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Sample records for few-nucleon transfer reactions

  1. Few-nucleon transfer reactions on deformed nuclei

    SciTech Connect

    van den Berg, A.M.

    1985-01-01

    Recent developments discussed include: alpha-transfer reactions on deformed nuclei, quasi-elastic neutron transfer reactions induced by /sup 58/Ni beams on spherical and deformed samarium nuclei, and the population of low-lying states in neutron rich nuclei using (particle,..gamma..) or (particle,e) coincidence methods. 37 refs., 10 figs. (LEW)

  2. Few-Nucleon Systems

    NASA Astrophysics Data System (ADS)

    Viviani, Michele

    The recent theoretical advances in the study of the statical and dynamical properties of few-nucleon systems are here reported, with particular attention to the research activities performed under the Italian MURST-PRIN project FISICA DEL NUCLEO E DEI SISTEMI A PIÙ CORPI. The latter studies also include the development of methods for dealing with pionic degrees of freedom, the determination of static properties of light nuclei, and the computation of few-nucleon reaction observables, including electroweak processes.

  3. Few-Nucleon Systems

    NASA Astrophysics Data System (ADS)

    Kievsky, A.

    2005-04-01

    Recent advances in the theoretical description of few-nucleon systems are reported. This research activity has been performed under the Italian project FISICA TEORICA DEL NUCLEO E DEI SISTEMI A MOLTI CORPI. Bound and scattering states as well as specific reactions are analyzed in connection with the current experimental activity.

  4. Recent Progresses in Ab-Initio Studies of Low-Energy Few-Nucleon Reactions of Astrophysical Interest

    NASA Astrophysics Data System (ADS)

    Marcucci, Laura E.

    2017-03-01

    We review the most recent theoretical studies of nuclear reactions of astrophysical interest involving few-nucleon systems. In particular, we focus on the radiative capture of protons by deuterons in the energy range of interest for Big Bang Nucleosynthesis. Related to this, we will discuss also the most recent calculation of tritium β -decay. Two frameworks will be considered, the conventional and the chiral effective field theory approach.

  5. Parity violation in few-nucleon systems

    NASA Astrophysics Data System (ADS)

    Schindler, Matthias

    2017-01-01

    Parity-violating interactions between nucleons are the manifestation of an interplay between strong and weak quark-quark interactions at the hadronic level. Because of the short range of the weak interactions, these parity-violating forces provide a unique probe of low-energy strong interactions. In addition, a better understanding of parity violation in nuclei could also shed light on problems in the hadronic weak interactions involving strange quarks. An ongoing experimental program is mapping out the weak component of the nuclear force in few-nucleon systems. Recent theoretical progress in analyzing and interpreting hadronic parity violation in such systems, based on effective field theory methods, will be described. This work was supported by the DOE Office of Science, Office of Nuclear Physics.

  6. Recent Experiments Involving Few-Nucleon Systems

    NASA Astrophysics Data System (ADS)

    Tornow, W.

    2014-08-01

    Recent experimental results are presented for reactions involving A = 3 to A = 6 nuclear systems. The emphasis is on unique data obtained at new experimental facilities. It is shown that the inertial confinement fusion facilities OMEGA and NIF provide a largely unexpected opportunity for experimental few-body physics to both obtain data of unprecedented quality and extend previous measurements to energies not accessible in the past. Whenever possible, data are compared to state-of-the-art theoretical calculations.

  7. Hard QCD rescattering in few nucleon systems

    NASA Astrophysics Data System (ADS)

    Maheswari, Dhiraj; Sargsian, Misak

    2017-01-01

    The theoretical framework of hard QCD rescattering mechanism (HRM) is extended to calculate the high energy γ3 He -> pd reaction at 900 center of mass angle. In HRM model , the incoming high energy photon strikes a quark from one of the nucleons in the target which subsequently undergoes hard rescattering with the quarks from the other nucleons generating hard two-body baryonic system in the final state of the reaction. Based on the HRM, a parameter free expression for the differential cross section for the reaction is derived, expressed through the 3 He -> pd transition spectral function, hard pd -> pd elastic scattering cross section and the effective charge of the quarks being interchanged in the hard rescattering process. The numerical estimates obtained from this expression for the differential cross section are in a good agreement with the data recently obtained at the Jefferson Lab experiment, showing the energy scaling of cross section with an exponent of s-17, also consistent with the quark counting rule. The angular and energy dependences of the cross section are also predicted within HRM which are in good agreement with the preliminary data of these distributions. Research is supported by the US Department of Energy.

  8. Study of the Few Nucleon Systems at CLAS

    NASA Astrophysics Data System (ADS)

    Zachariou, Nicholas

    2017-03-01

    The study of few nucleon systems with electromagnetic probes is an essential component of the scientific program carried out at the Thomas Jefferson National Accelerator Facility (JLab). Here we present measurements of exclusive reactions on light nuclei using real photon beams with energies up to 3 GeV and the CEBAF Large Acceptance Spectrometer (CLAS), a nearly 4π magnetic spectrometer, in order to study the properties of strongly interacting matter and the transition from hadronic (i.e in terms of nucleons and mesons) to partonic (in terms of quark and gluons) degrees of freedom in nuclear interactions. We discuss the progress made in understanding the relevant degrees of freedom using polarisation observables and cross sections of deuteron and ^3He photodisintegration in the few-GeV photon-energy region. In addition, recent high-statistics experiments with the CLAS detector have provided us with sufficient counting rates to study the effects of initial- and final-state interactions in reactions off the deuteron. Such data allow us to extract a large set of polarisation observables for final-state interactions in hyperon photoproduction and to study the properties of the hyperon-nucleon interaction. Initial-state effects are studied by mapping the dependence of experimental observables on the spectator-nucleon momentum. We also present recent results for polarisation observables for quasi-free K^+Λ off the bound proton in a deuteron as well as for final-state interactions in the reaction γ d→ K^+Λ n, and will discuss their impact on hyperon-nucleon studies.

  9. A relativistic theory of few-nucleon systems

    SciTech Connect

    Alfred Stadler

    2010-12-01

    This talk provides an overview of recent results for two- and three-nucleon systems obtained within the framework of the covariant spectator theory (CST). The main features of two recently published models for the neutron–proton interaction, that fit the 2007 world data base containing several thousands of neutron-proton scattering data below 350 MeV with χ 2/N data ≈ 1, are presented. These one-boson-exchange models, called WJC-1 and WJC-2, have a considerably smaller number of adjustable parameters than are present in realistic nonrelativistic potentials. When applied to the three-nucleon bound state, the correct binding energy is obtained without additional three-body forces. First calculations of the electromagnetic form factors of helium-3 and the triton in complete impulse approximation also give very reasonable results. One can conclude that the CST yields a very efficient description of few-nucleon systems, in which the relativistic formulation of the dynamics is an essential element.

  10. $\\chi$EFT studies of few-nucleon systems: a status report

    SciTech Connect

    Schiavilla, Rocco

    2016-06-01

    A status report on $\\chi$EFT studies of few-nucleon electroweak structure and dynamics is provided, including electromagnetic elastic form factors of few-nucleon systems, the $pp$ weak fusion and muon weak captures on deuteron and $^3$He, and a number of parity-violating processes induced by hadronic weak interactions.

  11. Chiral effective field theory analysis of hadronic parity violation in few-nucleon systems

    SciTech Connect

    Viviani, M.; Baroni, A.; Girlanda, L.; Kievsky, A.; Marcucci, L. E.; Schiavilla, R.

    2014-06-18

    Weak interactions between quarks induce a parity-violating (PV) component in the nucleon-nucleon potential, whose effects are currently being studied in a number of experiments involving few-nucleon systems. In the present work, we reconsider the derivation of this PV component within a chiral effective field theory (${\\chi }$EFT) framework. Purpose: The objectives of the present work are twofold. The first is to perform a detailed analysis of the PV nucleon-nucleon potential up to next-to-next-to-leading (N2LO) order in the chiral expansion, in particular, by determining the number of independent low-energy constants (LECs) at N2LO. The second objective is to investigate PV effects in a number of few-nucleon observables, including the $\\vec{p}$-p longitudinal asymmetry, the neutron spin rotation in n-p and n-d scattering, and the longitudinal asymmetry in the 3He( $\\vec{n}$,p)3H charge-exchange reaction. Methods: The ${\\chi }$EFT PV potential includes one-pion-exchange, two-pion-exchange, and contact terms as well as 1/M (M being the nucleon mass) nonstatic corrections. Dimensional regularization is used to renormalize pion loops. The wave functions for the A=2-4 nuclei are obtained by using strong two- and three-body potentials also derived, for consistency, from ${\\chi }$EFT. In the case of the A=3-4 systems, systems, the wave functions are computed by expanding on a hyperspherical harmonics functions basis. Results: We find that the PV potential at N2LO depends on six LECs: the pion-nucleon PV coupling constant h$1\\atop{π}$ and five parameters multiplying contact interactions. An estimate for the range of values of the various LECs is provided by using available experimental data, and these values are used to obtain predictions for the other PV observables. Conclusions: The ${\\chi }$EFT approach provides a very satisfactory framework to analyze PV effects in few-nucleon systems.

  12. Experimental Studies of Nuclear Interactions in Few-Nucleon Systems

    NASA Astrophysics Data System (ADS)

    Stephan, E.; Kistryn, St.; Kalantar-Nayestanaki, N.; Kozela, A.

    2017-03-01

    Systems of three nucleons (3N) can be treated as a testing ground for modern approaches to describe nuclear interactions. At intermediate energies, observables for 3N systems are sensitive to subtle effects of the dynamics beyond the pairwise nucleon-nucleon force, so-called 3N-force (3NF). For years the search for 3NF has been motivating precise measurements of observables of elastic nucleon-deuteron scattering and for the deuteron breakup reaction. Breakup of a deuteron in collision with a proton leads to the final state of three free nucleons, with variety of possible kinematic configurations, revealing locally enhanced sensitivity to particular aspects of the interaction dynamics, like 3NF, Coulomb force between protons, or relativistic effects. This feature makes the breakup reaction a very versatile tool for validation of the theoretical description. Reactions involving four nucleons pose immense challenges with regard to exact theoretical calculations for such systems. Nonetheless, they attract attention due to expected enhanced sensitivity to certain aspects of the nuclear dynamics, manifesting themselves in various channels and configurations. The most important results of recent experimental studies of 3N and 4N systems at intermediate energies are discussed. A brief survey of the ongoing projects is given.

  13. Electromagnetic structure of few-nucleon ground states

    DOE PAGES

    Marcucci, Laura E.; Gross, Franz L.; Peña, M. T.; ...

    2016-01-08

    Experimental form factors of the hydrogen and helium isotopes, extracted from an up-to-date global analysis of cross sections and polarization observables measured in elastic electron scattering from these systems, are compared to predictions obtained in three different theoretical approaches: the first is based on realistic interactions and currents, including relativistic corrections (labeled as the conventional approach); the second relies on a chiral effective field theory description of the strong and electromagnetic interactions in nuclei (labeled ChiEFT); the third utilizes a fully relativistic treatment of nuclear dynamics as implemented in the covariant spectator theory (labeled CST). Furthermore, for momentum transfers belowmore » Q < 5 fm-1 there is satisfactory agreement between experimental data and theoretical results in all three approaches. Conversely, at Q > 5 fm-1, particularly in the case of the deuteron, a relativistic treatment of the dynamics, as is done in the CST, is necessary. The experimental data on the deuteron A structure function extend to Q ~ 12 fm-1, and the close agreement between these data and the CST results suggests that, even in this extreme kinematical regime, there is no evidence for new effects coming from quark and gluon degrees of freedom at short distances.« less

  14. Electromagnetic structure of few-nucleon ground states

    SciTech Connect

    Marcucci, Laura E.; Gross, Franz L.; Peña, M. T.; Piarulli, M.; Schiavilla, Rocco; Sick, Ingo; Stadler, Alfred; Orden, J. W. Van; Viviani, Michele

    2016-01-08

    Experimental form factors of the hydrogen and helium isotopes, extracted from an up-to-date global analysis of cross sections and polarization observables measured in elastic electron scattering from these systems, are compared to predictions obtained in three different theoretical approaches: the first is based on realistic interactions and currents, including relativistic corrections (labeled as the conventional approach); the second relies on a chiral effective field theory description of the strong and electromagnetic interactions in nuclei (labeled ChiEFT); the third utilizes a fully relativistic treatment of nuclear dynamics as implemented in the covariant spectator theory (labeled CST). Furthermore, for momentum transfers below Q < 5 fm-1 there is satisfactory agreement between experimental data and theoretical results in all three approaches. Conversely, at Q > 5 fm-1, particularly in the case of the deuteron, a relativistic treatment of the dynamics, as is done in the CST, is necessary. The experimental data on the deuteron A structure function extend to Q ~ 12 fm-1, and the close agreement between these data and the CST results suggests that, even in this extreme kinematical regime, there is no evidence for new effects coming from quark and gluon degrees of freedom at short distances.

  15. Effective Field Theory and Isospin Violation in Few-Nucleon Systems

    SciTech Connect

    Evgeny Epelbaum

    2004-08-01

    I discuss the leading and subleading isospin--breaking three--nucleon forces in the chiral effective field theory framework. I have discussed the leading and subleading isospin-violating 3NFs. The leading contributions are generated by one- and two-pion exchange diagrams with their strength given by the strong neutron-proton mass difference. The subleading corrections are again given by one- and two-pion exchange diagrams, driven largely by the charged-to-neutral pion mass difference and also by the electromagnetic neutron-proton mass difference and the dimension two electromagnetic LEC f{sub 1}. In the future, these isospin-breaking forces should be used to analyze few-nucleon systems based on chiral EFT.

  16. Mass Transfer with Chemical Reaction.

    ERIC Educational Resources Information Center

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  17. Transfer reactions in nuclear astrophysics

    NASA Astrophysics Data System (ADS)

    Bardayan, D. W.

    2016-08-01

    To a high degree many aspects of the large-scale behavior of objects in the Universe are governed by the underlying nuclear physics. In fact the shell structure of nuclear physics is directly imprinted into the chemical abundances of the elements. The tranquility of the night sky is a direct result of the relatively slow rate of nuclear reactions that control and determines a star’s fate. Understanding the nuclear structure and reaction rates between nuclei is vital to understanding our Universe. Nuclear-transfer reactions make accessible a wealth of knowledge from which we can extract much of the required nuclear physics information. A review of transfer reactions for nuclear astrophysics is presented with an emphasis on the experimental challenges and opportunities for future development.

  18. Transfer reactions with heavy elements

    SciTech Connect

    Hoffman, D.C.

    1986-04-01

    Transfer reactions for several transuranium elements are studied. (/sup 248/Cm, /sup 249/Bk, /sup 249/CF, /sup 254/Es), /sup 16,18/O, /sup 20,22/Ne, and /sup 40,48/Ca projectiles are used. The production of neutron-rich heavy actinides is enhanced by the use of neutron-rich projectiles /sup 18/O and /sup 22/Ne. The maxima of the isotopic distributions occur at only 2 to 3 mass numbers larger for /sup 48/Ca than for /sup 40/Ca reactions with /sup 248/Cm. The cross sections decrease rapidly with the number of nucleons transferred. The use of neutron-rich targets favors the production of neutron-rich isotopes. ''Cold'' heavy targets are produced. Comparisons with simple calculations of the product excitation energies assuming binary transfers indicate that the maxima of the isotopic distributions occur at the lightest product isotope for which the energy exceeds the reaction barrier. The cross sections for transfer of the same nucleon clusters appear to be comparable for a wide variety of systems. 23 refs., 4 figs., 4 tabs.

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

    PubMed

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

    2015-10-14

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

  20. Exclusive Reactions at High Momentum Transfer

    NASA Astrophysics Data System (ADS)

    Radyushkin, Anatoly; Stoler, Paul

    2008-03-01

    . P. Szczepaniak and J. T. Londergan -- High energy break-up of few-nucleon systems / M. Sargsian -- Photodisintegration of the deuteron, and [symbol]He / R. Gilman -- A review of the few-body form factors / G. G. Petratos -- Nucleon form factor measurements and interpretation / C. F. Perdrisat -- Implications of G[symbol](Q[symbol])/G[symbol](Q[symbol]) / S. Dubnicka and A. Z. Dubnickova -- High Q[symbol] large acceptance G[symbol]/G[symbol] measurements using polarization transfer / L. Pentchev, C. F. Perdrisat and B. Wojtsekhowski -- A precise measurement of the neutron magnetic form factor G[symbol] in the few-GeV[symbol] region / G. P. Gilfoyle et al. (the CLAS collaboration) -- Magnetic form factor of the neutron up to 8 (GeV/c)[symbol] / B. Quinn -- Timelike form factors / K. K. Seth -- Polarization phenomena in e[symbol]e[symbol] [symbol] pp¯ revisited / A. Z. Dubnickova and S. Dubnicka -- Light-cone sum rules for form factors of the N[symbol] transition at Q[symbol] = 0 / J. Rohrwild -- Exclusive electroproduction of [symbol] mesons / A. N. Villano (for the JLab E01-002 collaboration) -- Exclusive electroproduction of [symbol] mesons in the S[symbol](1535) resonance region at high momentum transfer / M. M. Dalton (for the JLab E01-002 collaboration) -- Two-photon exchange in electron-proton elastic scattering: theory update / A. V. Afanasev -- Two-photon exchange contributions to elastic ep scattering in the non-local field formalism / P. Jain, S. D. Joglekar and S. Mitra -- Beyond the born approximation: a precise comparison of positron-proton and electron-proton elastic scattering in CLAS / J. Lachniet et al. -- Meson form factors in the space-like region / D. Gaskell -- Pion-nucleon distribution amplitudes / A. Peters -- [symbol] scattering in the 1/N[symbol] expansion / H. J. Kwee -- [symbol] annihilations into quasi-two-body final states at 10.58 GeV / Kai Yi -- Transition distribution amplitudes / J. P. Lansberg, B. Pire and L. Szymanowski -- Novel QCD

  1. Effects of nonlocality on transfer reactions

    NASA Astrophysics Data System (ADS)

    Titus, Luke

    Nuclear reactions play a key role in the study of nuclei away from stability. Single-nucleon transfer reactions involving deuterons provide an exceptional tool to study the single-particle structure of nuclei. Theoretically, these reactions are attractive as they can be cast into a three-body problem composed of a neutron, proton, and the target nucleus. Optical potentials are a common ingredient in reactions studies. Traditionally, nucleon-nucleus optical potentials are made local for convenience. The effects of nonlocal potentials have historically been included approximately by applying a correction factor to the solution of the corresponding equation for the local equivalent interaction. This is usually referred to as the Perey correction factor. In this thesis, we have systematically investigated the effects of nonlocality on (p,d) and (d,p) transfer reactions, and the validity of the Perey correction factor. We implemented a method to solve the single channel nonlocal equation for both bound and scattering states. We also developed an improved formalism for nonlocal interactions that includes deuteron breakup in transfer reactions. This new formalism, the nonlocal adiabatic distorted wave approximation, was used to study the effects of including nonlocality consistently in ( d,p) transfer reactions. For the (p,d) transfer reactions, we solved the nonlocal scattering and bound state equations using the Perey-Buck type interaction, and compared to local equivalent calculations. Using the distorted wave Born approximation we construct the T-matrix for (p,d) transfer on 17O, 41Ca, 49Ca, 127 Sn, 133Sn, and 209Pb at 20 and 50 MeV. Additionally we studied (p,d) reactions on 40Ca using the the nonlocal dispersive optical model. We have also included nonlocality consistently into the adiabatic distorted wave approximation and have investigated the effects of nonlocality on on (d,p) transfer reactions for deuterons impinged on 16O, 40Ca, 48Ca, 126Sn, 132Sn, 208Pb at 10

  2. Continuum effects in nuclear transfer reactions

    SciTech Connect

    Marta, H. D.; Donangelo, R.; Fernandez Niello, J. O.; Pacheco, A. J.

    2007-02-12

    We develop a semiclassical calculation for nuclear transfer reactions where the continuum is treated in an exact way, and compare the results with those of a treatment in which the continuum is neglected. We conclude that the influence of the continuum is very important for weakly bound reactants.

  3. Transfer reaction code with nonlocal interactions

    DOE PAGES

    Titus, L. J.; Ross, A.; Nunes, F. M.

    2016-07-14

    Here, we present a suite of codes (NLAT for nonlocal adiabatic transfer) to calculate the transfer cross section for single-nucleon transfer reactions, (d,N) or (N,d), including nonlocal nucleon-target interactions, within the adiabatic distorted wave approximation. For this purpose, we implement an iterative method for solving the second order nonlocal differential equation, for both scattering and bound states. The final observables that can be obtained with NLAT are dif- ferential angular distributions for the cross sections of A(d,N)B or B(N,d)A. Details on the implementation of the T-matrix to obtain the final cross sections within the adiabatic distorted wave approximation method aremore » also provided. This code is suitable to be applied for deuteron induced reactions in the range of Ed = 10–70 MeV, and provides cross sections with 4% accuracy.« less

  4. Transfer reaction code with nonlocal interactions

    SciTech Connect

    Titus, L. J.; Ross, A.; Nunes, F. M.

    2016-07-14

    Here, we present a suite of codes (NLAT for nonlocal adiabatic transfer) to calculate the transfer cross section for single-nucleon transfer reactions, (d,N) or (N,d), including nonlocal nucleon-target interactions, within the adiabatic distorted wave approximation. For this purpose, we implement an iterative method for solving the second order nonlocal differential equation, for both scattering and bound states. The final observables that can be obtained with NLAT are dif- ferential angular distributions for the cross sections of A(d,N)B or B(N,d)A. Details on the implementation of the T-matrix to obtain the final cross sections within the adiabatic distorted wave approximation method are also provided. This code is suitable to be applied for deuteron induced reactions in the range of Ed = 10–70 MeV, and provides cross sections with 4% accuracy.

  5. Transfer reaction code with nonlocal interactions

    NASA Astrophysics Data System (ADS)

    Titus, L. J.; Ross, A.; Nunes, F. M.

    2016-10-01

    We present a suite of codes (NLAT for nonlocal adiabatic transfer) to calculate the transfer cross section for single-nucleon transfer reactions, (d , N) or (N , d) , including nonlocal nucleon-target interactions, within the adiabatic distorted wave approximation. For this purpose, we implement an iterative method for solving the second order nonlocal differential equation, for both scattering and bound states. The final observables that can be obtained with NLAT are differential angular distributions for the cross sections of A(d , N) B or B(N , d) A. Details on the implementation of the T-matrix to obtain the final cross sections within the adiabatic distorted wave approximation method are also provided. This code is suitable to be applied for deuteron induced reactions in the range of Ed =10-70 MeV, and provides cross sections with 4% accuracy.

  6. Heat Transfer Characteristics of SHS Reactions

    DTIC Science & Technology

    1990-07-01

    A+R?0 Qt43 =5 -YA co ,/A FINAL REPORT AD- A225 769-=-_ HEAT TRANSFER CHARACTERISTICS OF SHS REACTIONS K. V. Logan, G. R. Villalobos, J. N. Harris, P...2741 Ta 180.9 3287 5731 Cr 52.0 2130 2945 lNb 95.9 2890 4919 W 183.8 3683 >6000 Mli 54.9 1518 2335 Fe 55.8 1808 3135 Co 58.9 1768 3201 Ni 58.7 1726

  7. Charge transfer reactions in Xe plasma expansion

    SciTech Connect

    Jiao, C. Q.; Garscadden, A.; Ganguly, B. N.

    2007-04-15

    Charge transfer reactions of fast Xe ions with hydrocarbons including methane (CH{sub 4}), ethene (C{sub 2}H{sub 4}), and propane (C{sub 3}H{sub 8}) are studied by adding these hydrocarbon gases into a cross flowing Xe plasma expansion. Branching ratios and relative reaction rates for the charge transfers of fast Xe{sup +} with each of the three hydrocarbon gases are measured under different rf powers of the inductively coupled Xe discharge. For CH{sub 4}/Xe system, we find that fast Xe{sup +} reacts readily with CH{sub 4} generating CH{sub 4}{sup +} and CH{sub 3}{sup +} in a ratio of 1:0.56, with an estimated rate coefficient of (2.3{+-}0.3)x10{sup -10} cm{sup 3}/s at 75 W rf power which slowly increases to (2.9{+-}0.3)x10{sup -10} cm{sup 3}/s at 250 W (error bars reflect only the uncertainties due to the unknown extent of the ion recombination that follows the charge transfer reaction). These observed charge transfer reactions are made possible by the kinetically excited Xe ions produced by free expansion of the plasma. For the C{sub 2}H{sub 4}/Xe system product ions C{sub 2}H{sub 4}{sup +} and C{sub 2}H{sub 2}{sup +} are observed, and for C{sub 3}H{sub 8}/Xe, C{sub 2}H{sub 4}{sup +} and C{sub 2}H{sub 5}{sup +} and minor product ions including C{sub 2}H{sub 2}{sup +} and C{sub 3}H{sub 7}{sup +} are observed.

  8. The influence of transfer reactions on the sub-barrier fusion enhancement in the systems {sup 58.64}Ni +, {sup 92,100}Mo

    SciTech Connect

    Rehm, K.E.; Jiang, C.L.; Esbensen, H.

    1995-08-01

    High resolution experiments performed during the past few years demonstrated that the various reaction modes occurring in heavy ion collisions can strongly influence each other. This interrelation of the different reaction modes brings a nuclear structure dependence to the fusion and deep-inelastic channels that were previously described in the framework of pure statistical models. In order to fully understand the interrelation between these reaction channels, a complete set of measurements including elastic and inelastic scattering, few-nucleon transfer and fusion is required. In continuation of our earlier measurements of the fusion cross sections in the system {sup 58,64}Ni + {sup 92,100}Mo we finished the studies of the quasielastic process in these systems. The experiments were done in inverse reaction kinematics using the split-pole spectrograph with its hybrid focal-plane detector for particle identification. The experiments with {sup 100}Mo beams were performed previously. First test runs with {sup 92}Mo showed the possible interference with {sup 98}Mo ions which could be eliminated by using the 13{sup +} charge state from the ECR source. The data from these experiments were completely analyzed. The smallest transfer cross sections are observed for the systems {sup 64}Ni + {sup 100}Mo and {sup 58}Ni + {sup 92}Mo, i.e., the most neutron-rich and neutron-deficient systems, respectively. For the other systems, {sup 64}Ni + {sup 92}Mo and {sup 58}Ni + {sup 100}Mo, the transfer cross sections at energies close to the barrier are about of equal magnitude. This observation does not correlate with the deviation of the experimental fusion cross sections from the coupled-channels predictions. While for {sup 58}Ni + {sup 100}Mo discrepancies between the experimental and theoretical fusion cross sections are observed, the system {sup 64}Ni + {sup 92}Mo which shows about the same transfer yields, is quite well described by the coupled-channels calculations.

  9. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom T.; Alexander, M. Lizabeth

    2003-06-11

    Proton transfer reaction mass spectrometry is a relatively new field that has attracted a great deal of interest in the last few years. This technique uses H₃Oþ as a chemical ionization (CI) reagent to measure volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) to parts per trillion by volume (pptv) range. Mass spectra acquired with a proton transfer reaction mass spectrometer (PTR-MS) are simple because proton transfer chemical ionization is ‘soft’ and results in little or no fragmentation. Unfortunately, peak identification can still be difficult due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). The use of an ITMS is appealing because of its ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates are possible that will allow for detection of multiple compounds. Here we present the first results from a proton transfer reaction ion trap mass spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype instrument in order to estimate possible detection limits of a second-generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated. Modifications are suggested that will enable further reduction in detection limits to the low-ppbv to high-pptv range. Furthermore, the applicability of MS/MS in differentiating between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making differentiation possible, even when a mixture of both species is present in the same sample. However, MS/MS spectra of acetone and propanal produce fragments with the same molecular masses but with different intensity ratios

  10. Oxygen-transfer reactions of methylrhenium oxides

    SciTech Connect

    Abu-Omar, M.M.; Espenson, J.H.; Appelman, E.H.

    1996-12-18

    Methylrhenium dioxide, CH{sub 3}ReO{sub 2} (or MDO), is produced from methylrhenium trioxide, CH{sub 3}ReO{sub 3} (or MTO), and hypophosphorous acid in acidic aqueous medium. Its mechanism is discussed in light of MTO`s coordination ability and the inverse kinetic isotope effect (kie): H{sub 2}P(O)OH, k = 0.028 L mol{sup -1} s{sup -1}; D{sub 2}P(O)OH, k = 0.039 L mol{sup -1} s{sup -1}. The Re(V) complex, MDO, reduces perchlorate and other inorganic oxoanions (XO{sub n}{sup -}, where X = Cl, Br, or I and N = 4 or 3). The rate is controlled by the first oxygen abstraction from perchlorate to give chlorate, with a second-order rate constant at pH 0 and 25 {degrees}C of 7.3 L mol{sup -1} s{sup -1}. Organic oxygen-donors such as sulfoxides and pyridine N-oxides oxidize MDO to MTO as do metal oxo complexes: VO{sup 2+}{sub (aq)}, VO{sub 2}{sup +}{sub (aq)}, HOMoO{sub 2}{sup +}{sub (aq)}, and MnO{sub 4}{sup -}. The reaction between V{sup 2+}{sub (aq)} with MTO and the reduction of VO{sup 2+} with MDO made it possible to determine the free energy for MDO/MTO. Oxygen-atom transfer from oxygen-donors to MDO involves nucleophilic attack of X-O on the electrophilic Re(V) center of MDO; the reaction proceeds via an [MDO{center_dot}XO] adduct, which is supported by the saturation kinetics observed for some. The parameters that control and facilitate the kinetics of such oxygen-transfer processes are suggested and include the force constant for the asymmetric stretching of the element-oxygen bond.

  11. A classical but new kinetic equation for hydride transfer reactions.

    PubMed

    Zhu, Xiao-Qing; Deng, Fei-Huang; Yang, Jin-Dong; Li, Xiu-Tao; Chen, Qiang; Lei, Nan-Ping; Meng, Fan-Kun; Zhao, Xiao-Peng; Han, Su-Hui; Hao, Er-Jun; Mu, Yuan-Yuan

    2013-09-28

    A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions.

  12. Electron Transfer and Reaction Mechanism of Laccases

    PubMed Central

    Jones, Stephen M.; Solomon, Edward I.

    2015-01-01

    Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC) where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force (ΔG°), reorganization energy (λ), and electronic coupling matrix element (HDA). Then the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e− reduction steps. The first 2e− step forms the peroxide intermediate (PI), followed by the second 2e− step to form the native intermediate (NI), which has been shown to be the catalytically relevant fully oxidized form of the enzyme. PMID:25572295

  13. Phosphoryl Transfer Reaction Snapshots in Crystals

    PubMed Central

    Gerlits, Oksana; Tian, Jianhui; Das, Amit; Langan, Paul; Heller, William T.; Kovalevsky, Andrey

    2015-01-01

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. The present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date. PMID:25925954

  14. [Mechanistic examination of organometallic electron transfer reactions: Annual report, 1989

    SciTech Connect

    Not Available

    1989-12-31

    Our mechanistic examination of electron transfer reactions between organometallic complexes has required data from our stopped-flow infrared spectrophotometer that was constructed in the first year. Our research on organometallic electron transfer reaction mechanisms was recognized by an invitation to the Symposium on Organometallic Reaction Mechanisms at the National ACS meeting in Miami. We have obtained a reasonable understanding of the electron transfer reactions between metal cations and anions and between metal carbonyl anions and metal carbonyl dimers. In addition we have begun to obtain data on the outer sphere electron transfer between metal carbonyl anions and coordination complexes and on reactions involving cluster anions.

  15. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom; Alexander, M. Lizabeth

    2003-07-07

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a relatively new field that has attracted a great deal of interest in the last several years. This technique uses H3O+ as a chemical ionization (CI) agent for measuring volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) - parts per trillion by volume (pptv) range. PTR-MS mass spectra are simple because the ionization method of proton transfer is “soft”, resulting in little or no fragmentation. Unfortunately, the simplicity of the mass spectra can cause problems in peak identification due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). ITMS is appealing because of the ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates can be realized for detection of multiple compounds. We present here the first results from a Proton Transfer Reaction Ion Trap Mass Spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype interface in order to estimate possible detection limits of a second generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated for the PTR-ITMS. Modifications are suggested that will enable further reduction in detection limits to the low ppbv to pptv range. Furthermore the applicability of MS/MS to differentiate between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making a differentiation possible even when a mixture of both species is present in the same sample. MS/MS spectra of acetone and propanal produce fragments with the same molecular weight but different ratios, allowing quantitative distinction only if one species

  16. Transfer-type products accompanying cold fusion reactions

    SciTech Connect

    Adamian, G.G.; Antonenko, N.V.

    2005-12-15

    Production of nuclei heavier than the target is treated for projectile-target combinations used in cold fusion reactions leading to superheavy nuclei. These products are related to transfer-type or to asymmetry-exit-channel quasifission reactions. The production of isotopes in the transfer-type reactions emitting of {alpha} particles with large energies is discussed.

  17. PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View

    NASA Astrophysics Data System (ADS)

    Mayer, James M.

    2004-01-01

    Proton-coupled electron transfer (PCET) reactions involve the concerted transfer of an electron and a proton. Such reactions play an important role in many areas of chemistry and biology. Concerted PCET is thermochemically more favorable than the first step in competing consecutive processes involving stepwise electron transfer (ET) and proton transfer (PT), often by >=1 eV. PCET reactions of the form X-H + Y X + H-Y can be termed hydrogen atom transfer (HAT). Another PCET class involves outersphere electron transfer concerted with deprotonation by another reagent, Y+ + XH-B Y + X-HB+ . Many PCET/HAT rate constants are predicted well by the Marcus cross relation. The cross-relation calculation uses rate constants for self-exchange reactions to provide information on intrinsic barriers. Intrinsic barriers for PCET can be comparable to or larger than those for ET. These properties are discussed in light of recent theoretical treatments of PCET.

