19-hydroxy- and 19-oxoandrostenedione, respectively, products of one and two hydroxylations at C-19. The isotope ratios of these derivatives revealed the presence of a tritium isotope effect in the first but not in the second hydroxylation at that site. When [19-C3H2]- and [4-14C]19-hydroxyandrostenedione were used as the substrate, the isotope ratio of the isolated 19-oxoandrostenedione showed no evidence of any isotope effect in its formation. Thus, the second hydroxylation at C-19 exhibits no isotope effect irrespective of whether androstenedione or 19-hydroxyandrostenedione are the substrates, and therefore, a concerted process and catalytic commitment are not responsible for the difference in isotope effects between the first and second C-19 hydroxylation by the placental aromatase complex. Radiometric kinetic analysis employing [19-C3H3]- and [1 beta,2 beta-3H]androstenedione as the comparative substrates provided evidence that the isotope effect is exerted solely through the Vmax component of the reaction. The distinction between the successive hydroxylations at C-19 in the aromatization sequence suggests, but does not prove, that different mechanisms, and hence different catalytic sites, may be involved in these steps.

  14. Combining stable isotope and eddy covariance measurements to investigate carbon exchanges between the atmosphere and a tallgrass prairie

    NASA Astrophysics Data System (ADS)

    Lai, C.; Schauer, A.; Owensby, C.; Ham, J.; Ehleringer, J.

    2002-12-01

    Stable isotope ratios of various ecosystem components were measured in a C4-dominated tallgrass prairie with co-existing eddy covariance system near Manhattan, Kansas. The carbon and oxygen isotope compositions of nighttime atmospheric CO2 were measured weekly since early spring of 2002. In May and July, δ18O of water vapor, leaf and stem water of three major species were measured every 3-4 hours for 2-3 consecutive days. The δ18O of precipitation and soil water, δ13C of whole plant, litter and soil organic matter were also measured during these intensive field campaigns. Preliminary results from stable isotope analyses revealed apparent diurnal cycles in the δ18O of leaf water (δ18Oleaf). The Craig-Gordon model was shown capable of predicting the mean δ18Oleaf of dominant species. The carbon isotope ratios of ecosystem respiration vary by nearly 10 per mil for the 2002 growing season, reflecting the seasonality of C3-C4 dominance. Prior to our July experiment, the region experienced a severe drought. The eddy covariance measurements indicate a substantial mid-day decline in the photosynthetic uptake presumably due to high air temperature and vapor pressure deficit in this period. Details on using stable isotope and flux measurements to partition net ecosystem exchange into photosynthetic and respiratory fluxes are discussed for this grassland ecosystem.

  15. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    NASA Technical Reports Server (NTRS)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  16. Incorporation of monomethylethanolamine into phosphatidylcholine by way of an exchange reaction followed by methylation

    SciTech Connect

    Moore, T.S. Jr. )

    1989-04-01

    Recent evidence by Datko and Mudd indicates that phosphatidylcholine (PC) may be synthesized by methylation of phosphatidylmonomethyl-ethanolamine (PMME), but perhaps not by utilization of phosphatidylethanolamine (PE) as a source of PMME. They provided evidence that a CDP derivative of monomethylethanolamine (MME) might be the source of the headgroup. Another possibility is incorporation of MME by an exchange reaction. We tested this by incubating MME with ER from castor bean endosperm and radiolabeled S- adenosylmethionine under conditions which would allow incorporation of the headgroup and methylation to PC. Under these conditions the reaction proceeded, with radiolabel appearing in both PC and phosphatidyldimethylethanolamine. Neither ethanolamine nor L-serine, both of which are known to undergo exchange reactions, yielded PC under the same conditions.

  17. Competition between charge exchange and chemical reaction - The D2/+/ + H system

    NASA Technical Reports Server (NTRS)

    Preston, R. K.; Cross, R. J., Jr.

    1973-01-01

    Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

  18. Advancing the Theory of Nuclear Reactions with Rare Isotopes: From the Laboratory to the Cosmos

    SciTech Connect

    Elster, Charlotte

    2015-06-01

    The mission of the TORUS Topical Collaboration is to develop new methods that will advance nuclear reaction theory for unstable isotopes by using three-body techniques to improve direct-reaction calculations, and, by using a new partial-fusion theory, to integrate descriptions of direct and compound-nucleus reactions. Ohio University concentrates its efforts on the first part of the mission. Since direct measurements are often not feasible, indirect methods, e.g. (d,p) reactions, should be used. Those (d,p) reactions may be viewed as three-body reactions and described with Faddeev techniques. Faddeev equations in momentum space have a long tradition of utilizing separable interactions in order to arrive at sets of coupled integral equations in one variable. While there exist several separable representations for the nucleon-nucleon interaction, the optical potential between a neutron (proton) and a nucleus is not readily available in separable form. For this reason we first embarked in introducing a separable representation for complex phenomenological optical potentials of Woods-Saxon type.

  19. Simple (17) O NMR method for studying electron self-exchange reaction between UO2 (2+) and U(4+) aqua ions in acidic solution.

    PubMed

    Bányai, István; Farkas, Ildikó; Tóth, Imre

    2016-06-01

    (17) O NMR spectroscopy is proven to be suitable and convenient method for studying the electron exchange by following the decrease of (17) O-enrichment in U(17) OO(2+) ion in the presence of U(4+) ion in aqueous solution. The reactions have been performed at room temperature using I = 5 M ClO4 (-) ionic medium in acidic solutions in order to determine the kinetics of electron exchange between the U(4+) and UO2 (2+) aqua ions. The rate equation is given as R = a[H(+) ](-2)  + R', where R' is an acid independent parallel path. R' depends on the concentration of the uranium species according to the following empirical rate equation: R' = k1 [UO(2 +) ](1/2) [U(4 +) ](1/2)  + k2 [UO(2 +) ](3/2) [U(4 +) ](1/2) . The mechanism of the inverse H(+) concentration-dependent path is interpreted as equilibrium formation of reactive UO2 (+) species from UO2 (2+) and U(4+) aqua ions and its electron exchange with UO2 (2+) . The determined rate constant of this reaction path is in agreement with the rate constant of UO2 (2+) -UO2 (+) , one electron exchange step calculated by Marcus theory, match the range given experimentally of it in an early study. Our value lies in the same order of magnitude as the recently calculated ones by quantum chemical methods. The acid independent part is attributed to the formation of less hydrolyzed U(V) species, i.e. UO(3+) , which loses enrichment mainly by electron exchange with UO2 (2+) ions. One can also conclude that (17) O NMR spectroscopy, or in general NMR spectroscopy with careful kinetic analysis, is a powerful tool for studying isotope exchange reactions without the use of sophisticated separation processes. Copyright © 2015 John Wiley & Sons, Ltd.

  20. Calculation of vibronic couplings for phenoxyl/phenol and benzyl/toluene self-exchange reactions: implications for proton-coupled electron transfer mechanisms.

    PubMed

    Skone, Jonathan H; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2006-12-27

    The vibronic couplings for the phenoxyl/phenol and the benzyl/toluene self-exchange reactions are calculated with a semiclassical approach, in which all electrons and the transferring hydrogen nucleus are treated quantum mechanically. In this formulation, the vibronic coupling is the Hamiltonian matrix element between the reactant and product mixed electronic-proton vibrational wavefunctions. The magnitude of the vibronic coupling and its dependence on the proton donor-acceptor distance can significantly impact the rates and kinetic isotope effects, as well as the temperature dependences, of proton-coupled electron transfer reactions. Both of these self-exchange reactions are vibronically nonadiabatic with respect to a solvent environment at room temperature, but the proton tunneling is electronically nonadiabatic for the phenoxyl/phenol reaction and electronically adiabatic for the benzyl/toluene reaction. For the phenoxyl/phenol system, the electrons are unable to rearrange fast enough to follow the proton motion on the electronically adiabatic ground state, and the excited electronic state is involved in the reaction. For the benzyl/toluene system, the electrons can respond virtually instantaneously to the proton motion, and the proton moves on the electronically adiabatic ground state. For both systems, the vibronic coupling decreases exponentially with the proton donor-acceptor distance for the range of distances studied. When the transferring hydrogen is replaced with deuterium, the magnitude of the vibronic coupling decreases and the exponential decay with distance becomes faster. Previous studies designated the phenoxyl/phenol reaction as proton-coupled electron transfer and the benzyl/toluene reaction as hydrogen atom transfer. In addition to providing insights into the fundamental physical differences between these two types of reactions, the present analysis provides a new diagnostic for differentiating between the conventionally defined hydrogen atom

  1. Isotope Effects and Mechanism of the Asymmetric BOROX Brønsted Acid Catalyzed Aziridination Reaction

    PubMed Central

    Vetticatt, Mathew J.; Desai, Aman A.; Wulff, William D.

    2013-01-01

    The mechanism of the chiral VANOL-BOROX Brønsted acid catalyzed aziridination reaction of imines and ethyldiazoacetate has been studied using a combination of experimental kinetic isotope effects and theoretical calculations. A stepwise mechanism where reversible formation of a diazonium ion intermediate precedes rate-limiting ring-closure to form the cis-aziridine is implicated. A revised model for the origin of enantio- and diastereoselectivity is proposed based on relative energies of the ring closing transition structures. PMID:23687986

  2. Mechanisms of Oxygen Isotopic Exchange and Isotopic Evolution of 18O/16O-Depleted Periclase Zone Marbles in the Alta Aureole, Utah, USA--Insights From ion Microprobe Analysis of Calcite

    NASA Astrophysics Data System (ADS)

    Bowman, J. R.; Valley, J. W.; Kita, N.

    2007-12-01

    .45 permil, two SD) across the entire gradient in δ18O, not just within the relatively homogeneous interiors of the two layers. Diffusion calculations indicate that conservative time scales required for isotopic homogenization of calcite grains by volume diffusion, 2000 to 62,000 years at 575-600°C, exceed significantly the timescale (approx. 1250 yrs) estimated for the prograde development of the δ18O gradient at the boundary between these two marble layers. The ion microprobe data and these diffusion calculations suggest instead that surface reaction mechanisms (e.g., dissolution-reprecipitation) accompanying recrystallization are responsible for the observed oxygen isotope homogeneity of these calcite grains. The ion microprobe data are consistent with, but do not require that metamorphic calcite forms in oxygen isotope exchange equilibrium with infiltrating fluid during prograde reaction and recrystallization. However the presence of retrograde calcite-dolomite temperatures (450- 550°C) recorded in calcite from the periclase zone suggests that both Mg exchange and oxygen isotope homogenization accompanied recrystallization during the early stages of retrograde cooling.

  3. Hydraulic controls of in-stream gravel bar hyporheic exchange and reactions

    NASA Astrophysics Data System (ADS)

    Trauth, Nico; Schmidt, Christian; Vieweg, Michael; Oswald, Sascha E.; Fleckenstein, Jan H.

    2015-04-01

    Hyporheic exchange transports solutes into the subsurface where they can undergo biogeochemical transformations, affecting fluvial water quality and ecology. A three-dimensional numerical model of a natural in-stream gravel bar (20 m × 6 m) is presented. Multiple steady state streamflow is simulated with a computational fluid dynamics code that is sequentially coupled to a reactive transport groundwater model via the hydraulic head distribution at the streambed. Ambient groundwater flow is considered by scenarios of neutral, gaining, and losing conditions. The transformation of oxygen, nitrate, and dissolved organic carbon by aerobic respiration and denitrification in the hyporheic zone are modeled, as is the denitrification of groundwater-borne nitrate when mixed with stream-sourced carbon. In contrast to fully submerged structures, hyporheic exchange flux decreases with increasing stream discharge, due to decreasing hydraulic head gradients across the partially submerged structure. Hyporheic residence time distributions are skewed in the log-space with medians of up to 8 h and shift to symmetric distributions with increasing level of submergence. Solute turnover is mainly controlled by residence times and the extent of the hyporheic exchange flow, which defines the potential reaction area. Although streamflow is the primary driver of hyporheic exchange, its impact on hyporheic exchange flux, residence times, and solute turnover is small, as these quantities exponentially decrease under losing and gaining conditions. Hence, highest reaction potential exists under neutral conditions, when the capacity for denitrification in the partially submerged structure can be orders of magnitude higher than in fully submerged structures.

  4. Alkoxy/halogen exchange reaction of molybdenum complexes containing phosphite with boron trihalides

    SciTech Connect

    Nakazawa, H.; Ohta, M.; Yoneda, H.

    1988-03-23

    The ability of boron trihalides, BX/sub 3/, to extract an OR group or halogens on a carbon atom has been applied to the preparation of transition-metal carbyne complexes from Fischer-type carbyne complexes and to the halogen exchange of transition-metal perfluoroalkyl carbonyl complexes. The specific reaction studied was that of fac-(Mo(bpy)-(CO)/sub 3/(P(OR)/sub 3/)) where bpy = 2,2'-bipyridine with BF/sub 3//center dot/OEt/sub 2/ and BCl/sub 3/. Reaction with the former resulted in replacement of one OR group by F, while in the latter reaction, two OR groups were replaced with two Cl atoms. In the first reaction, geometrical retention around the Mo atom was retained; but in the latter reaction, a change in geometry around the Mo atom was noted. 9 refs.

  5. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

    NASA Astrophysics Data System (ADS)

    Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

    2016-12-01

    Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

  6. Isotope geochemistry reveals ontogeny of dispersal and exchange between main-river and tributary habitats in smallmouth bass Micropterus dolomieu.

    PubMed

    Humston, R; Doss, S S; Wass, C; Hollenbeck, C; Thorrold, S R; Smith, S; Bataille, C P

    2017-02-01

    Radiogenic strontium isotope ratios ((87) Sr:(86) Sr) in otoliths were compared with isotope ratios predicted from models and observed in water sampling to reconstruct the movement histories of smallmouth bass Micropterus dolomieu between main-river and adjacent tributary habitats. A mechanistic model incorporating isotope geochemistry, weathering processes and basin accumulation reasonably predicted observed river (87) Sr:(86) Sr across the study area and provided the foundations for experimental design and inferring fish provenance. Exchange between rivers occurred frequently, with nearly half (48%) of the 209 individuals displaying changes in otolith (87) Sr:(86) Sr reflecting movement between isotopically distinct rivers. The majority of between-river movements occurred in the first year and often within the first few months of life. Although more individuals were observed moving from the main river into tributaries, this pattern did not necessarily reflect asymmetry in exchange. Several individuals made multiple movements between rivers over their lifetimes; no patterns were found, however, that suggest seasonal or migratory movement. The main-river sport fishery is strongly supported by recruitment from tributary spawning, as 26% of stock size individuals in the main river were spawned in tributaries. The prevailing pattern of early juvenile dispersal documented in this study has not been observed previously for this species and suggests that the process of establishing seasonal home-range areas occurs up to 2 years earlier than originally hypothesized. Extensive exchange between rivers would have substantial implications for management of M. dolomieu populations in river-tributary networks. © 2016 The Fisheries Society of the British Isles.

  7. Advancing the Theory of Nuclear Reactions with Rare Isotopes. From the Laboratory to the Cosmos

    SciTech Connect

    Nunes, Filomena

    2015-06-01

    The mission of the Topical Collaboration on the Theory of Reactions for Unstable iSotopes (TORUS) was to develop new methods to advance nuclear reaction theory for unstable isotopes—particularly the (d,p) reaction in which a deuteron, composed of a proton and a neutron, transfers its neutron to an unstable nucleus. After benchmarking the state-of-the-art theories, the TORUS collaboration found that there were no exact methods to study (d,p) reactions involving heavy targets; the difficulty arising from the long-range nature of the well known, yet subtle, Coulomb force. To overcome this challenge, the TORUS collaboration developed a new theory where the complexity of treating the long-range Coulomb interaction is shifted to the calculation of so-called form-factors. An efficient implementation for the computation of these form factors was a major achievement of the TORUS collaboration. All the new machinery developed are essential ingredients to analyse (d,p) reactions involving heavy nuclei relevant for astrophysics, energy production, and stockpile stewardship.

  8. The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang; Romanov, Douchko

    2016-12-01

    The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered. For drip times for Tdrip < 0.2τ, where τ is the precipitation time, we find for the change of the δ13C and δ18O values, respectively, after the time Tdrip ΔDIC(Tdrip) = ((λ + ɛ)Ceq/C0 - ɛ) Tdrip/τ + ((δeqatm - δ0) Tdrip/τinatm) + (δeqwater - δ0 - ɛw Tdrip/Tev) Tdrip/Twater The first term on the right hand side is the contribution from precipitation of calcite, the second stems from isotope exchange with the CO2 of the cave atmosphere, and the third results from isotope exchange between oxygen in the DIC and the oxygen in the water. λ, ε are kinetic parameters, τ is the time scale of precipitation, (δeqatm -δ0) and (δeqwater -δ0) are the differences between the corresponding initial δ-value δ0 and the value δeqatm,water if DIC were in isotope equilibrium with the atmosphere or in the case of oxygen with the water, respectively. τinatm and τwater are the time scales of approach to isotope equilibrium by the exchange reactions. Ceq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. Tev is the time needed for complete evaporation of the water layer. ε

  9. Isotopic resolution of fission fragments from 238U+12C transfer and fusion reactions

    NASA Astrophysics Data System (ADS)

    Caamaño, M.; Rejmund, F.; Derkx, X.; Schmidt, K.-H.; Andouin, L.; Bacri, C.-O.; Barreau, G.; Benlliure, J.; Casarejos, E.; Fernández-Domínguez, B.; Gaudefroy, L.; Golabek, C.; Jurado, B.; Lemasson, A.; Navin, A.; Rejmund, M.; Roger, T.; Shrivastava, A.; Schmitt, C.; Taieb, J.

    2009-10-01

    Recent results from an experiment at GANIL, performed to investigate the main properties of fission-fragment yields and energy distributions in different fissioning nuclei as a function of the excitation energy, in a neutron-rich region of actinides, are presented. Transfer reactions in inverse kinematics between a 238U beam and a 12C target produced different actinides, within a range of excitation energy below 30 MeV. These fissioning nuclei are identified by detecting the target-like recoil, and their kinetic and excitation energy are determined from the reconstruction of the transfer reaction. The large-acceptance spectrometer VAMOS was used to identify the mass, atomic number and charge state of the fission fragments in flight. As a result, the characteristics of the fission-fragment isotopic distributions of a variety of neutron-rich actinides are observed for the first time over the complete range of fission fragments.

  10. Velocity map imaging study of the reaction dynamics of the H + CH4 → H2 + CH3 reaction: the isotope effects.

    PubMed

    Pan, Huilin; Yang, Jiayue; Shuai, Quan; Zhang, Dong; Zhang, Weiqing; Wu, Guorong; Dai, Dongxu; Jiang, Bo; Zhang, Donghui; Yang, Xueming

    2014-04-03

    Following our previous study on the H + CD4 → HD + CD3 reaction [ Proc. Natl. Acad. Sci. U.S.A. 2010 , 107 , 12782 ], the reaction of H + CH4 → H2 + CH3 at collision energies ranging from 0.72 to 1.99 eV is studied using crossed-beam and time-sliced velocity map ion imaging techniques. The product angular and translational energy distributions at four different collision energies were derived from the measured images. The excitation function was also measured from these images together with a careful calibration of the H atom beam intensities at different collision energies. All of these results are compared with those of the H + CD4 reaction to investigate the isotope effects. The isotope effects are all observed in the product angular distributions, the translational energy distributions, and the excitation function and further confirm the reaction mechanism proposed in the previous study on the H + CD4 reaction.

  11. Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.; Sen, A. D.

    1995-01-01

    Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

  12. Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.; Sen, A. D.

    1995-01-01

    Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

  13. Secondary H/T and D/T isotope effects in enzymatic enolization reactions. Coupled motion and tunneling in the triosephosphate isomerase reaction.

    PubMed

    Alston, W C; Kanska, M; Murray, C J

    1996-10-01

    Secondary kH/kT kinetic isotope effects in H2O and kH/kT or kD/kT isotope effects in D2O have been measured for the triosephosphate isomerase-catalyzed conversion of dihydroxyacetone 3-phosphate (DHAP) to D-glyceraldehyde 3-phosphate. The proton transfer steps are made rate-limiting using [1(R)-2H]-labeled substrate in D2O to slow the chemical steps, relative to product release. After a small correction for the beta-equilibrium isotope effect for dehydration of DHAP, the H/T kinetic isotope effect kH/kT = 1.27 +/- 0.03 for [1(R)-2H,(S)-3H]-labeled substrate in D2O is subtantially larger than the equilibrium isotope effect for enolization of DHAP, KH/KT = 1.12. The H/T isotope effect is related to the D/T isotope effect with a Swain-Schaad exponent y = 4.4 +/- 1.3. These results are consistent with coupled motion of the C-1 primary and secondary hydrogens of DHAP and tunneling. Large secondary kinetic isotope effects are a general feature of enzymatic enolization reactions while nonenzymatic enolization reactions show secondary kinetic isotope effects that are substantially smaller than equilibrium effects [Alston, W. A., II, Haley, K., Kanski, R., Murray, C.J., & Pranata, J. (1996) J. Am. Chem Soc., 118, 6562-6569]. Possible origins for these differences in transition state structure are discussed.

  14. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

    PubMed Central

    2015-01-01

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  15. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    PubMed

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.

  16. Scaling hyporheic exchange and its influence on biogeochemical reactions in aquatic ecosystems

    USGS Publications Warehouse

    O'Connor, B.L.; Harvey, J.W.

    2008-01-01

    Hyporheic exchange and biogeochemical reactions are difficult to quantify because of the range in fluid-flow and sediment conditions inherent to streams, wetlands, and nearshore marine ecosystems. Field measurements of biogeochemical reactions in aquatic systems are impeded by the difficulty of measuring hyporheic flow simultaneously with chemical gradients in sediments. Simplified models of hyporheic exchange have been developed using Darcy's law generated by flow and bed topography at the sediment-water interface. However, many modes of transport are potentially involved (molecular diffusion, bioturbation, advection, shear, bed mobility, and turbulence) with even simple models being difficult to apply in complex natural systems characterized by variable sediment sizes and irregular bed geometries. In this study, we synthesize information from published hyporheic exchange investigations to develop a scaling relationship for estimating mass transfer in near-surface sediments across a range in fluid-flow and sediment conditions. Net hyporheic exchange was quantified using an effective diffusion coefficient (De) that integrates all of the various transport processes that occur simultaneously in sediments, and dimensional analysis was used to scale De to shear stress velocity, roughness height, and permeability that describe fluid-flow and sediment characteristics. We demonstrated the value of the derived scaling relationship by using it to quantify dissolved oxygen (DO) uptake rates on the basis of DO profiles in sediments and compared them to independent flux measurements. The results support a broad application of the De scaling relationship for quantifying coupled hyporheic exchange and biogeochemical reaction rates in streams and other aquatic ecosystems characterized by complex fluid-flow and sediment conditions.

  17. Neutrino nuclear responses for double beta decays and astro neutrinos by charge exchange reactions

    NASA Astrophysics Data System (ADS)

    Ejiri, Hiroyasu

    2014-09-01

    Neutrino nuclear responses are crucial for neutrino studies in nuclei. Charge exchange reactions (CER) are shown to be used to study charged current neutrino nuclear responses associated with double beta decays(DBD)and astro neutrino interactions. CERs to be used are high energy-resolution (He3 ,t) reactions at RCNP, photonuclear reactions via IAR at NewSUBARU and muon capture reactions at MUSIC RCNP and MLF J-PARC. The Gamow Teller (GT) strengths studied by CERs reproduce the observed 2 neutrino DBD matrix elements. The GT and spin dipole (SD) matrix elements are found to be reduced much due to the nucleon spin isospin correlations and the non-nucleonic (delta isobar) nuclear medium effects. Impacts of the reductions on the DBD matrix elements and astro neutrino interactions are discussed.

  18. Nuclear fragmentation and charge-exchange reactions induced by pions in the Δ -resonance region

    NASA Astrophysics Data System (ADS)

    Feng, Zhao-Qing

    2016-11-01

    The dynamics of the nuclear fragmentations and the charge exchange reactions in pion-nucleus collisions near the Δ (1232) resonance energies has been investigated within the Lanzhou quantum molecular dynamics transport model. An isospin-, momentum-, and density-dependent pion-nucleon potential is implemented in the model, which influences the pion dynamics, in particular the kinetic energy spectra, but weakly impacts the fragmentation mechanism. The absorption process in pion-nucleon collisions to form the Δ (1232) resonance dominates the heating mechanism of the target nucleus. The excitation energy transferred to the target nucleus increases with the pion kinetic energy and is similar for both π-- and π+-induced reactions. The magnitude of fragmentation of the target nucleus weakly depends on the pion energy. The isospin ratio in the pion double-charge exchange is influenced by the isospin ingredient of target nucleus.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

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

    2016-08-01

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

  1. Isotope Exchange and Fractionation Corrections for Extraction of Tritiated Water in Silica Gel by Freeze-Drying Techniques

    SciTech Connect

    Guthrie, E B; Shen, N C; Bandong, B B

    2001-09-24

    A concentration correction curve was established for measuring the activity concentration of airborne tritiated water collected with dried silica gel and extracted by the LLNL Environmental Monitoring Radiological Laboratory freeze-dry technique. A tracer study using standard tritiated water with silica gel showed that the concentration of tritium in the extracted water is lower than that in the adsorbed water by a fraction proportional to the amount of adsorbed water. The observed decrease in tritium concentration in the extracted water can be accounted for by dilution due to isotopic exchange with both non-tritiated water and hydroxyl groups within the silica gel matrix. For the range of 8-35% adsorbed water, which is typical of samples collected in LLNL monitoring stations, the derived exchangeable water in the silica gel material under investigation was (5.12 {+-} 0.08)%. The contribution of the H{sub 2}O/HTO vapor pressure effect using published empirical data in the literature was also considered in calculating the degree of isotopic exchange.

  2. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  3. Single-charge-exchange reactions and the neutron density at the surface of the nucleus

    NASA Astrophysics Data System (ADS)

    Loc, Bui Minh; Auerbach, Naftali; Khoa, Dao T.

    2017-07-01

    In this paper, we study the charge-exchange reaction to the isobaric analog state using two types of transition densities. One transition density is equal to the difference of the total neutron density minus the total proton density and the other one is the density of the excess neutrons only. We show that for projectiles that do not probe the interior of the nucleus but mostly the surface of this nucleus, distinct differences in the cross section arise when two types of transition densities are employed. We demonstrate this by considering the (3He,t ) reaction.

  4. Theoretical study of the proton exchange reaction: HCNH ++HCN↔HNC+HCNH +

    NASA Astrophysics Data System (ADS)

    Pichierri, Fabio

    2002-02-01

    The HCNH ++HCN↔HNC+HCNH + proton exchange reaction has been investigated by means of quantum chemical calculations with the RHF, MP2, CCSD(T), and B3LYP methods. The overall process corresponds to a proton-assisted HCN↔HNC isomerization whose activation barrier is about 10 kcal/mol lower than that of the corresponding 1,2-hydrogen shift. Furthermore, we found that the HNC+HCNH + reverse reaction represents a possible low-energy channel for the depletion of HNC in molecular clouds. This mechanism might be involved within the regulation of the HCN/HNC abundance ratio in the interstellar space.

  5. Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

    PubMed Central

    2014-01-01

    We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

  6. Carbon nanotube inner phase chemistry: the Cl- exchange SN2 reaction.

    PubMed

    Halls, Mathew D; Raghavachari, Krishnan

    2005-10-01

    Density functional calculations have been carried out to investigate the nature of the inner phase of a (6,6) carbon nanotube, using the Cl(-) exchange S(N)2 reaction as an indicator. Inside the carbon nanotube the classical barrier height increases by 6.6 kcal/mol due to the nanotube polarizability. This suggests that the inner phase environment can be considered a form of solid solvation, offering the possibility of obtaining altered guest properties and reactivity through dielectric stabilization.

  7. Sn cation valency dependence in cation exchange reactions involving Cu(2-x)Se nanocrystals.

    PubMed

    De Trizio, Luca; Li, Hongbo; Casu, Alberto; Genovese, Alessandro; Sathya, Ayyappan; Messina, Gabriele C; Manna, Liberato

    2014-11-19

    We studied cation exchange reactions in colloidal Cu(2-x)Se nanocrystals (NCs) involving the replacement of Cu(+) cations with either Sn(2+) or Sn(4+) cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu(2-x)Se NCs remains cubic regardless of the degree of copper deficiency (that is, "x") in the NC lattice. Also, Sn(4+) ions are comparable in size to the Cu(+) ions, while Sn(2+) ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn(4+) cations are used, alloyed Cu(2-4y)Sn(y)Se NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu(+) cations with Sn(4+) cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn(2+) cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu(2-x)Se/SnSe heterostructures, with no Cu-Sn-Se alloys.

  8. Exchange Reactions of Organotin and Organosilicon Compounds with Mild Fluorinating Agents

    DTIC Science & Technology

    1992-03-01

    AD-A251 352 CHEMICfIL RESEARCH, DEVELOPMENT i ENGINEERING CENTER CRDEC- EXCHANGE REACTIONS OF ORGANOTIN AND ORGANOSILICON COMPOUNDS WITH MILD...of Organotin and PR- 1C162622A554 Organosilicon Compounds with Mild Fluorinating Agents 6.AUTHOR(S) Roseman, David I., and Muller, August J. 7...methylphosphonic difluoride, boron trifluoride etherate, and perfluoroisobutene all react with both organosilicon and organotin . alkoxides to give

  9. Modeling dune-induced hyporheic exchange and nutrient reactions in stream sediments

    NASA Astrophysics Data System (ADS)

    Bardini, L.; Boano, F.; Cardenas, M. B.; Revelli, R.; Ridolfi, L.

    2012-04-01

    The exchange of water across the streambed plays an important role in the ecology of fluvial environments, since it assures the connections of surface and subsurface waters, which have very different peculiarities. Water-borne chemicals are also involved in the process: they enter the sediments with the water and they are transformed into oxidized or reduced substances by biogeochemical reactions, mediated by the hyporheic microbiota. In particular, organic substances can be used as electron donors in a series of redox reactions, with different electron acceptors, e.g., oxygen and nitrate. Nitrification and other secondary reactions also occur as soon as water enters the streambed. These pore-scale transformations concur to affect subsurface solute concentrations and, consequently, the chemistry of upwelling water and the quality of the stream environment. The exchange with the hyporheic zone occurs in response to variations in bed topography, with a very wide range of spatial and temporal scales. For instance, small-scale exchanges are mainly induced by river bed forms, like ripples and dunes, while large-scale exchanges depend on larger geomorphological features. In this work we focus on small-scale exchange induced by the presence of dunes on the streambed, investigating the interplay of hydrological and biogeochemical processes and their effects on solute spatial distribution in the sediments. We numerically simulate the turbulent water flow and the pressure distribution on the streambed and then we evaluate the coupled flow field and biogeochemical reactions in the hyporheic zone in steady-state conditions. Four representative reactive compounds are taken into account: dissolved organic carbon (DOC), oxygen (O2), nitrate (NO3-) and ammonium (NH4+). Sensitivity analyses are also performed to analyze the influence of hydrological and chemical properties of the system on solute reaction rates. The results demonstrate that the stream water quality can strongly

  10. Cumulative reaction probabilities and transition state properties: a study of the F + H2 reaction and its deuterated isotopic variants.

    PubMed

    Aoiz, F J; Herrero, V J; Sáez Rábanos, V

    2008-07-14

    A comparative quantum mechanical (QM) and quasiclassical trajectory (QCT) study of the cumulative reaction probabilities (CRPs) is presented in this work for the F + H(2) reaction and its isotopic variants for low values of the total angular momentum J. The agreement between the two sets of calculations is very good with the exception of some features whose origin is genuinely QM. The agreement also extends to the CRP resolved in the helicity quantum number k. The most remarkable feature is the steplike structure, which becomes clearly distinct when the CRPs are resolved in odd and even rotational states j. The analysis of these steps shows that each successive increment is due to the opening of the consecutive rovibrational states of the H(2) or D(2) molecule, which, in this case, nearly coincide with those of the transition state. Moreover, the height of each step reflects the number of helicity states compatible with a given J and j values, thus indicating that the various helicity states for a specific j have basically the same contribution to the CRPs at a given total energy. As a consequence, the dependence with k of the reactivity is practically negligible, suggesting very small steric restrictions for any possible orientation of the reactants. This behavior is in marked contrast to that found in the D + H(2) reaction, wherein a strong k dependence was found in the threshold and magnitude of the CRP. The advantages of a combined QCT and QM approaches to the study of CRPs are emphasized in this work.