  18. Biological phosphoryl-transfer reactions: understanding mechanism and catalysis.

    PubMed

    Lassila, Jonathan K; Zalatan, Jesse G; Herschlag, Daniel

    2011-01-01

    Phosphoryl-transfer reactions are central to biology. These reactions also have some of the slowest nonenzymatic rates and thus require enormous rate accelerations from biological catalysts. Despite the central importance of phosphoryl transfer and the fascinating catalytic challenges it presents, substantial confusion persists about the properties of these reactions. This confusion exists despite decades of research on the chemical mechanisms underlying these reactions. Here we review phosphoryl-transfer reactions with the goal of providing the reader with the conceptual and experimental background to understand this body of work, to evaluate new results and proposals, and to apply this understanding to enzymes. We describe likely resolutions to some controversies, while emphasizing the limits of our current approaches and understanding. We apply this understanding to enzyme-catalyzed phosphoryl transfer and provide illustrative examples of how this mechanistic background can guide and deepen our understanding of enzymes and their mechanisms of action. Finally, we present important future challenges for this field.

  19. Biological Phosphoryl-Transfer Reactions: Understanding Mechanism and Catalysis

    PubMed Central

    Lassila, Jonathan K.; Zalatan, Jesse G.; Herschlag, Daniel

    2012-01-01

    Phosphoryl-transfer reactions are central to biology. These reactions also have some of the slowest nonenzymatic rates and thus require enormous rate accelerations from biological catalysts. Despite the central importance of phosphoryl transfer and the fascinating catalytic challenges it presents, substantial confusion persists about the properties of these reactions. This confusion exists despite decades of research on the chemical mechanisms underlying these reactions. Here we review phosphoryl-transfer reactions with the goal of providing the reader with the conceptual and experimental background to understand this body of work, to evaluate new results and proposals, and to apply this understanding to enzymes. We describe likely resolutions to some controversies, while emphasizing the limits of our current approaches and understanding. We apply this understanding to enzyme-catalyzed phosphoryl transfer and provide illustrative examples of how this mechanistic background can guide and deepen our understanding of enzymes and their mechanisms of action. Finally, we present important future challenges for this field. PMID:21513457

  20. Visualized kinematics code for two-body nuclear reactions

    NASA Astrophysics Data System (ADS)

    Lee, E. J.; Chae, K. Y.

    2016-05-01

    The one or few nucleon transfer reaction has been a great tool for investigating the single-particle properties of a nucleus. Both stable and exotic beams are utilized to study transfer reactions in normal and inverse kinematics, respectively. Because many energy levels of the heavy recoil from the two-body nuclear reaction can be populated by using a single beam energy, identifying each populated state, which is not often trivial owing to high level-density of the nucleus, is essential. For identification of the energy levels, a visualized kinematics code called VISKIN has been developed by utilizing the Java programming language. The development procedure, usage, and application of the VISKIN is reported.

  1. Charge transfer states of the reaction center

    NASA Astrophysics Data System (ADS)

    Scherer, P. O. J.; Fischer, Sighart F.

    1998-08-01

    The energies of the low lying charge transfer states relevant for the photoinduced charge separation are analysed for Rps. viridis. The main prosthetic groups consisting of the special pair dimer P, the two adjacent monomers BL, and BM and the two pheophytines HL and HM are treated together with the surrounding residues quantum mechanically within a supermolecule approach on the basis of an INDO approximation. High order configuration interactions are incorporated to account for polarization effects and long range electrostatic effects of the protein are considered. The results are analyzed with regard to symmetry breaking effects between the L- and the M-branch. Internal reorganization effects within the dimer are also discussed.

  2. Deep Inelastic Transfer Reactions - A New Way to Exotic Nuclei?

    NASA Astrophysics Data System (ADS)

    Heinz, Sophie; Beliuskina, Olga

    2014-05-01

    We studied deep inelastic multinucleon transfer reactions in collisions of 64Ni+207Pb and 48Ca+238U at energies around the Coulomb barrier. The experiments were performed at the velocity filter SHIP at GSI Darmstadt. One of the goals was to investigate if deep inelastic transfer is superior to fragmentation reactions for producing neutron-rich isotopes in the astrophysically interesting region of nuclei along the magic neutron number N = 126. With both collision systems, rather neutron-rich transfer products were populated, some of them reaching out to the limits of the present chart of nuclides. New isotopes could not be identified. A comparison of the measured transfer cross-sections and yields with those from fragmentation reactions allowed for interesting conclusions.

  3. Photochemical electron transfer reactions of tirapazamine.

    PubMed

    Poole, James S; Hadad, Christopher M; Platz, Matthew S; Fredin, Zachary P; Pickard, Laura; Guerrero, Elisa Levya; Kessler, Margarita; Chowdhury, Goutam; Kotandeniya, Delshanee; Gates, Kent S

    2002-04-01

    The absorption and fluorescence spectra of 3-aminobenzo-1,2,4-triazine di-N-oxide (tirapazamine) have been recorded and exhibit a dependence on solvent that correlates with the Dimroth ET30 parameter. Time-dependent density functional theory calculations reveal that the transition of tirapazamine in the visible region is pi-->pi* in nature. The fluorescence lifetime is 98+/-2 ps in water. The fluorescence quantum yield is approximately 0.002 in water. The fluorescence of tirapazamine is efficiently quenched by electron donors via an electron-transfer process. Linear Stern-Volmer fluorescence quenching plots are observed with sodium azide, potassium thiocyanate, guanosine monophosphate and tryptophan (Trp) methyl ester hydrochloride. Guanosine monophosphate, tyrosine (Tyr) methyl ester hydrochloride and Trp methyl ester hydrochloride appear to quench the fluorescence at a rate greater than diffusion control implying that these substrates complex with tirapazamine in its ground state. This complexation was detected by absorption spectroscopy.

  4. Electron transfer reactions in microporous solids

    SciTech Connect

    Mallouk, T.E.

    1992-05-01

    We have studied electron transfer quenching of the excited state of Ru(bpy){sub 3}{sup 2+} in aqueous suspensions of zeolites Y, L, and mordenite. The internal pore network of the zeolite is ion-exchanged with methylviologen cations, which quench the excited state of the surface-bound sensitizer. A detailed study of the quenching and charge recombination kinetics, using time-resolved luminescence quenching and transient diffuse reflectance spectroscopies, shows to remarkable effects: first, the excited state quenching is entirely dynamic is large-pore zeolites (L and Y), even when they are prepared as apparently dry'' powders (which still contain significant amounts of internally sited water). Second, a lower limit for the diffusion coefficient of the MV{sup 2+} ion in these zeolites, determined by this technique, is 10{sup {minus}7} cm{sup 2}sec, i.e., only about one order of magnitude slower than a typical ion in liquid water, and 2--3 orders of magnitude faster than charge transfer diffusion of cations in polyelectrolyte films or membranes such as Nafion. Surface sensitization of internally platinized layered oxide semiconductors such as K{sub 4-x}H{sub x}Nb{sub 6}O{sub 17}{center dot}nH{sub 2}O (x {approx} 2.5) yields photocatalysts for the production of H{sub 2} and I{sub 3{minus}} in aqueous iodide solutions. Layered alkali niobates and titanates form a class of zeolitic wide-bandap semiconductors, and are the first examples of photocatalysts that evolve hydrogen from an electrochemically reversible (i.e., non-sacrificial) electron donor with visible light excitation.

  5. Heavy-Ion Transfer Reactions with Deformed Nuclei

    NASA Astrophysics Data System (ADS)

    Helmer, Karl Gerard

    1992-01-01

    One-neutron transfer reactions involving actinide nuclei are used to investigate the effects of rotational motion on transfer populations. Deexcitation gamma rays were measured using a particle -particle-gamma triple coincidence method. Rotational states up to 28^{+ }(30^{+}) were seen in ^{234}U originating from the reaction ^{235}U( ^{206}Pb, ^ {207}Pb)^{234} U at a laboratory bombarding energy of 1394 MeV. Angular distributions for both inelastic excitation and transfer are presented and the one-neutron transfer reaction cross section as well as the grazing angle have been extracted. This study demonstrates the feasibility of using heavy-ion induced transfer reactions for spectroscopic studies. The second section of this thesis explores the question of diabolical pair transfer in nuclear physics using the reactions ^{206}Pb( ^{156}Gd, ^ {154}Gd)^{208} Pb (diabolical case) and ^{206 }Pb(^{156}Gd, ^{158}Gd)^ {204}Pb (nondiabolic case) at a laboratory bombarding energy of 888 MeV. Early calculations by Nikam, Ring and Canto predicted oscillatory behavior of pair transfer matrix elements as the cranking frequency was varied, within the cranking Hartree-Fock-Bogoliubov (CHFB) model, and explained this behavior as a manifestation of Berry's phase. Significant suppression of the high spin population in the diabolical nucleus was predicted. The diabolical point is supplied by the crossing of the ground-state band with the two-quasiparticle band. The strength of this band interaction is predicted to be oscillatory with chemical potential in the CHFB model. The study of pair transfer populations can therefore shed light not only on the possible existence of Berry's phase in nuclear systems, but also on whether the band interaction goes strictly to zero as predicted by the CHFB model. The results of this experiment agree with the latest calculations that the expected effects are more subtle than the earliest calculations predicted.

  6. Path Sampling Methods for Enzymatic Quantum Particle Transfer Reactions.

    PubMed

    Dzierlenga, M W; Varga, M J; Schwartz, S D

    2016-01-01

    The mechanisms of enzymatic reactions are studied via a host of computational techniques. While previous methods have been used successfully, many fail to incorporate the full dynamical properties of enzymatic systems. This can lead to misleading results in cases where enzyme motion plays a significant role in the reaction coordinate, which is especially relevant in particle transfer reactions where nuclear tunneling may occur. In this chapter, we outline previous methods, as well as discuss newly developed dynamical methods to interrogate mechanisms of enzymatic particle transfer reactions. These new methods allow for the calculation of free energy barriers and kinetic isotope effects (KIEs) with the incorporation of quantum effects through centroid molecular dynamics (CMD) and the full complement of enzyme dynamics through transition path sampling (TPS). Recent work, summarized in this chapter, applied the method for calculation of free energy barriers to reaction in lactate dehydrogenase (LDH) and yeast alcohol dehydrogenase (YADH). We found that tunneling plays an insignificant role in YADH but plays a more significant role in LDH, though not dominant over classical transfer. Additionally, we summarize the application of a TPS algorithm for the calculation of reaction rates in tandem with CMD to calculate the primary H/D KIE of YADH from first principles. We found that the computationally obtained KIE is within the margin of error of experimentally determined KIEs and corresponds to the KIE of particle transfer in the enzyme. These methods provide new ways to investigate enzyme mechanism with the inclusion of protein and quantum dynamics.

  7. Femtochemistry of Intramolecular Charge and Proton Transfer Reactions in Solution

    SciTech Connect

    Douhal, Abderrazzak; Sanz, Mikel; Carranza, Maria Angeles; Organero, Juan Angel; Tormo, Laura

    2005-03-17

    We report on the first observation of ultrafast intramolecular charge- and proton-transfer reactions in 4'-dimethylaminoflavonol (DAMF) in solution. Upon femtosecond excitation of a non-planar structure of DMAF in apolar medium, the intramolecular charge transfer (ICT) does not occur, and a slow (2 ps) proton motion takes place. However, in polar solvents, the ICT is very fast (100-200 fs) and the produced structure is stabilized that proton motion takes place in few or tens of ps.

  8. Continuum effects in transfer reactions induced by heavy ions

    SciTech Connect

    Marta, H.D.; Donangelo, R.; Fernandez Niello, J.O.; Pacheco, A.J.

    2006-02-15

    In the usual treatment of transfer nuclear reactions, the continuum states of the transferred particle are neglected. Here we perform a semiclassical calculation that treats the continuum in an exact way. For comparison purposes, we perform a second calculation in which the continuum is completely disregarded. The results of these two calculations indicates that the influence of the continuum states may be very important in systems with weakly bound reactants.

  9. Organosilanols as catalysts in asymmetric aryl transfer reactions.

    PubMed

    Ozçubukçu, Salih; Schmidt, Frank; Bolm, Carsten

    2005-03-31

    [reaction: see text] Various ferrocene-based organosilanols have been synthesized in four steps starting from achiral ferrocene carboxylic acid. Applying these novel planar-chiral ferrocenes as catalysts in asymmetric phenyl transfer reactions to substituted benzaldehydes afforded products with high enantiomeric excesses. The best result (91% ee) was achieved in the addition to p-chlorobenzaldehyde with organosilanol 2b, which has a tert-butyl substituent on the oxazoline ring and an isopropyl group on the silanol fragment.

  10. Low Energy Transfer Reactions With {sup 11}Be

    SciTech Connect

    Johansen, Jacob

    2009-08-26

    The low-energy transfer reaction {sup 11}Be(d,p){sup 12}Be gives us the opportunity to investigate single particle excitations in {sup 12}Be. The breaking of the magic number N = 8 for {sup 12}Be can be studied by comparing spectroscopic data with theoretical predictions.

  11. Saponification reaction system: a detailed mass transfer coefficient determination.

    PubMed

    Pečar, Darja; Goršek, Andreja

    2015-01-01

    The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

  12. Mechanisms for control of biological electron transfer reactions

    PubMed Central

    Williamson, Heather R.; Dow, Brian A.; Davidson, Victor L.

    2014-01-01

    Electron transfer (ET) through and between proteins is a fundamental biological process. The rates and mechanisms of these ET reactions are controlled by the proteins in which the redox centers that donate and accept electrons reside. The protein influences the magnitudes of the ET parameters, the electronic coupling and reorganization energy that are associated with the ET reaction. The protein can regulate the rates of the ET reaction by requiring reaction steps to optimize the system for ET, leading to kinetic mechanisms of gated or coupled ET. Amino acid residues in the segment of the protein through which long range ET occurs can also modulate the ET rate by serving as staging points for hopping mechanisms of ET. Specific examples are presented to illustrate these mechanisms by which proteins control rates of ET reactions. PMID:25085775

  13. Photo-induced electron-transfer reactions in heterogeneous media

    NASA Astrophysics Data System (ADS)

    Yang, J. M.

    1981-11-01

    The conversion of solar energy into chemical energy was pursued by two approaches. One is the photo-induced electron transfer reactions in heterogeneous media, and the other is the photo-decomposition of water with liquid-junction solar cells. Photo-induced electron-transfer reactions in heterogeneous media with colloidal silica or poly-acrylate were studied by flash photolysis. In an effort to illustrate that small band-gap semiconductors can be protected from photo-corrosion through surface modification, the surface of polycrystalline ZnO was chemically coated with zinc phthalocyanine and the electron-transfer process across the coated ZnO-electrolyte interface was studied by photo-electrochemical techniques.

  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. 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.

  16. Multi-neutron transfer reactions at sub-barrier energies.

    SciTech Connect

    Rehm, K. E.

    1998-01-20

    The optimum conditions for multi-neutron transfer have been studied in the system {sup 58}Ni + {sup 124}Sn at bombarding energies at and below the Coulomb barrier. The experiments were performed in inverse kinematics with a {sup 124}Sn beam bombarding a {sup 58}Ni target. The particles were identified with respect to mass and Z in the split-pole spectrograph with a hybrid focal plane detector with mass and Z-resolutions of A/{Delta}A = 150 and Z/{Delta}Z = 70. At all energies the transfer of up to 6 neutrons was observed. The yields for these transfer reactions are found to decrease by about a factor of four for each transferred neutron.

  17. Enzymatic Catalysis of Proton Transfer and Decarboxylation Reactions.

    PubMed

    Richard, John P

    2011-07-08

    Deprotonation of carbon and decarboxylation at enzyme active sites proceed through the same carbanion intermediates as for the uncatalyzed reactions in water. The mechanism for the enzymatic reactions can be studied at the same level of detail as for nonenzymatic reactions, using the mechanistic tools developed by physical organic chemists. Triosephosphate isomerase (TIM) catalyzed interconversion of D-glyceraldehyde 3-phosphate and dihydroxyacetone phosphate is being studied as a prototype for enzyme catalyzed proton transfer, and orotidine monophosphate decarboxylase (OMPDC) catalyzed decarboxylation of orotidine 5'-monophosphate is being studied as a prototype for enzyme-catalyzed decarboxylation. (1)H NMR spectroscopy is an excellent analytical method to monitor proton transfer to and from carbon catalyzed by these enzymes in D2O. Studies of these partial enzyme-catalyzed exchange reactions provide novel insight into the stability of carbanion reaction intermediates, that is not accessible in studies of the full enzymatic reaction. The importance of flexible enzyme loops and the contribution of interactions between these loops and the substrate phosphodianion to the enzymatic rate acceleration are discussed. The similarity in the interactions of OMPDC and TIM with the phosphodianion of bound substrate is emphasized.

  18. Explicit inclusion of nonlocality in (d,p) transfer reactions

    DOE PAGES

    Titus, L. J.; Nunes, F. M.; Potel, G.

    2016-01-06

    Traditionally, nucleon-nucleus optical potentials are made local for convenience. In recent work we studied the effects of including nonlocal interactions explicitly in the final state for (d,p) reactions, within the distorted wave Born approximation. Our goal in this work is to develop an improved formalism for nonlocal interactions that includes deuteron breakup and to use it to study the effects of including nonlocal interactions in transfer (d,p) reactions, in both the deuteron and the proton channel. We extend the finite-range adiabatic distorted wave approximation to include nonlocal nucleon optical potentials. We apply our method to (d,p) reactions on 16O, 40Ca,more » 48Ca, 126Sn, 132Sn, and 208Pb at 10, 20 and 50 MeV. Here, we find that nonlocality in the deuteron scattering state reduces the amplitude of the wave function in the nuclear interior, and shifts the wave function outward. In many cases, this has the effect of increasing the transfer cross section at the first peak of the angular distributions. This increase was most significant for heavy targets and for reactions at high energies. Lastly, our systematic study shows that, if only local optical potentials are used in the analysis of experimental (d, p) transfer cross sections, the extracted spectroscopic factors may be incorrect by up to 40% due to the local approximation.« less

  19. Mass transfer model for two-layer TBP oxidation reactions

    SciTech Connect

    Laurinat, J.E.

    1994-09-28

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development.

  20. Modelling charge transfer reactions with the frozen density embedding formalism

    SciTech Connect

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

    The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two {pi}-stacked nucleobase dimers of B-DNA: 5{sup '}-GG-3{sup '} and 5{sup '}-GT-3{sup '}. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionals are used the electronic couplings are grossly overestimated.

  1. Proton Transfer Reactions Studied Using the VANDLE Neutron Detector Array

    NASA Astrophysics Data System (ADS)

    Thornsberry, C. R.; Burcher, S.; Gryzwacz, R.; Jones, K. L.; Paulauskas, S. V.; Smith, K.; Vostinar, M.; Allen, J.; Bardayan, D. W.; Blankstein, D.; Deboer, J.; Hall, M.; O'Malley, P. D.; Reingold, C.; Tan, W.; Cizewski, J. A.; Lepailleur, A.; Walter, D.; Febbraro, M.; Pain, S. D.; Marley, S. T.

    2016-09-01

    Proton transfer reactions, such as (d,n), are powerful tools for the study of single particle proton states of exotic nuclei. Measuring the outgoing neutron allows for the extraction of spectroscopic information from the recoil nucleus. With the development of new radioactive ion beam facilities, such as FRIB in the U.S., comes the need for new tools for the study of reactions involving radioactive nuclei. Neutron detectors, such as VANDLE, are sensitive to gamma rays in addition to neutrons. This results in high background rates for measurements with high external trigger rates. The use of discriminating recoil particle detectors, such as phoswich detectors, allow for the selection of a clean recoil tag by separating the recoil nucleus of interest from unreacted RIB components. Developments of low energy proton transfer measurements in inverse kinematics and recent (d,n) results will be presented. This work supported in part by the U.S. Department of Energy and the National Science Foundation.

  2. Modelling charge transfer reactions with the frozen density embedding formalism.

    PubMed

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

    The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two π-stacked nucleobase dimers of B-DNA: 5'-GG-3' and 5'-GT-3'. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionals are used the electronic couplings are grossly overestimated.

  3. Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Jianjun; Wang, Jianji; Stell, George

    2006-10-01

    The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying the solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.

  4. Fission of actinide nuclei using multi-nucleon transfer reactions

    NASA Astrophysics Data System (ADS)

    Léguillon, Romain; Nishio, Katsuhisa; Hirose, Kentaro; Orlandi, Riccardo; Makii, Hiroyuki; Nishinaka, Ichiro; Ishii, Tetsuro; Tsukada, Kazuaki; Asai, Masato; Chiba, Satoshi; Ohtsuki, Tsutomu; Araki, Shohei; Watanabe, Yukinobu; Tatsuzawa, Ryotaro; Takaki, Naoyuki

    2014-09-01

    We are promoting a campaign to measure fission-fragment mass distributions for neutron-rich actinide nuclei populated by transfer reactions from their ground state up to an excitation energy of several tens MeV. We thus obtain the excitation energy dependence of the mass distribution. The experiment was carried out at the 20 MV JAEA tandem facility at Tokai. We report on the data obtained in the direct reaction 18 O + 232 Th . Transfer-channels and excitation energies of the fissioning nuclei were identified using silicon dE-E detectors located at forward angle. Two fission fragments were detected in coincidence using multi-wire proportional counters. Fission fragment masses were determined by kinematic consideration. We obtained the fission fragment mass distributions for 13 nuclei from actinium to uranium and some fission barrier heights. We are promoting a campaign to measure fission-fragment mass distributions for neutron-rich actinide nuclei populated by transfer reactions from their ground state up to an excitation energy of several tens MeV. We thus obtain the excitation energy dependence of the mass distribution. The experiment was carried out at the 20 MV JAEA tandem facility at Tokai. We report on the data obtained in the direct reaction 18 O + 232 Th . Transfer-channels and excitation energies of the fissioning nuclei were identified using silicon dE-E detectors located at forward angle. Two fission fragments were detected in coincidence using multi-wire proportional counters. Fission fragment masses were determined by kinematic consideration. We obtained the fission fragment mass distributions for 13 nuclei from actinium to uranium and some fission barrier heights. Present study is supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan.

  5. Nucleon Transfer Reactions in Few-Body Nuclear Systems

    NASA Astrophysics Data System (ADS)

    Deltuva, A.

    2017-03-01

    Three- and four-body scattering is described solving Faddeev-Yakubovsky or equivalent Alt-Grassberger-Sandhas integral equations for transition operators in momentum-space. Several realistic nuclear interaction models are used; the Coulomb force between charged particles is taken into account via the screening and renormalization method. Differential cross sections and spin observables for various nucleon transfer reactions are calculated and compared with experimental data.

  6. 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.

  7. Laser driven hydrogen transfer reactions in atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Lester, Marsha I.

    2015-03-01

    Ozonolysis of alkenes, an important non-photolytic source of OH radicals in the troposphere, proceeds through energized Criegee intermediates that undergo unimolecular decay to produce OH radicals. In this work, infrared laser activation of cold methyl-substituted Criegee intermediates is utilized to drive hydrogen transfer from the methyl group to the terminal oxygen, followed by dissociation to OH radicals. State-selective excitation of the Criegee intermediates in the CH stretch overtone region combined with sensitive OH detection reveals the infrared spectra of CH3CHOO and (CH3)2 COO, effective barrier heights for the critical hydrogen transfer step, and rapid decay dynamics to OH products. Complementary theory provides insights on the infrared overtone spectra as well as vibrational excitations, structural changes, and energy required to move from the minimum energy configuration of the Criegee intermediates to the transition state for the hydrogen transfer reaction. Research supported by the National Science Foundation.

  8. Search for an Average Potential describing Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Suehiro, Teruo; Nakagawa, Takemi

    2001-10-01

    Variety of attempts such as coupled channels, non-locality corrections of optical potentials, projectile breakup etc. were made to resolve discrepancies between the distorted-wave Born approximation (DWBA) calculations and experimental differential cross section data of the transfer reactions initiated by light ions. The present work assumes that these discrepancies basically reflect detailed structure of the average interaction exerting on the nucleons involved in the transfer. Computations were carried out searching a potential that successfully describe both transfer reactions and the ordering and energies of neutron shells in the relevant nuclei. The (p,d) reactions on ^54,56Fe and ^58Ni at 40 and 50 MeV were taken for example, for which experimental data exist with good statistics in wider angular range. The potential was simulated by a sum of the volume and the derivative Wood-Saxon potential with seven free parameters. Finite-range DWBA calculations were done with the code DWUCK5(We are much indebted to Prof. P. D. Kunz for providing us with a PC version of the code DWUCK5, without which this work was impossible.). One set of such interaction potential was obtained which is markedly different from the volume Wood-Saxon potential customary used in the previous calculations. Implications of this potential will be discussed with regard to matter distributions of nuclei.

  9. Shell effects in fission, quasifission and multinucleon transfer reaction

    NASA Astrophysics Data System (ADS)

    Kozulin, E. M.; Knyazheva, G. N.; Itkis, I. M.; Kozulina, N. I.; Loktev, T. A.; Novikov, K. V.; Harca, I.

    2014-05-01

    Results of the study of mass-energy distributions of binary fragments for a wide range of nuclei with Z= 82-122 produced in reactions of ions located between 22Ne and 136Xe at energies close and below the Coulomb barrier are reported. The role of the shell effects, the influence of the entrance channel asymmetry and the deformations of colliding nuclei on the mechanism of the fusion-fission, quasifission and multinucleon transfer reactions are discussed. The observed peculiarities of the mass and energy distributions of reaction fragments are determined by the shell structure of the formed fragments. Special attention is paid on the symmetric fragment features in order to clarify the origin of these fragments (fission or quasifission). The influence of shell effects on the fragment yield in quasifission and multinucleon transfer reactions is considered. It is noted that the major part of the asymmetric quasifission fragments peaks around the region of the Z=82 and N=126 (double magic lead) and Z=28 and N=50 shells; moreover the maximum of the yield of the quasifission component is a mixing between all these shells. Hence, shell effects are everywhere present and determine the basic characteristics of fragment mass distributions.

  10. Light and heavy transfer products in 136Xe+238U multinucleon transfer reactions

    NASA Astrophysics Data System (ADS)

    Vogt, A.; Birkenbach, B.; Reiter, P.; Corradi, L.; Mijatović, T.; Montanari, D.; Szilner, S.; Bazzacco, D.; Bowry, M.; Bracco, A.; Bruyneel, B.; Crespi, F. C. L.; de Angelis, G.; Désesquelles, P.; Eberth, J.; Farnea, E.; Fioretto, E.; Gadea, A.; Geibel, K.; Gengelbach, A.; Giaz, A.; Görgen, A.; Gottardo, A.; Grebosz, J.; Hess, H.; John, P. R.; Jolie, J.; Judson, D. S.; Jungclaus, A.; Korten, W.; Leoni, S.; Lunardi, S.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Montagnoli, G.; Napoli, D.; Pellegri, L.; Pollarolo, G.; Pullia, A.; Quintana, B.; Radeck, F.; Recchia, F.; Rosso, D.; Şahin, E.; Salsac, M. D.; Scarlassara, F.; Söderström, P.-A.; Stefanini, A. M.; Steinbach, T.; Stezowski, O.; Szpak, B.; Theisen, Ch.; Ur, C.; Valiente-Dobón, J. J.; Vandone, V.; Wiens, A.

    2015-08-01

    Background: Multinucleon transfer reactions (MNT) are a competitive tool to populate exotic neutron-rich nuclei in a wide region of nuclei, where other production methods have severe limitations or cannot be used at all. Purpose: Experimental information on the yields of MNT reactions in comparison with theoretical calculations are necessary to make predictions for the production of neutron-rich heavy nuclei. It is crucial to determine the fraction of MNT reaction products which are surviving neutron emission or fission at the high excitation energy after the nucleon exchange. Method: Multinucleon transfer reactions in +238U 136Xe have been measured in a high-resolution γ -ray/particle coincidence experiment. The large solid-angle magnetic spectrometer PRISMA coupled to the high-resolution Advanced Gamma Tracking Array (AGATA) has been employed. Beamlike reaction products after multinucleon transfer in the Xe region were identified and selected with the PRISMA spectrometer. Coincident particles were tagged by multichannel plate detectors placed at the grazing angle of the targetlike recoils inside the scattering chamber. Results: Mass yields have been extracted and compared with calculations based on the grazing model for MNT reactions. Kinematic coincidences between the binary reaction products, i.e., beamlike and targetlike nuclei, were exploited to obtain population yields for nuclei in the actinide region and compared to x-ray yields measured by AGATA. Conclusions: No sizable yield of actinide nuclei beyond Z =93 is found to perform nuclear structure investigations. In-beam γ -ray spectroscopy is feasible for few-neutron transfer channels in U and the -2 p channel populating Th isotopes.

  11. Production of macromolecular chloramines by chlorine-transfer reactions.

    PubMed

    Bedner, Mary; MacCrehan, William A; Helz, George R

    2004-03-15

    Chlorination of treated wastewaters is undertaken to prevent dispersal of human pathogens into the environment. Except in well-nitrified effluents, the primary agents in chlorination, Cl2(g) or NaOCl(aq), are short-lived and quickly transfer oxidative chlorine to secondary agents (N-chloramines), which then participate in the disinfection process. Maturation of residual chlorine resulting from chlorine-transfer reactions is still poorly characterized. Using gel permeation and reversed-phase liquid chromatography combined with a novel, oxidant-specific detector, unanticipated trends during the maturation of residual chlorine in wastewater are identified. Within 2 min after addition of NaOCl, and continuing for several hours at least, significant amounts of oxidative chlorine are transferred to secondary agents that are moderately to strongly hydrophobic and to agents that have high relative molecular masses (Mr 1300-25000). It is hypothesized that hydrophobic stabilization of organic chloramines (RNHCl(o)) thermodynamically drives these transfers, making macromolecular chloramines the ultimate oxidative chlorine carriers. Macromolecular chloramines are expected to be sluggish oxidants, as observed in their reduction by sulfite, and are expected to be poor disinfectants. If transfer of oxidative chlorine to high Mr components occurs widely at treatment plants, then this phenomenon offers a new, physicochemical explanation for the well-known impotency of organic chloramines in wastewater disinfection.

  12. Electroweak reactions on light nuclei in chiral perturbation theory

    SciTech Connect

    Phillips, D. R.

    2010-08-04

    I discuss the calculation of electromagnetic and weak reactions in few-nucleon systems using potentials and current operators derived within chiral effective theory ({chi}ET). Computations up to O(P{sup 3}) relative to leading are considered. I first present results that show that at this order {chi}ET gives a good description of extant data on the deuteron's charge and quadrupole form factors for momentum transfers |q|<0.6 GeV. These predictions will be challenged by forthcoming data from BLAST and JLab. I then review calculations pertaining to the {chi}ET expansion for weak currents, which has reached unprecedentedaccuracy. When used to anlayze data on the weak-capture process, {sup 3}He({mu}{sup -},{upsilon}{sub {mu}}){sup 3}H, it yields a tight constraint on the conserved vector-current hypothesis.

  13. Multinucleon transfer reactions in the 40Ar+208Pb system

    NASA Astrophysics Data System (ADS)

    Mijatović, T.; Szilner, S.; Corradi, L.; Montanari, D.; Pollarolo, G.; Fioretto, E.; Gadea, A.; Goasduff, A.; Malenica, D. Jelavić; Mǎrginean, N.; Milin, M.; Montagnoli, G.; Scarlassara, F.; Soić, N.; Stefanini, A. M.; Ur, C. A.; Valiente-Dobón, J. J.

    2016-12-01

    We measured multinucleon transfer reactions in the 40Ar+208Pb system at an energy close to the Coulomb barrier, by employing the PRISMA magnetic spectrometer. We extracted differential and total cross sections of the different transfer channels, with a careful investigation of the total kinetic energy loss distributions. Comparisons between different systems having the same 208Pb target and with projectiles going from neutron-poor to neutron-rich nuclei, i.e., 40Ca, 58Ni, and 40Ar, as well as between the data and GRAZING calculations have been carried out. The neutron-rich (stable) 40Ar beam allowed us to get access to the channels involving proton pickup, whose behavior in connection with the production of neutron-rich heavy partner has been outlined.

  14. Chemical reaction fouling model for single-phase heat transfer

    SciTech Connect

    Panchal, C.B.; Watkinson, A.P.

    1993-08-01

    A fouling model was developed on the premise that the chemical reaction for generation of precursor can take place in the bulk fluid, in the thermalboundary layer, or at the fluid/wall interface, depending upon the interactive effects of flu id dynamics, heat and mass transfer, and the controlling chemical reaction. The analysis was used to examine the experimental data for fouling deposition of polyperoxides produced by autoxidation of indene in kerosene. The effects of fluid and wall temperatures for two flow geometries were analyzed. The results showed that the relative effects of physical parameters on the fouling rate would differ for the three fouling mechanisms; therefore, it is important to identify the controlling mechanism in applying the closed-flow-loop data to industrial conditions.

  15. Single-collision studies of energy transfer and chemical reaction

    SciTech Connect

    Valentini, J.J.

    1993-12-01

    The research focus in this group is state-to-state dynamics of reaction and energy transfer in collisions of free radicals such as H, OH, and CH{sub 3} with H{sub 2}, alkanes, alcohols and other hydrogen-containing molecules. The motivation for the work is the desire to provide a detailed understanding of the chemical dynamics of prototype reactions that are important in the production and utilization of energy sources, most importantly in combustion. The work is primarily experimental, but with an important and growing theoretical/computational component. The focus of this research program is now on reactions in which at least one of the reactants and one of the products is polyatomic. The objective is to determine how the high dimensionality of the reactants and products differentiates such reactions from atom + diatom reactions of the same kinematics and energetics. The experiments use highly time-resolved laser spectroscopic methods to prepare reactant states and analyze the states of the products on a single-collision time scale. The primary spectroscopic tool for product state analysis is coherent anti-Stokes Raman scattering (CARS) spectroscopy. CARS is used because of its generality and because the extraction of quantum state populations from CARS spectra is straightforward. The combination of the generality and easy analysis of CARS makes possible absolute cross section measurements (both state-to-state and total), a particularly valuable capability for characterizing reactive and inelastic collisions. Reactant free radicals are produced by laser photolysis of appropriate precursors. For reactant vibrational excitation stimulated Raman techniques are being developed and implemented.