  11. Kinetic Isotope Effects and Stereochemical Studies on a Ribonuclease Model: Hydrolysis Reactions of Uridine 3'-Nitrophenyl Phosphate.

    PubMed

    Hengge; Bruzik; Tobin; Cleland; Tsai

    2000-06-01

    The reactions of a ribonuclease model substrate, the compound uridine-3'-p-nitrophenyl phosphate, have been examined using heavy-atom isotope effects and stereochemical analysis. The cyclization of this compound is subject to catalysis by general base (by imidazole buffer), specific base (by carbonate buffer), and by acid. All three reactions proceed by the same mechanistic sequence, via cyclization to cUMP, which is stable under basic conditions but which is rapidly hydrolyzed to a mixture of 2'- and 3'-UMP under acid conditions. The isotope effects indicate that the specific base-catalyzed reaction exhibits an earlier transition state with respect to bond cleavage to the leaving group compared to the general base-catalyzed reaction. Stereochemical analysis indicates that both of the base-catalyzed reactions proceed with the same stereochemical outcome. It is concluded that the difference in the nucleophile in the two base-catalyzed reactions results in a difference in the transition state structure but both reactions are most likely concerted, with no phosphorane intermediate. The (15)N isotope effects were also measured for the reaction of the substrate with ribonuclease A. The results indicate that considerably less negative charge develops on the leaving group in the transition state than for the general base-catalyzed reaction in solution. Copyright 2000 Academic Press.

  12. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  13. Analysis of dynamical behavior of reactions associated with 118,120,122Xe* isotopes

    NASA Astrophysics Data System (ADS)

    Grover, Neha; Sharma, Ishita; Kaur, Gurvinder; Sharma, Manoj K.

    2017-03-01

    In reference to recent experiment, the dynamical aspects of reactions forming even mass isotopes of 118,120,122Xe* nuclei are examined using the collective clusterization approach and the ℓ-summed Wong model. The role of excitation energy (or temperature), deformations, orientations and angular momentum etc. has been investigated for the 28Si + 90,92,94Zr reactions. In order to account for the role of deformations, the evaporation residue (ER) cross sections of 122Xe* nucleus have been studied in reference to the available experimental data by using spherical as well as deformed fragmentation approach. We have used optimum and compact orientations respectively for β2 alone and for β4 included, which inturn provide nice agreement with the available experimental cross-sections. Also, the effect of isospin (N/Z ratio) of decay fragments has been explored in view of the fragmentation analysis and preformation probability of 118,120,122Xe* nuclei. Additionally, the role of projectile nucleus is also explored by studying the fragmentation path of 118Xe* nucleus in comparison to 123Ba* system. Further, the ER cross-sections have been predicted for various even mass isotopes of 116,118,120,124Xe. In addition to this, to explore the fusion characteristics of 28Si + 90,92,94Zr reactions, the Wong model as well as the ℓ-summed Wong model has also been employed. Here also, the role of deformation in formation of 122Xe* nucleus has been examined and the calculated cross-sections find decent agreement with the experimental data.

  14. Formation of Po isotopes in the reactions {sup 27}Al + {sup 175}Lu and {sup 31}P + {sup 169}Tm

    SciTech Connect

    Andreev, A.N.; Bogdanov, D.D.; Eremin, A.V.

    1995-05-01

    The excitation functions and the cross sections for the formation of {sup 192-198}Po isotopes in the reactions {sup 27}Al + {sup 175}Lu and {sup 31}P + {sup 169}Tm are measured. A comparison of the results obtained for these reactions with the data on the cross sections for the formation of Po isotopes in the reaction {sup 100}Mo + {sup 92-100}Mo leads to the conclusion that the characteristics of the evaporation channel do not depend on the mass of the bombarding ion up to the complete symmetry in the input channel. It is shown that the experimental data can be adequately described using the statistical approach to the deexcitation of a compound nucleus only under the assumption that the liquid-drop fission barrier is reduced significantly for neutron-deficient Po isotopes. 21 refs., 5 figs., 2 tabs.

  15. Oxygen-isotope exchange and mineral alteration in gabbros of the Lower Layered Series, Kap Edvard Holm Complex, East Greenland

    SciTech Connect

    Fehlhaber, K.; Bird, D.K. )

    1991-08-01

    Multiple intrusions of gabbros, mafic dikes, and syenites in the Kap Edvard Holm Complex gave rise to prolonged circulation of meteoric hydrothermal solutions and extreme isotope exchange and mineral alteration in the 3,600-m-thick Lower Layered Series gabbros. In the Lower Layered Series, {delta}{sup 18}O of plagioclase varies from +0.3{per thousand} to {minus}5.8{per thousand}, and it decreases with an increase in the volume of secondary talc, chlorite, and actinolite. In the same gabbros, pyroxenes have a more restricted range in {delta}{sup 18}O, from 5.0{per thousand} to 3.8{per thousand}, and values of {delta}{sup 18}O{sub pyroxene} are independent of the abundance of secondary minerals, which ranges from 14% to 30%. These relations indicate that large amounts of water continued to flow through the rocks at temperatures of < 500-600C, altering the gabbros to assemblages of talc + chlorite + actinolite {plus minus}epidote {plus minus}albite and causing significant oxygen-isotope exchange in plagioclase, but not in pyroxene. The extensive low-temperature secondary mineralization and {sup 18}O depletion of plagioclase in the Lower Layered Series are associated with the later emplacement of dikes and gabbros and syenites, which created new fracture systems and provided heat sources for hydrothermal fluid circulation. This produced subsolidus mineral alteration and isotope exchange in the Lower Layered Series that are distinct from those in the Skaergaard and Cuillin gabbros of the North Atlantic Tertiary province, but are similar to those observed in some oceanic gabbros.

  16. Submarine and superimposed contact metamorphic oxygen isotopic exchange in an oceanic area, Sawyers Bar area, central Klamath Mountains, California, USA

    SciTech Connect

    Ernst, W.G.; Kolodny, Y.

    1997-02-01

    New bulk-rock oxygen isotope data indicate a complicated history of fluid-rock interactions in the upper few kilometers of a basaltic arc. attending its Mesozoic accretion to the western margin of North America. Folded, multiply recrystallized, weakly metasomatized mafic volcanics and interstratified sediments of the Sawyers Bar terrane, an eastern segment of the western Triassic and Paleozoic belt, were investigated. The following scenario can now be reconstructed: (1) island-arc tholeiites (IATs), ocean-island basalts (OIBs), and distal turbidites were deposited in a subsea environment during Permian and Early Mesozoic time (170-245 Ma). Basaltic rocks underwent low-temperature alteration by seawater; recrystallization occurred at 100-200{degrees}C and < 1 kbar. Alkali exchange and variable Mg-enrichment were accompanied by increases in bulk-rock {delta}{sup 18}O values of the greenstones from 6 to approximately 10{per_thousand}, preceeding initial stages of island-arc formation. (2) Middle Jurassic (165-170 Ma) suturing of the seaward oceanic arc structurally beneath a landward, 227 Ma blueschist terrane resulted in regional deformation and greenschist-facies metamorphism. Pervasive overprinting took place without important chemical or isotopic exchange under conditions of 300-425{degrees}C, 3 {+-} 1 kbar. (3) Granitoid plutons, emplaced during late-Middle Jurassic time (160-165 Ma), heated adjacent wallrocks to {approximately}500-600{degrees}C at pressures of approximately 2-3 kbar; thermal upgrading resulted in devolatilization of isotopically heavy metasediments and in the exchange of high {delta}{sup 18}O fluids with intercalated greenstones. {delta}{sup 18}O values in IAT and OIB metavolcanics increased from 9 to 10{per_thousand} alone axial portions of NS-trending folds to more than 15{per_thousand} where metabasalts are intimately interlayered with the metasediments. 72 refs., 5 figs., 1 tab.

  17. EXFOR basics: A short guide to the nuclear reaction data exchange format

    SciTech Connect

    McLane, V.

    1996-07-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data.

  18. Modification of photosystem I reaction center by the extraction and exchange of chlorophylls and quinones.

    PubMed

    Itoh, S; Iwaki, M; Ikegami, I

    2001-10-30

    The photosystem (PS) I photosynthetic reaction center was modified thorough the selective extraction and exchange of chlorophylls and quinones. Extraction of lyophilized photosystem I complex with diethyl ether depleted more than 90% chlorophyll (Chl) molecules bound to the complex, preserving the photochemical electron transfer activity from the primary electron donor P700 to the acceptor chlorophyll A(0). The treatment extracted all the carotenoids and the secondary acceptor phylloquinone (A(1)), and produced a PS I reaction center that contains nine molecules of Chls including P700 and A(0), and three Fe-S clusters (F(X), F(A) and F(B)). The ether-extracted PS I complex showed fast electron transfer from P700 to A(0) as it is, and to FeS clusters if phylloquinone or an appropriate artificial quinone was reconstituted as A(1). The ether-extracted PS I enabled accurate detection of the primary photoreactions with little disturbance from the absorbance changes of the bulk pigments. The quinone reconstitution created the new reactions between the artificial cofactors and the intrinsic components with altered energy gaps. We review the studies done in the ether-extracted PS I complex including chlorophyll forms of the core moiety of PS I, fluorescence of P700, reaction rate between A(0) and reconstituted A(1), and the fast electron transfer from P700 to A(0). Natural exchange of chlorophyll a to 710-740 nm absorbing chlorophyll d in PS I of the newly found cyanobacteria-like organism Acaryochloris marina was also reviewed. Based on the results of exchange studies in different systems, designs of photosynthetic reaction centers are discussed.

  19. Evolution of the isotope composition of C and O in the DIC in a water film during precipitation of calcite to the surface of a stalagmite in the presence of isotope exchange with the CO2 of the cave atmosphere and evaporation of the water

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang; Romanov, Douchko

    2016-04-01

    In a thin water layer, super saturated with respect to calcite with pH of about 8, where the aqueous CO2 is in equilibrium with the pCO2 of the cave atmosphere, the following processes determine the temporal evolution of the isotope composition of carbon and oxygen in the dissolved inorganic carbon ( DIC). a) Precipitation of calcite driven by super saturation, whereby deposition rates Between the heavy and light isotopes are slightly different. b) Evaporation of water reducing the depth of the water layer and changing the isotope composition of oxygen in the water by Rayleigh-distillation. c) Isotope exchange between the CO2 in the cave atmosphere and the DIC for both carbon and oxygen. d) Isotope exchange between the oxygen in the water molecules and that in the DIC. All these processes can be described by a differential equation, which can be solved numerically. For small times a simple solution can be given. Δ_DIC(T_drip) = [ ( (⪉mbda + ɛ) C_eq/C0 - ɛ ) T_drip/τ + (δ^atm_eq - δ0 ) T_drip/τ^atm + (δ^water_eq-δ_0-ɛ_wT_drip/T_ev) T_drip/τ^water] Δ_DIC(T_drip) is the change of the δ13C and δ18O (given here as small numbers and not in the ‰ notation) after the drip time T_drip. ⪉mbda, ɛ are kinetic parameters of precipitation on the order of 10-2 and τ is the time scale of precipitation, typically about 1000 s. (δ^atm_eq - δ_0) and (δ^water_eq - δ_0) are the differences between the corresponding initial δ-value and that when DIC is in isotope equilibrium with the atmosphere or in the case of oxygen with the water. τ^atm and τ^water, both on the order of 10,000 s, are the time scales of the exchange reactions to approach isotope equilibrium. For carbon the last term (exchange with water) must be deleted. C_eq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. T_ev is the time needed to fully evaporate the water layer and

  20. The Isotope Exchange Method for Measuring Saturated Vapor Pressure and Diffusion coefficients - USSR -

    DTIC Science & Technology

    1960-06-16

    The availability of convenient radioactive isotopes of almost all elements of the periodic table makes this method universally applicable to the practical study of any substance in its condensed state.

  1. Deuteron-induced reactions on Ni isotopes up to 60 MeV

    NASA Astrophysics Data System (ADS)

    Avrigeanu, M.; Šimečková, E.; Fischer, U.; Mrázek, J.; Novak, J.; Štefánik, M.; Costache, C.; Avrigeanu, V.

    2016-07-01

    Background: The high complexity of the deuteron-nucleus interaction from the deuteron weak binding energy of 2.224 MeV is also related to a variety of reactions induced by the deuteron-breakup (BU) nucleons. Thus, specific noncompound processes as BU and direct reactions (DR) make the deuteron-induced reactions so different from reactions with other incident particles. The scarce consideration of only pre-equilibrium emission (PE) and compound-nucleus (CN) mechanisms led to significant discrepancies with experimental results so that recommended reaction cross sections of high-priority elements as, e.g., Ni have mainly been obtained by fit of the data. Purpose: The unitary and consistent BU and DR account in deuteron-induced reactions on natural nickel may take advantage of an extended database for this element, including new accurate measurements of particular reaction cross sections. Method: The activation cross sections of 64,61,60Cu, Ni,5765, and 55,56,57,58,59m,60Co nuclei for deuterons incident on natural Ni at energies up to 20 MeV, were measured by the stacked-foil technique and high-resolution gamma spectrometry using U-120M cyclotron of CANAM, NPI CAS. Then, within an extended analysis of deuteron interactions with Ni isotopes up to 60 MeV, all processes from elastic scattering until the evaporation from fully equilibrated compound system have been taken into account while an increased attention is paid especially to the BU and DR mechanisms. Results: The deuteron activation cross-section analysis, completed by consideration of the PE and CN contributions corrected for decrease of the total-reaction cross section from the leakage of the initial deuteron flux towards BU and DR processes, is proved satisfactory for the first time to all available data. Conclusions: The overall agreement of the measured data and model calculations validates the description of nuclear mechanisms taken into account for deuteron-induced reactions on Ni, particularly the BU and

  2. Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C–H Bond Activation Product Responsible for Hydrogen Isotope Exchange

    PubMed Central

    2016-01-01

    [IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE. PMID:27934314

  3. Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time

    NASA Astrophysics Data System (ADS)

    Lippold, Holger; Eidner, Sascha; Kumke, Michael U.; Lippmann-Pipke, Johanna

    2017-01-01

    Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of 160Tb as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable 159Tb or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of 160Tb was introduced prior to saturation with 159Tb, the expected partial desorption of 160Tb occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive

  4. Measurement of alpha-induced reaction cross sections on erbium isotopes for γ process studies

    NASA Astrophysics Data System (ADS)

    Kiss, G. G.; Szücs, T.; Török, Zs.; Fülöp, Zs.; Gyürky, Gy.; Halász, Z.; Somorjai, E.; Rauscher, T.

    2014-05-01

    The cross sections of the 162Er(α,γ)166Yb and 162,164,166Er(α,n)165,167,169Yb reactions have been measured at MTA Atomki. The radiative alpha capture reaction cross section was measured between Ec.m. = 11.21 MeV and Ec.m. = 16.09 MeV just above the astrophysically relevant energy region (which lies between 7.8 and 11.48 MeV at T9 = 3 GK). The 162Er(α,n)165Yb, 164Er(α,n)167Yb and 166Er(α,n)169Yb reactions were studied between Ec.m. = 12.19 and 16.09 MeV, Ec.m. = 13.17 and 16.59 MeV and Ec.m. = 12.68 and 17.08 MeV, respectively. The aim of this work is to provide experimental data for modeling the γ process which is thought to be responsible for the production of the proton-rich isotopes heavier than iron.

  5. Measurement of alpha-induced reaction cross sections on erbium isotopes for γ process studies

    SciTech Connect

    Kiss, G. G.; Szücs, T.; Török, Zs.; Fülöp, Zs.; Gyürky, Gy.; Halász, Z.; Somorjai, E.; Rauscher, T.

    2014-05-02

    The cross sections of the {sup 162}Er(α,γ){sup 166}Yb and {sup 162,164,166}Er(α,n){sup 165,167,169}Yb reactions have been measured at MTA Atomki. The radiative alpha capture reaction cross section was measured between E{sub c.m.} = 11.21 MeV and E{sub c.m.} = 16.09 MeV just above the astrophysically relevant energy region (which lies between 7.8 and 11.48 MeV at T{sub 9} = 3 GK). The {sup 162}Er(α,n){sup 165}Yb, {sup 164}Er(α,n){sup 167}Yb and {sup 166}Er(α,n){sup 169}Yb reactions were studied between E{sub c.m.} = 12.19 and 16.09 MeV, E{sub c.m.} = 13.17 and 16.59 MeV and E{sub c.m.} = 12.68 and 17.08 MeV, respectively. The aim of this work is to provide experimental data for modeling the γ process which is thought to be responsible for the production of the proton-rich isotopes heavier than iron.

  6. Phosphatidylinositol synthase and phosphatidylinositol/inositol exchange reactions in turkey erythrocyte membranes.

    PubMed Central

    McPhee, F; Lowe, G; Vaziri, C; Downes, C P

    1991-01-01

    Unlike human erythrocytes, those from avian species, such as turkeys and chicks, rapidly incorporate myo-[3H]inositol into membrane phospholipids. The mechanisms regulating [3H]Ins labelling of phosphatidylinositol have been investigated using turkey erythrocyte membranes. In the absence of added nucleotides, [3H]inositol incorporation appears to proceed via phosphatidylinositol/inositol exchange, with a Km for inositol of 0.01 mM. The reaction was dependent upon divalent cations, either Mg2+ or Mn2+, with the latter metal ion being the more effective. [3H]Inositol incorporation was accelerated by CMP, especially when the concentration of Ins was greater than the Km for the exchange reaction. CMP-dependent labelling of PtdIns had a Km for inositol of 0.3 mM and for CMP of 0.015 mM. Divalent cations were also required for this reaction: activity peaked at 0.5 mM-Mn2+ and declined at higher concentrations. At relatively high concentrations, Mg2+ was more effective than Mn2+, with peak activity being achieved above 10 mM. CMP-dependent incorporation of [3H]inositol appears to reflect an exchange reaction catalysed by PtdIns synthase. Definitive evidence for the occurrence of PtdIns synthase in turkey erythrocyte membranes was obtained by demonstrating the formation of [14C]CMP-phosphatidate from [14C]CMP. The radioactivity could be efficiently chased from [14C]CMP-phosphatidate in the presence of unlabelled inositol. The detection of PtdIns synthase activity in morphologically simple turkey erythrocytes should help to clarify the subcellular distribution of this important component of the phosphatidylinositol cycle. PMID:1850237

  7. Isotope Effects as Probes for Enzyme Catalyzed Hydrogen-Transfer Reactions

    PubMed Central

    Roston, Daniel; Islam, Zahidul; Kohen, Amnon

    2015-01-01

    Kinetic Isotope effects (KIEs) have long served as a probe for the mechanisms of both enzymatic and solution reactions. Here, we discuss various models for the physical sources of KIEs, how experimentalists can use those models to interpret their data, and how the focus of traditional models has grown to a model that includes motion of the enzyme and quantum mechanical nuclear tunneling. We then present two case studies of enzymes, thymidylate synthase and alcohol dehydrogenase, and discuss how KIEs have shed light on the C-H bond cleavages those enzymes catalyze. We will show how the combination of both experimental and computational studieshas changed our notion of how these enzymes exert their catalytic powers. PMID:23673528

  8. Fluid flow pathways through the oceanic crust: reaction permeability and isotopic tracing

    NASA Astrophysics Data System (ADS)

    McCaig, Andrew; Castelain, Teddy; Klein, Frieder

    2013-04-01

    It is generally assumed that the dominant means of creating permeability in ocean floor hydrothermal systems is fracturing, induced either by cooling or by tectonic stress. Here we show textural evidence that metamorphic reactions can create a hierarchy of permeable pathways through gabbroic rocks similar to a fracture hierarchy. Isotopic microsampling shows that just as with fractures, most flow occurs through the larger channelways, and that even at the microscale, flow can be extremely heterogeneous with alteration affecting only certain minerals in the framework, leaving others untouched. Reaction permeability is created in three ways; dissolution creating open porosity, microcracking due to volume increase reactions involving olivine, and expansion of water due to rapid heating in dyke margins, particularly when intruded into brecciated rocks. Our data comes from IODP Hole U1309D, which was drilled to 1400 mbsf in the footwall of the Atlantis Massif detachment fault at the Mid-Atlantic Ridge 30°N. The core is composed of gabbroic rocks interlayered with olivine rich troctolites, with several basalt/diabase sills in the top 130 m. The dominant alteration occurred in the greenschist facies, at depths at least 1 km below seafloor, and decreases in intensity downhole. Whole rock oxygen isotope values range from +5.5 permil to +1.5 permil, indicating variable degrees of interaction with seawater at temperatures generally > 250 °C. Gabbroic rocks and diabases exhibit a range of Sr isotope ratios from MORB values (0.70261) to intermediate ratios (0.70429). Microsampling shows that amphiboles are often more radiogenic than coexisting plagioclase and can sometimes be isotopically altered in the same rock as completely unaltered primary minerals. Large (10 cm) amphibole-filled vugs show values ranging up to 0.708, close to seawater. In some cases however the secondary minerals are virtually unaltered indicating low fluid fluxes in pervasive alteration. SEM textures in

  9. Knockout and fragmentation reactions using a broad range of tin isotopes

    NASA Astrophysics Data System (ADS)

    Rodríguez-Sánchez, J. L.; Benlliure, J.; Bertulani, C. A.; Vargas, J.; Ayyad, Y.; Alvarez-Pol, H.; Atkinson, J.; Aumann, T.; Beceiro-Novo, S.; Boretzky, K.; Caamaño, M.; Casarejos, E.; Cortina-Gil, D.; Díaz-Cortes, J.; Fernández, P. Díaz; Estrade, A.; Geissel, H.; Kelić-Heil, A.; Litvinov, Yu. A.; Mostazo, M.; Paradela, C.; Pérez-Loureiro, D.; Pietri, S.; Prochazka, A.; Takechi, M.; Weick, H.; Winfield, J. S.

    2017-09-01

    Production cross sections of residual nuclei obtained by knockout and fragmentation reactions of different tin isotopes accelerated at 1 A GeV have been measured with the fragment separator (FRS) at GSI, Darmstadt. The new measurements are used to investigate the neutron-excess dependence of the neutron- and proton-knockout cross sections. These cross sections are compared to Glauber model calculations coupled to a nuclear de-excitation code in order to investigate the role of the remnant excitations. This bench marking shows an overestimation of the cross sections for the removal of deeply bound nucleons. A phenomenological increase in the excitation energy induced in the remnants produced in these cases allows us to reproduce the measured cross sections.

  10. Production of medically useful bromine isotopes via alpha-particle induced nuclear reactions

    NASA Astrophysics Data System (ADS)

    Breunig, Katharina; Scholten, Bernhard; Spahn, Ingo; Hermanne, Alex; Spellerberg, Stefan; Coenen, Heinz H.; Neumaier, Bernd

    2017-09-01

    The cross sections of α-particle induced reactions on arsenic leading to the formation of 76,77,78Br were measured from their respective thresholds up to 37 MeV. Thin sediments of elemental arsenic powder were irradiated together with Al degrader and Cu monitor foils using the established stacked-foil technique. For determination of the effective α-particle energies and of the effective beam current through the stacks the cross-section ratios of the monitor nuclides 67Ga/66Ga were used. This should help resolve discrepancies in existing literature data. Comparison of the data with the available excitation functions shows some slight energy shifts as well as some differences in curve shapes. The calculated thick target yields indicate, that 77Br can be produced in the energy range Eα = 25 → 17 MeV free of isotopic impurities in quantities sufficient for medical application.

  11. Informing Neutron-Capture Rates through (d,p) Reactions on Neutron-Rich Tin Isotopes

    NASA Astrophysics Data System (ADS)

    Manning, B.; Cizewski, J. A.; Kozub, R. L.; Ahn, S.; Allmond, J. M.; Bardayan, D. W.; Chae, K. Y.; Chipps, K. A.; Howard, M. E.; Jones, K. L.; Liang, J. F.; Matos, M.; Nunes, F. M.; Nesaraja, C. D.; O'Malley, P. D.; Pain, S. D.; Peters, W. A.; Pittman, S. T.; Ratkiewicz, A.; Schmitt, K. T.; Shapira, D.; Smith, M. S.; Titus, L.

    2014-03-01

    Level energies and spectroscopic information for neutron-rich nuclei provide important input for r-process nucleosynthesis calculations; specifically, the location and strength of single-neutron l = 1 states when calculating neutron-capture rates. Surman and collaborators have performed sensitivity studies to show that varying neutron-capture rates can significantly alter final r-process abundances. However, there are many nuclei important to the r-process that cannot be studied. Extending studies to more neutron-rich nuclei will help constrain the nuclear shell-model in extrapolating to nuclei even further from stability. The (d,p) reaction has been measured with radioactive ion beams of 126Sn and 128Sn to complete the set of (d,p) studies on even mass tin isotopes from doubly-magic 132 to stable 124Sn. Work supported in part by the U.S. Department of Energy and National Science Foundation.

  12. Charge-exchange reactions and nuclear matrix elements for {beta}{beta} decay

    SciTech Connect

    Frekers, D.

    2009-11-09

    Charge-exchange reactions of (n, p) and (p, n) type at intermediate energies are a powerful tool for the study of nuclear matrix element in {beta}{beta} decay. The present paper reviews some of the most recent experiments in this context. Here, the (n, p) type reactions are realized through (d, {sup 2}He), where {sup 2}He refers to two protons in a singlet {sup 1}S{sub 0} state and where both of these are momentum analyzed and detected by the same spectrometer and detector. These reactions have been developed and performed exclusively at KVI, Groningen (NL), using an incident deuteron energy of 183 MeV. Final state resolutions of about 100 keV have routinely been available. On the other hand, the ({sup 3}He, t) reaction is of (p, n) type and was developed at the RCNP facility in Osaka (JP). Measurements with an unprecedented high resolution of 30 keV at incident energies of 420 MeV are now readily possible. Using both reaction types one can extract the Gamow-Teller transition strengths B(GT{sup +}) and B(GT{sup -}), which define the two ''legs'' of the {beta}{beta} decay matrix elements for the 2v{beta}{beta} decay The high resolution available in both reactions allows a detailed insight into the excitations of the intermediate odd-odd nuclei and, as will be shown, some unexpected features are being unveiled.

  13. Double-regge exchange limit for the γp→ K⁺K⁻p reaction

    SciTech Connect

    Shi, M.; Danilkin, I. V.; Fernández-Ramírez, C.; Mathieu, V.; Pennington, M. R.; Schott, D.; Szczepaniak, A. P.

    2015-02-01

    We apply the generalized Veneziano model (B₅ model) in the double-Regge exchange limit to the γp→K⁺K⁻p reaction. Four different cases defined by the possible combinations of the signature factors of leading Regge exchanges ((K*,a₂/f₂), (K*,ρ/ω), (K*₂,a₂/f₂), and (K*₂,ρ/ω)) have been simulated through the Monte Carlo method. Suitable event candidates for the double-Regge exchange high-energy limit were selected employing Van Hove plots as a better alternative to kinematical cuts in the K⁺K⁻p Dalitz plot. In this way we predict and analyze the double-Regge contribution to the K⁺K⁻p Dalitz plot, which constitutes one of the major backgrounds in the search for strangeonia, hybrids and exotics using γp→K⁺K⁻p reaction. We expect that data currently under analysis, and that to come in the future, will allow verification of the double-Regge behavior and a better assessment of this component of the amplitude.

  14. Exchanged cations and water during reactions in polypyrrole macroions from artificial muscles.

    PubMed

    Valero, Laura; Otero, Toribio F; Martínez, José G

    2014-02-03

    The movement of the bilayer (polypyrrole-dodecylbenzenesulfonate/tape) during artificial muscle bending under flow of current square waves was studied in aqueous solutions of chloride salts. During current flow, polypyrrole redox reactions result in variations in the volumes of the films and macroscopic bending: swelling by reduction with expulsion of cations and shrinking by oxidation with the insertion of cations. The described angles follow a linear function, different in each of the studied salts, of the consumed charge: they are faradaic polymeric muscles. The linearity indicates that cations are the only exchanged ions in the studied potential range. By flow of the same specific charge in every electrolyte, different angles were described by the muscle. The charge and the angle allow the number and volume of both the exchanged cations and the water molecules (related to a reference) between the film to be determined, in addition to the electrolyte per unit of charge during the driving reaction. The attained apparent solvation numbers for the exchanged cations were: 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.25, and 0.0 for Na(+), Mg(2+), La(3+), Li(+), Ca(2+), K(+), Rb(+), and Cs(+), respectively.

  15. Double-regge exchange limit for the γp→ K⁺K⁻p reaction

    DOE PAGES

    Shi, M.; Danilkin, I. V.; Fernández-Ramírez, C.; ...

    2015-02-01

    We apply the generalized Veneziano model (B₅ model) in the double-Regge exchange limit to the γp→K⁺K⁻p reaction. Four different cases defined by the possible combinations of the signature factors of leading Regge exchanges ((K*,a₂/f₂), (K*,ρ/ω), (K*₂,a₂/f₂), and (K*₂,ρ/ω)) have been simulated through the Monte Carlo method. Suitable event candidates for the double-Regge exchange high-energy limit were selected employing Van Hove plots as a better alternative to kinematical cuts in the K⁺K⁻p Dalitz plot. In this way we predict and analyze the double-Regge contribution to the K⁺K⁻p Dalitz plot, which constitutes one of the major backgrounds in the search for strangeonia,more » hybrids and exotics using γp→K⁺K⁻p reaction. We expect that data currently under analysis, and that to come in the future, will allow verification of the double-Regge behavior and a better assessment of this component of the amplitude.« less

  16. EXFOR systems manual: Nuclear reaction data exchange format. Revision 97/1

    SciTech Connect

    McLane, V.

    1997-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Center Network. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility rather than optimization of data processing in order to meet the diverse needs of the nuclear reaction data centers. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine).

  17. Theoretical rate constants and kinetic isotope effects in the reaction of methane with H, D, T, and Mu atoms.

    PubMed

    Espinosa-García, J

    2008-03-07

    The rate constants and kinetic isotope effects of the reaction of methane with four isotopes of hydrogen, protium (H), deuterium (D), tritium (T), and muonium (Mu), were studied using variational transition state theory with multidimensional tunneling on an analytical potential energy surface, PES-2002, previously constructed by our group. For the four isotopes, our kinetics results agree reasonably with available experimental measurements, improving previous theoretical results that used different potential energy surfaces and/or theoretical approaches. In the comparison of the reactivity between protium and muonium, which is the most severe test of the surface and theoretical method due to the large mass difference between the two isotopes, some sources of discrepancy between theory and experiment were analyzed. These were the zero-point energy, tunneling effect, and the role of the reactivity from methane excited vibrational states.