  16. Electrocatalysis of anodic and cathodic oxygen-transfer reactions

    SciTech Connect

    Wels, B.R.

    1990-09-21

    The electrocatalysis of oxygen-transfer reactions is discussed in two parts. In Part I, the reduction of iodate (IO{sub 3}{sup {minus}}) is examined as an example of cathodic oxygen transfer. On oxide-covered Pt electrodes (PtO), a large cathodic current is observed in the presence of IO{sub 3}{sup {minus}} to coincide with the reduction of PtO. The total cathodic charge exceeds the amount required for reduction of PtO and IO{sub 3}{sup {minus}} to produce an adsorbed product. An electrocatalytic link between reduction of IO{sub 3}{sup {minus}} and reduction of PtO is indicated. In addition, on oxide-free Pt electrodes, the reduction of IO{sub 3}{sup {minus}} is determined to be sensitive to surface treatment. The electrocatalytic oxidation of CN{sup {minus}} is presented as an example of anodic oxygen transfer in Part II. The voltametric response of CN{sup {minus}} is virtually nonexistent at PbO{sub 2} electrodes. The response is significantly improved by doping PbO{sub 2} with Cu. Cyanide is also oxidized effectively at CuO-film electrodes. Copper is concluded to serve as an adsorption site for CN{sup {minus}}. It is proposed that an oxygen tunneling mechanism comparable to electron tunneling does not occur at the electrode-solution interface. The adsorption of CN{sup {minus}} is therefore considered to be a necessary prerequisite for oxygen transfer. 201 refs., 23 figs., 2 tabs.

  17. Population of high spin states in very heavy ion transfer reactions. The experimental evidence

    SciTech Connect

    Guidry, M.W.

    1985-01-01

    Transfer reactions have been studied for some time with light heavy ions such as oxygen. Although states of spin I approx.10 h are sometimes populated in such reactions, it is assumed that collective excitation is small, and the transferred particles are responsible for the angular momentum transfer. In this paper we will discuss a qualitatively different kind of transfer reaction using very heavy ions (A greater than or equal to 40). In these reactions the collective excitation in both the entrance and exit channels is strong, and there may be appreciable angular momentum transfer associated with inelastic excitation. 12 refs., 13 figs.

  18. Electron transfer in native and mutated photosystem I reaction centers

    NASA Astrophysics Data System (ADS)

    Savikhin, Sergei; Xu, Wu; Chitnis, Parag; Struve, Walter

    2002-03-01

    Femtosecond time-resolved absorption difference studies were performed on photosystem I complexes from the cyanobacterium Synechocystis sp. PCC 6803. The overal electron transfer from the special pair P700 to the secondary acceptor A1 has been shown to be 10 ps, twice shorter than the previously estimated value. Similar studies were performed on more than 10 genetically engineered species, where protein structure was altered in the visinity of the reaction center (RC). The functioning of the PS I complex was found to be extremelly sensitive to the protein sequence in the immediate proximity of the RC: less than half of the studied mutations resulted in photosynthetically active complexes, and all of the latter had electron transfer dynamics indistinguishable from that of the wild type. Most of the mutations in the other areas of the PS I, including antenna, did not affect the photosynthetic function of this complex radically. These results confirm the extreme importance of the precise RC structure and demonstrate why millions of years of evolution resulted in only two types of topologically similar RC's shared by all photosynthetic organisms.

  19. Light ion transfer reactions with the HELIOS spectrometer

    SciTech Connect

    Back, B. B.; Collaboration: HELIOS Collaboration

    2012-10-20

    Light-ion induced transfer and inelastic scattering reactions on stable or long-lived targets have been used extensively to study the structure of nuclei near the line of {beta}-stability, and much of the detailed information on the single-particle structure of nuclei has been derived from such studies. Recently, however, a substantial expansion of the range of isotopes, for which this nuclear structure information can be obtained, has presented itself by using radioactive beams in inverse kinematics reactions. Such beams are now available at a number of facilities around the world, including the in-flight production method and CARIBU facility at ATLAS. The HELIOS spectrometer, which has been used since August 2008 at ATLAS, circumvents many of the problems associated with inverse kinematics. In this talk I will discuss the principle of the spectrometer as well as some of main physics results that have been obtained to date in nuclei ranging from {sup 13}B to {sup 137}Xe using both stable and radioactive beams.

  20. Prodrugs of aza nucleosides based on proton transfer reaction

    NASA Astrophysics Data System (ADS)

    Karaman, Rafik

    2010-12-01

    DFT calculation results for intramolecular proton transfer reactions in Kirby's enzyme models 1- 7 reveal that the reaction rate is quite responsive to geometric disposition, especially to distance between the two reactive centers, r GM, and the angle of attack, α (the hydrogen bonding angle). Hence, the study on the systems reported herein could provide a good basis for designing aza nucleoside prodrug systems that are less hydrophilic than their parental drugs and can be used, in different dosage forms, to release the parent drug in a controlled manner. For example, based on the calculated log EM, the cleavage process for prodrug 1ProD is predicted to be about 1010 times faster than that for prodrug 7ProD and about 104 times faster than prodrug 3ProD: rate 1ProD > rate 3ProD > rate 7ProD . Hence, the rate by which the prodrug releases the aza nucleoside drug can be determined according to the structural features of the linker (Kirby's enzyme model).

  1. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    SciTech Connect

    Suria, Sabartanty

    1995-02-10

    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  2. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    NASA Astrophysics Data System (ADS)

    Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

    2013-12-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 < 1 - 3) and for low (ξ0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually

  3. Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

    PubMed

    Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 < 1 - 3) and for low (ξ0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually

  4. Ions interacting with planar aromatic molecules: Modeling electron transfer reactions

    SciTech Connect

    Forsberg, B. O.; Alexander, J. D.; Chen, T.; Pettersson, A. T.; Gatchell, M.; Cederquist, H.; Zettergren, H.

    2013-02-07

    We present theoretical absolute charge exchange cross sections for multiply charged cations interacting with the Polycyclic Aromatic Hydrocarbon (PAH) molecules pyrene C{sub 14}H{sub 10}, coronene C{sub 24}H{sub 12}, or circumcoronene C{sub 54}H{sub 18}. These planar, nearly circular, PAHs are modelled as conducting, infinitely thin, and perfectly circular discs, which are randomly oriented with respect to straight line ion trajectories. We present the analytical solution for the potential energy surface experienced by an electron in the field of such a charged disc and a point-charge at an arbitrary position. The location and height of the corresponding potential energy barrier from this simple model are in close agreement with those from much more computationally demanding Density Functional Theory (DFT) calculations in a number of test cases. The model results compare favourably with available experimental data on single- and multiple electron transfer reactions and we demonstrate that it is important to include the orientation dependent polarizabilities of the molecules (model discs) in particular for the larger PAHs. PAH ionization energy sequences from DFT are tabulated and used as model inputs. Absolute cross sections for the ionization of PAH molecules, and PAH ionization energies such as the ones presented here may be useful when considering the roles of PAHs and their ions in, e.g., interstellar chemistry, stellar atmospheres, and in related photoabsorption and photoemission spectroscopies.

  5. Rates of primary electron transfer reactions in the photosystem I reaction center reconstituted with different quinones as the secondary acceptor

    SciTech Connect

    Kumazaki, Shigeichi; Kandori, Hideki; Yoshihara, Keitaro ); Iwaki, Masayo; Itoh, Shigeru ); Ikegamu, Isamu )

    1994-10-27

    Rates of sequential electron transfer reactions from the primary electron donor chlorophyll dimer (P700) to the electron acceptor chlorophyll a-686 (A[sub 0]) and to the secondary acceptor quinone (Q[sub [phi

  6. Study of elementary reactions and energy transfer processes involving the NH and CN free radicals

    NASA Astrophysics Data System (ADS)

    Dagdigian, Paul J.; Alexander, Millard H.

    1991-06-01

    Collaborative theoretical and experimental studies of a variety of elementary chemical reactions and collisional energy transfer processes involving small molecular free radicals, with particular emphasis on the NH and CN molecules, have been carried out. Specific topics studied include: molecular free radicals, collisional energy transfer, chemical reactions, excited states, and molecular decomposition.

  7. Laser ion source for multi-nucleon transfer reaction products

    NASA Astrophysics Data System (ADS)

    Hirayama, Y.; Watanabe, Y. X.; Imai, N.; Ishiyama, H.; Jeong, S. C.; Miyatake, H.; Oyaizu, M.; Kimura, S.; Mukai, M.; Kim, Y. H.; Sonoda, T.; Wada, M.; Huyse, M.; Kudryavtsev, Yu.; Van Duppen, P.

    2015-06-01

    We have developed a laser ion source for the target-like fragments (TLFs) produced in multi-nucleon transfer (MNT) reactions. The operation principle of the source is based on the in-gas laser ionization and spectroscopy (IGLIS) approach. In the source TLFs are thermalized and neutralized in high pressure and high purity argon gas, and are extracted after being selectively re-ionized in a multi-step laser resonance ionization process. The laser ion source has been implemented at the KEK Isotope Separation System (KISS) for β-decay spectroscopy of neutron-rich isotopes with N = 126 of nuclear astrophysical interest. The simulations of gas flow and ion-beam optics have been performed to optimize the gas cell for efficient thermalization and fast transporting the TLFs, and the mass-separator for efficient transport with high mass-resolving power, respectively. To confirm the performances expected at the design stage, off-line experiments have been performed by using 56Fe atoms evaporated from a filament in the gas cell. The gas-transport time of 230 ms in the argon cell and the measured KISS mass-resolving power of 900 are consistent with the designed values. The high purity of the gas-cell system, which is extremely important for efficient and highly-selective production of laser ions, was achieved and confirmed from the mass distribution of the extracted ions. After the off-line tests, on-line experiments were conducted by directly injecting energetic 56Fe beam into the gas cell. After thermalization of the injected 56Fe beam, laser-produced singly-charged 56Fe+ ions were extracted. The extraction efficiency and selectivity of the gas cell in the presence of plasma induced by 56Fe beam injection as well as the time profile of the extracted ions were investigated; extraction efficiency of 0.25%, a beam purity of >99% and an extraction time of 270 ms. It has been confirmed that the performance of the KISS laser ion source is satisfactory to start the measurements of

  8. Reaction electronic flux and its role in DNA intramolecular proton transfers.

    PubMed

    Durán, Rocío; Vöhringer-Martinez, Esteban; Toro-Labbé, Alejandro; Herrera, Bárbara

    2016-06-01

    Proton transfer reactions present a key step in many biological and chemical processes. Here, we focused on the electronic changes in the proton transfer reactions of the four DNA bases. In combination with the previous structural analysis the reaction electronic flux together with local descriptors as the Hirshfeld-I charges allow us to identify chemical events and rationalize the underlying reaction mechanism. Our results show that imine-enamine in adenine and citosyne, and keto-enol tautomerizations in thymine and guanine have different reaction mechanisms. The former involve net structural rearrangements driven by favoured electrostatic interactions between the proton and the acceptor atom whereas the keto-enol tautomerizations require electronic changes reflected in the reaction electronic flux and changes in the NBO bond orders which favour the proton transfer reaction.

  9. Observation of the one- to six-neutron transfer reactions at sub-barrier energies

    SciTech Connect

    Jiang, C.L.; Rehm, K.E.; Gehring, J.

    1995-08-01

    It was suggested many years ago that when two heavy nuclei are in contact during a grazing collision, the transfer of several correlated neutron-pairs could occur. Despite considerable experimental effort, however, so far only cross sections for up to four-neutron transfers have been uniquely identified. The main difficulties in the study of multi-neutron transfer reactions are the small cross sections encountered at incident energies close to the barrier, and various experimental uncertainties which can complicate the analysis of these reactions. We have for the first time found evidence for multi-neutron transfer reactions covering the full sequence from one- to six-neutron transfer reactions at sub-barrier energies in the system {sup 58}Ni + {sup 100}Mo.

  10. Few Nucleon Systems From Expanding About the Unitarity Limit

    NASA Astrophysics Data System (ADS)

    Griesshammer, Harald W.

    2017-01-01

    Can one understand the structure of nuclei at the physical point by an expansion about the unitarity limit? When the NN S-wave binding energies are zero, the NN system has no scale. Still, the 3 N system has one dimensionful quantity Λ*, related to the breaking of scale invariance to a discrete scaling symmetry (Efimov effect). The scale is set by the triton binding energy. While qualitatively this has been known for a long time, one may speculate that Nuclear Physics resides then in a sweet spot: bound weakly enough to be insensitive to the details of the nuclear interaction and thus to be described by ``pionless'' EFT; but dense enough that the NN scattering lengths are perturbatively close to the unitarity limit. In this case, Λ* sets the only low-energy scale of all observables. Without it, no scale exists, and all nuclei have zero or infinite binding energy in the unitarity limit. For A <= 4 nucleons, the spectrum is indeed described well in this simplified version: a converging, perturbative expansion around the unitarity limit, with controlled corrections in the inverse scattering lengths, the interaction ranges and isospin breaking. Supported in part by US DOE and George Washington University.

  11. Shell structure and few-nucleon removal in intranuclear cascade

    NASA Astrophysics Data System (ADS)

    Mancusi, D.; Boudard, A.; Carbonell, J.; Cugnon, J.; David, J.-C.; Leray, S.

    2015-02-01

    It is well known that intranuclear-cascade models generally overestimate the cross sections for one-proton removal from heavy, stable nuclei by a high-energy proton beam, but they yield reasonable predictions for one-neutron removal from the same nuclei and for one- nucleon removal from light targets. We use simple shell-model calculations to investigate the reasons of this deficiency. We find that a correct description of the neutron skin and of the energy density in the nuclear surface is crucial for the aforementioned observables. Neither ingredient is sufficient if taken separately.

  12. Real-time electron dynamics simulation of two-electron transfer reactions induced by nuclear motion

    NASA Astrophysics Data System (ADS)

    Suzuki, Yasumitsu; Yamashita, Koichi

    2012-04-01

    Real-time electron dynamics of two-electron transfer reactions induced by nuclear motion is calculated by three methods: the numerically exact propagation method, the time-dependent Hartree (TDH) method and the Ehrenfest method. We find that, as long as the nuclei move as localized wave packets, the TDH and Ehrenfest methods can reproduce the exact electron dynamics of a simple charge transfer reaction model containing two electrons qualitatively well, even when nonadiabatic transitions between adiabatic states occur. In particular, both methods can reproduce the cases where a complete two-electron transfer reaction occurs and those where it does not occur.

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

    PubMed

    Yamada, Atsushi; Kojima, Hidekazu; Okazaki, Susumu

    2014-08-28

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

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

    SciTech Connect

    Yamada, Atsushi; Kojima, Hidekazu; Okazaki, Susumu

    2014-08-28

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

  15. Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer

    NASA Astrophysics Data System (ADS)

    Sun, Yuming; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian

    2016-10-01

    Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C2-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What's more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

  16. Charge transfer reactions in multiply charged ion-atom collisions. [in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Steigman, G.

    1975-01-01

    Charge-transfer reactions in collisions between highly charged ions and neutral atoms of hydrogen and/or helium may be rapid at thermal energies. If these reactions are rapid, they will suppress highly charged ions in H I regions and guarantee that the observed absorption features from such ions cannot originate in the interstellar gas. A discussion of such charge-transfer reactions is presented and compared with the available experimental data. The possible implications of these reactions for observations of the interstellar medium, H II regions, and planetary nebulae are outlined.

  17. Role of core excitation in (d ,p ) transfer reactions

    NASA Astrophysics Data System (ADS)

    Deltuva, A.; Ross, A.; Norvaišas, E.; Nunes, F. M.

    2016-10-01

    Background: Recent work found that core excitations can be important in extracting structure information from (d ,p ) reactions. Purpose: Our objective is to systematically explore the role of core excitation in (d ,p ) reactions and to understand the origin of the dynamical effects. Method: Based on the particle-rotor model of n +10Be , we generate a number of models with a range of separation energies (Sn=0.1 -5.0 MeV), while maintaining a significant core excited component. We then apply the latest extension of the momentum-space-based Faddeev method, including dynamical core excitation in the reaction mechanism to all orders, to the 10Be(d ,p )11Be -like reactions, and study the excitation effects for beam energies Ed=15 -90 MeV. Results: We study the resulting angular distributions and the differences between the spectroscopic factor that would be extracted from the cross sections, when including dynamical core excitation in the reaction, and that of the original structure model. We also explore how different partial waves affect the final cross section. Conclusions: Our results show a strong beam-energy dependence of the extracted spectroscopic factors that become smaller for intermediate beam energies. This dependence increases for loosely bound systems.

  18. Role of core excitation in (d,p) transfer reactions

    DOE PAGES

    Deltuva, A.; Ross, A.; Norvaišas, E.; ...

    2016-10-24

    In our recent work we found that core excitations can be important in extracting structure information from (d,p) reactions. Our objective is to systematically explore the role of core excitation in (d,p) reactions and to understand the origin of the dynamical effects. Based on the particle-rotor model of n+Be10, we generate a number of models with a range of separation energies (Sn=0.1–5.0 MeV), while maintaining a significant core excited component. We then apply the latest extension of the momentum-space-based Faddeev method, including dynamical core excitation in the reaction mechanism to all orders, to the Be10(d,p)Be11-like reactions, and study the excitationmore » effects for beam energies Ed=15–90 MeV. We study the resulting angular distributions and the differences between the spectroscopic factor that would be extracted from the cross sections, when including dynamical core excitation in the reaction, and that of the original structure model. We also explore how different partial waves affect the final cross section. Our results show a strong beam-energy dependence of the extracted spectroscopic factors that become smaller for intermediate beam energies. Finally, this dependence increases for loosely bound systems.« less

  19. Structure of Light Neutron-rich Nuclei Studied with Transfer Reactions

    SciTech Connect

    Wuosmaa, A. H.

    2015-01-01

    Transfer reactions have been used for many years to understand the shell structure of nuclei. Recent studies with rare-isotope beams extend this work and make it possible to probe the evolution of shell structure far beyond the valley of stability, requiring measurements in inverse kinematics. We present a novel technical approach to measurements in inverse kinematics, and apply this method to different transfer reactions, each of which probes different properties of light, neutron-rich nuclei.

  20. Definition and determination of the triplet-triplet energy transfer reaction coordinate

    SciTech Connect

    Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Frutos, Luis Manuel; Acuña, A. Ulises

    2014-01-21

    A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail.

  1. SO2−· Electron Transfer Ion/Ion Reactions with Disulfide Linked Polypeptide Ions

    PubMed Central

    Chrisman, Paul A.; Pitteri, Sharon J.; Hogan, Jason M.; McLuckey, Scott A.

    2005-01-01

    Multiply-charged peptide cations comprised of two polypeptide chains (designated A and B) bound via a disulfide linkage have been reacted with SO2−· in an electrodynamic ion trap mass spectrometer. These reactions proceed through both proton transfer (without dissociation) and electron transfer (with and without dissociation). Electron transfer reactions are shown to give rise to cleavage along the peptide backbone, loss of neutral molecules, and cleavage of the cystine bond. Disulfide bond cleavage is the preferred dissociation channel and both Chain A (or B)—S· and Chain A (or B)—SH fragment ions are observed, similar to those observed with electron capture dissociation (ECD) of disulfide-bound peptides. Electron transfer without dissociation produces [M + 2H]+· ions, which appear to be less kinetically stable than the proton transfer [M + H]+ product. When subjected to collision-induced dissociation (CID), the [M + 2H]+· ions fragment to give products that were also observed as dissociation products during the electron transfer reaction. However, not all dissociation channels noted in the electron transfer reaction were observed in the CID of the [M + 2H]+· ions. The charge state of the peptide has a significant effect on both the extent of electron transfer dissociation observed and the variety of dissociation products, with higher charge states giving more of each. PMID:15914021

  2. Population of mixed-symmetry states via {alpha} transfer reactions

    SciTech Connect

    Alonso, C. E.; Arias, J. M.; Fortunato, L.; Vitturi, A.; Pietralla, N.

    2008-07-15

    Within the neutron-proton interacting boson model we study the population of mixed-symmetry states via {alpha} transfer processes. Closed expressions are deduced in the case of the limiting U{sub {pi}}{sub +{nu}}(5) and SU{sub {pi}}{sub +{nu}}(3). We find that the population of the lowest mixed-symmetry 2{sup +} state, vanishing along the N{sub {pi}}=N{sub {nu}} line, depends on the number of active bosons and is normally smaller than that of the lowest full symmetric 2{sup +} state. In particular, for deformed nuclei where the number of bosons is normally large, the relative population of the mixed-symmetry 2{sup +} state is of the order of a few percent. More favorable cases can be found near shell closures, as in the case of {alpha} transfer leading to {sup 140}Ba.

  3. The thermodynamics of charge transfer in DNA photolyase: using thermodynamic integration calculations to analyse the kinetics of electron transfer reactions.

    PubMed

    Krapf, Sebastian; Koslowski, Thorsten; Steinbrecher, Thomas

    2010-08-28

    DNA Photolyases are light sensitive oxidoreductases present in many organisms that participate in the repair of photodamaged DNA. They are capable of electron transfer between a bound cofactor and a chain of tryptophan amino acid residues. Due to their unique mechanism and important function, photolyases have been subject to intense study in recent times, with both experimental and computational efforts. In this work, we present a novel application of classical molecular dynamics based free energy calculations, combined with quantum mechanical computations, to biomolecular charge transfer. Our approach allows for the determination of all reaction parameters in Marcus' theory of charge transport. We were able to calculate the free energy profile for the movement of a positive charge along protein sidechains involved in the biomolecule's function as well as charge-transfer rates that are in good agreement with experimental results. Our approach to simulate charge-transfer reactions explicitly includes the influence of protein flexibility and solvent dynamics on charge-transfer energetics. As applied here to a biomolecular system of considerable scientific interest, we believe the method to be easily adaptable to the study of charge-transfer phenomena in biochemistry and other fields.

  4. 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.

  5. Neutron transfer reactions: Surrogates for neutron capture for basic and applied nuclear science

    SciTech Connect

    Cizewski, J. A.; Jones, K. L.; Kozub, R. L.; Pain, Steven D; Peters, W. A.; Adekola, Aderemi S; Allen, J.; Bardayan, Daniel W; Becker, J.; Blackmon, Jeff C; Chae, K. Y.; Chipps, K.; Erikson, Luke; Gaddis, A. L.; Harlin, Christopher W; Hatarik, Robert; Howard, Joshua A; Jandel, M.; Johnson, Micah; Kapler, R.; Krolas, W.; Liang, J Felix; Livesay, Jake; Ma, Zhanwen; Matei, Catalin; Matthews, C.; Moazen, Brian; Nesaraja, Caroline D; O'Malley, Patrick; Patterson, N. P.; Paulauskas, Stanley; Pelham, T.; Pittman, S. T.; Radford, David C; Rogers, J.; Schmitt, Kyle; Shapira, Dan; ShrinerJr., J. F.; Sissom, D. J.; Smith, Michael Scott; Swan, T. P.; Thomas, J. S.; Vieira, D. J.; Wilhelmy, J. B.; Wilson, Gemma L

    2009-04-01

    Neutron capture reactions on unstable nuclei are important for both basic and applied nuclear science. A program has been developed at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory to study single-neutron transfer (d,p) reactions with rare isotope beams to provide information on neutron-induced reactions on unstable nuclei. Results from (d,p) studies on {sup 130,132}Sn, {sup 134}Te and {sup 75}As are discussed.

  6. Femtosecond Dynamics of Norrish Type-II Reactions: Nonconcerted Hydrogen-Transfer and Diradical Intermediacy.

    PubMed

    De Feyter S; Diau; Zewail

    2000-01-01

    Norrish type-II and McLafferty rearrangements, which both involve an intramolecular transfer of a gamma H atom, can be differentiated on the femtosecond time scale. The McLafferty rearrangement results in ion fragmentation of the parent ketone, whereas the Norrish type-II reaction leads to a diradical species, which then either cyclizes or fragments (see scheme). For Norrish type-II reactions, the reaction time for the transfer of the hydrogen atom is within 70 - 90 fs, and the lifetime of the diradical intermediate is in the range of 400 - 700 ps at the total energy studied.

  7. Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

    PubMed Central

    Driver, Tom G.

    2011-01-01

    Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

  8. Transfer reaction experiments with radioactive beams: from halos to the r-process

    SciTech Connect

    Jones, K. L.

    2013-01-01

    Transfer reactions are a powerful probe of the properties of atomic nuclei. When used in inverse kinematics with radioactive ion beams they can provide detailed information on the structure of exotic nuclei and can inform nucleosynthesis calculations. There are a number of groups around the world who use these reactions, usually with particle detection in large silicon arrays. Sometimes these arrays are coupled to gamma-ray detectors, and occasionally smaller arrays of silicon detectors are mounted within a solenoid magnet. Modern techniques using transfer reactions in inverse kinematics are covered, with specific examples, many from measurements made with beams from the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory.

  9. Production of radioactive nuclides in inverse reaction kinematics

    NASA Astrophysics Data System (ADS)

    Traykov, E.; Rogachevskiy, A.; Bosswell, M.; Dammalapati, U.; Dendooven, P.; Dermois, O. C.; Jungmann, K.; Onderwater, C. J. G.; Sohani, M.; Willmann, L.; Wilschut, H. W.; Young, A. R.

    2007-03-01

    Efficient production of short-lived radioactive isotopes in inverse reaction kinematics is an important technique for various applications. It is particularly relevant when the isotope of interest is only a few nucleons away from a stable isotope. In this article production via charge exchange and stripping reactions in combination with a magnetic separator is explored. The relation between the separator transmission efficiency, the production yield, and the choice of beam energy is discussed. The results of some exploratory experiments will be presented.

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

    NASA Astrophysics Data System (ADS)

    Szafran, Mirosław

    1996-07-01

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

  11. Product distributions for some thermal energy charge transfer reactions of rare gas ions

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.; Laudenslager, J. B.; Huntress, W. T., Jr.; Futrell, J. H.

    1977-01-01

    Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.

  12. Density Functional Reactivity Theory Characterizes Charge Separation Propensity in Proton-Coupled Electron Transfer Reactions

    SciTech Connect

    Liu, Shubin; Ess, Daniel H.; Schauer, Cynthia

    2011-04-20

    Proton-coupled electron transfer (PCET) reactions occur in many biological and artificial solar energy conversion processes. In these reactions the electron is often transferred to a site distant to the proton acceptor site. In this work, we employ the dual descriptor and the electrophilic Fukui function from density functional reactivity theory (DFRT) to characterize the propensity for an electron to be transferred to a site other than the proton acceptor site. The electrophilic regions of hydrogen bond or van der Waal reactant complexes were examined using these DFRT descriptors to determine the region of space to which the electron is most likely to be transferred. This analysis shows that in PCET reactions the electrophilic region of the reactant complex does not include the proton acceptor site.

  13. 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.

  14. Transfer reaction studies in the region of heavy and superheavy nuclei at SHIP

    NASA Astrophysics Data System (ADS)

    Heinz, S.; Comas, V.; Hofmann, S.; Ackermann, D.; Heredia, J.; Heβberger, F. P.; Khuyagbaatar, J.; Kindler, B.; Lommel, B.; Mann, R.

    2011-02-01

    We studied multi-nucleon transfer reactions in the region of heavy and superheavy nuclei. The goal was to investigate these reactions as possibility to create new superheavy neutron-rich isotopes, which cannot be produced in fusion reactions. The experiments have been performed at the velocity filter SHIP at GSI. At SHIP we can detect and identify the heavy, target-like, transfer products. Due to the low background at the focal plane detector and the isotope identification via radioactive decays, the setup allows to reach an upper cross-section limit of 10 pb/sr within one day of beamtime. We investigated the systems 58,64Ni + 207Pb and 48Ca + 248Cm at beam energies below and up to 20% above the Coulomb barrier. At all energies we observed a massive transfer of protons and neutrons, where transfer products with up to eight neutrons more than the target nucleus could be identified.

  15. Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

    SciTech Connect

    Simpson, Brett Kimball

    2002-01-01

    Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO2 films] revealed that MnO2 film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO2 films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO2 films showed that the Fe(III)-doped RuO2-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO2 films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H2O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb10Sn20Ti70, Cu63Ni37 and Cu25Ni75 alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu63Ni37 alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO3- at the Cu-Ni alloy electrode is superior to

  16. The effect of the environment on the methyl transfer reaction mechanism between trimethylsulfonium and phenolate.

    PubMed

    Saez, David Adrian; Vogt-Geisse, Stefan; Inostroza-Rivera, Ricardo; Kubař, Tomáš; Elstner, Marcus; Toro-Labbé, Alejandro; Vöhringer-Martinez, Esteban

    2016-09-14

    Methyl transfer reactions play an important role in biology and are catalyzed by various enzymes. Here, the influence of the molecular environment on the reaction mechanism was studied using advanced ab initio methods, implicit solvation models and QM/MM molecular dynamics simulations. Various conceptual DFT and electronic structure descriptors identified different processes along the reaction coordinate e.g. electron transfer. The results show that the polarity of the solvent increases the energy required for the electron transfer and that this spontaneous process is located in the transition state region identified by the (mean) reaction force analysis and takes place through the bonds which are broken and formed. The inclusion of entropic contributions and hydrogen bond interactions in QM/MM molecular dynamics simulations with a validated DFTB3 Hamiltonian yields activation barriers in good agreement with the experimental values in contrast to the values obtained using two implicit solvation models.

  17. The kinetics of electron transfer reaction of methylene green and titanium trichloride in different solvents

    NASA Astrophysics Data System (ADS)

    Saeed, Rehana; Nadeem, Syed Muhammad Saqib

    2016-06-01

    The kinetics of the electron transfer reaction of methylene green and titanium trichloride was investigated in different solvents by spectrophotometry at different temperatures. The the reaction rate was determined by monitoring the absorbance as a function of time at λmax 655 nm. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of methylene green. The effect of an aqueous alcoholic solvent was studied in the acidic range of pH from 4 to 7. It was observed that the reaction rate increased with an increase in polarity of the reaction medium. The the reaction rate was high in acidic conditions and decreased with a further increase in acidity. The increase in temperature increased the rate of the electron transfer reaction of methylene green and titanium trichloride. The activation energy ( E a) was calculated by the Arrhenius relation. The absence of any reaction intermediate was confirmed by spectroscopic and kinetic investigations. A plausible mechanism for the reaction in line with outer-sphere reaction pathway has been proposed. Thermodynamic parameters such as the activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G), and entropy change (Δ S) were also evaluated

  18. Phosphoryl transfer by a concerted reaction mechanism in UMP/CMP-kinase.

    PubMed Central

    Hutter, M. C.; Helms, V.

    2000-01-01

    The reaction mechanism of phosphoryl transfer catalyzed by UMP/CMP-kinase from Dictyostelium discoideum was investigated by semiempirical AM1 molecular orbital computations of an active site model system derived from crystal structures that contain a transition state analog or a bisubstrate inhibitor. The computational results suggest that the nucleoside monophosphate must be protonated for the forward reaction while it is unprotonated in the presence of aluminium fluoride, a popular transition state analog for phosphoryl transfer reactions. Furthermore, a compactification of the active site model system during the reaction and for the corresponding complex containing AlF3 was observed. For the active site residues that are part of the LID domain, conformational flexibility during the reaction proved to be crucial. On the basis of the calculations, a concerted phosphoryl transfer mechanism is suggested that involves the synchronous shift of a proton from the monophosphate to the transferred PO3-group. The proposed mechanism is thus analogous to the phosphoryl transfer mechanism in cAMP-dependent protein kinase that phosphorylates the hydroxyl groups of serine residues. PMID:11152133

  19. Electrocatalysis of anodic, oxygen-transfer reactions at noble metal electrodes

    SciTech Connect

    Vitt, J.E.

    1992-06-09

    Voltammetry at rotated disk and rotated ring-disk electrodes was applied to the study of several aspects of anodic, oxygen-transfer reactions at noble electrodes. Anodic reactions which involve the transfer of oxygen from H{sub 2}O to the oxidation products generally exhibit a voltammetric response characterized by severe kinetic limitations. Mechanistic studies were performed at noble electrodes in order to contrive strategies for improving the kinetics of these reactions. Competitive adsorption studies were used to devise an adsorption hierarchy for Au rotated disk electrodes. It was concluded that adsorption was a prerequisite for oxidations involving the transfer of oxygen present on the electrodes surface as adsorbed hydroxyl radicals. The electrogenerated chemiluminescence (ECL) of luminol was studied at Au, Pt, Pd, glassy carbon, PbO{sub 2}, and Bi-doped PbO{sub 2} electrodes. The ECL intensity was determined to be inversely related to electrochemical activity for the oxidation of luminol. It was concluded that the oxygen-transfer oxidation of luminol to 3-aminophthalate ( n = 4 eq mol{sup {minus}1}) corresponded to the dark reaction, whereas the electron-transfer oxidation of luminol with n = 1 eq mol{sup {minus}1} initiated the chemiluminescent reaction in solution.

  20. Camptothecins guanine interactions: mechanism of charge transfer reaction upon photoactivation

    NASA Astrophysics Data System (ADS)

    Steenkeste, K.; Guiot, E.; Tfibel, F.; Pernot, P.; Mérola, F.; Georges, P.; Fontaine-Aupart, M. P.