  18. Kinetic isotope effects of peptidylglycine alpha-hydroxylating mono-oxygenase reaction.

    PubMed Central

    Takahashi, K; Onami, T; Noguchi, M

    1998-01-01

    Many bioactive polypeptides or neuropeptides possess a C-terminal alpha-amide group as a critical determinant for their optimal bioactivities. The amide functions are introduced by the sequential actions of peptidylglycine alpha-hydroxylating mono-oxygenase (PHM; EC 1.14.17.3) and peptidylamidoglycollate lyase (PAL; EC 4.3.2.5) from their glycine-extended precursors. In the present study we examined the kinetic isotope effects of the frog PHM reaction by competitive and non-competitive approaches. In the competitive approach we employed the double-label tracer method with D-Tyr-[U-14C]Val-Gly, D-Tyr-[3,4-3H]Val-[2,2-2H2]-Gly, and D-Tyr-Val-(R,S)[2-3H]Gly as substrates, and we determined the deuterium and tritium effects on Vmax/Km as 1.625+/-0.041 (mean+/-S. D.) and 2.71+/-0.16 (mean+/-S.D.), respectively. The intrinsic deuterium isotope effect (Dk) on the glycine hydroxylation reaction was estimated to be 6.5-10.0 (mean 8.1) by the method of Northrop [Northrop (1975) Biochemistry 14, 2644-2651]. In the non-competitive approach with N,N-dimethyl-1,4-phenylenediamine as a reductant, however, the deuterium effect on Vmax (DV) was approximately unity, although the deuterium effect on Vmax/Km (DV/K) was comparable to that obtained by the competitive approach. These results indicated that DV was completely masked by the presence of one or more steps much slower than the glycine hydroxylation step and that DV/K was diminished from Dk by a large forward commitment to catalysis. The addition of PAL, however, increased the apparent DV from 1.0 to 1.2, implying that the product release step was greatly accelerated by PAL. These results suggest that the product release is rate-limiting in the overall PHM reaction. The large Dk indicated that the glycine hydroxylation catalysed by PHM might proceed in a stepwise mechanism similar to that proposed for the dopamine beta-hydroxylase reaction [Miller and Klinman (1983) Biochemistry 22, 3091-3096]. PMID:9806894

  19. Controlling plasmonic "hot spots" in nanoparticle assemblies using ligand place-exchange reactions

    NASA Astrophysics Data System (ADS)

    Bao, Lanlan

    This thesis describes the 1) selective attachment of Au nanoparticles (NPs) to the edges of Au nanoplates via ligand place-exchange reactions, 2) preparation of coupled Au nanoplates via ligand place-exchange reactions, 3) attachment of Au NPs to Au nanorods via ligand place-exchange reactions, 4) study of the dynamics of ligand place-exchange reactions on Au nanoplates, 5) study of the changes in the optical properties of Au nanoplates upon attachment of Au NPs by observing the shift in the localized surface plasmon resonance (LSPR) band, and 6) study of the surface-enhanced Raman spectroscopy (SERS) enhancement of analyte molecules located in the "hot-spots" of coupled Au nanoplate-Au NP structures. We regio-selectively attached 20 nm Au NPs to Au nanoplates by first assembling hexanethiol (HT) onto Au nanoplates, then exchanging HT with 4-aminothiophenol (4-ATP) using different reaction times, and finally electrostatically attaching the negatively-charged Au NPs to the positively-charged 4-ATP ligands bound to the Au nanoplates. We prepared nanoplate-NP assemblies with 100% of the NPs attached to vertex sites or 100% attached to vertex and edge sites using 1 h and 2 h exchange times, respectively. The location and number of bound Au NPs to the nanoplates as a function of exchange time provided information about the mechanism of the ligand place-exchange reaction on the Au nanoplate surface. Ligand place-exchange starts from the vertex sites, then proceeds at the edge sites and finally occurs at smooth terrace sites for longer times. Direct exchange at terraces is possible but the data suggests it occurs mostly through lateral migration of the 4-ATP ligands from vertex/edge sites to the terrace. The data also suggests that phase segregation of 4-ATP ligands and HT ligands occurs on the terrace sites for longer times. The ligand place-exchange strategy also leads to interesting coupled Au nanoplate-Au nanoplate and Au nanorod-Au NP assemblies. The optical

  20. On the synthesis of neutron-rich isotopes along the N = 126 shell in multinucleon transfer reactions

    NASA Astrophysics Data System (ADS)

    Beliuskina, O.; Heinz, S.; Zagrebaev, V.; Comas, V.; Heinz, C.; Hofmann, S.; Knöbel, R.; Stahl, M.; Ackermann, D.; Heßberger, F. P.; Kindler, B.; Lommel, B.; Maurer, J.; Mann, R.

    2014-10-01

    We performed experimental and theoretical studies of deep inelastic multinucleon transfer reactions in heavy-ion collisions at Coulomb barrier energies. Our goal was to investigate if deep inelastic transfer is superior to fragmentation reactions for producing neutron-rich isotopes in the astrophysically interesting region along the closed neutron shell N = 126 . Here, we will present our results obtained in reactions of 64Ni + 207Pb at 5.0 MeV/nucleon. The experiment was performed at the velocity filter SHIP at GSI Darmstadt. Several transfer products on the neutron-rich side were populated but new isotopes were not observed. A comparison of the measured transfer cross-sections and production yields with those from fragmentation reactions allowed for interesting conclusions.

  1. New data on cross sections for partial and total photoneutron reactions on the isotopes {sup 91,94}Zr

    SciTech Connect

    Varlamov, V. V.; Makarov, M. A.; Peskov, N. N.; Stepanov, M. E.

    2015-07-15

    Experimental data on {sup 91,94}Zr photodisintegration that were obtained in a beam of quasimonoenergetic annihilation photons by the method of neutron multiplicity sorting are analyzed. It is found that the cross sections for the (γ, 1n), (γ, 2n), and (γ, 3n) reactions on both isotopes do not meet the objective data-reliability criteria formulated earlier. Within the experimental–theoretical method for evaluating partial-reaction cross sections that satisfy these criteria, new data on the cross sections for the aforementioned partial reactions, as well as for the (γ, sn) = (γ, 1n) + (γ, 2n) + (γ, 3n) +... total photoneutron reaction, are obtained for the isotopes {sup 91,94}Zr.

  2. Theoretical Investigations for Anomalous Fractionation of Sulfur Isotopes during a surface reaction

    NASA Astrophysics Data System (ADS)

    Otake, T.; Lasaga, A. C.; Watanabe, Y.; Ohmoto, H.

    2009-12-01

    While SO2 photolysis by UV radiation has been the most widely accepted process to cause Anomalous Isotope Fractionation (AIF: i.e., large deviation from the mass-dependent relationships) of sulfur in nature, recent experimental evidence demonstrated that thermochemical reduction of sulfate by simple amino acids also produce AIF (Watanabe et al., 2009). Their study provides an alternative process that may have caused AIF signatures in Archean sedimentary rocks: reactions between organic matter in sediments and sulfate-rich hydrothermal solutions. Our theoretical investigations (Lasaga et al. 2008) supported their study and suggested that a surface reaction is another mechanism that can cause AIF of sulfur. Applying squire adsorption-well and Morse potential models for adsorption of sulfur species on a solid surface, we showed that a combination of small chemisorption energies (<30 kJ/mole) with possible discontinuities in the number of bound energy levels for different sulfur isotopes may lead to AIF effects in heterogeneous reactions between a surface and sulfur-bearing species. We also performed ab initio calculations for SO2 adsorption onto a naphthalene molecule, which simulates a kerogen surface. The results indicate the possibility of producing large AIF effects (e.g., δ33S/δ34S ≈ 1.08, δ36S/δ34S ≈ 0.84, Δ33S = 7.0 - 13.6‰, Δ36S = -13.0 - -25.2‰) by heterogeneous reactions between organic matter and sulfur-bearing solutions under hydrothermal conditions. The results also indicate that AIF signatures may increase with increasing temperature because the discontinuity occurs at high energy states. However, more recently, Balan et al. (2009) dismissed the surface reaction as a possible AIF mechanism. They recognized a significant overlap of wavefunctions between the last bound state and first unbound state for the systems where the boundary wall was arbitrarily set very close to the surface. The overlap led them to include the unbound state in the

  3. Sulfur-33 Isotope Tracing of the Hydrodesulfurization Process: Insights into the Reaction Mechanism, Catalyst Characterization and Improvement.

    PubMed

    Sushkevich, Vitaly L; Popov, Andrey G; Ivanova, Irina I

    2017-08-28

    The novel approach based on (33) S isotope tracing is proposed for the elucidation of hydrodesulfurization (HDS) mechanisms and characterization of molybdenum sulfide catalysts. The technique involves sulfidation of the catalyst with (33) S-isotope-labeled dihydrogen sulfide, followed by monitoring the fate of the (33) S isotope in the course of the hydrodesulfurization reaction by online mass spectrometry and characterization of the catalyst after the reaction by temperature-programmed oxidation with mass spectrometry (TPO-MS). The results point to different pathways of thiophene transformation over Co or Ni-promoted and unpromoted molybdenum sulfide catalysts, provide information on the role of promoter and give a key for the design of new efficient HDS catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed

    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.

  5. Isotopic exchange in the system YBa{sub 2}Cu{sub 3}{sup 16}O{sub 6.92}+{sup 18}O{sub 2}

    SciTech Connect

    Kir`yakov, N.V.; Borshch, V.N.; Grigoryan, E.A.

    1995-09-01

    Processes of isotopic exchange between gaseous {sup 18O}{sub 2} and oxygen-16 of complex oxide ceramics of the initial composition YBa{sub 2}Cu{sub 3}{sup 16}O{sub 6.92} were studied in the temperature range 293 - 923K. The maximum extent of isotopic exchange ,equal to 3.8 {plus_minus} 0.3 atoms per molecule of cuprate, was achieved at 923 K. The spectra of temperature-programmed desorption of labile oxygen of the {sup 18}0-enriched ceramics were obtained. Almost complete isotopic exchange is supposed to occur for chain (01) and bridge (04) oxygen atoms in the crystalline structure of the cuprate, thus assuming their involvement in catalytic oxidation processes on the surface at T> 800 K.

  6. Revised Calculations of the Production Rates for Co Isotopes in Meteorites Using New Cross Sections for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Brooks, F. D.; Buffler, A.; Allie, M. S.; Herbert, M. S.; Nchodu, M. R.; Makupula, S.; Ullmann, J.; Reedy, R. C.; Jones, D. T. L.

    2002-01-01

    New cross section measurements for reactions induced by neutrons with energies greater than 70 MeV are used to calculate the production rates for cobalt isotopes in meteorites and these new calculations are compared to previous estimates. Additional information is contained in the original extended abstract.

  7. Revised Calculations of the Production Rates for Co Isotopes in Meteorites Using New Cross Sections for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Brooks, F. D.; Buffler, A.; Allie, M. S.; Herbert, M. S.; Nchodu, M. R.; Makupula, S.; Ullmann, J.; Reedy, R. C.; Jones, D. T. L.

    2002-01-01

    New cross section measurements for reactions induced by neutrons with energies greater than 70 MeV are used to calculate the production rates for cobalt isotopes in meteorites and these new calculations are compared to previous estimates. Additional information is contained in the original extended abstract.

  8. Gas chromatography mass spectrometry study of hydrogen deuterium exchange reactions of volatile hydrides of As, Sb, Bi, Ge and Sn in aqueous media

    NASA Astrophysics Data System (ADS)

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

    2006-07-01

    The H-D exchange processes in MH n or MD n hydrides (M = As, Sb, Bi, n = 3; M = Ge, Sn, n = 4) taking place when they are in contact with H 2O or D 2O solution at different pH or pD values (interval of pH = [0,13]) have been investigated using gas chromatography-mass spectrometry (GC-MS). MH n or MD n compounds were injected into the headspace of reaction vials (4-12 ml) containing 1-2 ml of buffered solution maintained under stirring or shaking conditions. The isotopic composition of the gaseous phase hydrides/deuterides was determined at regular intervals in the range of time 0-15 min. The MH n or MD n compounds were synthesized in separate vials and their purity was checked separately before injection into the reaction vials. The mass spectra were deconvoluted in order to estimate the relative abundance of each species formed following the H-D exchange process (AsH nD 3- n , SbH nD 3- n, BiH nD 3- n, n = 0-3; GeH nD 4- n, SnH nD 4- n, n = 0-4) and the relative abundance of H and D. In the investigated pH (or pD) interval arsanes and stibanes undergo H-D exchange in alkaline media for pH > 7. No H-D exchange was detected for the other hydrides, where the prevailing process is their decomposition in the aqueous phase. A reaction model, based on the formation of protonated or deprotonated intermediates is proposed for H-D exchange of MH n or MD n compounds placed in contact with H 2O or D 2O at different pH or pD values. The H-D exchange in the already formed hydrides can be source of the interference in mechanistic studies on hydride formation performed using labeled reagents; no H-D exchange was detected within the following pH intervals that can be considered free from interference: arsanes pH = [0,7), stibanes pH = [0,7), bismuthanes, germanes and stannanes pH = [0,13].

  9. Protein Structure-Function Correlation in Living Human Red Blood Cells Probed by Isotope Exchange-based Mass Spectrometry.

    PubMed

    Narayanan, Sreekala; Mitra, Gopa; Muralidharan, Monita; Mathew, Boby; Mandal, Amit K

    2015-12-01

    To gain insight into the underlying mechanisms of various biological events, it is important to study the structure-function correlation of proteins within cells. Structural probes used in spectroscopic tools to investigate protein conformation are similar across all proteins. Therefore, structural studies are restricted to purified proteins in vitro and these findings are extrapolated in cells to correlate their functions in vivo. However, due to cellular complexity, in vivo and in vitro environments are radically different. Here, we show a novel way to monitor the structural transition of human hemoglobin upon oxygen binding in living red blood cells (RBCs), using hydrogen/deuterium exchange-based mass spectrometry (H/DX-MS). Exploiting permeability of D2O across cell membrane, the isotope exchange of polypeptide backbone amide hydrogens of hemoglobin was carried out inside RBCs and monitored using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). To explore the conformational transition associated with oxygenation of hemoglobin in vivo, the isotope exchange kinetics was simplified using the method of initial rates. RBC might be considered as an in vivo system of pure hemoglobin. Thus, as a proof-of-concept, the observed results were correlated with structural transition of hemoglobin associated with its function established in vitro. This is the first report on structural changes of a protein upon ligand binding in its endogenous environment. The proposed method might be applicable to proteins in their native state, irrespective of location, concentration, and size. The present in-cell approach opens a new avenue to unravel a plethora of biological processes like ligand binding, folding, and post-translational modification of proteins in living cells.

  10. Isotopic shifts in chemical exchange systems. 1. Large isotope effects in the complexation of Na/sup +/ isotopes by macrocyclic polyethers

    SciTech Connect

    Knoechel, A.; Wilken, R.D.

    1981-09-23

    The complexation of /sup 24/Na/sup +/ and /sup 22/Na/sup +/ by 18 of the most widely used macrocyclic polyethers (crown ethers and monocyclic and bicyclic aminopolyethers) has been investigated in view of possible equilibrium isotope shifts. Solvated salts and polyether complexes were distributed differently into two phases and isotope ratios determined in both phases. Chloroform/water systems were shown to be particularly suitable to the investigations allowing favorable distribution for Na/sup +/ and 13 of the 18 polyethers employed. With crown ethers /sup 24/Na/sup +/ enrichment varied from nonsignficant values (for large crown ethers) up to 3.1 +- 0.4% (18-crown-6). In the case of bicyclic aminopolyethers, ligands with cages of optimum size to accommodate Na/sup +/ showed /sup 24/Na/sup +/ enrichment between O (nonsignificant) (2.2/sub B/2./sub B/) and 5.2 +- 1.8% (2.2.1). In contrast, for 2.2.2. and its derivatives, being too large for Na/sup +/, /sup 22/Na/sup +/ enrichment varying from O (nonsignificant) (2.2.2.p) up to 5.4 +- 0.5% (2.2.2.) has been observed. These values are remarkably high. They are explained by different bonding in solvate structure and polyether complex by using the theoretical approach of Bigeleisen.

  11. Search for Tetraneutron by Pion Double Charge Exchange Reaction at J-PARC

    NASA Astrophysics Data System (ADS)

    Fujioka, Hiroyuki; Fukuda, Tomokazu; Harada, Toru; Hiyama, Emiko; Itahashi, Kenta; Kanatsuki, Shunsuke; Nagae, Tomofumi; Nanamura, Takuya; Nishi, Takahiro

    Tetraneutron (4n) has come back in the limelight, because of recent observation of a candidate resonant state at RIBF. We propose to investigate the pion double charge exchange (DCX) reaction, i.e., 4He(π-, π+), as an alternative way to populate tetraneutron. An intense π- beam with the kinetic energy of ˜850 MeV, much higher than that in past experiments at LAMPF and TRIUMF, will open up a possibility to improve the experimental sensitivity of the formation cross section, which will be much smaller than hitherto known DCX cross sections such as 9Be(π-, π+)9He (g.s.).

  12. Neutron skin thickness of {sup 90}Zr determined by charge exchange reactions

    SciTech Connect

    Yako, K.; Sakai, H.; Sagawa, H.

    2006-11-15

    Charge exchange spin-dipole (SD) excitations of {sup 90}Zr are studied by the {sup 90}Zr(p,n) and {sup 90}Zr(n,p) reactions at 300 MeV. A multipole decomposition technique is employed to obtain the SD strength distributions in the cross-section spectra. For the first time, a model-independent SD sum rule value is obtained: 148{+-}12 fm{sup 2}. The neutron skin thickness of {sup 90}Zr is determined to be 0.07{+-}0.04 fm from the SD sum rule value.

  13. Reaction of dimethyl ether with hydroxyl radicals: kinetic isotope effect and prereactive complex formation.

    PubMed

    Bänsch, Cornelie; Kiecherer, Johannes; Szöri, Milan; Olzmann, Matthias

    2013-09-05

    The kinetic isotope effect of the reactions OH + CH3OCH3 (DME) and OH + CD3OCD3 (DME-d6) was experimentally and theoretically studied. Experiments were carried out in a slow-flow reactor at pressures between 5 and 21 bar (helium as bath gas) with production of OH by laser flash photolysis of HNO3 and time-resolved detection of OH by laser-induced fluorescence. The temperature dependences of the rate coefficients obtained can be described by the following modified Arrhenius expressions: k(OH+DME) = (4.5 ± 1.3) × 10(-16) (T/K)(1.48) exp(66.6 K/T) cm(3) s(-1) (T = 292-650 K, P = 5.9-20.9 bar) and k(OH+DME-d6) = (7.3 ± 2.2) × 10(-23) (T/K)(3.57) exp(759.8 K/T) cm(3) s(-1) (T = 387-554 K, P = 13.0-20.4 bar). A pressure dependence of the rate coefficients was not observed. The agreement of our experimental results for k(OH+DME) with values from other authors is very good, and from a fit to all available literature data, we derived the following modified Arrhenius expression, which reproduces the values obtained in the temperature range T = 230-1500 K at pressures between 30 mbar and 21 bar to better than within ±20%: k(OH+DME) = 8.45 × 10(-18) (T/K)(2.07) exp(262.2 K/T) cm(3) s(-1). For k(OH+DME-d6), to the best of our knowledge, this is the first experimental study. For the analysis of the reaction pathway and the kinetic isotope effect, potential energy diagrams were calculated by using three different quantum chemical methods: (I) CCSD(T)/cc-pV(T,Q)Z//MP2/6-311G(d,p), (II) CCSD(T)/cc-pV(T,Q)Z//CCSD/cc-pVDZ, and (III) CBS-QB3. In all three cases, the reaction is predicted to proceed via a prereaction OH-ether complex with subsequent intramolecular hydrogen abstraction and dissociation to give the methoxymethyl radical and water. Overall rate coefficients were calculated by assuming a thermal equilibrium between the reactants and the prereaction complex and by calculating the rate coefficients of the hydrogen abstraction step from canonical transition state theory

  14. Pt loaded carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas

    NASA Astrophysics Data System (ADS)

    Singh, Rashmi; Singh, Ashish; Kohli, D. K.; Singh, M. K.; Gupta, P. K.

    2013-06-01

    We report development and characterization of platinum doped carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas. The carbon aerogel with uniformly dispersed platinum nanoparticles was prepared by adding platinum precursor during the sol-gel process. Thereafter colloidal PTFE was mixed with the platinum doped carbon aerogel powder and coated on Dixon rings to obtain hydrophobic catalyst with required mechanical strength. Detailed studies have been carried out to observe the effect of physical characteristics of the catalyst powder (surface area and pore size of aerogels, Pt cluster size and its valence state etc) and the different coating parameters (PTFE to Pt-CA ratio and Pt loading on Dixon ring) on volume transfer rate (Ky.a) for H/D reaction. Ky.a values of ˜0.8 m3 (STP).s-1. m-3 were obtained for Pt loading of 7% and Pt cluster size of 3 nm at atmospheric pressure.

  15. The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere.

    PubMed

    Johnson, Jennifer E; Berry, Joseph A

    2013-10-01

    The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics. © 2013 John Wiley & Sons Ltd.

  16. Stereodynamics study of the exchange reaction O (3P) + CH4 → H + OCH3

    NASA Astrophysics Data System (ADS)

    Cheng, Da-Hai; Yuan, Jiu-Chuang; Yang, Tian-Gang; Chen, Mao-Du

    2013-06-01

    A new London—Eyring—Polanyi—Sato potential energy surface is employed in this work to study the stereo properties of the O(3P) + CH4 → H + CH3O reaction in its rovibrationally ground state using the quasiclassical trajectory method (QCT). Our calculations are performed at a range of collision energies, Ec = 1.5 eV~ 3.5 eV, and the excitation function obtained by the QCT method accords well with the experimental data. The product rotational polarization is calculated, and the product shows a strong rotational polarization in the centre-of-mass coordinate system. The orientation of the product rotational angular momenta is sensitive to the increase in collision energy, and the alignment of the product rotational angular momenta shows some of the properties of the heavy heavy—light mass combination reactions. In the isotopic substituted reaction study, when the H atoms in methane are replaced by D atoms, the rotational polarization is obviously reduced. The polarization-dependent differential cross section is also studied by this QCT calculation to provide detailed information about the rotational alignment and orientation of the product.

  17. Weak interaction processes in supernovae: New probes using charge exchange reaction at intermediate energies

    NASA Astrophysics Data System (ADS)

    Frekers, Dieter

    2005-04-01

    Spin-isospin-flip excitations in nuclei at vanishing momentum transfer are generally referred to as Gamov-Teller (GT) transitions. They are being studied because the simplicity of the excitation makes them an ideal probe for testing nuclear structure models. In astrophysics, GT transitions provide an important input for model calculations and element formation during the explosive phase of a massive star at the end of its life-time. GT transitions in the β- direction (also referred to as isospin lowering T< transitions) have extensively been studied through (p,n) and (3He,t) charge-exchange reactions [B.D. Anderson et al., Phys. Rev. C 36 (1987) 2195, B.D. Anderson et al., Phys. Rev. C 43 (1991) 50, J. Rapaport et al., Phys. Rev. C 24 (1981) 335, H. Akimune et al., Nucl. Phys. A 569 (1994) 245c, Y. Fujita et al., Phys. Lett. B 365 (1996) 29]. The generally good resolution allows easy extraction of the GT distribution and the total B(GT-) strength in the final nucleus. On the other hand, determination of B(GT+) strength through a charge-exchange reaction in the T> direction were mostly done with secondary neutron beams, and as such, they come with significant experimental difficulties. TRIUMF has pioneered this field in the late 80's and early 90's with a rich and highly successful (n,p) program using a several hundred MeV neutron beam from a 7Li(p,n)7Be reaction [R. Helmer, Can. J. Phys. 65 (1987) 588]. In this paper we present the (d,2He) reaction at intermediate energies as another and potentially even more powerful tool for charge-exchange reactions in the T>, resp. β+ direction. The key issue here will be the high resolution of order 100 keV, which provides new and sometimes unexpected insight into nuclear structure phenomena. This program has been launched at the AGOR Superconducting Cyclotron Facility at the KVI Groningen. By now, it covers a wide field of physics questions ranging from few-body physics, the structure of halo-nuclei, to questions pertaining

  18. Review of computer simulations of isotope effects on biochemical reactions: From the Bigeleisen equation to Feynman's path integral.

    PubMed

    Wong, Kin-Yiu; Xu, Yuqing; Xu, Liang

    2015-11-01

    Enzymatic reactions are integral components in many biological functions and malfunctions. The iconic structure of each reaction path for elucidating the reaction mechanism in details is the molecular structure of the rate-limiting transition state (RLTS). But RLTS is very hard to get caught or to get visualized by experimentalists. In spite of the lack of explicit molecular structure of the RLTS in experiment, we still can trace out the RLTS unique "fingerprints" by measuring the isotope effects on the reaction rate. This set of "fingerprints" is considered as a most direct probe of RLTS. By contrast, for computer simulations, oftentimes molecular structures of a number of TS can be precisely visualized on computer screen, however, theoreticians are not sure which TS is the actual rate-limiting one. As a result, this is an excellent stage setting for a perfect "marriage" between experiment and theory for determining the structure of RLTS, along with the reaction mechanism, i.e., experimentalists are responsible for "fingerprinting", whereas theoreticians are responsible for providing candidates that match the "fingerprints". In this Review, the origin of isotope effects on a chemical reaction is discussed from the perspectives of classical and quantum worlds, respectively (e.g., the origins of the inverse kinetic isotope effects and all the equilibrium isotope effects are purely from quantum). The conventional Bigeleisen equation for isotope effect calculations, as well as its refined version in the framework of Feynman's path integral and Kleinert's variational perturbation (KP) theory for systematically incorporating anharmonicity and (non-parabolic) quantum tunneling, are also presented. In addition, the outstanding interplay between theory and experiment for successfully deducing the RLTS structures and the reaction mechanisms is demonstrated by applications on biochemical reactions, namely models of bacterial squalene-to-hopene polycyclization and RNA 2'-O

  19. Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

    SciTech Connect

    Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

    2009-07-06

    Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

  20. O2 activation by binuclear Cu sites: Noncoupled versus exchange coupled reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Solomon, Edward I.

    2004-09-01

    Binuclear Cu proteins play vital roles in O2 binding and activation in biology and can be classified into coupled and noncoupled binuclear sites based on the magnetic interaction between the two Cu centers. Coupled binuclear Cu proteins include hemocyanin, tyrosinase, and catechol oxidase. These proteins have two Cu centers strongly magnetically coupled through direct bridging ligands that provide a mechanism for the 2-electron reduction of O2 to a µ-2:2 side-on peroxide bridged species. This side-on bridged peroxo-CuII2 species is activated for electrophilic attack on the phenolic ring of substrates. Noncoupled binuclear Cu proteins include peptidylglycine -hydroxylating monooxygenase and dopamine -monooxygenase. These proteins have binuclear Cu active sites that are distant, that exhibit no exchange interaction, and that activate O2 at a single Cu center to generate a reactive CuII/O2 species for H-atom abstraction from the C-H bond of substrates. O2 intermediates in the coupled binuclear Cu enzymes can be trapped and studied spectroscopically. Possible intermediates in noncoupled binuclear Cu proteins can be defined through correlation to mononuclear CuII/O2 model complexes. The different intermediates in these two classes of binuclear Cu proteins exhibit different reactivities that correlate with their different electronic structures and exchange coupling interactions between the binuclear Cu centers. These studies provide insight into the role of exchange coupling between the Cu centers in their reaction mechanisms.

  1. Accurate time-dependent wave packet study of the Li + H₂⁺ reaction and its isotopic variants.

    PubMed

    Aslan, E; Bulut, N; Castillo, J F; Bañares, L; Roncero, O; Aoiz, F J

    2012-01-12

    The dynamics and kinetics of the Li + H₂⁺ reaction and its isotopic variants (D₂⁺ and T₂⁺) have been studied by using a time-dependent wave packet (TDWP) coupled-channel (CC) method on the ab initio potential energy surface (PES) of Martinazzo et al. [J. Chem. Phys. 2003, 119, 21]. Total initial v = 0, j = 0 state-selected reaction probabilities for the Li + H₂⁺ reaction and its isotopic variants have been calculated from the threshold up to 1 eV for total angular momenta J from 0 to 90. Integral cross sections have been evaluated from the reaction probabilities at collision energies from threshold (≈0.2 eV) up to 1.0 eV collision. The calculated rate constants as a function of temperature show an Arrhenius type behavior in the 200 ≤ T ≤ 1000 K temperature interval. It has been found to be a considerable large intermolecular kinetic isotope effect. The TDWP-CC results are in overall good agreement with those obtained applying the TDWP Centrifugal-Sudden (CS) approximation, showing that the CS approximation is rather accurate for the title reaction.

  2. Identification of a Critical Intermediate in Galvanic Exchange Reactions by Single-Nanoparticle Resolved Kinetics

    NASA Astrophysics Data System (ADS)

    Smith, Jeremy George; Jain, Prashant

    2014-06-01

    The realization of common materials transformations in nanocrystalline systems is fostering the development of novel nanostructures and allowing a deep look into the atomistic mechanisms involved. Galvanic corrosion is one such transformation. We studied galvanic replacement within individual metal nanoparticles by using plasmonic spectroscopy. This proved to be a powerful approach to studying materials transformations in the absence of ensemble averaging. Individual nanoscale units act as domains that can be interrogated optically in isolation, whereas the averaging of all such domains provides a bulk reaction trajectory. Single-nanoparticle reaction trajectories showed that a Ag nanoparticle exposed to Au3+ makes an abrupt transition into a nanocage structure. The transition is limited by a critical structural event, which we identified by electron microscopy to comprise the formation of a nanosized void, similar to the pitting process commonly observed in the corrosion of metals. Trajectories also revealed a surprisingly strong nonlinearity of the reaction kinetics, which we explain by a model involving the critical coalescence of vacancies into a growing void. The critical void size for galvanic exchange to spontaneously proceed was found to be 20 atomic vacancies. In the future we hope to extend this approach to examine a wide variety of materials transformations and chemical reactions.

  3. Thermomechanics of a temperature sensitive covalent adaptable polymer with bond exchange reactions.

    PubMed

    Sun, XiaoHao; Wu, HengAn; Long, Rong

    2016-11-04

    We study a covalent adaptable polymer that can rearrange its network topology through thermally activated bond exchange reactions. When the polymer is deformed, such a network rearrangement leads to macroscopic stress relaxation, which allows the polymer to be thermoformed without a mold. Based on a previously developed constitutive model, we investigate thermal-mechanical behaviors of this material under a non-uniform and evolving temperature field through numerical simulations. Our focus is on the complex coupling between mechanical deformation, heat conduction and bond exchange reactions. Several examples are presented to illustrate the effects of non-uniform heating: uniaxial tension under heat conduction, torsion of a thin strip with local heating and thermal imprinting. Our results show that during non-uniform heating the material in the high temperature region creeps. This causes a redistribution of the deformation field and thus results in a final shape that deviates from the prescribed shape. The final shapes after thermoforming can be tuned by controlling the extent of heat conduction through different combinations of heating temperature and time. For example, with high temperature and a short heating time, it is possible to approximately confine stress relaxation and thus shape fixity within the local heating region. This is not the case if low temperature and a long heating time are used. These results can be utilized to design the temporal and spatial sequences of local heating during thermoforming to achieve various complex final shapes.

  4. Charge-exchange reactions on double-β decaying nuclei populating Jπ=2- states

    NASA Astrophysics Data System (ADS)

    Frekers, D.; Alanssari, M.; Ejiri, H.; Holl, M.; Poves, A.; Suhonen, J.

    2017-03-01

    The (3He,t ) charge-exchange reaction populating Jπ=2- states has been examined at 420 MeV incident energy for a series of double-β decaying nuclei, i.e., 76Ge, 82Se, 96Zr, 100Mo, 128Te, 130Te, and 136Xe. The measurements were carried out at the Grand Raiden spectrometer of the Research Center for Nuclear Physics at the University Osaka with typical spectral resolution of 30-40 keV. It is found that the charge-exchange reaction leading to 2- spin-dipole states is selective to the σ τ part of the interaction much similar to the observed selectivity to Gamow-Teller transitions. In the present case, the Δ L =1 peak cross sections at finite momentum transfers are used to extract the spin-isospin part of the low-lying transition strength near the Fermi surface (i.e., Ex≤5 MeV). Relative strength values are confronted with various model calculations, i.e., the interacting shell model, the quasiparticle random-phase approximation, and the Fermi surface quasiparticle model. The impact on the nuclear matrix elements for the neutrinoless double-β decay is discussed.

  5. Probable graft-vs-graft reaction in an infant after exchange transfusion and marrow transplantation.

    PubMed

    Lauer, B A; Githens, J H; Hayward, A R; Conrad, P D; Yanagihara, R T; Tubergen, D G

    1982-07-01

    A newborn with graft-vs-host (GVH) disease following an exchange transfusion was treated by attempting to eradicate the incompatible graft and to reconstitute the child hematologically and immunologically with a bone marrow transplant. The patient was a female term infant (blood group B, Rh+ Coombs test positive) who received a one-unit group O, Rh- exchange transfusion from an unrelated female donor for hyperbilirubinemia due to ABO incompatibility on day 2. Signs of acute GVH disease began on day 8 and the clinical diagnosis was supported by skin biopsy. With antithymocyte globulin and high dose dexamethasone, the GVH reaction improved somewhat. Cyclophosphamide, 200 mg/kg total dose, was given over four days followed by a marrow graft from a brother who was HLA-A, B identical, and probably also D locus compatible in mixed lymphocyte culture. All signs of GVH resolved with cyclophosphamide treatment and hematologic reconstitution was evident by 14 days after transplant. Two weeks later the GVH reaction and aplastic anemia recurred and Y chromatin was detected in only 6% of marrow cells. The infant died on day 80. Autopsy showed disseminated candidiasis, disseminated cytomegalovirus infection, thymic dysplasia, hypoplastic marrow, and other histopathologic changes consistent with GVH disease. The persistence of female cells in blood and bone marrow and the destruction of the reconstituted marrow suggest that the original incompatible transfusion-derived graft was not eliminated and that it ultimately rejected the histocompatible marrow graft.