    2002-01-01

    The potent activity exhibited by the antitumoral camptothecin (CPT) and its analog irinotecan (CPT-11) is known to be related to a close contact between the drug and the nucleic acid base guanine. This specificity of interaction between these two chromophores was examined by following changes in the photophysical properties of the drug using steady-state as well as time-resolved absorption and fluorescence methods. The observed effects on absorption, fluorescence emission and singlet excited state lifetimes give evidence for the occurrence of a stacking complex formation restricted to the quinoline part of CPT or CPT-11 and the guanine base but also with the adenine base. The triplet excited state properties of the drugs have been also characterized in absence and in presence of guanosine monophosphate and reveal the occurrence of an electron transfer from the guanine base to the drug. Support for this conclusion was obtained from the studies of a set of biological targets of various oxido-reduction potentials, adenosine monophosphate, cytidine, cytosine, tryptophan, tyrosine and phenylalanine. This finding gives an interpretation of the CPT-induced guanine photolesions previously reported in the literature. These data taken together are discussed in connection with the drug activity. The stacking complex CPT/guanine is necessary but not sufficient to explain the role of the chirality and of the lactone structure in the function of the drug. A stereospecific interaction with the enzyme topoisomerase I seems necessary to stabilize the stacking complex. The first experiments using time-resolved fluorescence by two-photon excitation confirms that CPT does not bind to the isolated enzyme.

  1. Near resonant charge transfer in the reaction F(+) + CO - F + CO(+)

    NASA Astrophysics Data System (ADS)

    Kusunoki, I.; Ishikawa, T.

    1985-06-01

    Charge transfer reactions in the F(+) + CO system were investigated using a F(+) ion beam in the energy range 10-300 eVlab. The electronically excited product CO(+) A2Pi(i) was observed by the emission from the A-X transitions. At low collisional energy the dominant product is in the vibrational level v' = 5. The reaction cross section sigma(5) is about 1 A-sq at 12 eVc.m. and decreases with increasing collision energy. The large cross section at v' = 5 can be interpreted by near-resonant charge-transfer reactions. The rotational temperature of the product is about 300 K, which is the temperature of the reactant CO gas. For the resonant charge transfer, the translational energy is not effective, but the electronic and vibrational energy couple with each other strongly.

  2. High throughput engineering to revitalize a vestigial electron transfer pathway in bacterial photosynthetic reaction centers.

    PubMed

    Faries, Kaitlyn M; Kressel, Lucas L; Wander, Marc J; Holten, Dewey; Laible, Philip D; Kirmaier, Christine; Hanson, Deborah K

    2012-03-09

    Photosynthetic reaction centers convert light energy into chemical energy in a series of transmembrane electron transfer reactions, each with near 100% yield. The structures of reaction centers reveal two symmetry-related branches of cofactors (denoted A and B) that are functionally asymmetric; purple bacterial reaction centers use the A pathway exclusively. Previously, site-specific mutagenesis has yielded reaction centers capable of transmembrane charge separation solely via the B branch cofactors, but the best overall electron transfer yields are still low. In an attempt to better realize the architectural and energetic factors that underlie the directionality and yields of electron transfer, sites within the protein-cofactor complex were targeted in a directed molecular evolution strategy that implements streamlined mutagenesis and high throughput spectroscopic screening. The polycistronic approach enables efficient construction and expression of a large number of variants of a heteroligomeric complex that has two intimately regulated subunits with high sequence similarity, common features of many prokaryotic and eukaryotic transmembrane protein assemblies. The strategy has succeeded in the discovery of several mutant reaction centers with increased efficiency of the B pathway; they carry multiple substitutions that have not been explored or linked using traditional approaches. This work expands our understanding of the structure-function relationships that dictate the efficiency of biological energy-conversion reactions, concepts that will aid the design of bio-inspired assemblies capable of both efficient charge separation and charge stabilization.

  3. A two-dimensional energy surface of the phosphoryl transfer reaction catalyzed by phosphoserine phosphatase

    NASA Astrophysics Data System (ADS)

    Re, Suyong; Jung, Jaewoon; Ten-no, Seiichiro; Sugita, Yuji

    2009-10-01

    The phosphoryl transfer reaction from phospho- L-serine (pSer), catalyzed by phosphoserine phosphatase, is investigated using the hybrid quantum mechanics/molecular mechanics calculations. The two-dimensional energy surface along the phosphoryl and proton transfer distances reveals early protonation of the leaving group oxygen of pSer, prior to the transition state (TS), which triggers subsequent phosphoryl transfer reaction. Calculated electronic properties of the phosphoryl group at the active site suggest significant metaphosphate-like character of TS, which is consistent with kinetic experiments on related phosphatases. The features are not obtained with a one-dimensional search along the phosphoryl transfer coordinate, due to inadequate description of proton movement.

  4. Two-nucleon transfer reactions as a test of quantum phase transitions in nuclei

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Iachello, F.

    2017-03-01

    A quantal and a semiclassical analysis of two-nucleon transfer intensities is done within the framework of the interacting boson model. The expected features of these quantities for the quantum phase transition (QPT) between spherical, U(5), and axially deformed, SU(3), shapes are discussed. Experimental data for (p ,t ) and (t ,p ) transfer reactions clearly show the occurrence of QPTs in Gd, Sm, and Nd.

  5. Observation of the one- to six-neutron transfer reactions at sub- barrier energies

    SciTech Connect

    Jiang, C.L.; Rehm, K.E.; Gehring, J.; Glagola, B.; Kutschera, W.; Rhein, M.; Wuosmaa, A.H.

    1994-04-01

    An unambiguous determination of the cross sections for the one- to six neutron transfer reactions has been made in the system {sup 58}Ni + {sup 100}Mo. The cross sections for multi-neutron transfer processes show an exponential falloff in agreement with recent theoretical calculations. Upper limits for the absolute yields to the ground states have been extracted which are smaller by a factor of ten as compared to theoretical predictions.

  6. Highly enantioselective asymmetric Henry reaction catalyzed by novel chiral phase transfer catalysts derived from cinchona alkaloids.

    PubMed

    Vijaya, Ponmuthu Kottala; Murugesan, Sepperumal; Siva, Ayyanar

    2016-10-25

    A new type of di-site chiral phase transfer catalyst has been designed and synthesized from cinchona alkaloids as a chiral precursor. The prepared catalysts are applied in the asymmetric Henry reaction to a wide range of aldehydes using mild concentrations of a base and solvent and under room-temperature conditions. Under the optimized reaction conditions, the highest chemical yields up to 99% along with an excellent enantiomeric excess (ee) up to 99% were obtained using the prepared cinchona alkaloid based chiral phase transfer catalysts.

  7. Control of interspecies electron transfer flow during anaerobic digestion: dynamic diffusion reaction models for hydrogen gas transfer in microbial flocs.

    PubMed

    Ozturk, S S; Palsson, B O; Thiele, J H

    1989-02-05

    Dynamic reaction diffusion models were used to analyze the consequences of aggregation for syntrophic reactions in methanogenic ecosystems. Flocs from a whey digestor were used to measure all model parameters under the in situ conditions of a particular defined biological system. Fermentation simulations without adjustable parameters could precisely predict the kinetics of H(2) gas production of digestor flocs during syntrophic methanogenesis from ethanol. The results demonstrated a kinetic compartmentalization of H(2) metabolism inside the flocs. The interspecies electron transfer reaction was mildly diffusion controlled. The H(2) gas profiles across the flocs showed high H (2) concentrations inside the flocs at any time. Simulations of the syntrophic metabolism at low substrate concentrations such as in digestors or sediments showed that it is impossible to achieve high H(2) gas turnovers at simultaneously low steady-state H(2) concentrations. This showed a mechanistic contradiction in the concept of postulated low H(2) microenvironments for the anaerobic digestion process. The results of the computer experiments support the conclusion that syntrophic H(2) production may only be a side reaction of H(2) independent interspecies electron transfer in methanogenic ecosystems.

  8. Diagnostic criteria for the characterization of quasireversible electron transfer reactions by cyclic square wave voltammetry.

    PubMed

    Mann, Megan A; Helfrick, John C; Bottomley, Lawrence A

    2014-08-19

    Theory for cyclic square wave voltammetry of quasireversible electron transfer reactions is presented and experimentally verified. The impact of empirical parameters on the shape of the current-voltage curve is examined. From the trends, diagnostic criteria enabling the use of this waveform as a tool for mechanistic analysis of electrode reaction processes are presented. These criteria were experimentally confirmed using Eu(3+)/Eu(2+), a well-established quasireversible analyte. Using cyclic square wave voltammetry, both the electron transfer coefficient and rate were calculated for this analyte and found to be in excellent agreement with literature. When properly applied, these criteria will enable nonexperts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

  9. Neutrino Reactions on Two-Nucleon System and Core-Collapse Supernova

    SciTech Connect

    Nasu, Shota

    2011-10-21

    The neutrino reactions on nucleon and nucleus play important role in core-collapse supernova. Recently it is pointed that light nuclei(A = 2,3) can be abundant at the various stage of supernova environment. As an important mechanism of neutrino reaction on a few nucleon system, we study the neutrino emissivity on neutron fusion reaction nn{yields}de{sup -}{nu}-bar{sub e}.

  10. Transfer reactions using a low-energy {sup 11}Be beam

    SciTech Connect

    Johansen, Jacob

    2011-10-28

    A series of experiments have been performed to investigate neutron rich beryllium isotopes. Scattering as well as one neutron transfer reactions have been studied using a {sup 11}Be beam on deuteron targets. Bound states of {sup 10,11,12}Be have been studied and reaction cross sections have been calculated. The elastic scattering cross section has shown remarkable structure due to the halo structure of {sup 11}Be.

  11. Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer

    NASA Astrophysics Data System (ADS)

    Castonguay, Thomas C.; Wang, Feng

    2008-03-01

    In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

  12. Interplay between oxygen demand reactions and kinetic gas-water transfer in porous media.

    PubMed

    Oswald, Sascha E; Griepentrog, Marco; Schirmer, Mario; Balcke, Gerd U

    2008-08-01

    Gas-water phase transfer associated with the dissolution of trapped gas in porous media is a key process that occurs during pulsed gas sparging operations in contaminated aquifers. Recently, we applied a numerical model that was experimentally validated for abiotic situations, where multi-species kinetic inter-phase mass transfer and dissolved gas transport occurred during pulsed gas penetration-dissolution events [Balcke, G.U., Meenken, S., Hoefer, C. and Oswald, S.E., 2007. Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging. Environmental Science & Technology 41(12), 4428-4434]. Here we extend the model by using a reactive term to describe dissolved oxygen demand reactions via the formation of a reaction product, and to study the effects of such an aerobic degradation process on gas-water mass transfer and dissolution of trapped gas in porous media. As a surrogate for microbial oxygen reduction, first-order oxygen demand reactions were based on the measured oxidation of alkaline pyrogallol in column experiments. This reaction allows for adjusting the rate to values close to expected biodegradation rates and detection of the reaction product. The experiments and model consistently demonstrated accelerated oxygen gas-water mass transfer with increasing oxygen demand rates associated with an influence on the partitioning of other gases. Thus, as the oxygen demand accelerates, less gas phase residues, consisting mainly of nitrogen, are observed, which is in general beneficial to the performance of field biosparging operations. Model results additionally predict how oxygen demand influences oxygen mass transfer for a range of biodegradation rates. A typical field case scenario was simulated to illustrate the observed coupling of oxygen consumption and gas bubble dissolution. The model provides a tool to improve understanding of trapped gas behavior in porous media and contributes to a model-assisted biosparging.

  13. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    SciTech Connect

    Laurinat, J.E.

    1994-11-04

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments.

  14. Measurements and coupled reaction channels analysis of one and two proton transfer reactions for 28Si+90,94Zr systems

    NASA Astrophysics Data System (ADS)

    Kalkal, Sunil; Mandal, S.; Jhingan, A.; Gehlot, J.; Sugathan, P.; Golda, K. S.; Madhavan, N.; Garg, Ritika; Goyal, Savi; Mohanto, Gayatri; Verma, S.; Sandal, Rohit; Behera, Bivash; Eleonora, G.; Wollersheim, H. J.; Singh, R.

    2011-10-01

    Measurements of angular distributions for one and two proton stripping reactions for 28Si+90,94Zr systems were performed at lab energy 120 MeV with 28Si beam at Inter University Accelerator Center, New Delhi. Theoretical calculations performed using the quantum mechanical coupled reaction channels code FRESCO (including various intermediate states involving target and projectile excitations before and/or after transfer along with sequential transfer) were able to reproduce one and two proton transfer angular distributions for both the systems reasonably well. It was found that the DWBA calculations could describe the one proton transfer data well for both the systems but failed to reproduce the angular distributions for two proton transfer channels. The present measurements underline the importance of sequential transfer at energies much above the Coulomb barrier. We had also performed transfer reaction measurements for these systems in the sub- and near barrier region using recoil mass separator.

  15. Transfer to the continuum calculations of quasifree (p,pn) and (p,2p) reactions

    NASA Astrophysics Data System (ADS)

    Gomez-Ramos, M.; Moro, A. M.

    2016-05-01

    Nucleon removal (p, pn) and (p, 2p) reactions at intermediate energies have gained renewed attention in recent years as a tool to extract information from exotic nuclei. The information obtained from these experiments is expected to be sensitive to deeper portions of the wave function of the removed nucleon than knockout reactions with heavier targets. In this contribution, we present calculations for (p, 2p) and (p, pn) reactions performed within the so-called transfer to the continuum method (TR*). Results for stable and unstable nuclei are presented, and compared with experimental data, when available.

  16. Marcus Theory: Thermodynamics CAN Control the Kinetics of Electron Transfer Reactions

    ERIC Educational Resources Information Center

    Silverstein, Todd P.

    2012-01-01

    Although it is generally true that thermodynamics do not influence kinetics, this is NOT the case for electron transfer reactions in solution. Marcus Theory explains why this is so, using straightforward physical chemical principles such as transition state theory, Arrhenius' Law, and the Franck-Condon Principle. Here the background and…

  17. Single-drop reactive extraction/extractive reaction with forced convective diffusion and interphase mass transfer

    NASA Technical Reports Server (NTRS)

    Kleinman, Leonid S.; Red, X. B., Jr.

    1995-01-01

    An algorithm has been developed for time-dependent forced convective diffusion-reaction having convection by a recirculating flow field within the drop that is hydrodynamically coupled at the interface with a convective external flow field that at infinity becomes a uniform free-streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet, or reactions can take place in both phases. The algorithm has been implemented, and for comparison results are shown here for the case of no reaction in either phase and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.

  18. Single-drop reactive extraction/extractive reaction with forced convective diffusion and interphase mass transfer

    NASA Technical Reports Server (NTRS)

    Kleinman, Leonid S.; Reed, X. B., Jr.

    1995-01-01

    An algorithm has been developed for the forced convective diffusion-reaction problem for convection inside and outside a droplet by a recirculating flow field hydrodynamically coupled at the droplet interface with an external flow field that at infinity becomes a uniform streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet or reactions can take place in both phases. The algorithm has been implemented and results are shown here for the case of no reaction and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.

  19. Proton-transfer reactions of nitroalkanes: the role of aci-nitro species.

    PubMed

    Sato, Makoto; Kitamura, Yutaka; Yoshimura, Nobuyoshi; Yamataka, Hiroshi

    2009-02-06

    Proton-transfer reactions of two systems, ionization of a series of small carbon acids in water (the Pearson system) and reactions of substituted phenylnitromethanes, were examined in detail computationally. Comparison of experimental reactivity and pK(a) with calculated relative activation barrier and reaction energy for the Pearson system suggested that the origin of the well-know nitroalkane anomaly does not reside in the reactivity but in the equilibrium. For the reactions of substituted phenylnitromethanes, proton transfers among three species, PhCH(2)NO(2), PhCHNO(2)(-), and PhCH=NO(2)H, were examined, and the role of the aci-nitro species (PhCH=NO(2)H) was evaluated on the basis of its stability and reactivity. Protonation of PhCHNO(2)(-) by H(2)O was suggested to occur kinetically on the oxygen site, but due to its instability PhCH=NO(2)H does not contribute to the overall reaction energetics. The protonation of PhCHNO(2)(-) under acidic conditions occurs on the oxygen site to give PhCH=NO(2)H both kinetically and thermodynamically. The aci-nitro species thus formed appears to give PhCH(2)NO(2) via intramolecular H(2)O-mediated proton transfer, but a possibility of the route through PhCHNO(2)(-)-C-protonation would not be fully eliminated.

  20. Two-quasiparticle states in {sup 250}Bk studied by decay scheme and transfer reaction spectroscopy

    SciTech Connect

    Ahmad, I.; Kondev, F. G.; Koenig, Z. M.; McHarris, Wm. C.; Yates, S. W.

    2008-05-15

    Two-quasiparticle states in {sup 250}Bk were investigated with decay scheme studies and the single-neutron transfer reaction {sup 249}Bk(d,p){sup 250}Bk. Mass-separated sources of {sup 254}Es were used for {alpha} singles and {alpha}-{gamma} coincidence measurements. These studies, plus previous studies of {sup 254}Es{sup m} {alpha} decay and the {sup 249}Bk(n,{gamma}) reaction, provide spins and parities of the observed levels. The transfer reaction {sup 249}Bk(d,p){sup 250}Bk was used to deduce neutron single-particle components of the observed bands. Six pairs of singlet and triplet states, formed by the coupling of proton and neutron one-quasiparticle states, were identified. The splitting energies between the triplet and singlet states were found to be in agreement with previous calculations.

  1. A spectroscopist's view of energy states, energy transfers, and chemical reactions.

    PubMed

    Moore, C Bradley

    2007-01-01

    This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments.

  2. Transfer of learning in choice reactions: contributions of specific and general components of manual responses.

    PubMed

    Yamaguchi, Motonori; Proctor, Robert W

    2009-01-01

    Manifestations of learned skills and knowledge are known to be context-dependent. However, a study of perceptual-motor learning [Tagliabue, M., Zorzi, M., & Umiltà, C. (2002). Cross-modal re-mapping influences the Simon effect. Memory and Cognition, 30, 18-23] reported context-independent transfer of a learned stimulus-response (S-R) mapping to a task in which the mapping is no longer relevant. Although similar results were observed in subsequent studies, these studies also provided an indication that the transfer is context-dependent. The present study investigated the issue of context-dependence of the transfer of a learned S-R mapping. In experiment 1, groups of participants performed choice-reaction tasks with either the same or different response modes (keypresses or joystick movements) in the practice and transfer sessions. Smaller transfer effects were observed for those who switched response mode in the transfer session than for those who did not, indicating that transfer of the learned mapping is context-dependent. However, transfer also occurred for the former group, indicating that the transfer effect is dependent on both general and specific response components. In experiment 2, the same task conditions were examined, but with action effects consistent across the practice and transfer sessions, which were assumed to introduce a contextual feature that was common to the two sessions. The influence of action effects on transfer depended on the practiced response. The results are discussed in terms of feature overlap between the learning and test contexts, and an association network model of learning and response selection.

  3. Dynamic flexibility in the light reactions of photosynthesis governed by both electron and proton transfer reactions.

    PubMed

    Kramer, David M; Avenson, Thomas J; Edwards, Gerald E

    2004-07-01

    Plant photosynthesis performs the remarkable feat of converting light energy into usable chemical forms, which involves taming highly reactive intermediates without harming plant cells. This requires an apparatus that is not only efficient and robust but also flexible in its responses to changing environmental conditions. It also requires that the output of the energy-storing reactions be matched with the demands of metabolism. This article addresses the mechanisms by which this flexibility is achieved for short-term environmental changes. We argue that chloroplasts need two types of flexible mechanisms: one for modulating the output ratio of ATP:NADPH, which involves cyclic electron flux around photosystem I; and another for changing the regulatory sensitivity of the light-harvesting antenna to electron (and proton) flow.

  4. Barrier heights of hydrogen-transfer reactions with diffusion quantum monte carlo method.

    PubMed

    Zhou, Xiaojun; Wang, Fan

    2017-04-30

    Hydrogen-transfer reactions are an important class of reactions in many chemical and biological processes. Barrier heights of H-transfer reactions are underestimated significantly by popular exchange-correlation functional with density functional theory (DFT), while coupled-cluster (CC) method is quite expensive and can be applied only to rather small systems. Quantum Monte-Carlo method can usually provide reliable results for large systems. Performance of fixed-node diffusion quantum Monte-Carlo method (FN-DMC) on barrier heights of the 19 H-transfer reactions in the HTBH38/08 database is investigated in this study with the trial wavefunctions of the single-Slater-Jastrow form and orbitals from DFT using local density approximation. Our results show that barrier heights of these reactions can be calculated rather accurately using FN-DMC and the mean absolute error is 1.0 kcal/mol in all-electron calculations. Introduction of pseudopotentials (PP) in FN-DMC calculations improves efficiency pronouncedly. According to our results, error of the employed PPs is smaller than that of the present CCSD(T) and FN-DMC calculations. FN-DMC using PPs can thus be applied to investigate H-transfer reactions involving larger molecules reliably. In addition, bond dissociation energies of the involved molecules using FN-DMC are in excellent agreement with reference values and they are even better than results of the employed CCSD(T) calculations using the aug-cc-pVQZ basis set. © 2017 Wiley Periodicals, Inc.

  5. Measurements and coupled reaction channels analysis of one- and two-proton transfer reactions for the 28Si + 90,94Zr systems

    NASA Astrophysics Data System (ADS)

    Kalkal, Sunil; Mandal, S.; Jhingan, A.; Gehlot, J.; Sugathan, P.; Golda, K. S.; Madhavan, N.; Garg, Ritika; Goyal, Savi; Mohanto, Gayatri; Sandal, Rohit; Chakraborty, Santosh; Verma, Shashi; Behera, Bivash; Eleonora, G.; Wollersheim, H. J.; Singh, R.

    2012-03-01

    Measurements of angular distributions for one- and two-proton stripping reactions for 28Si + 90,94Zr systems were performed at 120 MeV. The experiment was carried out with the 28Si beam at Inter University Accelerator Center, New Delhi. The theoretical calculations were performed using the quantum mechanical coupled reaction channels code fresco. The distorted wave Born approximation calculations reproduced the experimental angular distributions for the one-proton transfer channel for both the systems reasonably well but failed for the two-proton transfer channel. Coupled channels calculations including various intermediate states (involving target and projectile inelastic excitations before and/or after transfer) along with the sequential transfer were able to reproduce the two-proton transfer angular distributions for both the systems reasonably well. It seems that at an energy above the Coulomb barrier, there is significant contribution of the indirect multistep and sequential transfer to the two-proton stripping reaction.

  6. Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

    PubMed

    Mohrig, Jerry R

    2013-07-16

    Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

  7. Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers: volume change, enthalpy, and entropy of electron-transfer reactions in manganese-depleted photosystem II core complexes.

    PubMed

    Hou, J M; Boichenko, V A; Diner, B A; Mauzerall, D

    2001-06-19

    We have previously reported the thermodynamic data of electron transfer in photosystem I using pulsed time-resolved photoacoustics [Hou et al. (2001) Biochemistry 40, 7109-7116]. In the present work, using preparations of purified manganese-depleted photosystem II (PS II) core complexes from Synechocystis sp. PCC 6803, we have measured the DeltaV, DeltaH, and estimated TDeltaS of electron transfer on the time scale of 1 micros. At pH 6.0, the volume contraction of PS II was determined to be -9 +/- 1 A3. The thermal efficiency was found to be 52 +/- 5%, which corresponds to an enthalpy change of -0.9 +/- 0.1 eV for the formation of the state P680+Q(A-) from P680*. An unexpected volume expansion on pulse saturation of PS II was observed, which is reversible in the dark. At pH 9.0, the volume contraction, the thermal efficiency, and the enthalpy change were -3.4 +/- 0.5 A3, 37 +/- 7%, and -1.15 +/- 0.13 eV, respectively. The DeltaV of PS II, smaller than that of PS I and bacterial centers, is assigned to electrostriction and analyzed using the Drude-Nernst equation. To explain the small DeltaV for the formation of P680+Q(A-) or Y(Z*)Q(A-), we propose that fast proton transfer into a polar region is involved in this reaction. Taking the free energy of charge separation of PS II as the difference between the energy of the excited-state P680* and the difference in the redox potentials of the donor and acceptor, the apparent entropy change (TDeltaS) for charge separation of PS II is calculated to be negative, -0.1 +/- 0.1 eV at pH 6.0 (P680+Q(A-)) and -0.2 +/- 0.15 eV at pH 9.0 (Y(Z*)Q(A-)). The thermodynamic properties of electron transfer in PS II core reaction centers thus differ considerably from those of bacterial and PS I reaction centers, which have DeltaV of approximately -27 A3, DeltaH of approximately -0.4 eV, and TDeltaS of approximately +0.4 eV.

  8. Correcting reaction rates measured by saturation-transfer magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Gabr, Refaat E.; Weiss, Robert G.; Bottomley, Paul A.

    2008-04-01

    Off-resonance or spillover irradiation and incomplete saturation can introduce significant errors in the estimates of chemical rate constants measured by saturation-transfer magnetic resonance spectroscopy (MRS). Existing methods of correction are effective only over a limited parameter range. Here, a general approach of numerically solving the Bloch-McConnell equations to calculate exchange rates, relaxation times and concentrations for the saturation-transfer experiment is investigated, but found to require more measurements and higher signal-to-noise ratios than in vivo studies can practically afford. As an alternative, correction formulae for the reaction rate are provided which account for the expected parameter ranges and limited measurements available in vivo. The correction term is a quadratic function of experimental measurements. In computer simulations, the new formulae showed negligible bias and reduced the maximum error in the rate constants by about 3-fold compared to traditional formulae, and the error scatter by about 4-fold, over a wide range of parameters for conventional saturation transfer employing progressive saturation, and for the four-angle saturation-transfer method applied to the creatine kinase (CK) reaction in the human heart at 1.5 T. In normal in vivo spectra affected by spillover, the correction increases the mean calculated forward CK reaction rate by 6-16% over traditional and prior correction formulae.

  9. Diagnostic Criteria for the Characterization of Electrode Reactions with Chemically Coupled Reactions Preceding the Electron Transfer by Cyclic Square Wave Voltammetry.

    PubMed

    Helfrick, John C; Mann, Megan A; Bottomley, Lawrence A

    2016-08-18

    Theory for cyclic square wave voltammetry of electrode reactions with chemical reactions preceding the electron transfer is presented. Theoretical voltammograms were calculated following systematic variation of empirical parameters to assess their impact on the shape of the voltammogram. From the trends obtained, diagnostic criteria for this mechanism were deduced. When properly applied, these criteria will enable non-experts in voltammetry to assign the electrode reaction mechanism and accurately measure reaction kinetics.

  10. Quantifying electron transfer reactions in biological systems: what interactions play the major role?

    PubMed

    Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov'yov, Ilia A

    2015-12-22

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome-a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor.

  11. Key Role of Active-Site Water Molecules in Bacteriorhodopsin Proton-Transfer Reactions

    SciTech Connect

    Bondar, A.N.; Baudry, Jerome Y; Suhai, Sandor; Fischer, S.; Smith, Jeremy C

    2008-10-01

    The functional mechanism of the light-driven proton pump protein bacteriorhodopsin depends on the location of water molecules in the active site at various stages of the photocycle and on their roles in the proton-transfer steps. Here, free energy computations indicate that electrostatic interactions favor the presence of a cytoplasmic-side water molecule hydrogen bonding to the retinal Schiff base in the state preceding proton transfer from the retinal Schiff base to Asp85. However, the nonequilibrium nature of the pumping process means that the probability of occupancy of a water molecule in a given site depends both on the free energies of insertion of the water molecule in this and other sites during the preceding photocycle steps and on the kinetic accessibility of these sites on the time scale of the reaction steps. The presence of the cytoplasmic-side water molecule has a dramatic effect on the mechanism of proton transfer: the proton is channeled on the Thr89 side of the retinal, whereas the transfer on the Asp212 side is hindered. Reaction-path simulations and molecular dynamics simulations indicate that the presence of the cytoplasmic-side water molecule permits a low-energy bacteriorhodopsin conformer in which the water molecule bridges the twisted retinal Schiff base and the proton acceptor Asp85. From this low-energy conformer, proton transfer occurs via a concerted mechanism in which the water molecule participates as an intermediate proton carrier.

  12. Quantifying electron transfer reactions in biological systems: what interactions play the major role?

    NASA Astrophysics Data System (ADS)

    Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov'Yov, Ilia A.

    2015-12-01

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome-a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor.

  13. Quantifying electron transfer reactions in biological systems: what interactions play the major role?

    PubMed Central

    Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov’yov, Ilia A.

    2015-01-01

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome–a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor. PMID:26689792

  14. Development of ORRUBA: A Silicon Array for the Measurement of Transfer Reactions in Inverse Kinematics

    SciTech Connect

    Pain, S. D.; Bardayan, Daniel W; Blackmon, Jeff C; Chae, K. Y.; Chipps, K.; Cizewski, J. A.; Hatarik, Robert; Johnson, Micah; Jones, K. L.; Kapler, R.; Kozub, R. L.; Livesay, Jake; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D; O'Malley, Patrick; Smith, Michael Scott; Swan, T. P.; Thomas, J. S.; Wilson, Gemma L

    2009-01-01

    The development of high quality radioactive beams has made possible the measurement of transfer reactions in inverse kinematics on unstable nuclei. Measurement of (d,p) reactions on neutron-rich nuclei yield data on the evolution of nuclear structure away from stability, and are of astrophysical interest. Experimentally, (d,p) reactions on heavy (Z=50) fission fragments are complicated by the strongly inverse kinematics, and relatively low beam intensities. Consequently, ejectile detection with high resolution in position and energy, a high dynamic range and a high solid angular coverage is required. The Oak Ridge Rutgers University Barrel Array (ORRUBA) is a new silicon detector array optimized for the measurement of (d,p) reactions in inverse kinematics.

  15. Generalized Holstein model for spin-dependent electron-transfer reactions

    NASA Astrophysics Data System (ADS)

    Yang, Li-Ping; Ai, Qing; Sun, C. P.

    2012-03-01

    Some chemical reactions are described by electron transfer (ET) processes. The underlying mechanism could be modeled as a polaron motion in the molecular crystal—the Holstein model. By taking spin degrees of freedom into consideration, we generalize the Holstein model (molecular crystal model) to microscopically describe an ET chemical reaction. In our model, the electron spins in the radical pair simultaneously interact with a magnetic field and their nuclear-spin environments. By virtue of the perturbation approach, we obtain the chemical reaction rates for different initial states. It is discovered that the chemical reaction rate of the triplet state demonstrates its dependence on the direction of the magnetic field while the counterpart of the singlet state does not. This difference is attributed to the explicit dependence of the triplet state on the direction when the axis is rotated. Our model may provide a possible candidate for the microscopic origin of the avian compass.

  16. Population of isomeric states in fusion and transfer reactions in beams of loosely bound nuclei near the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Skobelev, N. K.

    2015-07-01

    The influence of the mechanisms of nuclear reactions on the population of 195 m Hg and 197 m Hg(7/2-), 198 m Tl and 196 m Tl(7+), and 196 m Au and 198 m Au(12-) isomeric nuclear states obtained in reactions induced by beams of 3He, 6Li, and 6He weakly bound nuclei is studied. The behavior of excitation functions and high values of isomeric ratios ( δ m/ δ g) for products of nuclear reactions proceeding through a compound nucleus and involving neutron evaporation are explained within statistical models. Reactions in which the emission of charged particles occurs have various isomeric ratios depending on the reaction type. The isomeric ratio is lower in direct transfer reactions involving charged-particle emission than in reactions where the evaporation of charged particles occurs. Reactions accompanied by neutron transfer usually have a lower isomeric ratio, which behaves differently for different direct-reaction types (stripping versus pickup reactions).

  17. Rates of primary electron transfer in photosynthetic reaction centres and their mechanistic implications

    NASA Astrophysics Data System (ADS)

    Fleming, G. R.; Martin, J. L.; Breton, J.

    1988-05-01

    The conversion of light energy to chemical energy during photosyn-thesis involves the transfer of electrons between pigments embedded in a membrane protein. This process occurs with high quantum efficiency, the result of extremely fast electron transfer over a long distance preventing back transfer and energy loss. Recently the three-dimensional structures of the photosynthetic reaction centres of the bacteria Rhodopseudomonas viridis1 and Rhodobacter sphaeroides2 have been determined, allowing a molecular descrip-tion of the primary charge separation process. There are two symmetrically related branches of pigments in the structure (L and M), extending from the special pair of bacteriochlorophyll molecules (P) to the two bacteriopheophytins (HL and HM) via two bacteriochlorophylls (BLand BM). Many features of the electron transfer process are poorly understood, such as the nature of the excited states involved, the identity of the primary charge separation step and the roles of the protein and of B3-13. We have determined the rates of electron transfer in isolated reaction centre complexes of Rps. viridis and Rb. sphaeroides as a function of temperature. The rates increase as temperature is decreased, which may be due to either changes in electronic coupling of the pigments or changes in the population of coupled vibrational modes, or a combination of the two. We see no evidence of a B-L intermediate, which sets a lower limit on the rate of electron transfer from BL to HL. This is so high as to rule out transfer by two non-adiabatic steps.

  18. Differential quantum tunneling contributions in nitroalkane oxidase catalyzed and the uncatalyzed proton transfer reaction

    PubMed Central

    Major, Dan T.; Heroux, Annie; Orville, Allen M.; Valley, Michael P.; Fitzpatrick, Paul F.; Gao, Jiali

    2009-01-01

    The proton transfer reaction between the substrate nitroethane and Asp-402 catalyzed by nitroalkane oxidase and the uncatalyzed process in water have been investigated using a path-integral free-energy perturbation method. Although the dominating effect in rate acceleration by the enzyme is the lowering of the quasiclassical free energy barrier, nuclear quantum effects also contribute to catalysis in nitroalkane oxidase. In particular, the overall nuclear quantum effects have greater contributions to lowering the classical barrier in the enzyme, and there is a larger difference in quantum effects between proton and deuteron transfer for the enzymatic reaction than that in water. Both experiment and computation show that primary KIEs are enhanced in the enzyme, and the computed Swain-Schaad exponent for the enzymatic reaction is exacerbated relative to that in the absence of the enzyme. In addition, the computed tunneling transmission coefficient is approximately three times greater for the enzyme reaction than the uncatalyzed reaction, and the origin of the difference may be attributed to a narrowing effect in the effective potentials for tunneling in the enzyme than that in aqueous solution. PMID:19926855

  19. Analysis of the role of neutron transfer in asymmetric fusion reactions at subbarrier energies

    SciTech Connect

    Ogloblin, A. A.; Zhang, H. Q.; Lin, C. J.; Jia, H. M.; Khlebnikov, S. V.; Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S.; Trzaska, W. H.; Xu, X. X.; Yang, F.; Sargsyan, V. V. Adamian, G. G.; Antonenko, N. V.; Scheid, W.

    2015-12-15

    The excitation functions were measured for the {sup 28}Si + {sup 208}Pb complete-fusion (capture) reaction at deep subbarrier energies. The results were compared with the cross sections predicted within the quantum diffusion approach. The role of neutron transfer in the case of positive Q values in the {sup 28}Si + {sup 124}Sn, {sup 208}Pb; {sup 30}Si + {sup 124}Sn, {sup 208}Pb; {sup 20}Ne + {sup 208}Pb; {sup 40}Ca + {sup 96}Zr; and {sup 134}Te + {sup 40}Ca complete-fusion (capture) reactions is discussed.

  20. Cathodic Aromatic C,C Cross-Coupling Reaction via Single Electron Transfer Pathway.

    PubMed

    Qu, Yang; Tateno, Hiroyuki; Matsumura, Yoshimasa; Kashiwagi, Tsuneo; Atobe, Mahito

    2017-03-07

    We have successfully developed a novel cathodic cross-coupling reaction of aryl halides with arenes. Utilization of the cathodic single electron transfer (SET) mechanism for activation of aryl halides enables the cross-coupling reaction to proceed without the need for any transition metal catalysts or single electron donors in a mild condition. The SET from a cathode to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle also consists entirely of anion radical intermediates.

  1. Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

    PubMed

    Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

    2014-09-18

    We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

  2. Excitation transfer in the in-vitro reaction of photobacterium luciferase bioluminescence

    NASA Astrophysics Data System (ADS)

    Lee, John W.

    1992-04-01

    Fluorescence dynamics methods are used to probe the mechanism by which the chemi- energized intermediates of the bacterial luciferase catalyzed oxidation of FMNH2 and tetradecanal are able to excite the ligand of lumazine protein to its first excited singlet state. A fluorescence dynamics study of the effect of lumazine protein on the reaction of several types of luciferase has recently been published (Biochemistry 30 6825, 1991). This present report examines the case of the Photobacterium leiognathi luciferase reaction in more detail. The fluorescence anisotropy of a mixture of this luciferase fluorescent transient mixed with lumazine protein decays rapidly with a correlation time of 5 ns, interpreted as due to energy transfer. There is no sign of a longer time corresponding to the rotation of the proteins themselves. No rise time of the lumazine (acceptor) fluorescence on exciting into the fluorescent transient (donor) absorption is measureable, so that no straightforward estimate of the energy transfer rate can be made.

  3. X-ray Crystal Structures Elucidate the Nucleotidyl Transfer Reaction of Transcript Initiation Using Two Nucleotides

    SciTech Connect

    M Gleghorn; E Davydova; R Basu; L Rothman-Denes; K Murakami

    2011-12-31

    We have determined the X-ray crystal structures of the pre- and postcatalytic forms of the initiation complex of bacteriophage N4 RNA polymerase that provide the complete set of atomic images depicting the process of transcript initiation by a single-subunit RNA polymerase. As observed during T7 RNA polymerase transcript elongation, substrate loading for the initiation process also drives a conformational change of the O helix, but only the correct base pairing between the +2 substrate and DNA base is able to complete the O-helix conformational transition. Substrate binding also facilitates catalytic metal binding that leads to alignment of the reactive groups of substrates for the nucleotidyl transfer reaction. Although all nucleic acid polymerases use two divalent metals for catalysis, they differ in the requirements and the timing of binding of each metal. In the case of bacteriophage RNA polymerase, we propose that catalytic metal binding is the last step before the nucleotidyl transfer reaction.

  4. Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

    SciTech Connect

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.

  5. Proton transfer reaction mass spectrometry: on-line trace gas analysis at the ppb level

    NASA Astrophysics Data System (ADS)

    Hansel, A.; Jordan, A.; Holzinger, R.; Prazeller, P.; Vogel, W.; Lindinger, W.

    1995-11-01

    A system for trace gas analysis using proton transfer reaction mass spectrometry (PTR-MS) has been developed which allows for on-line measurements of components with concentrations as low as 1 ppb. The method is based on reactions of H3O+ ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of analysis of breath taken from smokers and non-smokers as well as from patients suffering from cirrhosis of the liver, and of air in buildings as well as of ambient air taken at a road crossing demonstrate the wide range of applicability of this method. An enhanced level of acetonitrile in the breath is a most suitable indicator that a person is a smoker. Enhanced levels of propanol strongly indicate that a person has a severe liver deficiency.

  6. Two-Phase Reactions in Microdroplets without the Use of Phase-Transfer Catalysts.

    PubMed

    Yan, Xin; Cheng, Heyong; Zare, Richard N

    2017-02-22

    Many important chemical transformations occur in two-phase reactions, which are widely used in chemical, pharmaceutical, and polymer manufacturing. We present an efficient method for performing two-phase reactions in microdroplets sheared by sheath gas without using a phase-transfer catalyst. This avoids disadvantages such as thermal instability, high cost, and, especially, the need to separate and recycle the catalysts. We show that various alcohols can be oxidized to the corresponding aldehydes and ketones within milliseconds in moderate to good yields (50-75 %). The scale-up of the present method was achieved at an isolated rate of 1.2 mg min(-1) for the synthesis of 4-nitrobenzylaldehyde from 4-nitrobenzyl alcohol in the presence of sodium hypochlorite. The biphasic nature of this process, which avoids use of a phase-transfer catalyst, greatly enhances synthetic effectiveness.

  7. Protein modifications affecting triplet energy transfer in bacterial photosynthetic reaction centers.

    PubMed Central

    Laible, P D; Chynwat, V; Thurnauer, M C; Schiffer, M; Hanson, D K; Frank, H A

    1998-01-01

    The efficiency of triplet energy transfer from the special pair (P) to the carotenoid (C) in photosynthetic reaction centers (RCs) from a large family of mutant strains has been investigated. The mutants carry substitutions at positions L181 and/or M208 near chlorophyll-based cofactors on the inactive and active sides of the complex, respectively. Light-modulated electron paramagnetic resonance at 10 K, where triplet energy transfer is thermally prohibited, reveals that the mutations do not perturb the electronic distribution of P. At temperatures > or = 70 K, we observe reduced signals from the carotenoid in most of the RCs with L181 substitutions. In particular, triplet transfer efficiency is reduced in all RCs in which a lysine at L181 donates a sixth ligand to the monomeric bacteriochlorophyll B(B). Replacement of the native Tyr at M208 on the active side of the complex with several polar residues increased transfer efficiency. The difference in the efficiencies of transfer in the RCs demonstrates the ability of the protein environment to influence the electronic overlap of the chromophores and thus the thermal barrier for triplet energy transfer. PMID:9591686

  8. Directionality of electron-transfer reactions in photosystem I of prokaryotes: universality of the bidirectional electron-transfer model.

    PubMed

    Santabarbara, Stefano; Kuprov, Ilya; Poluektov, Oleg; Casal, Antonio; Russell, Charlotte A; Purton, Saul; Evans, Michael C W

    2010-11-25

    The electron-transfer (ET) reactions in photosystem I (PS I) of prokaryotes have been investigated in wild-type cells of the cyanobacterium Synechocystis sp. PCC 6803, and in two site-directed mutants in which the methionine residue of the reaction center subunits PsaA and PsaB, which acts as the axial ligand to the primary electron chlorophyll acceptor A(0), was substituted with histidine. Analysis by pulsed electron paramagnetic resonance spectroscopy at 100 K indicates the presence of two forms of the secondary spin-correlated radical pairs, which are assigned to [P(700)(+)A(1A)(-)] and [P(700)(+)A(1B)(-)], where A(1A) and A(1B) are the phylloquinone molecules bound to the PsaA and the PsaB reaction center subunits, respectively. Each of the secondary radical pair forms is selectively observed in either the PsaA-M688H or the PsaB-M668H mutant, whereas both radical pairs are observed in the wild type following reduction of the iron-sulfur cluster F(X), the intermediate electron acceptor between A(1) and the terminal acceptors F(A) and F(B). Analysis of the time and spectral dependence of the light-induced electron spin echo allows the resolution of structural differences between the [P(700)(+)A(1A)(-)] and [P(700)(+)A(1B)(-)] radical pairs. The interspin distance is 25.43 ± 0.01 Å for [P(700)(+)A(1A)(-)] and 24.25 ± 0.01 Å for [P(700)(+)A(1B)(-)]. Moreover, the relative orientation of the interspin vector is rotated by ~60° with respect to the g-tensor of the P(700)(+) radical. These estimates are in agreement with the crystallographic structural model, indicating that the cofactors bound to both reaction center subunits of prokaryotic PS I are actively involved in electron transport. This work supports the model that bidirectionality is a general property of type I reaction centers from both prokaryotes and eukaryotes, and contrasts with the situation for photosystem II and other type II reaction centers, in which ET is strongly asymmetric. A revised model

  9. Integral Equation Calculation of Solvent Activation Free Energies for Electron and Proton Transfer Reactions

    DTIC Science & Technology

    1993-11-04

    6. AUTHOR(S) P.P. Schmidt Indrani Bhattacharya- Kodali and Gregory Voth 7. PERFORMING ORGANIZATION NAME(S) AND AODRESS(ES) 8. PERIORMING ORGANIZATION...13. ABSTRACT (Maimum 200 words) The extended reference interaction site method (RISM) integral equation theory is applied to calculate the solvent...Integral Equation Calculation of Solvent Activation Free Energies for Electron and Proton Transfer Reactions Indrani Bhattacharya- Kodali and Gregory A. Voth

  10. Controlling the conductance of molecular junctions using proton transfer reactions: A theoretical model study

    NASA Astrophysics Data System (ADS)

    Hofmeister, Chriszandro; Coto, Pedro B.; Thoss, Michael

    2017-03-01

    The influence of an intramolecular proton transfer reaction on the conductance of a molecular junction is investigated employing a generic model, which includes the effects of the electric field of the gate and leads electrodes and the coupling to a dissipative environment. Using a quantum master equation approach it is shown that, depending on the localization of the proton, the junction exhibits a high or low current state, which can be controlled by external electric fields. Considering different regimes, which range from weak to strong hydrogen bonds in the proton transfer complex and comprise situations with high and low barriers, necessary preconditions to achieve control are analyzed. The results show that systems with a weak hydrogen bond and a significant energy barrier for the proton transfer can be used as molecular transistors or diodes.

  11. Stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder.

    PubMed

    Najib, Najwa; Bachok, Norfifah; Arifin, Norihan Md; Ishak, Anuar

    2014-02-26

    This paper is about the stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder. The governing partial differential equations in cylindrical form are transformed into ordinary differential equations by a similarity transformation. The transformed equations are solved numerically using a shooting method. Results for the skin friction coefficient, Schmidt number, velocity profiles as well as concentration profiles are presented for different values of the governing parameters. Effects of the curvature parameter, stretching/shrinking parameter and Schmidt number on the flow and mass transfer characteristics are examined. The study indicates that dual solutions exist for the shrinking cylinder but for the stretching cylinder, the solution is unique. It is observed that the surface shear stress and the mass transfer rate at the surface increase as the curvature parameter increases.

  12. Donor-site giant cell reaction following backfill with synthetic bone material during osteochondral plug transfer.

    PubMed

    Fowler, Donald E; Hart, Joseph M; Hart, Jennifer A; Miller, Mark D

    2009-10-01

    Osteochondral defects are common in younger, active patients. Multiple strategies have been used to treat these lesions, including microfracture and osteochondral plug transfer. We describe a patient experiencing chronic knee pain and a full-thickness cartilage defect on the lateral femoral condyle. After failing conservative management and microfracture surgery, the patient underwent osteochondral autograft plug transfer, with backfilling of the donor sites using synthetic bone graft substitute. Initial recovery was uncomplicated until the patient experienced pain following a twist of the knee. Magnetic resonance imaging for the subsequent knee injury revealed poor healing at the donor sites. The donor sites were debrided, and specimens revealed a foreign body giant cell reaction. Donor-site morbidity is of primary concern during osteochondral plug transfer; however, insufficient data exist to support the use of synthetic bone graft material. Our results indicate that off-label use of synthetic bone graft substitute during a primary procedure requires further investigation.

  13. The ^12C(^7Li,^6Li)^13C Transfer Reaction

    NASA Astrophysics Data System (ADS)

    Bartosz, E. E.; Keeley, N.; Kemper, K. W.

    2001-04-01

    We present the first complete set of analysing powers, including all third rank ones, for a ^7Li induced transfer reaction. Data were obtained for transfers to the 1/2^-, 1/2^+ and 5/2^+ states of ^13C at 0.0, 3.09 and 3.85 MeV excitation energies respectively, induced by a 34 MeV polarised ^7Li beam. This experiment was motivated by the complete failure of previous DWBA and CCBA calculations to describe transfers to the 1/2^+ state (K.W. Kemper, et al./, Phys. Rev. C 38, 2664 (1988).). Extensive coupled-discretised-continuum-channels (CDCC) calculations using cluster-folding (CF) model form-factors have been carried out and show that the failure to describe the 1/2^+ data is not a result of a dynamical effect.

  14. Excited-state hydrogen atom transfer reaction in solvated 7-hydroxy-4-methylcoumarin.

    PubMed

    De Silva, Nuwan; Minezawa, Noriyuki; Gordon, Mark S

    2013-12-12

    Excited-state enol to keto tautomerization of 7-hydroxy-4-methylcoumarin (C456) with three water molecules (C456:3H2O), is theoretically investigated using time-dependent density functional theory (TDDFT) combined with the polarizable continuum model and 200 waters explicitly modeled with the effective fragment potential. The tautomerization of C456 in the presence of three water molecules is accompanied by an asynchronous quadruple hydrogen atom transfer reaction from the enol to the keto tautomer in the excited state. TDDFT with the PBE0 functional and the DH(d,p) basis set is used to calculate the excited-state reaction barrier height, absorption (excitation), and fluorescence (de-excitation) energies. These results are compared with the available experimental and theoretical data. In contrast to previous work, it is predicted here that the coumarin 456 system undergoes a hydrogen atom transfer, not a proton transfer. The calculated reaction barrier of the first excited state of C456:3H2O with 200 water molecules is found to be -0.23 kcal/mol without zero-point energy (-5.07 kcal/mol with zero point energy, i.e., the activation energy).

  15. Proton Coupled Electron Transfer Reactions at the Surface of Metal Oxide Nanomaterials

    NASA Astrophysics Data System (ADS)

    Braten, Miles N.

    Nanostructured metal oxide materials are found in many products and processes in our society today, but they play a particularly important role in the conversion and storage of energy. The materials are used as catalysts and redox active supports in devices such as dye sensitized solar cells, solid oxide fuel cells, and flow batteries, where they transfer and store electrons and charge balancing cations. Oftentimes electron transfer is modulated by the cations and when the cation is a proton, these redox reactions are known as proton coupled electron transfer (PCET) reactions. The work described in this dissertation focuses on understanding the PCET reactivity of nanocrystalline metal oxide materials. Chapter 1 introduces the concept of PCET and provides background information on the zinc oxide (ZnO) nanocrystals (NCs) which the majority of the research is focused on. Chapter 2 examines the chemistry that occurs during the photoreduction of ZnO NCs. Chapter 3 describes experiments probing how ZnO NC capping ligand concentration and NC size modulate PCET reaction rates. Chapter 4 describes experiments that compare the PCET reactivity of ZnO NCs with different numbers of electrons and protons stored on them. Chapter 5 describes attempts to observe the electrochemical reduction of ZnO NCs attached to gold electrodes. Finally, Chapter 6 contains attempts to identify a nanostructured metal oxide alkane oxidation catalyst for use in fuel cell.

  16. Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

    SciTech Connect

    Hsiao, Yun-Lin.

    1990-09-21

    The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

  17. Enantioselective N-Heterocyclic Carbene-Catalyzed β-Hydroxylation of Enals Using Nitroarenes: An Atom Transfer Reaction That Proceeds via Single Electron Transfer

    PubMed Central

    2015-01-01

    A novel oxidative N-heterocyclic carbene-catalyzed reaction pathway has been discovered. Alkyl and aryl enals undergo β-hydroxylation via oxygen atom transfer from electron-deficient nitrobenzenes, followed by trapping of the resultant acyl azolium by the solvent. The proposed mechanism involves a single electron transfer event to initiate the reaction followed by radical recombination. This represents a profound mechanistic departure from the established two-electron disconnects in NHC catalysis. PMID:25302860

  18. Energetic comparison between photoinduced electron-transfer reactions from NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from NADH model compounds to p-benzoquinone derivatives

    SciTech Connect

    Fukuzumi, S.; Koumitsu, S.; Hironaka, K.; Tanaka, T.

    1987-01-21

    Kinetic studies on photoinduced electron-transfer reactions from dihydropyridine compounds (PyH/sub 2/) as being NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from PyH/sub 2/ to p-benzoquinone derivatives (Q) in the absence and presence of Mg/sup 2 +/ ion are reported by determining over 150 rate constants. These results, combined with the values of Gibbs energy change of the photoinduced electron-transfer reactions as well as those of each step of the hydride-transfer reactions as being the e/sup -/-H/sup +/-e/sup -/ sequence, which are determined independently, revealed that the rate constants of the photoinduced electron-transfer reactions obey the Rehm-Weller-Gibbs energy relationship and that the activation barrier of the hydride-transfer reactions from PyH/sub 2/ to Q is dependent solely on the Gibbs energy changes of the initial electron transfer from PyH/sub 2/ to Q and the following proton transfer from PyH/sub 2//sup .+/ to Q/sup .-/ and thus independent of the Gibbs energy change of the final electron transfer from PyH/sup ./ to QH/sup ./. The retarding effect of Mg/sup 2 +/ ion observed on the photoinduced electron transfer and hydride-transfer reactions of PyH/sub 2/ is ascribed to the positive shifts of the redox potentials of the ground and excited states of PyH/sub 2/ due to the complex formation with Mg/sup 2 +/ ion.

  19. Ozonation of polycyclic aromatic hydrocarbons in oil/water-emulsions: mass transfer and reaction kinetics.

    PubMed

    Kornmüller, Anja; Wiesmann, Udo

    2003-03-01

    The ozonation of highly condensed polycyclic aromatic hydrocarbons (PAH) was studied in oil/water-emulsions, which are comparable to poorly water-soluble PAH in industrial wastewaters and at contaminated sites. As there was a lack of knowledge about the ozonation in oil/water-emulsions, first the ozone mass transfer was studied and optimized from the gas to the water phase and from the water to the oil phase. The ratio of mass transfer and oxidation reaction was determined by the Hatta-number and revealed a slow, quasi homogeneous reaction of ozone with PAH inside the oil droplets. Because the ozone gas concentration had no influence under the optimized conditions, the selective PAH-ozonation could be described microkinetically by a direct ozone reaction of pseudo-first order regarding PAH-concentrations. The determined PAH mean reaction rate constants of 1.02 min(-1) in oil/water-emulsions are in the upper range as found for PAH dissolved in water. These results give a new insight into the ozonation in the three-phase systems and into the treatment of highly condensed, hardly biodegradable PAH.

  20. Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

    NASA Technical Reports Server (NTRS)

    Chaban, Galina M.; Salter, Latasha M.; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

  1. A computational study of the phosphoryl transfer reaction between ATP and Dha in aqueous solution.

    PubMed

    Bordes, I; Ruiz-Pernía, J J; Castillo, R; Moliner, V

    2015-10-28

    Phosphoryl transfer reactions are ubiquitous in biology, being involved in processes ranging from energy and signal transduction to the replication genetic material. Dihydroxyacetone phosphate (Dha-P), an intermediate of the synthesis of pyruvate and a very important building block in nature, can be generated by converting free dihydroxyacetone (Dha) through the action of the dihydroxyacetone kinase enzyme. In this paper the reference uncatalyzed reaction in solution has been studied in order to define the foundations of the chemical reaction and to determine the most adequate computational method to describe this electronically complex reaction. In particular, the phosphorylation reaction mechanism between adenosine triphosphate (ATP) and Dha in aqueous solution has been studied by means of quantum mechanics/molecular mechanics (QM/MM) Molecular Dynamics (MD) simulations with the QM subset of atoms described with semi-empirical and DFT methods. The results appear to be strongly dependent on the level of calculation, which will have to be taken into account for future studies of the reaction catalyzed by enzymes. In particular, PM3/MM renders lower free energy barriers and a less endergonic process than AM1d/MM and PM6/MM methods. Nevertheless, the concerted pathway was not located with the former combination of potentials.

  2. Proton transfer reactions between nitric acid and acetone, hydroxyacetone, acetaldehyde and benzaldehyde in the solid phase.

    PubMed

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-05

    The heterogeneous and homogeneous reactions of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with solid nitric acid (HNO(3)) films have been studied with Reflection-Absorption Infrared Spectroscopy (RAIRS) under Ultra-High Vacuum (UHV) conditions in the 90-170 K temperature range. In the bulk or at the surface of the films, nitric acid transfers its proton to the carbonyl function of the organic molecules, producing protonated acetone-H(+), hydroxyacetone-H(+), acetaldehyde-H(+) and benzaldehyde-H(+), and nitrate anions NO(3)(-), a reaction not observed when nitric acid is previously hydrated [J. Lasne, C. Laffon and Ph. Parent, Phys. Chem. Chem. Phys., 2012, 14, 697]. This provides a molecular-scale description of the carbonyl protonation reaction in an acid medium, the first step of the acid-catalyzed condensation of carbonyl compounds, fuelling the growth of secondary organic aerosols (SOA) in the atmosphere.

  3. Electrostriction effects on electron transfer reactions in solution. I. Adiabatic regime

    NASA Astrophysics Data System (ADS)

    Jeon, Jonggu; Kim, Hyung J.

    1997-04-01

    The outer-sphere unimolecular electron transfer reactions, DA⇌D+A-, in polar solvents are studied theoretically. By employing a recent theory of fluctuating cavities [H. J. Kim, J. Chem. Phys. 105, 6818, 6833 (1996)], we construct a nonequilibrium free energy formulation that accounts for both the solvation and electrostriction aspects of the changing solute dipole moment during the reaction. With a two-state diabatic description for the solute electronic structure, we obtain a two-dimensional free energy surface in terms of the cavity radius a and a solvent coordinate that gauges the nonequilibrium solvent orientational polarization Por. The equilibrium a values for the reactant and product states are found to differ significantly, indicating that the cavity reorganization plays an important role in the reaction free energetics and dynamics. The reaction mechanism and rate constant are analyzed via the solution-phase reaction path, which is found to vary markedly with the relative time scales of the Por and a motions. To be specific, the charge transfer proceeds in a concerted fashion with active participation of both Por and a when their characteristic times are comparable. By contrast, a stepwise mechanism results when there is a large mismatch between the Por and a time scales. In the slow cavity limit where a is much slower than Por, the reorganization through the cavity size adjustment precedes the barrier crossing that occurs exclusively along the Por coordinate. In the opposite fast cavity regime where Por is mainly responsible for activation and deactivation, it is found that the saddle point on the free energy surface is no longer rate-determining due to the nonlinear residual entropic effects. A brief comparison with other reaction systems involving charge shift in solution is also made.

  4. Proton transfer reactions associated with the reaction of the fully reduced, purified cytochrome C oxidase with molecular oxygen and ferricyanide.

    PubMed

    Capitanio, Nazzareno; Capitanio, Giuseppe; De Nitto, Emanuele; Boffoli, Domenico; Papa, Sergio

    2003-04-29

    A study is presented on proton transfer associated with the reaction of the fully reduced, purified bovine heart cytochrome c oxidase with molecular oxygen or ferricyanide. The proton consumption associated with aerobic oxidation of the four metal centers changed significantly with pH going from approximately 3.0 H(+)/COX at pH 6.2-6.3 to approximately 1.2 H(+)/COX at pH 8.0-8.5. Rereduction of the metal centers was associated with further proton uptake which increased with pH from approximately 1.0 H(+)/COX at pH 6.2-6.3 to approximately 2.8 H(+)/COX at pH 8.0-8.5. Anaerobic oxidation of the four metal centers by ferricyanide resulted in the net release of 1.3-1.6 H(+)/COX in the pH range 6.2-8.2, which were taken up by the enzyme on rereduction of the metal centers. The proton transfer elicited by ferricyanide represents the net result of deprotonation/protonation reactions linked to anaerobic oxidoreduction of the metal centers. Correction for the ferricyanide-induced pH changes of the proton uptake observed in the oxidation and rereduction phase of the reaction of the reduced oxidase with oxygen gave a measure of the proton consumption in the reduction of O(2) to 2H(2)O. The results show that the expected stoichiometric proton consumption of 4H(+) in the reduction of O(2) to 2H(2)O is differently associated, depending on the actual pH, with the oxidation and reduction phase of COX. Two H(+)/COX are initially taken up in the reduction of O(2) to two OH(-) groups bound to the binuclear Fe a(3)-Cu(B) center. At acidic pHs the third and fourth protons are also taken up in the oxidative phase with formation of 2H(2)O. At alkaline pHs the third and fourth protons are taken up with formation of 2H(2)O only upon rereduction of COX.

  5. Blue bottle light: lecture demonstrations of homogeneous and heterogeneous photo-induced electron transfer reactions.

    PubMed

    Mills, Andrew; Lawrie, Katherine; McFarlane, Michael

    2009-03-01

    The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e.blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.

  6. Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

    NASA Astrophysics Data System (ADS)

    Pavlovich, V. S.

    2006-05-01

    A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P+B L - states (where P is a special pair, BL is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational hα mode with frequency 130 150 cm-1 controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P+B L - is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm-1 for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and BL and then to bacteriopheophytin HL.

  7. One-electron transfer reactions of the couple NAD. /NADH. [Pulse radiolysis

    SciTech Connect

    Grodkowski, J.; Neta, P.; Carlson, B.W.; Miller, L.

    1983-08-04

    One-electron transfer reactions involving nicotinamide-adenine dinucleotide in its oxidized and reducd forms (NAD./NADH) were studied by pulse radiolysis in aqueous solutions. One-electron oxidation of NADH by various phenoxyl radicals and phenothiazine cation radicals was found to take place with rate constants in the range of 10/sup 5/ to 10/sup 8/ M/sup -1/ s/sup -1/, depending on the redox potential of the oxidizing species. In all cases, NAD. is formed quantitatively with no indication for the existence of the protonated form (NADH/sup +/.). The spectrum of NAD., as well as the rates of oxidation of NADH by phenoxyl and by (chlorpromazine)/sup +/. were independent of pH between pH 4.5 and 13.5. Reaction of deuterated NADH indicated only a small kinetic isotope effect. All these findings point to an electron transfer mechanism. On the other hand, attempts to observe the reverse electron transfer, i.e., one-electron reduction of NAD. to NADH by radicals such as semiquinones, showed that k was less than 10/sup 4/ to 10/sup 5/ M/sup -1/ s/sup -1/, so that it was unobservable. Consequently, it was not possible to achieve equilibrium conditions which would have permitted the direct measurement of the redox potential for NAD./NADH. One-electron reduction of NAD. appears to be an unlikely process. 1 table.

  8. The electron-transfer reaction between azurin and the cytochrome c oxidase from Pseudomonas aeruginosa.

    PubMed

    Parr, S R; Barber, D; Greenwood, C; Brunori, M

    1977-11-01

    A stopped-flow investigation of the electron-transfer reaction between oxidized azurin and reduced Pseudomonas aeruginosa cytochrome c-551 oxidase and between reduced azurin and oxidized Ps. aeruginosa cytochrome c-551 oxidase was performed. Electrons leave and enter the oxidase molecule via its haem c component, with the oxidation and reduction of the haem d1 occurring by internal electron transfer. The reaction mechanism in both directions is complex. In the direction of oxidase oxidation, two phases assigned on the basis of difference spectra to haem c proceed with rate constants of 3.2 X 10(5)M-1-S-1 and 2.0 X 10(4)M-1-S-1, whereas the haem d1 oxidation occurs at 0.35 +/- 0.1S-1. Addition of CO to the reduced enzyme profoundly modifies the rate of haem c oxidation, with the faster process tending towards a rate limit of 200S-1. Reduction of the oxidase was similarly complex, with a fast haem c phase tending to a rate limit of 120S-1, and a slower phase with a second-order rate of 1.5 X 10(4)M-1-S-1; the internal transfer rate in this direction was o.25 +/- 0.1S-1. These results have been applied to a kinetic model originally developed from temperature-jump studies.

  9. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    SciTech Connect

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in {approximately}240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH{sub 2}I{sub 2} and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a {approximately}350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  10. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    SciTech Connect

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  11. Probable new type of reaction mechanism: Double. cap alpha. direct transfer process

    SciTech Connect

    Xu Shu-wei; Wu Guo-hua; Miao Rong-zhi; Han Fei

    1983-10-01

    It is assumed that /sup 8/Be consists of two ..cap alpha.. particles which are close to each other in configuration space. A spectroscopic density of /sup 8/Be cluster in the residue nuclei is then obtained, which is proportional to the square of the preformation probability of ..cap alpha.. particle at nuclear surface. Using the improved method of parametrization of EFR-DWBA overlap integral,/sup 1//sup en-dash//sup 2/ we calculate the double differential energy spectra and angular distributions of ..cap alpha.. particles for the reactions /sup 209/Bi (/sup 12/C, ..cap alpha..) /sup 217/Fr and extract the preformation probability of ..cap alpha.. particle at the surface of /sup 217/Fr nuclei from fitting the experimental data. The agreement within the range of calculation error between the preformation probabilities extracted from transfer reactions and ..cap alpha.. decay suggests that the reaction /sup 209/Bi(/sup 12/C, ..cap alpha..) /sup 217/Fr may be explained as a double ..cap alpha.. direct transfer process.

  12. Electron transfer reactions in the alkene mono-oxygenase complex from Nocardia corallina B-276.

    PubMed Central

    Gallagher, S C; Cammack, R; Dalton, H

    1999-01-01

    Nocardia corallina B-276 possesses a multi-component enzyme, alkene mono-oxygenase (AMO), that catalyses the stereoselective epoxygenation of alkenes. The reductase component of this system has been shown by EPR and fluorescence spectroscopy to contain two prosthetic groups, an FAD centre and a [2Fe-2S] cluster. The role of these centres in the epoxygenation reaction was determined by midpoint potential measurements and electron transfer kinetics. The order of potentials of the prosthetic groups of the reductase were FAD/FAD.=-216 mV, [2Fe-2S]/[2Fe-2S].=-160 mV and FAD./FAD.=-134 mV. Combined, these data implied that the reductase component supplied the energy required for the epoxygenation reaction and allowed a prediction of the mechanism of electron transfer within the AMO complex. The FAD moiety was reduced by bound NADH in a two-electron reaction. The electrons were then transported to the [2Fe-2S] centre one at a time, which in turn reduced the di-iron centre of the epoxygenase. Reduction of the di-iron centre is required for oxygen binding and substrate oxidation. PMID:10085230

  13. Monitoring Chemical and Biological Electron Transfer Reactions with a Fluorogenic Vitamin K Analogue Probe.

    PubMed

    Belzile, Mei-Ni; Godin, Robert; Durantini, Andrés M; Cosa, Gonzalo

    2016-12-21

    We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of vitamin K, B-VKQ, prepared by coupling vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.

  14. Electronic shift register memory based on molecular electron-transfer reactions

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

    1989-01-01

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

  15. Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids

    NASA Astrophysics Data System (ADS)

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Velayudham, Murugesan; Rajagopal, Seenivasan

    2016-07-01

    Three [Os(NN)3]2+ complexes (NN = polypyridine) with ligands of varying hydrophobicity were synthesized and characterized by NMR spectral techniques. The geometry of the molecules are optimized by DFT calculations. The interaction between [Os(NN)3]2+ complexes and phenolate ion in ground state is confirmed by absorption spectral study and the binding constant values are in the range of 3-740 M-1. The photoinduced electron transfer reaction of these [Os(NN)3]2+ complexes with phenols and phenolic acids at pH 12.5 leads to the formation of phenoxyl radical confirmed through transient absorption spectral study. Binding constants and electron transfer rate constants within the [Os(NN)3]2+-phenolate ion adduct account for the change for the overall quenching constant with the change of structure of reactants.

  16. Steric effect in the energy transfer reaction of Ar(3P2)+N2

    NASA Astrophysics Data System (ADS)

    Watanabe, D.; Ohoyama, H.; Matsumura, T.; Kasai, T.

    2006-08-01

    Steric effect for N2(C,Πu3) formation in the energy transfer reaction of Ar(P23)+N2 was directly measured by using an oriented Ar(P23,MJ=2) beam at a collision energy of 0.06eV. The N2(C,Πu3) chemiluminescence intensity was measured as a function of the magnetic orientation field direction in the collision frame. A significant alignment effect on the energy transfer probability was observed. The relative reactivity for each magnetic substate in the collision frame σ∣MJ'∣ was determined to be σ∣2∣:σ∣1∣:σ0=0.50:0.60:1.00. It is suggested that the observed steric effect is primarily due to the favorable configuration of the 3p orbital for the efficient overlap with the 2σu molecular orbital of N2.

  17. Learned cardiac control with heart rate biofeedback transfers to emotional reactions.

    PubMed

    Peira, Nathalie; Pourtois, Gilles; Fredrikson, Mats

    2013-01-01

    Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i) short lasting biofeedback training improves heart rate regulation and (ii) the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available.

  18. 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.