  6. Therapeutic plasma exchange: a second-line treatment for brodifacoum poisoning following an anaphylactoid reaction to vitamin K.

    PubMed

    Deng, Ying; Qiu, Li

    2017-01-01

    Vitamin K1 is the first-line therapy to brodifacoum poisoning. Anaphylactoid reactions may occur anytime during intravenous administration of vitamin K1 injection. Vitamin K1 must be ceased when anaphylactoid reactions emerge, and therapeutic plasma exchange could be a second-line option.

  7. Production of neutron-rich Ca, Sn, and Xe isotopes in transfer-type reactions with radioactive beams

    SciTech Connect

    Adamian, G. G.; Antonenko, N. V.; Lacroix, D.

    2010-12-15

    The production cross sections of neutron-rich isotopes {sup 52,54,56,58,60}Ca, {sup 136,138,140,142}Sn, and {sup 146,148,150,152}Xe are predicted for future experiments in the diffusive multinucleon transfer reactions {sup 86,90,92,94}Kr, {sup 124,130,132,134}Sn, {sup 136,140,142,146}Xe, and {sup 138,144,146}Ba+{sup 48}Ca with stable and radioactive beams at incident energies close to the Coulomb barrier. Because of the small cross sections, the production of neutron-rich isotopes requires the optimal choice of projectile-target combinations and bombarding energies.

  8. Spectroscopy of neutron-rich Fe isotopes populated in the {sup 64}Ni+{sup 238}U reaction

    SciTech Connect

    Lunardi, S.; Lenzi, S. M.; Farnea, E.; Bazzacco, D.; Beghini, S.; Mason, P.; Mengoni, D.; Montagnoli, G.; Recchia, F.; Scarlassara, F.; Ur, C. A.; Vedova, F. Della; Gadea, A.; Corradi, L.; Angelis, G. de; Fioretto, E.; Napoli, D. R.; Orlandi, R.; Stefanini, A. M.; Valiente-Dobon, J. J.

    2007-09-15

    The neutron-rich Fe isotopes from A=61 to 66 were studied through multinucleon transfer reactions by bombarding a {sup 238}U target with a 400 MeV {sup 64}Ni beam. Unambiguous identification of prompt {gamma} rays belonging to each nucleus was achieved using coincidence relationships with the ions detected in a high-acceptance magnetic spectrometer. The new data extend our knowledge of the level structure of Fe isotopes, which is discussed in terms of the systematics of the region and compared with large-scale shell-model calculations.

  9. Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals

    NASA Astrophysics Data System (ADS)

    Opeida, I. A.; Litvinov, Yu. E.; Kushch, O. V.; Kompanets, M. A.; Shendrik, A. N.; Matvienko, A. G.; Novokhatko, A. A.

    2016-11-01

    The kinetics of the reactions of hydrogen atom abstraction from the C-H bonds of substrates of different structures by phthalimide- N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor-acceptor interactions affect the reaction between phthalimide- N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.

  10. Attempt to produce the isotopes of element 108 in the fusion reaction {sup 136}Xe+{sup 136}Xe

    SciTech Connect

    Oganessian, Yu. Ts.; Dmitriev, S. N.; Yeremin, A. V.; Aksenov, N. V.; Bozhikov, G. A.; Chepigin, V. I.; Chelnokov, M. L.; Lebedev, V. Ya.; Malyshev, O. N.; Petrushkin, O. V.; Shishkin, S. V.; Svirikhin, A. I.; Tereshatov, E. E.; Vostokin, G. K.

    2009-02-15

    A setup of the experiment on the production of the isotopes with Z=108 in the fusion reaction {sup 136}Xe+{sup 136}Xe and the obtained results are presented. At the excitation energy 0{<=}E{sub x}{<=}30 MeV of the {sup 272}Hs* compound nucleus the upper limit of the cross section for evaporation residues {sigma}{sub (1-3)n}{<=}4 pb has been measured. The experimental results together with the data from asymmetric reactions point to a strong limitation of the Hs compound nucleus formation with increasing Coulomb forces in the entrance channel of the reaction.

  11. EXCHANGE

    SciTech Connect

    Boltz, J.C.

    1992-09-01

    EXCHANGE is published monthly by the Idaho National Engineering Laboratory (INEL), a multidisciplinary facility operated for the US Department of Energy (DOE). The purpose of EXCHANGE is to inform computer users about about recent changes and innovations in both the mainframe and personal computer environments and how these changes can affect work being performed at DOE facilities.

  12. Communication: Rigorous quantum dynamics of O + O{sub 2} exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

    SciTech Connect

    Li, Yaqin; Sun, Zhigang E-mail: dawesr@mst.edu; Jiang, Bin; Guo, Hua E-mail: dawesr@mst.edu; Xie, Daiqian; Dawes, Richard E-mail: dawesr@mst.edu

    2014-08-28

    The kinetics and dynamics of several O + O{sub 2} isotope exchange reactions have been investigated on a recently determined accurate global O{sub 3} potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged “reef” structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.

  13. Communication: Rigorous quantum dynamics of O + O2 exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients.

    PubMed

    Li, Yaqin; Sun, Zhigang; Jiang, Bin; Xie, Daiqian; Dawes, Richard; Guo, Hua

    2014-08-28

    The kinetics and dynamics of several O + O2 isotope exchange reactions have been investigated on a recently determined accurate global O3 potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged "reef" structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.

  14. Communication: Rigorous quantum dynamics of O + O2 exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

    NASA Astrophysics Data System (ADS)

    Li, Yaqin; Sun, Zhigang; Jiang, Bin; Xie, Daiqian; Dawes, Richard; Guo, Hua

    2014-08-01

    The kinetics and dynamics of several O + O2 isotope exchange reactions have been investigated on a recently determined accurate global O3 potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged "reef" structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.

  15. Stratosphere-troposphere exchange: Inferences from the isotopic composition of water vapor

    NASA Astrophysics Data System (ADS)

    Keith, David W.

    2000-06-01

    Air may cross the tropical tropopause either by gradual ascent or in localized episodes associated with convection. While observations demonstrate that water vapor mixing ratios of air entering the tropical stratosphere are consistent with the mean tropical tropopause temperature, they do not resolve key mechanistic questions, such as the relative contribution of gradual or episodic transport, or the role of thin cirrus. As Moyer et al. [1996] clearly argue, observations of the isotopic content of water entering the tropical stratosphere can provide a strong constraint on models of water vapor transport across the tropopause. For example, stratospheric HDO is too abundant to be compatible with the assumption that all moisture enters the stratosphere as vapor during convection. Analysis of recent H218O observations shows that kinetic effects cannot explain the HDO excess. Lofting and evaporation of cloud ice can explain the observed stratospheric water vapor content and its isotopic composition, but the relative importance of gradual or episodic transport remains unresolved.

  16. Isotope exchange experiments on TEXTOR and TORE SUPRA using Ion Cyclotron Wall Conditioning and Glow Discharge Conditioning

    NASA Astrophysics Data System (ADS)

    Wauters, T.; Douai, D.; Lyssoivan, A.; Philipps, V.; Brémond, S.; Freisinger, M.; Kreter, A.; Lombard, G.; Marchuk, O.; Mollard, P.; Paul, M. K.; Pegourié, B.; Reimer, H.; Sergienko, G.; Tsitrone, E.; Vervier, M.; Van Wassenhove, G.; Wünderlich, D.; Van Schoor, M.; Van Oost, G.

    2011-08-01

    This contribution reports on isotope exchange studies with both Ion Cyclotron Wall Conditioning (ICWC) and Glow Discharge Conditioning (GDC) in TEXTOR and TORE SUPRA. The discharges have been carried out in H2, D2 (ICWC and GDC) and He/H2 mixtures (ICWC). The higher reionization probability in ICWC compared to GDC, following from the 3 to 4 orders of magnitude higher electron density, leads to a lower pumping efficiency of wall desorbed species. GDC has in this analysis (5-10) times higher removal rates of wall desorbed species than ICWC, although the wall release rate is 10 times higher in ICWC. Also the measured high retention during ICWC can be understood as an effect of the high reionization probability. The use of short RF pulses (∼1 s) followed by a larger pumping time significantly improves the ratio of implanted over recovered particles, without severely lowering the total amount of removed particles.

  17. Substituent effects on the vibronic coupling for the phenoxyl/phenol self-exchange reaction.

    PubMed

    Ludlow, Michelle K; Skone, Jonathan H; Hammes-Schiffer, Sharon

    2008-01-17

    The impact of substituents on the vibronic coupling for the phenoxyl/phenol self-exchange reaction, which occurs by a proton-coupled electron transfer mechanism, is investigated. The vibronic couplings are calculated with a grid-based nonadiabatic method and a nuclear-electronic orbital nonorthogonal configuration interaction method. The quantitative agreement between these two methods for the unsubstituted phenoxyl/phenol system and the qualitative agreement in the predicted trends for the substituted phenoxyl/phenol systems provides a level of validation for both methods. Analysis of the results indicates that electron-donating groups enhance the vibronic coupling, while electron-withdrawing groups attenuate the vibronic coupling. Thus, if all other aspects of the reaction are the same, then electron-donating groups will increase the rate, while electron-withdrawing groups will decrease the rate. Correlations between the vibronic coupling and physical properties of the phenol are also analyzed. Negative Hammett constants correspond to higher vibronic couplings, while positive Hammett constants correspond to similar or slightly lower vibronic couplings relative to the unsubstituted phenoxyl/phenol system. In addition, lower bond dissociation enthalpies, ionization potentials, and redox potentials, as well as higher pKa values, tend to correspond to higher vibronic couplings relative to the unsubstituted phenoxyl/phenol system. The observed trends enable the prediction of the impact of general substituents on the vibronic coupling, and hence the rate, for the phenoxyl/phenol self-exchange reaction. The fundamental physical insights obtained from these studies are applicable to other proton-coupled electron transfer systems.

  18. Determination of component mobilities in bimineralic reaction rims using isotopically doped starting materials

    NASA Astrophysics Data System (ADS)

    Joachim, Bastian; Abart, Rainer; Höschen, Carmen; Heinrich, Wilhelm

    2013-04-01

    Rim growth experiments were performed between monticellite (CaMgSiO4) single crystals and wollastonite (CaSiO3) powder at 900° C and 1.2 GPa to produce bimineralic diopside (CaMgSi2O6) + merwinite (Ca3MgSi2O8) reaction rims. Symmetrical makeup of the internal rim microstructure implies that rims grow from the original interface towards both reactants at identical rates, indicating that solely MgO-diffusion controls overall rim growth with logD (MgO) = -16.3 ± 0.2 m2s-1 (Joachim et al. 2012). Presence of ppm-amounts of water significantly affects the internal rim microstructure. At "very dry" condition, a lamellar microstructure of alternating palisade-shaped diopside and merwinite grains elongated normal to the reaction front is generated, indicating that CaO and SiO2-mobilities are significantly smaller compared to the MgO-mobility. In presence of minute amounts of water a segregated multilayer microstructure with almost perfectly monomineralic merwinite - diopside - merwinite layers oriented parallel to the reaction front develops, indicating a sufficient additional mobility of either CaO or SiO2 compared to MgO. We used isotopically doped wollastonite (44Ca29SiO3) to identify, which component mobility, CaO or SiO2, is enhanced in presence of ppm amounts of water. Both, 44Ca stemming from the wollastonite as well as 40Ca stemming from the monticellite are distributed across the entire rim. In addition to that, small amounts of 40Ca are found within the wollastonite and substantial amounts of 44Ca are found in the monticellite starting material. In contrast to that, 28Si and 29Si remain in the regions that were originally occupied by their respective source materials monticellite and wollastonite, indicating that the SiO2-mobility is comparatively low. This suggests that the presence of small amounts of water significantly enhances the relative mobility of CaO. Consequently minute amounts of water may not only affect overall rim growth kinetics but also the

  19. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Pascal, Bruce D.; Bauman, Joseph D.; Patel, Disha; Arnold, Eddy; Griffin, Patrick R.

    2015-01-01

    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched (15N-labeled) p51 and unlabeled p66. In order to enable detection of 15N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% 15N model. Our results demonstrated that 15N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but 15N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the nonnucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV co-crystal structure. PMID:25763479

  20. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Goswami, Devrishi; Tuske, Steve; Pascal, Bruce D; Bauman, Joseph D; Patel, Disha; Arnold, Eddy; Griffin, Patrick R

    2015-04-07

    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched ((15)N-labeled) p51 and unlabeled p66. To enable detection of (15)N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% (15)N model. Our results demonstrated that (15)N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but (15)N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the non-nucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV cocrystal structure.

  1. Kinetic and Vibrational Isotope Effects of Proton Transfer Reactions in Channelrhodopsin-2

    PubMed Central

    Resler, Tom; Schultz, Bernd-Joachim; Lórenz-Fonfría, Víctor A.; Schlesinger, Ramona; Heberle, Joachim

    2015-01-01

    Channelrhodopsins (ChRs) are light-gated cation channels. After blue-light excitation, the protein undergoes a photocycle with different intermediates. Here, we have recorded transient absorbance changes of ChR2 from Chlamydomonas reinhardtii in the visible and infrared regions with nanosecond time resolution, the latter being accomplished using tunable quantum cascade lasers. Because proton transfer reactions play a key role in channel gating, we determined vibrational as well as kinetic isotope effects (VIEs and KIEs) of carboxylic groups of various key aspartic and glutamic acid residues by monitoring their C=O stretching vibrations in H2O and in D2O. D156 exhibits a substantial KIE (>2) in its deprotonation and reprotonation, which substantiates its role as the internal proton donor to the retinal Schiff base. The unusual VIE of D156, upshifted from 1736 cm−1 to 1738 cm−1 in D2O, was scrutinized by studying the D156E variant. The C=O stretch of E156 shifted down by 8 cm−1 in D2O, providing evidence for the accessibility of the carboxylic group. The C=O stretching band of E90 exhibits a VIE of 9 cm−1 and a KIE of ∼2 for the de- and the reprotonation reactions during the lifetime of the late desensitized state. The KIE of 1 determined in the time range from 20 ns to 5 ms is incompatible with early deprotonation of E90. PMID:26200864

  2. Evidence for Oxygen-Isotope Exchange in Chondrules and Refractory Inclusions During Fluid-Rock Interaction on the CV Chondrite Parent Body

    NASA Astrophysics Data System (ADS)

    Krot, A. N.; Nagashima, K.

    2016-08-01

    Plagioclase in chondrules, CAIs and AOAs from the carbonaceous chondrite Kaba (CV3.1) experienced oxygen-isotope exchange with a metasomatic fluid responsible for the formation of magnetite, fayalite and Ca,Fe-rich silicates on the CV parent body.

  3. Enhanced catalytic performance of copper-exchanged SAPO-34 molecular sieve in methanol-to-olefin reaction.

    PubMed

    Kim, Sun Jung; Park, Ji Won; Lee, Kwang Young; Seo, Gon; Song, Mee Kyung; Jeong, Soon-Yong

    2010-01-01

    Methanol-to-olefin (MTO) reaction over copper-exchanged SAPO-34 catalysts was investigated in order to extend their catalyst life. The exchange of copper ions into the cages of an SAPO-34 molecular sieve was confirmed by ESR, XPS, and 129Xe NMR techniques. Copper ions located in its cages considerably reduced its deactivation rate in the MTO reaction, while those dispersed on the external surface of the SAPO-34 molecular sieve accelerated the deactivation due to the limited mass transfer through the pore entrances. The 13C NMR and UV-VIS spectroscopy investigations of the materials occluded on the copper-exchanged SAPO-34 catalysts during the MTO reaction clearly showed that the copper ions exchanged in the cages suppressed the further condensation of alkyl aromatics to large, fused polycyclic aromatic hydrocarbons (PAHs). Theoretical calculations for the SAPO-34 and copper-exchanged SAPO-34 molecular sieves supported this observation because copper ions located in the cages stabilized the alkyl aromatics. Therefore, the exchange of copper ions into the SAPO-34 molecular sieve stabilized the reactive intermediates, alkyl aromatics, of the MTO reaction and suppressed their further condensation to PAHs, thereby slowing the deactivation.