  19. Catalysis of nitrosyl transfer reactions by a dissimilatory nitrite reductase (cytochrome c,d1).

    PubMed

    Kim, C H; Hollocher, T C

    1984-02-25

    The dissimilatory nitrite reductase (cytochrome c,d1) from Pseudomonas aeruginosa was observed at pH 7.5 to catalyze nitrosyl transfer (nitrosation) between [15N]nitrite and several N-nucleophiles or H2 18O, with rate enhancement of the order of 10(8) relative to analogous chemical reactions. The reducing system (ascorbate, N,N,N',N'-tetramethylphenylenediamine) could reduce nitrite (but not NO) enzymatically and had essentially no direct chemical reactivity toward nitrite or NO. The N-nitrosations showed saturation kinetics with respect to the nucleophile and, while exhibiting Vmax values which varied by about 40-fold, nevertheless showed little or no dependence of Vmax on nucleophile pKa. The N-nitrosations and NO-2/H2O-18O exchange required the reducing system, whereas NO/H2O-18O exchange was inhibited by the reducing system. NO was not detected to serve as a nitrosyl donor to N-nucleophiles. These and other kinetic observations suggest that the enzymatic nitrosyl donor is an enzyme-bound species derived from reduced enzyme and one molecule of nitrite, possibly a heme-nitrosyl compound (E-FeII X NO+) for which there is precedence. Nitrosyl transfer to N-nucleophiles may occur within a ternary complex of enzyme, nitrite, and nucleophile. Catalysis of nitrosyl transfer by nitrite reductase represents a new class of enzymatic reactions and may present another example of electrophilic catalysis by a metal center. The nitrosyl donor trapped by these reactions is believed to represent an intermediate in the reduction of nitrite by cytochrome c,d1.

  20. Studies of Nuclei Close to 132Sn Using Single-Neutron Transfer Reactions

    SciTech Connect

    Jones, K. L.; Pain, S. D.; Kozub, R. L.; Adekola, Aderemi S; Bardayan, Daniel W; Blackmon, Jeff C; Catford, Wilton N; Chae, K. Y.; Chipps, K.; Cizewski, J. A.; Erikson, Luke; Gaddis, A. L.; Greife, U.; Grzywacz, R. K.; Harlin, Christopher W; Hatarik, Robert; Howard, Joshua A; James, J.; Kapler, R.; Krolas, W.; Liang, J Felix; Ma, Zhanwen; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D; O'Malley, Patrick; Patterson, N. P.; Paulauskas, Stanley; Shapira, Dan; ShrinerJr., J. F.; Sikora, M.; Sissom, D. J.; Smith, Michael Scott; Swan, T. P.; Thomas, J. S.; Wilson, Gemma L

    2009-01-01

    Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of 132Sn, 130Sn, and 134Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for 133Sn, 131Sn and 135Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf7/2 nature of the ground state of 133Sn, and 2p3/2 for the 3.4 MeV state in 131Sn.

  1. Studies of nuclei close to {sup 132}Sn using single-neutron transfer reactions

    SciTech Connect

    Jones, K. J.; Pain, S. D.; Kozub, R. L.; Howard, J. A.; O'Malley, P. D.; Paulauskas, S. V.; Shriner, J. F.; Sissom, D. J.; Adekola, A. S.; Bardayan, D. W.; Blackmon, J. C.; Liang, J. F.; Nesaraja, C. D.; Shapira, D.; Smith, M. S.; Catford, W. N.; Harlin, C.; Patterson, N. P.; Swan, T. P.; Wilson, G. L.

    2009-03-04

    Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of {sup 132}Sn, {sup 130}Sn, and {sup 134}Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for {sup 133}Sn, {sup 131}Sn and {sup 135}Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf{sub 7/2} nature of the ground state of {sup 133}Sn, and 2p{sub 3/2} for the 3.4 MeV state in {sup 131}Sn.

  2. Silicon Nano-well Arrays for Reliable Pattern Transfer and Locally Confined High Temperature Reactions

    PubMed Central

    Wi, Jung-Sub; Wilson, Robert J.; Lee, Donkoun; White, Robert M.; Wang, Shan X.

    2011-01-01

    Si nano-well arrays, with precisely controlled undercut Si sidewall profiles and flat bottomed pockets, enable uniform nanoscale pattern transfer from resists to metal deposits without degradation of the initial lithographic resolution, as verified by formation of arrays of Au nano-dots with 10 nm diameter. An additional functionality of the Si nano-wells as local nano-reactors, where the patterned material is enclosed in a Si pocket during high temperature reaction, is demonstrated by thermally inducing a phase transformation of the as-deposited A1 phase of FePt nano-dots to the high coercivity, chemically ordered L10 phase. PMID:21709347

  3. Heat and Mass Transfer in Unsteady Rotating Fluid Flow with Binary Chemical Reaction and Activation Energy

    PubMed Central

    Awad, Faiz G.; Motsa, Sandile; Khumalo, Melusi

    2014-01-01

    In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

  4. Species differences in unlocking B-side electron transfer in bacterial reaction centers

    DOE PAGES

    Dylla, Nicholas P.; Faries, Kaitlyn M.; Wyllie, Ryan M.; ...

    2016-06-21

    The structure of the bacterial photosynthetic reaction center (RC) reveals symmetry-related electron transfer (ET) pathways, but only one path is used in native RCs. Analogous mutations have been made in two Rhodobacter (R.) species. A glutamic acid at position 133 in the M subunit increases transmembrane charge separation via the naturally inactive (B-side) path through impacts on primary ET in mutant R. sphaeroidesRCs. Prior work showed that the analogous substitution in the R. capsulatusRC also increases B-side activity, but mainly affects secondary ET. Finally, the overall yields of transmembrane ET are similar, but enabled in fundamentally different ways.

  5. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions.

    PubMed

    Wang, Xue Lu; Liu, Wenqing; Yu, Yan-Yan; Song, Yanhong; Fang, Wen Qi; Wei, Daxiu; Gong, Xue-Qing; Yao, Ye-Feng; Yang, Hua Gui

    2016-06-17

    Proton transfer (PT) processes in solid-liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid-liquid phases.

  6. Population of collective bands in Dy isotopes using heavy ion induced transfer reactions

    SciTech Connect

    Cresswell, A.J.; Butler, P.A.; Cline, D.; Cunningham, R.A.; Devlin, M.; Hannachi, F.; Ibbotson, R.; Jones, G.D.; Jones, P.M.; Simon, M.; Simpson, J.; Smith, J.F.; Wu, C.Y. ||

    1995-10-01

    It is demonstrated that low-lying collective bands in deformed nuclei are strongly populated by quasielastic heavy ion transfer reactions at near barrier energies. The {sup 161}Dy({sup 61}Ni,{sup 62}Ni){sup 160}Dy and {sup 161}Dy({sup 61}Ni,{sup 60}Ni){sup 162}Dy reactions at a beam energy of 270 MeV have been studied using a particle-{gamma} technique. Significant population of sidebands in {sup 160}Dy was observed, particularly the {ital S} band built upon the [{nu}({ital i}{sub 13/2})]{sup 2} configuration and the {ital K}{sup {pi}}=1{sup {minus}}, 2{sup {minus}}, and {gamma} bands. For {sup 162}Dy the only sideband significantly populated was the {gamma} band.

  7. BALANCE : a computer program for calculating mass transfer for geochemical reactions in ground water

    USGS Publications Warehouse

    Parkhurst, David L.; Plummer, L. Niel; Thorstenson, Donald C.

    1982-01-01

    BALANCE is a Fortran computer designed to define and quantify chemical reactions between ground water and minerals. Using (1) the chemical compositions of two waters along a flow path and (2) a set of mineral phases hypothesized to be the reactive constituents in the system, the program calculates the mass transfer (amounts of the phases entering or leaving the aqueous phase) necessary to account for the observed changes in composition between the two waters. Additional constraints can be included in the problem formulation to account for mixing of two end-member waters, redox reactions, and, in a simplified form, isotopic composition. The computer code and a description of the input necessary to run the program are presented. Three examples typical of ground-water systems are described. (USGS)

  8. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions

    PubMed Central

    Wang, Xue Lu; Liu, Wenqing; Yu, Yan-Yan; Song, Yanhong; Fang, Wen Qi; Wei, Daxiu; Gong, Xue-Qing; Yao, Ye-Feng; Yang, Hua Gui

    2016-01-01

    Proton transfer (PT) processes in solid–liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid–liquid phases. PMID:27311326

  9. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    PubMed

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  10. Theoretical Study of Proton Coupled Electron Transfer Reactions: The Effect of Hydrogen Bond Bending Motion.

    PubMed

    Liu, Yang; Liu, Hao; Song, Kai; Xu, Yang; Shi, Qiang

    2015-06-25

    We investigate theoretically the effect of hydrogen bond bending motion on the proton coupled electron transfer (PCET) reaction, using a model system where an intramolecular hydrogen-bonded phenol group is the proton donor. It is shown that, in a two-dimensional (2D) model of the PCET reaction, the bending and stretching vibrational motions are separated, and due to the hydrogen bond configuration and anharmonicity of the potential energy surface, the bending vibration can play a role in the PCET reaction. The results are also compared with two different sets of one-dimensional models (1D-linear and 1D-curved). Due to contributions of the bending motion, the rate constants in the 2D model are larger than those in the 1D-linear model, although the differences between the total rate constants and KIEs for 2D and 1D models are not major. Results from the 1D-curved model lie between the 2D- and 1D-linear models, indicating that it can include some effect of bending motion in reducing the potential energies along the reaction path.

  11. The impact of porosity waves on crustal reaction progress and CO2 mass transfer

    NASA Astrophysics Data System (ADS)

    Tian, Meng; Ague, Jay J.

    2014-03-01

    Rocks below the brittle-ductile transition can deform viscously and compact while fluid percolates through (two-phase solid-fluid flow). We investigate chemical reaction systematics during two-phase flow using one-dimensional numerical models in which reactive H2O-CO2 fluid ascends down-temperature toward the surface, driving the retrograde reaction: 7CO2+3Calcite+Tremolite=5Dolomite+8Quartz+H2O. The reaction progress is compared to that predicted by fluid-rock reaction during “standard” Darcian flow. A range of layer thicknesses (km-scale) in one- and two-layer systems were investigated at pressure-temperature conditions below the brittle-ductile transition corresponding to ∼13-20 km depth. Model porosity waves of wavelength ∼5 km were generated repeatedly at the base of the flow region using a solitary wave solution with a prescribed initial wave amplitude A = (maximum porosity)/(background porosity of 10-3). Simulation of reaction progress and carbon transfer for the Darcian flow model and for porosity wave transport with A=5, 2.5 and 1.25 yield the following results. First, the overall reaction progress in the two fluid transport models is mainly controlled by the time-integrated fluid flux, and is not strongly dependent on the flow regime. The implication is that the fluid pressure gradient anomalies in the regional-scale porosity waves modeled herein play a negligible role in driving reaction progress. Second, although there are high fluid velocities and thus strong advection in large amplitude porosity waves, the kinetic parameters adopted from experiments predict that the fluid compositions approach local fluid-rock equilibrium in both transport models. Third, regional-scale carbonate-bearing rock layers may be substantial sinks for carbon in ascending fluids if sufficient porosity and permeability can be maintained during reaction. Finally, typical models of retrograde reactions predict that porosity ultimately becomes clogged and, thus, fluid flow

  12. Cu-N dopants boost electron transfer and photooxidation reactions of carbon dots.

    PubMed

    Wu, Wenting; Zhan, Liying; Fan, Weiyu; Song, Jizhong; Li, Xiaoming; Li, Zhongtao; Wang, Ruiqin; Zhang, Jinqiang; Zheng, Jingtang; Wu, Mingbo; Zeng, Haibo

    2015-05-26

    The broadband light-absorption ability of carbon dots (CDs) has inspired their application in photocatalysis, however this has been impeded by poor electron transfer inside the CDs. Herein, we report the preparation of Cu-N-doped CDs (Cu-CDs) and investigate both the doping-promoted electron transfer and the performance of the CDs in photooxidation reactions. The Cu-N doping was achieved through a one-step pyrolytic synthesis of CDs with Na2 [Cu(EDTA)] as precursor. As confirmed by ESR, FTIR, and X-ray photoelectron spectroscopies, the Cu species chelates with the carbon matrix through Cu-N complexes. As a result of the Cu-N doping, the electron-accepting and -donating abilities were enhanced 2.5 and 1.5 times, and the electric conductivity was also increased to 171.8 μs cm(-1) . As a result of these enhanced properties, the photocatalytic efficiency of CDs in the photooxidation reaction of 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate is improved 3.5-fold after CD doping.

  13. Hybrid quantum/classical path integral approach for simulation of hydrogen transfer reactions in enzymes.

    PubMed

    Wang, Qian; Hammes-Schiffer, Sharon

    2006-11-14

    A hybrid quantum/classical path integral Monte Carlo (QC-PIMC) method for calculating the quantum free energy barrier for hydrogen transfer reactions in condensed phases is presented. In this approach, the classical potential of mean force along a collective reaction coordinate is calculated using umbrella sampling techniques in conjunction with molecular dynamics trajectories propagated according to a mapping potential. The quantum contribution is determined for each configuration along the classical trajectory with path integral Monte Carlo calculations in which the beads move according to an effective mapping potential. This type of path integral calculation does not utilize the centroid constraint and can lead to more efficient sampling of the relevant region of conformational space than free-particle path integral sampling. The QC-PIMC method is computationally practical for large systems because the path integral sampling for the quantum nuclei is performed separately from the classical molecular dynamics sampling of the entire system. The utility of the QC-PIMC method is illustrated by an application to hydride transfer in the enzyme dihydrofolate reductase. A comparison of this method to the quantized classical path and grid-based methods for this system is presented.

  14. Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

    DOE PAGES

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; ...

    2015-06-11

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemore » of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.« less

  15. Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

    PubMed Central

    Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

    2015-01-01

    We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

  16. Influence of Active Site Conformations on the Hydride Transfer step of the Thymidylate Synthase Reaction Mechanism

    PubMed Central

    Świderek, Katarzyna; Kohen, Amnon; Moliner, Vicent

    2015-01-01

    The hydride transfer from C6 of tetrahydrofolate to the reaction’s exocyclic methylene-dUMP intermediate is the rate limiting step in thymidylate synthase (TSase) catalysis. This step has been studied by means of QM/MM Molecular Dynamics simulations to generate the corresponding free energy surfaces. The use of two different initial X-ray structures has allowed exploring different conformational spaces and exploring the existence of chemical paths with not only different reactivities, but also different reaction mechanisms. The results confirm that this chemical conversion takes place preferentially via a concerted mechanism where the hydride transfer is conjugated to thiol-elimination from the product. The findings also confirm the labile character of the substrate-enzyme covalent bond established between the C6 of the nucleotide substrate and a conserved cysteine residue. The calculations also reproduce and rationalize a normal H/T 2° kinetic isotope effect measured for that step. From a computational point of view, the results demonstrate that the use of an incomplete number of coordinates to describe the real reaction coordinate can render biased results. PMID:25868526

  17. Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole water complexes

    NASA Astrophysics Data System (ADS)

    Yi, Ping G.; Liang, Yong H.; Tang, Zhen Q.

    2006-03-01

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO · (H 2O) nn = 1-3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K 2 is the most stable isomer in the gas phase, and the tautomer K 1 to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE cis ↔ 3WK 1 and 2WE trans ↔ 2WK 2 is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E cis and K 1 cannot happen without solvent-assisted.

  18. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

    PubMed

    Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

    2015-02-21

    Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ < 332 nm. The obtained results clearly show that H-atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared

  19. Baicalin inhibits the fenton reaction by enhancing electron transfer from Fe (2+) to dissolved oxygen.

    PubMed

    Nishizaki, Daisuke; Iwahashi, Hideo

    2015-01-01

    Sho-saiko-to is an herbal medicine that is known to have diverse pharmacological activities and has been used for the treatment of various infectious diseases. Here, we examined the effects of baicalin, a compound isolated from Sho-saiko-to, and the effects of the iron chelator quinolinic acid on the Fenton reaction. The control reaction mixture contained 0.1 M 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 0.2 mM H 2 O 2, 0.2 mM FeSO 4( NH 4)2 SO 4, and 40 mM sodium phosphate buffer (pH 7.4). Upon the addition of 0.6 mM baicalin or quinolinic acid to the control reaction mixture, the ESR peak heights of DMPO/OH radical adducts were measured as 32% ± 1% (baicalin) and 166% ± 27% (quinolinic acid) of that of the control mixture. In order to clarify why baicalin and quinolinic acid exerted opposite effects on the formation of hydroxyl radicals, we measured oxygen consumption in the presence of either compound. Upon the addition of 0.6 mM baicalin (or quinolinic acid) to the control reaction mixture without DMPO and H 2 O 2, the relative oxygen consumption rates were found to be 449% ± 40% (baicalin) and 18% ± 9% (quinolinic acid) of that of the control mixture without DMPO and H 2 O 2, indicating that baicalin facilitated the transfer of electrons from Fe (2+) to dissolved oxygen. Thus, the great majority of Fe (2+) turned into Fe (3+), and the formation of hydroxyl radicals was subsequently inhibited in this reaction.

  20. Excited state intramolecular charge transfer reaction in nonaqueous electrolyte solutions: Temperature dependence

    NASA Astrophysics Data System (ADS)

    Pradhan, Tuhin; Gazi, Harun Al Rasid; Biswas, Ranjit

    2009-08-01

    Temperature dependence of the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in ethyl acetate (EA), acetonitrile (ACN), and ethanol at several concentrations of lithium perchlorate (LiClO4) has been investigated by using the steady state and time resolved fluorescence spectroscopic techniques. The temperature range considered is 267-343 K. The temperature dependent spectral peak shifts and reaction driving force (-ΔGr) in electrolyte solutions of these solvents can be explained qualitatively in terms of interaction between the reactant molecule and ion-atmosphere. Time resolved studies indicate that the decay kinetics of P4C is biexponential, regardless of solvents, LiClO4 concentrations, and temperatures considered. Except at higher electrolyte concentrations in EA, reaction rates in solutions follow the Arrhenius-type temperature dependence where the estimated activation energy exhibits substantial electrolyte concentration dependence. The average of the experimentally measured activation energies in these three neat solvents is found to be in very good agreement with the predicted value based on data in room temperature solvents. While the rate constant in EA shows a electrolyte concentration induced parabolic dependence on reaction driving force (-ΔGr), the former in ethanol and ACN increases only linearly with the increase in driving force (-ΔGr). The data presented here also indicate that the step-wise increase in solvent reorganization energy via sequential addition of electrolyte induces the ICT reaction in weakly polar solvents to crossover from the Marcus inverted region to the normal region.

  1. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions

    NASA Astrophysics Data System (ADS)

    Belal, Tarek S.; El-Kafrawy, Dina S.; Mahrous, Mohamed S.; Abdel-Khalek, Magdi M.; Abo-Gharam, Amira H.

    2016-02-01

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524 nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490 nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415 nm. The fourth method involves the formation of a yellow complex peaking at 361 nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8 μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method.

  2. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions.

    PubMed

    Belal, Tarek S; El-Kafrawy, Dina S; Mahrous, Mohamed S; Abdel-Khalek, Magdi M; Abo-Gharam, Amira H

    2016-02-15

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415nm. The fourth method involves the formation of a yellow complex peaking at 361nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method.

  3. Probing the charge transfer reaction coordinate of 4-(dimethylamino)benzonitrile with femtosecond stimulated Raman spectroscopy.

    PubMed

    Rhinehart, Justin M; Mehlenbacher, Randy D; McCamant, David

    2010-11-18

    Femtosecond stimulated Raman spectroscopy (FSRS) and femtosecond transient absorption have been used to probe the photoinduced charge transfer (CT) dynamics of 4-(dimethylamino)benzonitrile in methanol and n-hexane. Through a combined analysis of temporal changes in the Raman modes and transient absorption kinetics, a more complete picture of the reaction coordinate of the intramolecular charge transfer process has been established. FSRS spectra of the phenyl C═C stretching mode (Wilson mode 8a) at 1607 cm(-1), which shifts to 1581 cm(-1) in the CT state, and transient absorption measurements ranging from 360 to 700 nm support internal conversion from the locally excited to the charge transfer state in 4-5 ps and then a subsequent vibrational relaxation within the CT state manifold on a 6-8 ps time scale. Dramatic shifting and narrowing of the 1581 cm(-1) quinoidal C═C stretch (ν(8a)) on the ∼7 ps time scale indicates that the quinoidal distortion is an important probe of the CT reaction dynamics. The cause of the spectral shifts is determined by comparing the observed shifts in the vibrational spectrum to anharmonic couplings computed for the benzonitrile radical anion by density functional theory (DFT) and with quantitative theoretical models of the solvent induced vibrational peak shifts. The DFT calculations indicate that the 10 cm(-1) downshift of the C═C stretch is most likely attributable to significant vibrational excitation in nontotally symmetric modes that are strongly anharmonically coupled to the C═C stretch.

  4. Study of multi-nucleon transfer reactions in 58, 64Ni + 207Pb collisions at the velocity filter SHIP

    NASA Astrophysics Data System (ADS)

    Comas, V. F.; Heinz, S.; Hofmann, S.; Ackermann, D.; Heredia, J. A.; Heßberger, F. P.; Khuyagbaatar, J.; Kindler, B.; Lommel, B.; Mann, R.

    2013-09-01

    We investigated multi-nucleon transfer reactions in collisions of 58Ni + 207Pb and 64Ni + 207Pb at Coulomb barrier energies. The new aspect is that we used a velocity filter (SHIP at GSI) for the separation of the heavy target-like transfer products from background events. The isotopic identification was performed via the decay properties of the reaction products. The goal of the experiment was to study the characteristics of multi-nucleon transfer reactions in the region of heavy nuclei and the applicability of existing separation and detection techniques, which are usually used for identification of heavy fusion-evaporation residues, to heavy transfer products. This was motivated by recent theoretical results from macroscopic-microscopic models which suggest deep inelastic transfer reactions in heavy systems as a means to produce new neutron-rich isotopes in the region of N = 126 and in the region of superheavy nuclei. In this paper we present the isotopic yields, the excitation functions and the excitation energies of the heavy transfer products with Z > 82 as well as the influence of shell effects on the reaction products. The influence of the different neutron numbers of the projectiles is also discussed.

  5. Cross-linked metalloproteins: Novel systems for the study of intraprotein electron-transfer reactions

    SciTech Connect

    Peerey, L.M.

    1990-01-01

    My initial research shows, for the first time, that proteins can be cross-linked selectively via transition-metal compounds to form stable protein complexes. Incubation of horse heat cytochrome c (designated cyt) with reagents PtCl{sub 4}{sup 2{minus}} and trans-(Pt(2-Fpy){sub 2}Cl{sub 2}) under mild conditions yields stable diprotein complexes trans-(PtCl{sub 2}(cyt){sub 2}) and trans-(Pt(2-Fpy){sub 2}(cyt){sub 2}), respectively (2-Fpy is 2-fluoropyridine). The complexes are purified and characterized chromatographically. Spectroscopic and electrochemical measurements indicate that the structural and redox properties of the cytochrome c molecules remain virtually unaltered upon cross-linking. The diprotein complexes are stable indefinitely under ordinary conditions and yet they can be cleaved, and the native protein restored, in a mild reaction. Subsequent research focused on oxidoreduction reactions involving the electrostatic and the covalent complex of horse heart cytochrome c and Phaseolus vulgaris plastocyanin, and exploring the importance of the protein rearrangement for the intracomplex electron-transfer reaction. Cytochrome c and plastocyanin are cross-linked one-to-one by a carbodiimide, in the same general orientation in which they associate electrostatically. Four isomers of the covalent diprotein complex, which probably differ slightly from one another in the manner of cross-linking, are separated efficiently by cation-exchange chromatography. Electron transfer kinetics of the covalent and electrostatic diprotein complexes are studied using stopped-flow, pulse radiolysis, and flash photolysis experiments. 135 refs., 5 figs., 15 tabs.

  6. Understanding Charge Transfer Reactions at the Interface of Plasmas in Contact with Liquids

    NASA Astrophysics Data System (ADS)

    Go, David

    2015-09-01

    Plasmas in and in contact with liquids offer a very rich physical and chemical environment where a multitude of species (electrons, ions, neutrals) and physical phenomena (light, electric fields) intersect. With emerging applications in medicine, environmental remediation, and materials synthesis, it has become paramount to understand the many processes occurring at the interface in order to design and optimize new technologies. Perhaps the most important plasma species is the electron, and it thus reasonable to assume it can play a critical role when plasmas are brought in contact with liquids as well. Over the past several years, our group has focused on deciphering the nature of electron transfer from a plasma to liquid and the subsequent chemistry the electrons induce. Our experimental configuration is the plasma equivalent of an electrochemical or electrolytic cell, where the cathode and anode are submerged in an electrolyte solution and current is carried by reduction reactions at the cathode and oxidation reactions at the anode. When the cathode is replaced by a plasma, the circuit is explicitly completed by the injection of plasma electrons into the solution where they stably solvate before inducing reduction reactions. Recently, we have demonstrated the first direct detection of these stably solvated electrons using a novel total internal reflection absorption spectroscopy experiment, resulting in the first measurement of the optical absorption spectrum for plasma-solvated electrons. Further, we have shown that the lifetime of these electrons can be significantly reduced if suitable solution- and plasma-phase scavengers are used to react quickly with these electrons. These results highlight the complexity of the plasma-liquid interface and how charge-transfer processes often compete with other chemistry that occurs at the plasma-liquid interface, such as the dissolution of plasma species into the liquid. This work was supported by the U.S. Army Research

  7. Lithium ion phase-transfer reaction at the interface between the lithium manganese oxide electrode and the nonaqueous electrolyte.

    PubMed

    Kobayashi, Shota; Uchimoto, Yoshiharu

    2005-07-14

    The lithium ion phase-transfer reaction between the spinel lithium manganese oxide electrode and a nonaqueous electrolyte was investigated by the ac impedance spectroscopic method. The dependence of the impedance spectra on the electrochemical potential of the lithium ion in the electrode, the lithium salt concentration in the electrolyte, the kind of solvent, and the measured temperature were examined. Nyquist plots, obtained from the impedance measurements, consist of two semicircles for high and medium frequency and warburg impedance for low frequency, indicating that the reaction process of two main steps for high and medium frequency obey the Butler-Volmer type equation and could be related to the charge-transfer reaction process accompanied with lithium ion phase-transfer at the interface. The dependency on the solvent suggests that both steps in the lithium ion phase-transfer at the electrode/electrolyte interface include the desolvation process and have high activation barriers.

  8. Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions

    SciTech Connect

    Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F.; Wu, Adam; Franz, James A.; Mayer, James M.

    2009-03-10

    Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors MIILH and oxyl radicals. [FeII(H2bip)3]2+, [FeII(H2bim)3]2+, [CoII(H2bim)3]2+ and RuII(acac)2(py-imH) [H2bip = 2,2’-bi-1,4,5,6-tetrahydro¬pyrimidine, H2bim = 2,2’-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2’-pyridyl)¬imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or tBu3PhO• (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex MIIIL, and TEMPOH or tBu3PhOH. Solution equilibrium measurements for the reactions of Co and Fe complexes with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer: ΔSºHAT = -30 ± 2 cal mol-1 K-1 for the two iron complexes and -41 ± 2 cal mol-1 K-1 for [CoII(H2bim)3]2+. The ΔSºHAT for TEMPO + RuII(acac)2(py-imH) is much closer to zero, 4.9 ± 1.1 cal mol-1 K-1. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [FeII(H2bip)3]2+ + TEMPO, thus also confirming ΔSºHAT. Calorimetry on TEMPOH + tBu3PhO• gives ΔHºHAT = 11.2 ± 0.5 kcal mol-1 which matches the enthalpy predicted from the difference in literature solution BDEs. An evaluation of the literature BDEs of both TEMPOH and tBu3PhOH is briefly presented and new estimates are included on the relative enthalpy of solvation for tBu3PhO• vs. tBu3PhOH. The primary contributor to the large magnitude of the ground-state entropy |ΔSºHAT| for the metal complexes is vibrational entropy, ΔSºvib. The common assumption that ΔSºHAT ≈ 0 for HAT reactions, developed for organic and small gas phase molecules, does not hold for transition metal based HAT reactions. The trend in magnitude of |ΔSºHAT| for reactions with TEMPO, RuII(acac)2(py-imH) << [FeII(H2bip)3]2+ = [FeII(H2bim)3]2+ < [CoII(H2bim)3]2+, is surprisingly well predicted by the trends for electron transfer half-reaction entropies, ΔSºET, in aprotic solvents. ΔSºET and

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

    PubMed

    Zhu, Hongying; Huang, Guangming

    2015-03-31

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

  10. Production of neutron-rich transcalifornium nuclei in 238U-induced transfer reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Long; Su, Jun; Xie, Wen-Jie; Zhang, Feng-Shou

    2016-11-01

    In order to produce more unknown neutron-rich transcalifornium nuclei, the collisions of 238U with the targets 248Cm, 249Cf, and 250Cm are investigated within the framework of the dinuclear system model. The production cross sections of unknown neutron-rich nuclei with Z =99 -104 in these reactions are predicted. The influences of N /Z ratios and charge numbers of the targets on the production cross sections are studied. It is found that high N /Z ratios of 248Cm and 250Cm targets enhance the production cross sections of neutron-rich transcalifornium nuclei. However, due to high charge number of the target 249Cf the predicted production cross sections of unknown neutron-rich nuclei with Z =104 in the reaction 238U+249Cf are higher than those in 238U+248Cm . We also have studied the entrance angular momentum effects on production probabilities of transfer products in the reaction 238U+248Cm . It is found that the formation probabilities of the final neutron-rich products increase first and then decrease with the increasing J .

  11. Neutron transfer reactions induced by {sup 8}Li on {sup 9}Be

    SciTech Connect

    Guimaraes, V.; Lichtenthaeler, R.; Camargo, O.; Barioni, A.; Assuncao, M.; Kolata, J. J.; Amro, H.; Becchetti, F. D.; Jiang, Hao; Aguilera, E. F.; Lizcano, D.; Martines-Quiroz, E.; Garcia, H.

    2007-05-15

    Angular distributions for the elastic scattering of {sup 8}Li on {sup 9}Be and the neutron transfer reactions {sup 9}Be({sup 8}Li,{sup 7}Li){sup 10}Be and {sup 9}Be({sup 8}Li,{sup 9}Li){sup 8}Be were measured with a 27 MeV {sup 8}Li radioactive nuclear beam. Spectr- oscopic factors for {sup 8}Li (multiply-in-circle sign)n{sup 9}Li and {sup 7}Li (multiply-in-circle sign)n{sup 8}Li bound systems were obtained from the comparison between the experimental differential cross section and finite-range distorted-wave Born approximation calculations with the code FRESCO. The spectroscopic factors obtained were compared to shell model calculations and to other experimental values from (d,p) reactions. Using the present values for the spectroscopic factor, cross sections for the direct neutron-capture reactions {sup 7}Li(n,{gamma}){sup 8}Li and {sup 8}Li(n,{gamma}){sup 9}Li were calculated in the framework of a potential model.

  12. Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation

    PubMed Central

    Hu, Xiao-Qiang; Qi, Xiaotian; Chen, Jia-Rong; Zhao, Quan-Qing; Wei, Qiang; Lan, Yu; Xiao, Wen-Jing

    2016-01-01

    Compared with the popularity of various C-centred radicals, the N-centred radicals remain largely unexplored in catalytic radical cascade reactions because of a lack of convenient methods for their generation. Known methods for their generation typically require the use of N-functionalized precursors or various toxic, potentially explosive or unstable radical initiators. Recently, visible-light photocatalysis has emerged as an attractive tool for the catalytic formation of N-centred radicals, but the pre-incorporation of a photolabile groups at the nitrogen atom largely limited the reaction scope. Here, we present a visible-light photocatalytic oxidative deprotonation electron transfer/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediation strategy for catalytic N-radical cascade reaction of unsaturated hydrazones. This mild protocol provides a broadly applicable synthesis of 1,6-dihydropyradazines with complete regioselectivity and good yields. The 1,6-dihydropyradazines can be easily transformed into diazinium salts that showed promising in vitro antifungal activities against fungal pathogens. DFT calculations are conducted to explain the mechanism. PMID:27048886

  13. Multinucleon transfer in O,1816,19F+208Pb reactions at energies near the fusion barrier

    NASA Astrophysics Data System (ADS)

    Rafferty, D. C.; Dasgupta, M.; Hinde, D. J.; Simenel, C.; Simpson, E. C.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; McNeil, S. D.; Ramachandran, K.; Vo-Phuoc, K.; Wakhle, A.

    2016-08-01

    Background: Nuclear reactions are complex, involving collisions between composite systems where many-body dynamics determines outcomes. Successful models have been developed to explain particular reaction outcomes in distinct energy and mass regimes, but a unifying picture remains elusive. The irreversible transfer of kinetic energy from the relative motion of the collision partners to their internal states, as is known to occur in deep inelastic collisions, has yet to be successfully incorporated explicitly into fully quantal reaction models. The influence of these processes on fusion is not yet quantitatively understood. Purpose: To investigate the population of high excitation energies in transfer reactions at sub-barrier energies, which are precursors to deep inelastic processes, and their dependence on the internuclear separation. Methods: Transfer probabilities and excitation energy spectra have been measured in collisions of O,1816,19F+208Pb , at various energies below and around the fusion barrier, by detecting the backscattered projectile-like fragments in a Δ E -E telescope. Results: The relative yields of different transfer outcomes are strongly driven by Q values, but change with the internuclear separation. In 16O+208Pb , single nucleon transfer dominates, with a strong contribution from -2 p transfer close to the Coulomb barrier, though this channel becomes less significant in relation to the -2 p 2 n transfer channel at larger separations. For 18O+208Pb , the -2 p 2 n channel is the dominant charge transfer mode at all separations. In the reactions with 19F,-3 p 2 n transfer is significant close to the barrier, but falls off rapidly with energy. Multinucleon transfer processes are shown to lead to high excitation energies (up to ˜15 MeV), which is distinct from single nucleon transfer modes which predominantly populate states at low excitation energy. Conclusions: Kinetic energy is transferred into internal excitations following transfer, with this

  14. Activation of Two Sequential H-transfers in the Thymidylate Synthase Catalyzed Reaction

    PubMed Central

    Islam, Zahidul; Strutzenberg, Timothy S.; Ghosh, Ananda K.; Kohen, Amnon

    2015-01-01

    Thymidylate synthase (TSase) catalyzes the de novo biosynthesis of thymidylate, a precursor for DNA, and is thus an important target for chemotherapeutics and antibiotics. Two sequential C-H bond cleavages catalyzed by TSase are of particular interest: a reversible proton abstraction from the 2′-deoxy-uridylate substrate, followed by an irreversible hydride transfer forming the thymidylate product. QM/MM calculations of the former predicted a mechanism where the abstraction of the proton leads to formation of a novel nucleotide-folate intermediate that is not covalently bound to the enzyme (Wang, Z.; Ferrer, S.; Moliner, V.; Kohen, A. Biochemistry 2013, 52, 2348–2358). Existence of such intermediate would hold promise as a target for a new class of drugs. Calculations of the subsequent hydride transfer predicted a concerted H-transfer and elimination of the enzymatic cysteine (Kanaan, N.; Ferrer, S.; Marti, S.; Garcia-Viloca, M.; Kohen, A.; Moliner, V. J. Am. Chem. Soc. 2011, 133, 6692–6702). A key to both C-H activations is a highly conserved arginine (R166) that stabilizes the transition state of both H-transfers. Here we test these predictions by studying the R166 to lysine mutant of E. coli TSase (R166K) using intrinsic kinetic isotope effects (KIEs) and their temperature dependence to assess effects of the mutation on both chemical steps. The findings confirmed the predictions made by the QM/MM calculations, implicate R166 as an integral component of both reaction coordinates, and thus provide critical support to the nucleotide-folate intermediate as a new target for rational drug design. PMID:26576323

  15. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture.

    PubMed

    Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

    2015-05-28

    The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol(-1). On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol(-1). The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  16. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture

    NASA Astrophysics Data System (ADS)

    Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

    2015-05-01

    The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  17. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture

    SciTech Connect

    Kasai, Yukako; Yoshida, Norio Nakano, Haruyuki

    2015-05-28

    The co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water–acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is −10.6 kcal mol{sup −1}. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol{sup −1}. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  18. Femtosecond Dynamics of Fundamental Reaction Processes in Liquids: Proton Transfer, Geminate Recombination, Isomerization and Vibrational Relaxation.

    NASA Astrophysics Data System (ADS)

    Schwartz, Benjamin Joel

    Femtosecond and picosecond transient absorption spectroscopy are used to probe several fundamental aspects of chemical reactivity in the condensed phase including proton transfer, germinate recombination, isomerization and vibrational relaxation. The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured for the first time, and the effects of external hydrogen-bonding interactions on the proton transfer are studied in detail. The proton transfer takes place in ~240 fsec in non-polar environments, but becomes faster than the instrumental resolution of 110 fsec in methanol solutions. A simple model is proposed to explain these results. The dynamics following photodissociation of CH _2I_2 and other small molecules provide the first direct observations of germinate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results also show that recombination yields but not rates depend on the molecular details of the solvent environment and suggest that recombination kinetics are dominated by a single collision with the surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. The data show no simple correlation between the hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes. This strongly implies that the isomerization of these systems does not provide a suitable testing ground for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in the photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial

  19. Energy transfer and reaction dynamics of matrix-isolated 1,2-difluoroethane-d4

    NASA Astrophysics Data System (ADS)

    Raff, Lionel M.

    1990-09-01

    The molecular dynamics of vibrationally excited 1,2-difluoroethane-d4 isolated in Ar, Kr, and Xe matrices at 12 K are investigated using trajectory methods. The matrix model is an fcc crystal containing 125 unit cells with 666 atoms in a cubic (5×5×5) arrangement. It is assumed that 1,2-difluoroethane-d4 is held interstitially within the volume bounded by the innermost unit cell of the crystal. The transport effects of the bulk are simulated using the velocity reset method introduced by Riley, Coltrin, and Diestler [J. Chem. Phys. 88, 5934 (1988)]. The system potential is written as the separable sum of a lattice potential, a lattice-molecule interaction and a gas-phase potential for 1,2-difluoroethane. The first two of these are assumed to have pairwise form while the molecular potential is a modified form of the global potential previously developed for 1,2-difluoroethane [J. Phys. Chem. 91, 3266 (1987)]. Calculated sublimation energies for the pure crystals are in good accord with the experimental data. The distribution of metastable-state energies for matrix-isolated 1,2-difluoroethane-d4 is Gaussian in form. In krypton, the full width at half maximum for the distribution is 0.37 eV. For a total excitation energy of 6.314 eV, the observed dynamic processes are vibrational relaxation, orientational exchange, and four-center DF elimination reactions. The first of these processes is characterized by a near linear, first-order decay curve with rate coefficients in the range 1.30-1.48×1011 s-1. The average rates in krypton and xenon are nearly equal. The process is slightly slower in argon. The decay curves exhibit characteristic high-frequency oscillations that are generally seen in energy transfer studies. It is demonstrated that these oscillations are associated with the frequencies for intramolecular energy transfer so that the entire frequency spectrum for such transfer processes can be obtained from the Fourier transform of the decay curve. Orientational

  20. Structural and dynamical control of the reaction rate in protein electron transfer

    NASA Astrophysics Data System (ADS)

    Balabin, Ilya A.

    Electron transfer (ET) reactions in proteins are key steps in many vital bioenergetic processes, and the reaction rate is known to be highly sensitive to the protein structure in some cases. For most bioenergetic reactions, as described by the Fermi Golden rule, the rate is proportional to a product of the average square of the effective electronic donor to acceptor coupling and a Franck-Condon factor, which accounts for the nuclear control of the energy gap. The nuclear factor is reasonably well described in Marcus theory and its modifications, and this work is focused on the mechanisms that control the effective coupling. About ten years ago, the Pathways model described for the first time how protein environment may control the effective coupling. In this work, a novel theoretical approach is developed to explore the mechanisms of structural and dynamical control beyond the qualitative level of the Pathways model. In Chapter 1, the assumptions of the Pathways model, its limitations and effects of the structure and the electronic Hamiltonian are investigated for model chain-like bridges using the Dyson's equations. In Chapter II, the framework to explore the sensitivity of the effective coupling to quality of the electronic Hamiltonian, the interference among the dominant pathways and the bridge dynamics is presented. This analysis employs the Green's function technique and includes combined molecular dynamics and electronic structure calculations. Finally, in Chapter III, this framework is tested on the bacterial photosynthetic reaction center, and the mechanisms of the structural and dynamical control for different ET steps are discussed.

  1. Hypochlorous acid-mediated protein oxidation: how important are chloramine transfer reactions and protein tertiary structure?

    PubMed

    Pattison, David I; Hawkins, Clare L; Davies, Michael J

    2007-08-28

    Hypochlorous acid (HOCl) is a powerful oxidant generated from H2O2 and Cl- by the heme enzyme myeloperoxidase, which is released from activated leukocytes. HOCl possesses potent antibacterial properties, but excessive production can lead to host tissue damage that occurs in numerous human pathologies. As proteins and amino acids are highly abundant in vivo and react rapidly with HOCl, they are likely to be major targets for HOCl. In this study, two small globular proteins, lysozyme and insulin, have been oxidized with increasing excesses of HOCl to determine whether the pattern of HOCl-mediated amino acid consumption is consistent with reported kinetic data for isolated amino acids and model compounds. Identical experiments have been carried out with mixtures of N-acetyl amino acids (to prevent reaction at the alpha-amino groups) that mimic the protein composition to examine the role of protein structure on reactivity. The results indicate that tertiary structure facilitates secondary chlorine transfer reactions of chloramines formed on His and Lys side chains. In light of these data, second-order rate constants for reactions of Lys side chain and Gly chloramines with Trp side chains and disulfide bonds have been determined, together with those for further oxidation of Met sulfoxide by HOCl and His side chain chloramines. Computational kinetic models incorporating these additional rate constants closely predict the experimentally observed amino acid consumption. These studies provide insight into the roles of chloramine formation and three-dimensional structure on the reactions of HOCl with isolated proteins and demonstrate that kinetic models can predict the outcome of HOCl-mediated protein oxidation.

  2. Energetics of protein fluctuations: Ligand binding to myoglobin and electron transfer in reaction center

    NASA Astrophysics Data System (ADS)

    McMahon, Benjamin Hamilton

    We have measured the temperature dependent kinetics of two different protein reactions: Psp+Qsbsp{A}{-}-> PQsb{A} electron transfer (ET) in the photosynthetic reaction (RC), and recombination of carbonmonoxide (CO) to myoglobin (Mb) after flash photolysis. The ET reaction allows determination of the temperature dependence of energy dissipation as RC adapts to charge transfer on the 100 ms, 10sp3 and 10sp4 s time scales at temperatures from 5 to 300 K. The adaptation, or conformational relaxation, of RC is observed in four distinct tiers of conformational substrates, with average apparent Arrhenius activation enthalpies of 17, 50, 78, and 110 kJ/mol and pre-exponential factors of 10sp{13},\\ 10sp{15},\\ 10sp{21}, and 10sp{25}\\ ssp{-1}, respectively. This parameterization provides a prediction of the time course of relaxations at all temperatures. At 300 K, relaxations are expected to occur from 1 ps to 1 ms; at lower temperatures the distribution of relaxation times broaden. We extend this study to samples of different pH, viscosity, and salt composition. We observe kinetics of CO recombination to horse heart myoglobin between 10 ns and 100 s at temperatures from 80 to 320 K. Essentially all recombination is visible in this time window, allowing the effect of relaxations to be observed on the nanosecond time scale at high temperatures, as well as microsecond to second time scales at lower temperatures. Variation of the solvent pH from 5.1 to 8.0 changes the average low temperature enthalpy barrier to recombination from 6 to 13 kJ/mol, shifting the time scale probed by the recombination reaction by an order of magnitude. Addition of 500 mM KCl, KSCN, or (NHsb4)sb2SOsb4 significantly changes the probability of geminate recombination without affecting either the enthalpy barrier to recombination or the energetics of CO entry to and exit from the heme pocket of the protein. We present a model of recombination which emphasizes the role of protein fluctuations in

  3. Chemoselectivity in Chemical Biology: Acyl Transfer Reactions with Sulfur and Selenium

    PubMed Central

    2012-01-01

    A critical source of insight into biological function is derived from the chemist’s ability to create new covalent bonds between molecules, whether they are endogenous or exogenous to a biological system. A daunting impediment to selective bond formation, however, is the myriad of reactive functionalities present in biological milieu. The high reactivity of the most abundant molecule in biology, water, makes the challenges all the more difficult. We have met these challenges by exploiting the reactivity of sulfur and selenium in acyl transfer reactions. The reactivity of both sulfur and selenium is high compared with that of their chalcogen congener, oxygen. In this Account, we highlight recent developments in this arena, emphasizing contributions from our laboratory. One focus of our research is furthering the chemistry of native chemical ligation (NCL) and expressed protein ligation (EPL), two related processes that enable the synthesis and semisynthesis of proteins. These techniques exploit the lower pKa of thiols and selenols relative to alcohols. Although a deprotonated hydroxyl group in the side chain of a serine residue is exceedingly rare in a biological context, the pKa values of the thiol in cysteine (8.5) and of the selenol in selenocysteine (5.7) often render these side chains anionic under physiological conditions. NCL and EPL take advantage of the high nucleophilicity of the thiolate as well as its utility as a leaving group, and we have expanded the scope of these methods to include selenocysteine. Although the genetic code limits the components of natural proteins to 20 or so α-amino acids, NCL and EPL enable the semisynthetic incorporation of a limitless variety of nonnatural modules into proteins. These modules are enabling chemical biologists to interrogate protein structure and function with unprecedented precision. We are also pursuing the further development of the traceless Staudinger ligation, through which a phosphinothioester and azide

  4. Population of isomeric states in fusion and transfer reactions in beams of loosely bound nuclei near the Coulomb barrier

    SciTech Connect

    Skobelev, N. K.

    2015-07-15

    The influence of the mechanisms of nuclear reactions on the population of {sup 195m}Hg and {sup 197m}Hg(7/2{sup −}), {sup 198m}Tl and {sup 196m}Tl(7{sup +}), and {sup 196m}Au and {sub 198m}Au(12{sup −}) isomeric nuclear states obtained in reactions induced by beams of {sup 3}He, {sup 6}Li, and {sup 6}He weakly bound nuclei is studied. The behavior of excitation functions and high values of isomeric ratios (δ{sub m}/δ{sub g}) for products of nuclear reactions proceeding through a compound nucleus and involving neutron evaporation are explained within statistical models. Reactions in which the emission of charged particles occurs have various isomeric ratios depending on the reaction type. The isomeric ratio is lower in direct transfer reactions involving charged-particle emission than in reactions where the evaporation of charged particles occurs. Reactions accompanied by neutron transfer usually have a lower isomeric ratio, which behaves differently for different direct-reaction types (stripping versus pickup reactions)

  5. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum–classical approximation. II. Proton transfer reaction in non-polar solvent

    SciTech Connect

    Kojima, H.; Yamada, A.; Okazaki, S.

    2015-05-07

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum–classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute–solvent interactions.

  6. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

    NASA Astrophysics Data System (ADS)

    Kojima, H.; Yamada, A.; Okazaki, S.

    2015-05-01

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

  7. Spectrophotometric determination of bisoprolol in pharmaceutical preparations by charge transfer reactions

    NASA Astrophysics Data System (ADS)

    Ulu, Sevgi Tatar; Kel, Elif

    2012-06-01

    A simple, rapid and sensitive method for the spectrophotometric determination, of bisoprolol was developed. The proposed methods were based on the charge-transfer reactions of bisoprolol, as n-electron donor, with 7,7,8,8-tetracyanoqumodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as π-acceptors to give highly colored complexes. The proposed methods were validated according to the ICH guidelines with respect to linearity, limit of detection, limit of quantification, accuracy, precision, recovery and specificity. Beer's law is obeyed over the concentration ranges of 10-60 and 10-80 μg/mL bisoprolol with TCNQ and DDQ, respectively. The proposed methods were successfully applied to the assay of bisoprolol in pharmaceutical preparations.

  8. Electron transfer reactions in microporous solids. Progress report, September 1990--January 1993

    SciTech Connect

    Mallouk, T.E.

    1993-01-01

    Basic thrust the research program involves use of microporous solids (zeolites, clays, layered and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. Purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H{sub 2} and I{sub 3}{sup {minus}}, or H{sub 2} and O{sub 2)} from each other. Spectroscopic and electrochemical methods are used to study the kinetics of electron transfer reactions in these hybrid molecular/solid state assemblies.

  9. Chemical reactivity imprint lithography on graphene: Controlling the substrate influence on electron transfer reactions

    NASA Astrophysics Data System (ADS)

    Wang, Qing Hua; Jin, Zhong; Kim, Ki Kang; Hilmer, Andrew; Paulus, Geraldine; Shih, Chih-Jen; Ham, Moon-Ho; Sanchez-Yamagishi, Javier; Watanabe, Kenji; Taniguchi, Takashi; Kong, Jing; Jarillo-Herrero, Pablo; Strano, Michael

    2012-02-01

    The chemical functionalization of graphene enables control over electronic properties and interactions with other materials. Graphene's chemical reactivity is strongly influenced by the underlying substrate. In this paper, we show a stark difference in the rate of electron transfer chemistry with aryl diazonium salts on monolayer graphene supported on a broad range of substrates. Reactions proceed rapidly when graphene is on SiO2 and Al2O3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces. The effect cannot be explained by the overall graphene doping levels alone, and can instead be described using a reactivity model accounting for substrate-induced electron-hole puddles in graphene. Raman spectroscopic mapping is used to characterize the effect of the substrates on graphene. Reactivity imprint lithography (RIL) is demonstrated as a technique for spatially patterning chemical groups on graphene by patterning the underlying substrate, and is applied to the covalent tethering of proteins on graphene.

  10. 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.

  11. Neutron spectroscopic factors of 55Ni hole-states from (p,d) transfer reactions

    NASA Astrophysics Data System (ADS)

    Sanetullaev, A.; Tsang, M. B.; Lynch, W. G.; Lee, Jenny; Bazin, D.; Chan, K. P.; Coupland, D.; Henzl, V.; Henzlova, D.; Kilburn, M.; Rogers, A. M.; Sun, Z. Y.; Youngs, M.; Charity, R. J.; Sobotka, L. G.; Famiano, M.; Hudan, S.; Shapira, D.; Peters, W. A.; Barbieri, C.; Hjorth-Jensen, M.; Horoi, M.; Otsuka, T.; Suzuki, T.; Utsuno, Y.

    2014-09-01

    Spectroscopic information has been extracted on the hole-states of 55Ni, the least known of the quartet of nuclei (55Ni, 57Ni, 55Co and 57Cu), one nucleon away from 56Ni, the N=Z=28 double magic nucleus. Using the H1(Ni56,d)Ni55 transfer reaction in inverse kinematics, neutron spectroscopic factors, spins and parities have been extracted for the f7/2, p3/2 and the s1/2 hole-states of 55Ni. These new data provide a benchmark for large basis calculations that include nucleonic orbits in both the sd and pf shells. State of the art calculations have been performed to describe the excitation energies and spectroscopic factors of the s1/2 hole-state below Fermi energy.

  12. Isomer-specific product formation in the proton transfer reaction of HOCO+ with CO

    NASA Astrophysics Data System (ADS)

    Carrascosa, Eduardo; Stei, Martin; Kainz, Martin A.; Wester, Roland

    2015-12-01

    The proton transfer reaction HOCO++CO → HCO+/HOC+ has been studied using crossed-beam velocity map imaging. Angular and energy differential cross sections were obtained for collision energies from 0.3 to 2.3 eV. Scattering in forward direction together with a prominent scattering angle-dependent internal excitation is found at all collision energies. The exothermic HCO+ product appears to be very dominant even at energies above the energy threshold for the formation of metastable HOC+ ion. To determine the HOC+ contribution for different angular ranges, a model has been developed. We obtain an upper limit for the HOC+ product isomer fraction of <2%. In theoretical calculations, we find the CO2-catalysed isomerisation channel to be energetically accessible. However, it may not have a strong impact on the isomer ratio. Chemical dynamics simulations are needed to shed more light on this question.

  13. Near-resonant versus nonresonant chemiluminescent charge-transfer reactions of atomic ions with HCl

    NASA Astrophysics Data System (ADS)

    Glenewinkel-Meyer, Th.; Ottinger, Ch.

    1994-01-01

    Charge-transfer reactions of C+, O+, F+, Ar+ and some other atomic ions with hydrogen chloride were investigated at collision energies between <1 eV and 1 keV. The electronically excited products HCl+ (A 2Σ+) were detected by means of the A 2Σ+→X 2Πi optical emission. In some cases the spectra showed, at low collision energies, an enhanced excitation of specific vibrational HCl+(A,v') levels: for C+, v'=1; for O+, v'=3 as well as v'=1; and for F+, v'=6. These levels are populated in near-resonant, slightly exothermic processes. Their rotational temperature was on the order of 600-700 K. For the other vibrational levels the excitation is off-resonance, mostly endothermic, and here the rotational temperature was 1000-4000 K. Corresponding data are also given for DCl. The selectivity for certain vibrational states is explained by crossings between the vibronic entrance and exit state energy surfaces, calculated from classical electrostatic multipole potentials. The cross sections for the near-resonant reactions decrease monotonically with increasing collision energy, while for the endothermic channels they rise steeply from threshold to a plateau. With argon ions the excitation function exhibits an unusual shape. Here the charge-transfer cross sections for all vibrational levels go through a maximum just above threshold, which is followed by a distinct minimum at about 10 eVc.m.. This may be due to formation of a long-lived collision complex (Ar-HCl)+.

  14. Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; Camaioni, Donald M; Li, Jun; Dougherty, William G; Kassel, W Scott; Twamley, Brendan; DuBois, Daniel L

    2009-10-14

    This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H(2) gas to form B-H bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX(3) (X = OR, SPh, F, H; R = Ph, p-C(6)H(4)OMe, C(6)F(5), (t)Bu, Si(Me)(3)) compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (DeltaG(o)(H(-))) were determined for HRh(dmpe)(2) and HRh(depe)(2), where dmpe = 1,2-bis(dimethylphosphinoethane) and depe = 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt(3)](-) on this scale. Isodesmic reactions between [HBEt(3)](-) and selected BX(3) compounds to form BEt(3) and [HBX(3)](-) were examined computationally to determine their relative hydride affinities. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX(3) compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B-H bonds from B-X bonds, and the extent to which BX(3) compounds are reduced by transition-metal hydride complexes forming species containing multiple B-H bonds depends on the heterolytic B-X bond energy. An example is the reduction of B(SPh)(3) using HRh(dmpe)(2) in the presence of triethylamine to form Et(3)N-BH(3) in high yields.

  15. Spectroscopic studies of energy transfer in photosynthetic reaction centers of higher plants

    SciTech Connect

    Tabbutt, S.

    1987-09-01

    The focus of this thesis is excitation transfer and primary photochemistry in spinach chloroplasts and sub-chloroplast particles. The fluorescence kinetics are measured with a synchronously pumped, mode-locked dye laser excitation source and a reverse single photon-counting timing detection system. Very little has been reported on the fluorescence properties of photosystem I (PS I) due to its relatively weak emission compared to photosystem II (PS II). Using a PS I complex isolated from spinach, two emission bands, 690 nm and 722 nm were observed. The 690 nm fluorescence kinetics has an instrument limited (25 ps) rise and is best fit to three exponential decay components: slow, 2.2 to 2.5 ns; middle, 250 to 300 ps; and fast, 40 to 100 ps. Both the yield and kinetics are temperature independent (77 to 295K). The 722 nm emission is dramatically temperature dependent. At 295K the fluorescence lifetimes at 720 nm are identical to those at 690 nm. Upon lowering the temperature the lifetimes of all three decay components increase, a measurable risetime (>25 ps) grows in at temperatures below 265K, and the fluorescence intensity at 722 nm increases about 20-fold from 295K to 77K. These studies provide excitation transfer rates and activation energies within the PS I centers. The PS I emission data can be explained by two Chl a species: an antenna pool emitting at 690 nm and the reaction center emitting at 722 nm. The PSI reaction center complex (CP1) fluorescence intensity under continuous actinic illumination (690 nm) decreased by about 20% with the same kinetics as the optical bleaching at 699 nm. The kinetics and magnitudes of the fluorescence decrease and photobleaching depend upon excitation intensity, ascorbate concentration, ferri/ferrocyanide redox titration and phenasinemethosulfate concentration. 168 refs., 38 figs., 4 tabs.

  16. Inter-and intraspecific variation in excited-state triplet energy transfer rates in reaction centers of photosynthetic bacteria.

    SciTech Connect

    Laible, P. D.; Morris, Z. S.; Thurnauer, M. C.; Schiffer, M.; Hanson, D. K.

    2003-08-01

    In protein-cofactor reaction center (RC) complexes of purple photosynthetic bacteria, the major role of the bound carotenoid (C) is to quench the triplet state formed on the primary electron donor (P) before its sensitization of the excited singlet state of molecular oxygen from its ground triplet state. This triplet energy is transferred from P to C via the bacteriochlorophyll monomer B{sub B}. Using time-resolved electron paramagnetic resonance (TREPR), we have examined the temperature dependence of the rates of this triplet energy transfer reaction in the RC of three wild-type species of purple nonsulfur bacteria. Species-specific differences in the rate of transfer were observed. Wild-type Rhodobacter capsulatus RCs were less efficient at the triplet transfer reaction than Rhodobacter sphaeroides RCs, but were more efficient than Rhodospirillum rubrum RCs. In addition, RCs from three mutant strains of R. capsulatus carrying substitutions of amino acids near P and B{sub B} were examined. Two of the mutant RCs showed decreased triplet transfer rates compared with wild-type RCs, whereas one of the mutant RCs demonstrated a slight increase in triplet transfer rate at low temperatures. The results show that site-specific changes within the RC of R. capsulatus can mimic interspecies differences in the rates of triplet energy transfer. This application of TREPR was instrumental in defining critical energetic and coupling factors that dictate the efficiency of this photoprotective process.

  17. Observation of three behaviors in confined liquid water within a nanopool hosting proton-transfer reactions.

    PubMed

    Douhal, Abderrazzak; Angulo, Gonzalo; Gil, Michal; Organero, Juan Angel; Sanz, Mikel; Tormo, Laura

    2007-05-17

    In this contribution, we report on studies of rotational and diffusional dynamics of 7-hydroxyquinoline (7HQ) within a reverse micelle (RM) containing different amounts of water. Analyzed in terms of the wobbling-in-a-cone model, the data reveal structural and dynamical properties of the nanopool. We clearly observed three regions in the behavior of confined water molecules within the RM hosting a double proton-transfer reaction between the probe and water. This observation remarkably reproduces the change of calculated water density within this life-mimicking medium. The number of water molecules per AOT head in the transition regions changes from 2 to 5, the latter being very near to the full solvation number (6) of the RM heads. Moreover, the H-bonds breaking and making within the RM to give new structures of the probe strongly affect the environment fluidization in different extents, reflected in different relaxation times of these structures; however, they are of similar sizes. We discuss the role of RM confinement and the proton-transfer dynamics on the behavior of water and their relationships to the packing of water molecules in the studied range of concentrations.

  18. Relative antioxidant efficiency of a large series of carotenoids in terms of one electron transfer reactions.

    PubMed

    Galano, Annia

    2007-11-08

    The relative antioxidant efficiency, expressed as electron donating capability, of a large series of carotenoids has been studied using density functional theory. Their reactivity toward nine different radicals has been modeled as well as the electron transfer between pairs of carotenoids, one of which is present as a radical cation. The influence of the solvent polarity has also been studied. Torulene was found to be the most easily oxidized carotenoid, followed by lycopene. This higher reactivity is proposed in the present work for the first time, and the potential implications of such a finding are discussed. Since torulene has not been previously studied, compared to other carotenoids in terms of oxidation potentials, further experimental studies are suggested in order to confirm or reject this prediction. Ionization potential seems to be a magnitude calculable at low computational cost that correctly predicts the relative ease of oxidation in a series of carotenoids. The nuclear reorganization energy associated with electron-transfer reactions has been calculated in a very simple but apparently efficient way that allows computation of free energy barriers and relative rate constants in good agreement with the experimental values. In addition, an additive correction is proposed to include the effect of increasing the size of basis sets on the energies of Car(n) --> Car(n-1)(*+) processes. The general agreement between different calculated magnitudes and the corresponding available experimental data supports the predictions from this work.

  19. Proton-transfer reactions of acridine in water-containing ionic-liquid-rich mixtures.

    PubMed

    Kumar, Vinod; Pandey, Ashish; Pandey, Siddharth

    2013-12-02

    To assess the potential of ionic liquids (ILs) as a solubilizing media that facilitates proton-transfer reactions, acridine prototropism is investigated using UV/Vis molecular absorbance as well as steady-state and time-resolved fluorescence with different ILs in the presence of a small amount of dilute acid or base. It is found that protonation and deprotonation of acridine, when dissolved in different ILs, can be triggered by the addition of a small amount of dilute aqueous HCl and NaOH, respectively, in both the ground and excited states, irrespective of the identity of the IL. However, the amount of dilute acid/base needed to protonate/deprotonate acridine dissolved in different ILs is found to vary from one IL to another. Steady-state fluorescence measurements also imply the presence of interactions between the acidic proton(s) of IL cation and excited acridine. The interconversion of neutral and protonated acridine, as well as the presence of a weakly fluorescent complex between excited acridine and the acidic proton(s) of the IL cation, is further corroborated by the parameters recovered from the fitting of the excited-state intensity-decay data. It is established that ILs as solubilizing media readily support facile proton transfer in both ground and excited states.

  20. Ab initio study on an excited-state intramolecular proton-transfer reaction in ionic liquid.

    PubMed

    Hayaki, Seigo; Kimura, Yoshifumi; Sato, Hirofumi

    2013-06-06

    An excited-state intramolecular proton transfer (ESIPT) reaction of 4'-N,N-dimethylamino-3-hydroxyflavone in room temperature ionic liquid is theoretically investigated using RISM-SCF-SEDD, which is a hybrid method of molecular liquid theory and ab initio molecular orbital theory. The photo-excitation and proton-transfer processes are computed by considering the solvent fluctuation. The calculated absorption and emission energy are in good agreement with the experiments. The changes in the dipole moment indicate that the drastic solvation relaxation is accompanied by the excitation and an ESIPT process, which is consistent with the remarkable dynamic Stokes shift observed in the experiments. We calculated the nonequilibrium free-energy contour as a function of the proton coordinate and the solvation coordinate. We conclude that although immediately after the excitation the barrier height of the ESIPT process is relatively small, the barrier becomes larger as the solvation relaxation to the excited normal state proceeds. The solvation relaxation process is also investigated on the basis of microscopic solvation structure obtained by RISM calculations.

  1. Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit

    DOE PAGES

    Das, Amit; Gerlits, Oksana O.; Heller, William T.; ...

    2015-06-19

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, themore » thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.« less

  2. Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit

    SciTech Connect

    Das, Amit; Gerlits, Oksana O.; Heller, William T.; Kovalevskyi, Andrii Y.; Langan, Paul; Tian, Jianhui

    2015-06-19

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.

  3. Phosphoryl Transfer Reaction Snapshots in Crystals: INSIGHTS INTO THE MECHANISM OF PROTEIN KINASE A CATALYTIC SUBUNIT.

    PubMed

    Gerlits, Oksana; Tian, Jianhui; Das, Amit; Langan, Paul; Heller, William T; Kovalevsky, Andrey

    2015-06-19

    To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca(2+) ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca(2+) cations with Mg(2+) ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. The present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.

  4. High resolution parallel reaction monitoring with electron transfer dissociation for middle-down proteomics.

    PubMed

    Sweredoski, Michael J; Moradian, Annie; Raedle, Matthias; Franco, Catarina; Hess, Sonja

    2015-08-18

    In recent years, middle-down proteomics has emerged as a popular technique for the characterization and quantification of proteins not readily amenable to typical bottom-up approaches. So far, all high resolution middle-down approaches are done in data-dependent acquisition mode, using both collision-induced dissociation or electron capture/transfer dissociation techniques. Here, we explore middle-down proteomics with electron transfer dissociation using a targeted acquisition mode, parallel reaction monitoring (PRM), on an Orbitrap Fusion. As an example of a highly modified protein, we used histone H3 fractions from untreated and DMSO-treated Murine ErythroLeukemia (MEL) cells. We first determined optimized instrument parameters to obtain high sequence coverage using a synthetic standard peptide. We then setup a combined method of both MS1 scans and PRM scans of the 20 most abundant combinations of methylation and acetylation of the +10 charge state of the N-terminal tail of H3. Weak cation exchange hydrophilic interaction chromatography was used to separate the N-terminal H3 tail, primarily, by its acetylation and, to a secondary degree, by its methylation status, which aided in the interpretation of the results. After deconvolution of the highly charged ions, peaks were annotated to a minimum set of 254 H3 proteoforms in the untreated and treated samples. Upon DMSO treatment, global quantitation changes from the MS1 level show a relative decrease of 2, 3, 4, and 5 acetylations and an increase of 0 and 1 acetylations. A fragment ion map was developed to visualize specific differences between treated and untreated samples. Taken together, the data presented here show that middle-down proteomics with electron transfer dissociation using PRM is a novel, attractive method for the effective analysis and quantification of large and highly modified peptides.

  5. Primary charge separation and energy transfer in the photosystem I reaction center of higher plants

    SciTech Connect

    White, N.T.H.; Beddard, G.S.; Thorne J.R.G.; Feehan, T.M.; Keyes, T.E.; Heathcote, P.

    1996-07-18

    Using low intensity femtosecond duration laser pulses at 708 nm, we have observed absorption transients associated with electron transfer through the primary electron acceptor A{sub 0} in the photosystem I (PSI) reaction center from spinach under nonreducing conditions. At this wavelength the electron donor P{sub 700} is excited directly, although some antenna chlorophylls are also excited. Using a nanosecond duration preflash of 690 nm to oxidize P{sub 700}, and then measuring the absorption transients from the antenna alone, it is possible by subtraction to isolate the absorption transients arising from electron transfer. We discuss this method critically. Th spectrum of A{sub 0}{sup -}-A{sub 0} does not appear promptly but takes nearly 3 ps to reach maximum intensity and resembles those spectra previously obtained from higher plants, with a maximum bleaching at 685{+-}2 nm and a shoulder in the region 670-675 nm. The decay time of the primary radical pair P{sub 700}{sup +}A{sub 0}{sup -} is calculated as 20 ps. Analysis of absorption transients indicates that the intrinsic rate constant forming the primary radical pair P{sub 700}{sup +}A{sub 0}{sup -} cannot be measured directly because energy migration in the antenna is fast and quenching is approaching `trap limited` behavior. With use of a detailed model of the antenna energy migration based on the X-ray structure, the intrinsic rate constant for electron transfer is estimated as k{sub 1} nearly equals 0.7 ps{sup -1}. 81 refs., 15 figs., 1 tab.

  6. Delayed Gelation Through Chain-Transfer Reactions: Mechanism For Stress Reduction In Methacrylate Networks

    PubMed Central

    Pfeifer, Carmem S.; Wilson, Nicholas D.; Shelton, Zachary R.; Stansbury, Jeffrey W.