  4. Silicate-SiO reaction in a protoplanetary disk recorded by oxygen isotopes in chondrules

    NASA Astrophysics Data System (ADS)

    Tanaka, Ryoji; Nakamura, Eizo

    2017-07-01

    The formation of planetesimals and planetary embryos during the earliest stages of the solar protoplanetary disk largely determined the composition and structure of the terrestrial planets. Within a few million years of the birth of the Solar System, chondrule formation and the accretion of the parent bodies of differentiated achondrites and the terrestrial planets took place in the inner protoplanetary disk 1,2 . Here we show that, for chondrules in unequilibrated enstatite chondrites, high-precision Δ17O values (where Δ17O is the deviation of the δ17O value from a terrestrial silicate fractionation line) vary significantly (ranging from -0.49 to +0.84‰) and fall on an array with a steep slope of 1.27 on a three-oxygen-isotope plot. This array can be explained by the reaction between an olivine-rich chondrule melt and an SiO-rich gas derived from vaporized dust and nebular gas. Our study suggests that a large proportion of the building blocks of planetary embryos formed by successive silicate-gas interaction processes: silicate-H2O followed by silicate-SiO interactions under more oxidized and reduced conditions, respectively, within a few million years of the formation of the Solar System.

  5. Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

    NASA Astrophysics Data System (ADS)

    Marzouk, E. R.; Chenery, S. R.; Young, S. D.

    2013-12-01

    The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop

  6. Magnesium retention on the soil exchange complex controlling Mg isotope variations in soils, soil solutions and vegetation in volcanic soils, Iceland

    NASA Astrophysics Data System (ADS)

    Opfergelt, S.; Burton, K. W.; Georg, R. B.; West, A. J.; Guicharnaud, R. A.; Sigfusson, B.; Siebert, C.; Gislason, S. R.; Halliday, A. N.

    2014-01-01

    Understanding the biogeochemical cycle of magnesium (Mg) is not only crucial for terrestrial ecology, as this element is a key nutrient for plants, but also for quantifying chemical weathering fluxes of Mg and associated atmospheric CO2 consumption, requiring distinction of biotic from abiotic contributions to Mg fluxes exported to the hydrosphere. Here, Mg isotope compositions are reported for parent basalt, bulk soils, clay fractions, exchangeable Mg, seasonal soil solutions, and vegetation for five types of volcanic soils in Iceland in order to improve the understanding of sources and processes controlling Mg supply to vegetation and export to the hydrosphere. Bulk soils (δ26Mg = -0.40 ± 0.11‰) are isotopically similar to the parent basalt (δ26Mg = -0.31‰), whereas clay fractions (δ26Mg = -0.62 ± 0.12‰), exchangeable Mg (δ26Mg = -0.75 ± 0.14‰), and soil solutions (δ26Mg = -0.89 ± 0.16‰) are all isotopically lighter than the basalt. These compositions can be explained by a combination of mixing and isotope fractionation processes on the soil exchange complex. Successive adsorption-desorption of heavy Mg isotopes leads to the preferential loss of heavy Mg from the soil profile, leaving soils with light Mg isotope compositions relative to the parent basalt. Additionally, external contributions from sea spray and organic matter decomposition result in a mixture of Mg sources on the soil exchange complex. Vegetation preferentially takes up heavy Mg from the soil exchange complex (Δ26Mgplant-exch = +0.50 ± 0.09‰), and changes in δ26Mg in vegetation reflect changes in bioavailable Mg sources in soils. This study highlights the major role of Mg retention on the soil exchange complex amongst the factors controlling Mg isotope variations in soils and soil solutions, and demonstrates that Mg isotopes provide a valuable tool for monitoring biotic and abiotic contributions of Mg that is bioavailable for plants and is exported to the hydrosphere.

  7. Optimization and application of ICPMS with dynamic reaction cell for precise determination of 44Ca/40Ca isotope ratios.

    PubMed

    Boulyga, Sergei F; Klötzli, Urs; Stingeder, Gerhard; Prohaska, Thomas

    2007-10-15

    An inductively coupled plasma mass spectrometer with dynamic reaction cell (ICP-DRC-MS) was optimized for determining (44)Ca/(40)Ca isotope ratios in aqueous solutions with respect to (i) repeatability, (ii) robustness, and (iii) stability. Ammonia as reaction gas allowed both the removal of (40)Ar+ interference on (40)Ca+ and collisional damping of ion density fluctuations of an ion beam extracted from an ICP. The effect of laboratory conditions as well as ICP-DRC-MS parameters such a nebulizer gas flow rate, rf power, lens potential, dwell time, or DRC parameters on precision and mass bias was studied. Precision (calculated using the "unbiased" or "n - 1" method) of a single isotope ratio measurement of a 60 ng g(-1) calcium solution (analysis time of 6 min) is routinely achievable in the range of 0.03-0.05%, which corresponded to the standard error of the mean value (n = 6) of 0.012-0.020%. These experimentally observed RSDs were close to theoretical precision values given by counting statistics. Accuracy of measured isotope ratios was assessed by comparative measurements of the same samples by ICP-DRC-MS and thermal ionization mass spectrometry (TIMS) by using isotope dilution with a (43)Ca-(48)Ca double spike. The analysis time in both cases was 1 h per analysis (10 blocks, each 6 min). The delta(44)Ca values measured by TIMS and ICP-DRC-MS with double-spike calibration in two samples (Ca ICP standard solution and digested NIST 1486 bone meal) coincided within the obtained precision. Although the applied isotope dilution with (43)Ca-(48)Ca double-spike compensates for time-dependent deviations of mass bias and allows achieving accurate results, this approach makes it necessary to measure an additional isotope pair, reducing the overall analysis time per isotope or increasing the total analysis time. Further development of external calibration by using a bracketing method would allow a wider use of ICP-DRC-MS for routine calcium isotopic measurements, but it

  8. Ion-molecule reactions involving HCO+ and N2H+: Isotopologue equilibria from new theoretical calculations and consequences for interstellar isotope fractionation

    NASA Astrophysics Data System (ADS)

    Mladenović, M.; Roueff, E.

    2014-06-01

    Aims: We revisit with new augmented accuracy the theoretical dynamics of basic isotope exchange reactions involved in the 12C/13C, 16O/18O, and 14N/15N balance because these reactions have already been studied experimentally in great detail. Methods: Electronic structure methods were employed to explore potential energy surfaces, full-dimensional rovibrational calculations to compute rovibrational energy levels that are numerically exact, and chemical network models to estimate the abundance ratios under interstellar conditions. Results: New exothermicities, derived for HCO+ reacting with CO, provide rate coefficients markedly different from previous theoretical values in particular at low temperatures, resulting in new abundance ratios relevant for carbon chemistry networks. In concrete terms, we obtain a reduction in the abundance of H12C18O+ and an increase in the abundance of H13C16O+ and D13C16O+. In all studied cases, the reaction of the ion with a neutral polarizable molecule proceeds through the intermediate proton-bound complex found to be very stable. For the complexes OCH+··· CO, OCH+··· OC, COHOC+, N2··· HCO+, N2H+··· OC, and N2HN2+, we also calculated vibrational frequencies and dissociation energies. Conclusions: The linear proton-bound complexes possess sizeable dipole moments, which may facilitate their detection.

  9. Quantification of tritium ``heels`` and isotope exchange mechanisms in La-Ni-Al tritides

    SciTech Connect

    Wermer, J.R.

    1992-07-27

    Formation of tritium heels in LANA (LaNi{sub 5-x}Al{sub x}) 0.30 (x=0.30) and 0.75 tritides was quantified; size of the heel is dependent on storage and processing conditions. Absorption-desorption cycling of the tritide beds mitigates formation of the tritium heel and can reduce its size. The higher pressure material LANA 0.30 showed slower heel formation than LANA 0.75; this allows more tritium to be removed at the maximum processing temperature. In plant application, LANA 0.30 beds are used as compressors; except during compressor operation, their aging will be very slow. Tritium heel removal by D exchange was demonstrated. Absorption-desorption cycling during an exchange cycle does not improve the exchange efficiency. Residual tritium can be removed to very low levels. For a tritide bed scheduled for removal from the process, a final tritium level can be estimated based on the number of D exchange cycles. 13 refs, 8 figs, 6 tabs.

  10. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  11. Boron isotope exchange in a heterogeneous boron-boron fluoride system

    SciTech Connect

    Begak, O.Yu.; Fedorov, V.V.

    1988-11-01

    Studies have been made on exchange between /sup 10/B and /sup 11/B in heterogeneous systems containing finely divided amorphous boron and BF/sub 3/ gas. The kinetic and thermodynamic parameters have been examined. The self-diffusion coefficient for boron in amorphous boron has been determined at 973-1273 K.

  12. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  13. Rare events via multiple reaction channels sampled by path replica exchange

    NASA Astrophysics Data System (ADS)

    Bolhuis, Peter G.

    2008-09-01

    Transition path sampling (TPS) was developed for studying activated processes in complex systems with unknown reaction coordinate. Transition interface sampling (TIS) allows efficient evaluation of the rate constants. However, when the transition can occur via more than one reaction channel separated by a high barrier, TPS and TIS are ineffective in sampling both channels. The combination of replica exchange with TIS can overcome this problem. This work shows how, by including both the backward and forward reactions, the corresponding rate constants, as well as the free energy barrier can be computed in a single simulation. The method is illustrated on a two dimensional potential using the Langevin dynamics. In addition, a simpler algorithm based on only forward shooting from the interfaces is shown to give equally accurate results, and forms a bridge between the transition interface and the forward flux sampling methods. The diffusive behavior of the replicas can be used to assess the quality of the choice of the order parameter used for the interfaces.

  14. Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2016-12-01

    Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

  15. Synthesis of ordered mesoporous crystalline CuS and Ag2S materials via cation exchange reaction

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Xu, Weiming; Bao, Haifeng; Shi, Yifeng

    2015-02-01

    Cation exchange reaction is a strong tool for the synthesis of new ionic nanomaterials. Most of them are isolated nanoparticles with simple geometric features, such as nanodots, nanorods and nanospheres. In this work, we demonstrated that ordered mesoporous CdS with a complex cubic Ia3d gyroidal 3D bicontinuous porous structure and large particle size can be successfully converted to crystalline CuS and Ag2S materials via cation exchange reaction without destroying the well-defined nanostructure. The change in crystal structure is an important factor for a successful conversion when the reaction is carried out without the presence of a silica template. In addition, the cation exchange reaction is sufficient for a complete compositional conversion, even when the mesostructured CdS precursor is embedded inside a mesoporous silica matrix. Our results indicate that cation exchange reaction may be applied to highly complex nanostructures with extremely large particle sizes.Cation exchange reaction is a strong tool for the synthesis of new ionic nanomaterials. Most of them are isolated nanoparticles with simple geometric features, such as nanodots, nanorods and nanospheres. In this work, we demonstrated that ordered mesoporous CdS with a complex cubic Ia3d gyroidal 3D bicontinuous porous structure and large particle size can be successfully converted to crystalline CuS and Ag2S materials via cation exchange reaction without destroying the well-defined nanostructure. The change in crystal structure is an important factor for a successful conversion when the reaction is carried out without the presence of a silica template. In addition, the cation exchange reaction is sufficient for a complete compositional conversion, even when the mesostructured CdS precursor is embedded inside a mesoporous silica matrix. Our results indicate that cation exchange reaction may be applied to highly complex nanostructures with extremely large particle sizes. Electronic supplementary

  16. Photonuclear reactions on the cadmium isotopes {sup 106,108}Cd at the bremsstrahlung endpoint energy of 55.5 MeV

    SciTech Connect

    Belyshev, S. S.; Kuznetsov, A. A.; Stopani, K. A. Khankin, V. V.

    2016-09-15

    The gamma-activation technique was used to measure the absolute yields of photonuclear reactions on the cadmium isotopes {sup 106,108}Cd. The results obtained in this way were compared with the results of the calculations based on the statistical model. For reactions on the isotope {sup 108}Cd, agreement between these theoretical and experimental results is good, but the experimental ratio of the yields of photoproton and photoneutron reactions on the isotope {sup 106}Cd differs substantially from its theoretical counterpart. The results of our present study are discussed from the point of view of the production of bypassed nuclei in the p-process of nucleosynthesis.

  17. Delta excitations and shell-model information in heavy-ion, charge-exchange reactions

    NASA Technical Reports Server (NTRS)

    Deutchman, P. A.; Maung, K. M.; Norbury, J. W.; Rasmussen, J. O.; Townsend, L. W.

    1986-01-01

    We calculate total cross sections for coherent pion production using localized plane-wave approximations for the shell-structure of valence nucleons that are excited to delta particles in the intermediate state in the (12C, 12B) and (12C, 12N) charge-exchange, heavy-ion reactions. We find comparable agreement to projectile downshift data for 12C(12C, 12B)12N. Then we improve the formalism by replacing the localized plane wave bound states with harmonic oscillator states which are imbedded in a multipole expansion approach and calculate pion differential cross sections to test for the sensitivity of the spectra to the single-particle mass parameter.

  18. The monomethylethanolamine- and dimethylethanolamine-base exchange reactions of rat-brain microsomal fraction.

    PubMed

    Kanfer, J N

    1986-12-05

    The ability of crude rat-brain microsome preparations to convert DME and MME to their corresponding phospholipid was explored. In common with the other base-exchange reactions, the incorporations of DME and MME were stimulated by about 1-4 mM Ca2+, possessed slightly alkaline pH optima, were energy independent and were unaffected by exogenous phospholipids. The Km values were 0.97 mM and 0.5 mM and the Vmax values were 9.6 nmol/mg protein per h and 6.25 nmol/mg protein per h for DME and MME, respectively. The P3 fraction of the brain and heart had the highest specific activities of particles prepared from several tissues.

  19. Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions.

    PubMed

    Zhang, Dandan; Yang, Yiming; Bekenstein, Yehonadav; Yu, Yi; Gibson, Natalie A; Wong, Andrew B; Eaton, Samuel W; Kornienko, Nikolay; Kong, Qiao; Lai, Minliang; Alivisatos, A Paul; Leone, Stephen R; Yang, Peidong

    2016-06-15

    Here, we demonstrate the successful synthesis of brightly emitting colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) nanowires (NWs) with uniform diameters and tunable compositions. By using highly monodisperse CsPbBr3 NWs as templates, the NW composition can be independently controlled through anion-exchange reactions. CsPbX3 alloy NWs with a wide range of alloy compositions can be achieved with well-preserved morphology and crystal structure. The NWs are highly luminescent with photoluminescence quantum yields (PLQY) ranging from 20% to 80%. The bright photoluminescence can be tuned over nearly the entire visible spectrum. The high PLQYs together with charge transport measurements exemplify the efficient alloying of the anionic sublattice in a one-dimensional CsPbX3 system. The wires increased functionality in the form of fast photoresponse rates and the low defect density suggest CsPbX3 NWs as prospective materials for optoelectronic applications.

  20. Spin dipole nuclear matrix elements for double beta decay nuclei by charge-exchange reactions

    NASA Astrophysics Data System (ADS)

    Ejiri, H.; Frekers, D.

    2016-11-01

    Spin dipole (SD) strengths for double beta-decay (DBD) nuclei were studied experimentally for the first time by using measured cross sections of (3He, t) charge-exchange reactions (CERs). Then SD nuclear matrix elements (NMEs) {M}α ({{SD}}) for low-lying 2- states were derived from the experimental SD strengths by referring to the experimental α = GT (Gamow-Teller) and α = F (Fermi) strengths. They are consistent with the empirical NMEs M({{SD}}) based on the quasi-particle model with the empirical effective SD coupling constant. The CERs are used to evaluate the SD NME, which is associated with one of the major components of the neutrino-less DBD NME.