    2011-01-01

    Chain-transfer reactions from thiols to methacrylates are expected to delay gelation and possibly reduce stress at the bonded interface of dental restorations. Thiol additives with varying structures were combined with a dimethacrylate commonly used in dental materials. Polymerization stress/modulus development were monitored by a tensometer/rheometer, respectively, both coupled with RT-NIR. For all thiol-modified materials, conversion and modulus were 5–25 % higher than the control, and maximum reaction rate was 25–50 % lower. Gel point conversions were 12–22 % (control=5 %), and deceleration was observed at later stages in conversion (30–60 %; control=15 %). Consequently, even with increased conversion/modulus, stress values were either equal or reduced compared to the control. This approach does not require any modification in the bonding/photoactivation procedures, and seems promising for stress management not only in polymeric dental materials, but also for other applications of glassy, crosslinked photopolymers, as long as thiol volatility is addressed. PMID:21799544

  7. A single residue controls electron transfer gating in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Shlyk, Oksana; Samish, Ilan; Matěnová, Martina; Dulebo, Alexander; Poláková, Helena; Kaftan, David; Scherz, Avigdor

    2017-03-01

    Interquinone QA‑ → QB electron-transfer (ET) in isolated photosystem II reaction centers (PSII-RC) is protein-gated. The temperature-dependent gating frequency “k” is described by the Eyring equation till levelling off at T ≥ 240 °K. Although central to photosynthesis, the gating mechanism has not been resolved and due to experimental limitations, could not be explored in vivo. Here we mimic the temperature dependency of “k” by enlarging VD1-208, the volume of a single residue at the crossing point of the D1 and D2 PSII-RC subunits in Synechocystis 6803 whole cells. By controlling the interactions of the D1/D2 subunits, VD1-208 (or 1/T) determines the frequency of attaining an ET-active conformation. Decelerated ET, impaired photosynthesis, D1 repair rate and overall cell physiology upon increasing VD1-208 to above 130 Å3, rationalize the >99% conservation of small residues at D1-208 and its homologous motif in non-oxygenic bacteria. The experimental means and resolved mechanism are relevant for numerous transmembrane protein-gated reactions.

  8. Study of fluorescence characteristics of the charge-transfer reaction of quinolone agents with bromanil

    NASA Astrophysics Data System (ADS)

    Li, Wen-Ying; Chen, Xiao-Fang; Xuan, Chun-Sheng

    2009-01-01

    A spectrofluorimetric method was discussed for the determination of three antibacterial quinolone derivatives, ofloxacin (OFL), norfloxacin (NOR) and ciprofloxacin (CIP) through charge-transfer complexation (CTC) with 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, TBBQ). The method was based on the reaction of these drugs as n-electron donors with the π-acceptor TBBQ. TBBQ was found to react with these drugs to produce a kind of yellow complexes and the fluorescence intensities of the complexes were enhanced by 29-36 times more than those of the corresponding monomers. UV-vis, 1H NMR and XPS techniques were used to study the complexes formed. The various experimental parameters affecting the fluorescence intensity were studied and optimized. Under optimal reaction conditions, the rectilinear calibration graphs were obtained in the concentration range of 0.021-2.42 μg mL -1, 0.017-2.63 μg mL -1 and 0.019-2.14 μg mL -1 for OFL, NOR and CIP, respectively. The methods developed were applied successfully to the determination of the subject drugs in their pharmaceutical dosage forms with good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  9. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

    DOE PAGES

    Zheng, Haiyan; Li, Kuo; Cody, George D.; ...

    2016-08-25

    Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH···N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3more » bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.« less

  10. A single residue controls electron transfer gating in photosynthetic reaction centers

    PubMed Central

    Shlyk, Oksana; Samish, Ilan; Matěnová, Martina; Dulebo, Alexander; Poláková, Helena; Kaftan, David; Scherz, Avigdor

    2017-01-01

    Interquinone QA− → QB electron-transfer (ET) in isolated photosystem II reaction centers (PSII-RC) is protein-gated. The temperature-dependent gating frequency “k” is described by the Eyring equation till levelling off at T ≥ 240 °K. Although central to photosynthesis, the gating mechanism has not been resolved and due to experimental limitations, could not be explored in vivo. Here we mimic the temperature dependency of “k” by enlarging VD1-208, the volume of a single residue at the crossing point of the D1 and D2 PSII-RC subunits in Synechocystis 6803 whole cells. By controlling the interactions of the D1/D2 subunits, VD1-208 (or 1/T) determines the frequency of attaining an ET-active conformation. Decelerated ET, impaired photosynthesis, D1 repair rate and overall cell physiology upon increasing VD1-208 to above 130 Å3, rationalize the >99% conservation of small residues at D1-208 and its homologous motif in non-oxygenic bacteria. The experimental means and resolved mechanism are relevant for numerous transmembrane protein-gated reactions. PMID:28300167

  11. Probing Nonadiabaticity in the Proton-Coupled Electron Transfer Reaction Catalyzed by Soybean Lipoxygenase

    PubMed Central

    2014-01-01

    Proton-coupled electron transfer (PCET) plays a vital role in many biological and chemical processes. PCET rate constant expressions are available for various well-defined regimes, and determining which expression is appropriate for a given system is essential for reliable modeling. Quantitative diagnostics have been devised to characterize the vibronic nonadiabaticity between the electron–proton quantum subsystem and the classical nuclei, as well as the electron–proton nonadiabaticity between the electrons and proton(s) within the quantum subsystem. Herein these diagnostics are applied to a model of the active site of the enzyme soybean lipoxygenase, which catalyzes a PCET reaction that exhibits unusually high deuterium kinetic isotope effects at room temperature. Both semiclassical and electronic charge density diagnostics illustrate vibronic and electron–proton nonadiabaticity for this PCET reaction, supporting the use of the Golden rule nonadiabatic rate constant expression with a specific form of the vibronic coupling. This type of characterization will be useful for theoretical modeling of a broad range of PCET processes. PMID:25258676

  12. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

    PubMed

    Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

    2016-09-19

    Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

  13. Kinetics and mechanism of bimolecular electron transfer reaction in quinone-amine systems in micellar solution

    SciTech Connect

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2005-02-22

    Photoinduced electron transfer (ET) reactions between anthraquinone derivatives and aromatic amines have been investigated in sodium dodecyl sulphate (SDS) micellar solutions. Significant static quenching of the quinone fluorescence due to high amine concentration in the micellar phase has been observed in steady-state measurements. The bimolecular rate constants for the dynamic quenching in the present systems k{sub q}{sup TR}, as estimated from the time-resolved measurements, have been correlated with the free energy changes {delta}G{sup 0} for the ET reactions. Interestingly it is seen that the k{sub q}{sup TR} vs {delta}G{sup 0} plot displays an inversion behavior with maximum k{sub q}{sup TR} at around 0.7 eV, a trend similar to that predicted in Marcus ET theory. Like the present results, Marcus inversion in the k{sub q}{sup TR} values was also observed earlier in coumarin-amine systems in SDS and TX-100 micellar solutions, with maximum k{sub q}{sup TR} at around the same exergonicity. These results thus suggest that Marcus inversion in bimolecular ET reaction is a general phenomenon in micellar media. Present observations have been rationalized on the basis of the two-dimensional ET (2DET) theory, which seems to be more suitable for micellar ET reactions than the conventional ET theory. For the quinone-amine systems, it is interestingly seen that k{sub q}{sup TR} vs {delta}G{sup 0} plot is somewhat wider in comparison to that of the coumarin-amine systems, even though the maxima in the k{sub q}{sup TR} vs {delta}G{sup 0} plots appear at almost similar exergonicity for both the acceptor-donor systems. These observations have been rationalized on the basis of the differences in the reaction windows along the solvation axis, as envisaged within the framework of the 2DET theory, and arise due to the differences in the locations of the quinones and coumarin dyes in the micellar phase.

  14. Solvent free energy curves for electron transfer reactions: A nonlinear solvent response model

    NASA Astrophysics Data System (ADS)

    Ichiye, Toshiko

    1996-05-01

    Marcus theory for electron transfer assumes a linear response of the solvent so that both the reactant and product free energy curves are parabolic functions of the solvent polarization, each with the same solvent force constant k characterizing the curvature. Simulation data by other workers indicate that the assumption of parabolic free energy curves is good for the Fe2+-Fe3+ self-exchange reaction but that the k of the reactant and product free energy curves are different for the reaction D0+A0→D1-+A1+. However, the fluctuations sampled in these simulations were not large enough to reach the activation barrier region, which was thus treated either by umbrella sampling or by parabolic extrapolation. Here, we present free energy curves calculated from a simple model of ionic solvation developed in an earlier paper by Hyun, Babu, and Ichiye, which we refer to here as the HBI model. The HBI model describes the nonlinearity of the solvent response due to the orientation of polar solvent molecules. Since it is a continuum model, it may be considered the first-order nonlinear correction to the linear response Born model. Moreover, in the limit of zero charge or infinite radius, the Born model and the Marcus relations are recovered. Here, the full free energy curves are calculated using analytic expressions from the HBI model. The HBI reactant and product curves have different k for D0+A0→D1-+A1+ as in the simulations, but examining the full curves shows they are nonparabolic due to the nonlinear response of the solvent. On the other hand, the HBI curves are close to parabolic for the Fe2+-Fe3+ reaction, also in agreement with simulations, while those for another self-exchange reaction D0-A1+ show greater deviations from parabolic behavior than the Fe2+-Fe3+ reaction. This indicates that transitions from neutral to charged species will have the largest deviations. Thus, the second moment of the polarization is shown to be a measure of the deviation from Marcus

  15. 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.

  16. Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions

    SciTech Connect

    Zhang, Wei; Bock, David C.; Pelliccione, Christopher J.; Li, Yan; Wu, Lijun; Zhu, Yimei; Marschilok, Amy. C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Wang, Feng

    2016-03-08

    Metal oxides, such as Fe3O4, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple-electron transfer reactions leading to high capacity in Fe3O4, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O2–) and cations (Li+, Fe3+/Fe2+) using multiple synchrotron X-ray and electron-beam techniques, in combination with ab-initio calculations. Results from this study provide the first experimental evidence that the cubic-close-packed (ccp) O-anion array in Fe3O4 is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O-anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock-salt-like phases (LixFe3O4; 0 < x < 2), then into a cation-segregated phase (Li2O•FeO), and finally converting into metallic Fe and Li2O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO-like phases. Lastly, these results may offer new insights into the structure-determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.

  17. Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions

    DOE PAGES

    Zhang, Wei; Bock, David C.; Pelliccione, Christopher J.; ...

    2016-03-08

    Metal oxides, such as Fe3O4, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple-electron transfer reactions leading to high capacity in Fe3O4, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O2–) and cations (Li+, Fe3+/Fe2+) using multiple synchrotron X-ray and electron-beam techniques, in combination with ab-initio calculations. Results from this study provide the first experimental evidence that the cubic-close-packed (ccp) O-anion array in Fe3O4 is sustained throughout the lithiation and delithiation processes,more » thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O-anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock-salt-like phases (LixFe3O4; 0 < x < 2), then into a cation-segregated phase (Li2O•FeO), and finally converting into metallic Fe and Li2O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO-like phases. Lastly, these results may offer new insights into the structure-determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.« less

  18. Nucleon-nucleon correlations in heavy ion transfer reactions: Recent investigations at energies far below the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Corradi, Lorenzo

    2015-10-01

    Excitation functions of one- and two-neutron transfer channels have been measured for the 96Zr+40Ca and 116Sn+60Ni systems at bombarding energies ranging from the Coulomb barrier to ˜25% below. Target-like recoils have been identified in A, Z and velocity with the large solid angle magnetic spectrometer PRISMA. The experimental transfer probabilities have been compared, in absolute values and in slope, with semiclassical microscopic calculations which incorporate nucleon-nucleon pairing correlations. For the first time in a heavy ion collision, one was able to provide a consistent description of one and two neutron transfer reactions by incorporating, in the reaction mechanism, all known structure information of entrance and exit channels nuclei. In particular, there is no need to introduce any enhancement factor for the description of two neutron transfer, of course very important are the correlations induced by the pairing interaction.

  19. Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; O'Hagan, Molly J; Camaioni, Donald M; Dougherty, William G; Kassel, W Scott; DuBois, Daniel L

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)].

  20. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX₃ Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L.

    2011-10-31

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H₂ gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)₂ (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX₃ compounds having a hydride affinity (HA) greater than or equal to the HA of BEt₃. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)₂ and [HNi(dmpe)₂]+, to form B–H bonds. The hydride donor abilities (ΔGH °) of HCo(dmpe)₂ and [HNi(dmpe)₂]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX₃ compounds. The collective data guided our selection of BX₃ compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)₂ was observed to transfer H to BX₃ compounds with X = H, OC₆F₅, and SPh. The reaction with B(SPh)₃ is accompanied by the formation of dmpe-(BH₃)₂ and dmpe-(BH₂(SPh))₂ products that follow from a reduction of multiple B–SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)₂ and B(SPh)₃ in the presence of triethylamine result in the formation of Et₃N–BH₂SPh and Et₃N–BH₃ with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)₂]+ with B(SPh)₃ under analogous conditions give Et₃N–BH₂SPh as the final product along with the nickel–thiolate complex [Ni(dmpe)₂(SPh)]+. The synthesis and characterization of HCo(dedpe)₂ (dedpe = Et₂PCH₂CH₂PPh₂) from H₂ and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)₂Co(dedpe)₂][BF₄].

  1. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans

  2. DFT/B3LYP study of the substituent effect on the reaction enthalpies of the individual steps of single electron transfer-proton transfer and sequential proton loss electron transfer mechanisms of phenols antioxidant action.

    PubMed

    Klein, Erik; Lukes, Vladimír

    2006-11-09

    The reaction enthalpies related to the individual steps of two phenolic antioxidants action mechanisms, single electron transfer-proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET), for 30 meta and para-substituted phenols (ArOH) were calculated using DFT/B3LYP method. These mechanisms represent the alternative ways to the extensively studied hydrogen atom transfer (HAT) mechanism. Except the comparison of calculated reaction enthalpies with available experimental and/or theoretical values, obtained enthalpies were correlated with Hammett constants. We have found that electron-donating substituents induce the rise in the enthalpy of proton dissociation (PDE) from ArOH+* radical cation (second step in SET-PT) and in the proton affinities of phenoxide ions ArO- (reaction enthalpy of the first step in SPLET). Electron-withdrawing groups cause the increase in the reaction enthalpies of the processes where electron is abstracted, i.e., in the ionization potentials of ArOH (first step in SET-PT) and in the enthalpy of electron transfer from ArO- (second step in SPLET). Found results indicate that all dependences of reaction enthalpies on Hammett constants of the substituents are linear. The calculations of liquid-phase reaction enthalpies for several para-substituted phenols indicate that found trends hold also in water, although substituent effects are weaker. From the thermodynamic point of view, entering SPLET mechanism represents the most probable process in water.

  3. Response function of the magnetic spectrometer PRISMA for the multinucleon transfer reaction {sup 40}Ar+{sup 208}Pb

    SciTech Connect

    Mijatovic, T.; Szilner, S.; Corradi, L.; Courtin, S.; Farnea, E.; Fioretto, E.; Gadea, A.; Goasduff, A.; Haas, F.; Jelavic-Malenica, D.; Lunardi, S.; Mengoni, D.; Montagnoli, G.; Montanari, D.; Pollarolo, G.; Recchia, F.; Sahin, E.; Scarlassara, F.; Soic, N.; Stefanini, A. M.; and others

    2012-10-20

    Multinucleon transfer reaction {sup 40}Ar+{sup 208}Pb has been investigated with the PRISMA-CLARA experimental setup in LNL, INFN, Italy. The experimental differential cross sections have been obtained for different transfer channels by measuring more than {Delta}{theta}{sub lab} = 20 Degree-Sign covered by three angular settings of PRISMA. Results have been compared with the semiclassical calculation GRAZING. Since the understanding of the reaction mechanism depends strongly on the determination of absolute cross section, effect of transport of ions through PRISMA has been studied via a Monte Carlo simulation code.

  4. Invariant Coordinates in Breakup Reactions

    NASA Astrophysics Data System (ADS)

    Skwira-Chalot, I.; Ciepał, I.; Kistryn, St.; Kozela, A.; Parol, W.; Stephan, E.

    2017-03-01

    Systematic experimental studies of few-nucleon systems expose various dynamical ingredients which play an important role in correct description of observables, such as three-nucleon force, Coulomb force and relativistic effects. A large set of existing experimental data for ^1H(d, p p)n reaction allows for systematic investigations of these dynamical effects, which vary with energy and appear with different strength in certain observables and phase space regions. Moreover, systematic comparisons with exact theoretical calculations, done in variables related to the system dynamics in a possibly direct ways is a very important tool to verify and improve the existing description of the nucleon interaction. Examples of experimental data for a breakup reaction, transformed to the variables based on Lorentz-invariants are compared with modern theoretical calculations.

  5. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    PubMed

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

  6. Determination of rate and equilibrium constants for the reactions between electron transfer mediators and proteins by linear sweep voltammetry.

    PubMed

    Parker, V D; Roddick, A; Seefeldt, L C; Wang, H; Zheng, G

    1997-07-01

    Redox proteins undergo measurable charge transfer at electrodes only under special circumstances, while they readily take part in electron transfer reactions with mediators in solution. Advantage was taken of the latter fact to develop a new method to study the kinetics and equilibria of protein-mediator electron transfer reactions. It was shown that rate and equilibrium constants for the electron exchange between electron transfer mediator and the protein can be obtained from the analysis of the perturbation of the linear sweep voltammetry (LSV) response of the mediator due to the presence of the protein. The experiments were carried out under conditions where the protein does not interact with the electrode. Theoretical data obtained by digital simulation are presented to show the conditions under which rate and equilibrium constants are accessible by the LSV technique. The electron transfer reactions between ferri- and ferrocytochrome c and N,N,N',N'-tetramethylphenylenediamine and the corresponding radical cation in phosphate-buffered saline (0.04 M phosphate, pH 7.4, 0.1 M NaCl) buffer were selected to demonstrate the technique. These studies resulted in an equilibrium constant equal to 1.0 and forward and reverse rate constants equal to 1.6 x 10(4) M-1 s-1. The data available from this method include forward and reverse rate constants for electron transfer and the formal potential for the protein redox couple.

  7. 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.

  8. A molecular Debye-Hückel approach to the reorganization energy of electron transfer reactions in an electric cell.

    PubMed

    Xiao, Tiejun; Song, Xueyu

    2014-10-07

    Electron transfer near an electrode immersed in ionic fluids is studied using the linear response approximation, namely, mean value of the vertical energy gap can be used to evaluate the reorganization energy, and hence any linear response model that can treat Coulomb interactions successfully can be used for the reorganization energy calculation. Specifically, a molecular Debye-Hückel theory is used to calculate the reorganization energy of electron transfer reactions in an electric cell. Applications to electron transfer near an electrode in molten salts show that the reorganization energies from our molecular Debye-Hückel theory agree well with the results from MD simulations.

  9. Effect of different hand positions on trunk and shoulder kinematics and reaction forces in sitting pivot transfer.

    PubMed

    Kim, Sung Shin; Her, Jin Gan; Ko, Tae Sung

    2015-07-01

    [Purpose] The purpose of this study was to compare the changes in trunk and shoulder angles, and reaction forces under the two hands elicited by different hand base of support positions during sitting pivot transfer. [Subjects and Methods] Eighteen unimpaired subjects performed independent sitting pivot transfer. Subjects performed sitting pivot transfer between an initial seat to a target seat by only using their hands positioned at the same height as and lower than the seat position. Trunk and shoulder kinematics, and reaction forces on the trailing and leading hands were calculated. Mean peak joint angles and forces were compared between the hand positions using the pared t-test for the lift phase of the transfer. [Results] There were significant increases in the trunk angles of forward and lateral flexion, even though rotation decreased while transferring in the lower hand position. Increased shoulder flexion, anterior/posterior forces and reduced lateral forces were also shown. [Conclusion] Placing the hands of the supporting arms lower than the seat position during sitting pivot transfer was identified as having biomechanical advantages. Therefore, the lower hand position can be recommended as an effective and safe method for sitting pivot transfer by patients with spinal cord injury and can be utilized as a reference data for considering the appropriate height of aids for a wheelchair.

  10. Effect of different hand positions on trunk and shoulder kinematics and reaction forces in sitting pivot transfer

    PubMed Central

    Kim, Sung Shin; Her, Jin Gan; Ko, Tae Sung

    2015-01-01

    [Purpose] The purpose of this study was to compare the changes in trunk and shoulder angles, and reaction forces under the two hands elicited by different hand base of support positions during sitting pivot transfer. [Subjects and Methods] Eighteen unimpaired subjects performed independent sitting pivot transfer. Subjects performed sitting pivot transfer between an initial seat to a target seat by only using their hands positioned at the same height as and lower than the seat position. Trunk and shoulder kinematics, and reaction forces on the trailing and leading hands were calculated. Mean peak joint angles and forces were compared between the hand positions using the pared t-test for the lift phase of the transfer. [Results] There were significant increases in the trunk angles of forward and lateral flexion, even though rotation decreased while transferring in the lower hand position. Increased shoulder flexion, anterior/posterior forces and reduced lateral forces were also shown. [Conclusion] Placing the hands of the supporting arms lower than the seat position during sitting pivot transfer was identified as having biomechanical advantages. Therefore, the lower hand position can be recommended as an effective and safe method for sitting pivot transfer by patients with spinal cord injury and can be utilized as a reference data for considering the appropriate height of aids for a wheelchair. PMID:26310994

  11. The ^2H(e,e'p)n Reaction at High Four-Momentum Transfer

    SciTech Connect

    Hassan Ibrahim

    2006-12-31

    This dissertation presents the highest four-momentum transfer, Q^2,quasielastic (x_Bj = 1) results from Experiment E01-020 which systematically explored the 2He(e,e'p)n reaction ("Electro-disintegration" of the deuteron) at three different four-momentum transfers, Q^2 = 0.8, 2.1, and 3.5 GeV^2 and missing momenta, P_miss = 0, 100, 200, 300, 400, and 500 GeV including separations of the longitudinal-transverse interference response function, R_LT, and extractoin of the longitudinal-transverse asymmetry, A_LT. This systematic approach will help to understand the reaction mechanism and the deuteron structure down to the short range part of the nucleon-nucleon interaction which is one of the fundamental missions of nuclear physics. By studying the very short distance structure of the deuteron, one may also determine whether or to what extent the description of nuclei in terms of nucleon/meson degrees of freedom must be supplemented by inclusion of explicit quark effects. The unique combination of energy, current, duty factor, and control of systematics for Hall A at Jefferson Lab made Jefferson Lab the only facility in the world where these systematic studies of the deuteron can be undertaken. This is especially true when we want to understand the short range structure of the deuteron where high energies and high luminosity/duty factor are needed. All these features of Jefferson Lab allow us to examine large missing momenta (short range scales) at kinematics where the effects of final state interactions (FSI), meson exchange currents (MEC), and isobar currents (IC) are minimal, making the extraction of the deuteron structure less model-dependent. Jefferson Lab also provides the kinematical flexibility to perform the separation of R_LT over a broad range of missing momenta and momentum transfers. Experiment E01-020 use the standard Hall A equipment in coincidence configuration in addition to the cryogenic target system. The low and middle Q^2 kinematics were completed

  12. Chemical evolution of a travertine-depositing stream: geochemical processes and mass transfer reactions

    SciTech Connect

    Lorah, M.M.; Herman, J.S.

    1988-09-01

    This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO/sub 2/ outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO/sub 2/ partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO/sub 2/ and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO/sub 2/ outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO/sub 2/ along the entire 5.2-km flow path. Outgassing of CO/sub 2/ drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO/sub 2/ by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO/sub 2/ outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO/sub 2/. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

  13. Kinetics of acyl transfer reactions in organic media catalysed by Candida antarctica lipase B.

    PubMed

    Martinelle, M; Hult, K

    1995-09-06

    The acyl transfer reactions catalysed by Candida antartica lipase B in organic media followed a bi-bi ping-pong mechanism, with competitive substrate inhibition by the alcohols used as acyl acceptors. The effect of organic solvents on Vm and Km was investigated. The Vm values in acetonitrile was 40-50% of those in heptane. High Km values in acetonitrile compared to those in heptane could partly be explained by an increased solvation of the substrates in acetonitrile. Substrate solvation caused a 10-fold change in substrate specificity, defined as (Vm/Km)ethyl octanoate/(Vm/Km)octanoic acid, going from heptane to acetonitrile. Deacylation was the rate determining step for the acyl transfer in heptane with vinyl- and ethyl octanoate as acyl donors and (R)-2-octanol as acyl acceptor. With 1-octanol, a rate determining deacylation step in heptane was indicated using the same acyl donors. Using 1-octanol as acceptor in heptane, S-ethyl thiooctanoate had a 25- to 30-fold lower Vm/Km value and vinyl octanoate a 4-fold higher Vm/Km value than that for ethyl octanoate. The difference showed to be a Km effect for vinyl octanoate and mainly a Km effect for S-ethyl thiooctanoate. The Vm values of the esterification of octanoic acid with different alcohols was 10-30-times lower than those for the corresponding transesterification of ethyl octanoate. The low activity could be explained by a low pH around the enzyme caused by the acid or a withdrawing of active enzyme by nonproductive binding by the acid.

  14. Calculated coupling of electron and proton transfer in the photosynthetic reaction center of Rhodopseudomonas viridis.

    PubMed Central

    Lancaster, C R; Michel, H; Honig, B; Gunner, M R

    1996-01-01

    Based on new Rhodopseudomonas (Rp.) viridis reaction center (RC) coordinates with a reliable structure of the secondary acceptor quinone (QB) site, a continuum dielectric model and finite difference technique have been used to identify clusters of electrostatically interacting ionizable residues. Twenty-three residues within a distance of 25 A from QB (QB cluster) have been shown to be strongly electrostatically coupled to QB, either directly or indirectly. An analogous cluster of 24 residues is found to interact with QA (QA cluster). Both clusters extend to the cytoplasmic surface in at least two directions. However, the QB cluster differs from the QA cluster in that it has a surplus of acidic residues, more strong electrostatic interactions, is less solvated, and experiences a strong positive electrostatic field arising from the polypeptide backbone. Consequently, upon reduction of QA or QB, it is the QB cluster, and not the QA cluster, which is responsible for substoichiometric proton uptake at neutral pH. The bulk of the changes in the QB cluster are calculated to be due to the protonation of a tightly coupled cluster of the three Glu residues (L212, H177, and M234) within the QB cluster. If the lifetime of the doubly reduced state QB2- is long enough, Asp M43 and Ser L223 are predicted to also become protonated. The calculated complex titration behavior of the strongly interacting residues of the QB cluster and the resulting electrostatic response to electron transfer may be a common feature in proton-transferring membrane protein complexes. Images FIGURE 2 p2482-a FIGURE 6 FIGURE 8 FIGURE 10 PMID:8744288

  15. Control and Automation of Fluid Flow, Mass Transfer and Chemical Reactions in Microscale Segmented Flow

    NASA Astrophysics Data System (ADS)

    Abolhasani, Milad

    Flowing trains of uniformly sized bubbles/droplets (i.e., segmented flows) and the associated mass transfer enhancement over their single-phase counterparts have been studied extensively during the past fifty years. Although the scaling behaviour of segmented flow formation is increasingly well understood, the predictive adjustment of the desired flow characteristics that influence the mixing and residence times, remains a challenge. Currently, a time consuming, slow and often inconsistent manual manipulation of experimental conditions is required to address this task. In my thesis, I have overcome the above-mentioned challenges and developed an experimental strategy that for the first time provided predictive control over segmented flows in a hands-off manner. A computer-controlled platform that consisted of a real-time image processing module within an integral controller, a silicon-based microreactor and automated fluid delivery technique was designed, implemented and validated. In a first part of my thesis I utilized this approach for the automated screening of physical mass transfer and solubility characteristics of carbon dioxide (CO2) in a physical solvent at a well-defined temperature and pressure and a throughput of 12 conditions per hour. Second, by applying the segmented flow approach to a recently discovered CO2 chemical absorbent, frustrated Lewis pairs (FLPs), I determined the thermodynamic characteristics of the CO2-FLP reaction. Finally, the segmented flow approach was employed for characterization and investigation of CO2-governed liquid-liquid phase separation process. The second part of my thesis utilized the segmented flow platform for the preparation and shape control of high quality colloidal nanomaterials (e.g., CdSe/CdS) via the automated control of residence times up to approximately 5 minutes. By introducing a novel oscillatory segmented flow concept, I was able to further extend the residence time limitation to 24 hours. A case study of a

  16. Analysis of secondary organic aerosols from ozonolysis of isoprene by proton transfer reaction mass spectrometry

    NASA Astrophysics Data System (ADS)

    Inomata, Satoshi; Sato, Kei; Hirokawa, Jun; Sakamoto, Yosuke; Tanimoto, Hiroshi; Okumura, Motonori; Tohno, Susumu; Imamura, Takashi

    2014-11-01

    To understand the mechanism of formation of the secondary organic aerosols (SOAs) produced by the ozonolysis of isoprene, proton transfer reaction mass spectrometry (PTR-MS) was used to identify the semi-volatile organic compounds (SVOCs) produced in both the gaseous and the aerosol phases and to estimate the gas-aerosol partitioning of each SVOC in chamber experiments. To aid in the identification of the SVOCs, the products were also studied with negative ion-chemical ionization mass spectrometry (NI-CIMS), which can selectively detect carboxylic acids and hydroperoxides. The gaseous products were observed by on-line PTR-MS and NI-CIMS, whereas the SVOCs in SOAs collected on a filter were vaporized by heating the filter and were then analysed by off-line PTR-MS and NI-CIMS. The formation of oligomeric hydroperoxides involving a Criegee intermediate as a chain unit was observed in both the gaseous and the aerosol phases by NI-CIMS. PTR-MS also detected oligomeric hydroperoxides as protonated molecules from which a H2O molecule was eliminated, [M-OH]+. In the aerosol phase, oligomers involving formaldehyde and methacrolein as chain units were observed by PTR-MS in addition to oligomeric hydroperoxides. The gas-aerosol partitioning of each component was calculated from the ion signals in the gaseous and aerosol phases measured by PTR-MS. From the gas-aerosol partitioning, the saturated vapour pressures of the oligomeric hydroperoxides were estimated. Measurements by a fast-mobility-particle-sizer spectrometer revealed that the increase of the number density of the particles was complete within a few hundred seconds from the start of the reaction.

  17. Spectrophotometric determination of terfenadine in pharmaceutical preparations by charge-transfer reactions.

    PubMed

    Khaled, Elmorsy

    2008-06-15

    A simple, rapid and accurate method for the spectrophotometric determination of terfenadine has been developed. The proposed method based on the charge-transfer reactions of terfenadine, as n-electron donor, with 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, p-CLA) as pi-acceptors to give highly colored complexes. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the highest sensitivity. Beer's law is obeyed over the concentration ranges of 3-72, 3-96, 12-168 and 24-240 microg mL(-1) terfenadine using TCNQ, TCNE, DDQ and p-CLA, respectively, with correlation coefficients 0.9999, 0.9974, 0.9997 and 0.9979 and detection limits 0.3, 0.4, 2.6 and 12.3 microg mL(-1), for the reagents in the same order. DDQ and p-CLA react spontaneously with terfenadine to give colored complexes that can be applied for the flow injection analysis of terfenadine in the concentration ranges 2.4-120 and 24-240 microg with correlation coefficients 0.9990 and 0.9985 and detection limits 0.8 and 2.7 microg for DDQ and p-CLA, respectively, in addition to the high sampling through output of 40 sample h(-1).

  18. 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

  19. First half-reaction mechanism of nitric oxide synthase: the role of proton and oxygen coupled electron transfer in the reaction by quantum mechanics/molecular mechanics.

    PubMed

    Cho, Kyung-Bin; Carvajal, Maria Angels; Shaik, Sason

    2009-01-08

    The first half-reaction of nitric oxide synthase (NOS) is investigated by means of quantum mechanical/molecular mechanical (QM/MM) calculations. An energetically feasible arginine hydroxylation path was found only when the iron-oxy complex accepted one proton from an external source. The so formed species has not been considered in heme chemistry; it is described as Por(+*)Fe(III)-OOH and is characterized by the same molecular constituency as the more known ferric-hydroperoxide species, compound 0, but has a cation-radical porphyrin moiety. The reaction itself is found to involve proton coupled electron transfer (PCET) and oxygen coupled electron transfer (OCET) steps en route to the formation of compound I and the ultimate monooxygenation of arginine. The cofactor H(4)B turns out to be a key player in the mechanism acting alternatively as an electron donor (when neutral) and an electron sink (when in its radical-cation state) and, thereby, providing the electron transfer component in the various coupled proton and oxygen transfer steps (see Scheme 4 ). The various pieces of this mechanism account for many of the experimental observations, such as the following: (a) the origins of the second proton supplied to the heme, (b) the elusiveness of compound I, (c) the inactivity of peroxide-shunt pathways in NOS first half-reaction, (d) the inhibition of the H(4)B analogue 4-amino-H(4)B due to protonation at the N3 position, (e) the roles of Trp188 (iNOS numbering) and the crystal water at the active site (W115), and so on. Alternative mechanistic hypotheses are tested and excluded, and a new mechanism for the NOS second half-reaction is proposed.

  20. Proton-electron transfer pathways in the reactions of peroxyl and dpph˙ radicals with hydrogen-bonded phenols.

    PubMed

    Amorati, Riccardo; Menichetti, Stefano; Viglianisi, Caterina; Foti, Mario C

    2012-12-18

    The kinetics of the reaction of peroxyl and dpph˙ radicals with phenols H-bonded to N-bases have been studied for the first time. Electron-transfer processes are observed in MeCN but only with the dpph˙ radical.

  1. Diphenylbutadienes Syntheses by Means of the Wittig Reaction: Experimental Introduction to the Use of Phase Transfer Catalysis.

    ERIC Educational Resources Information Center

    Gillois, J.; And Others

    1980-01-01

    The synthesis of 1,4-diphenylbutadiene by means of the Wittig reaction is presented as suitable for organic chemistry students at the end of a basic laboratory program to apply laboratory skills and display understanding of the use of phase transfer catalysis and its application in syntheses. (CS)

  2. A Short Account of RRKM Theory of Unimolecular Reactions and of Marcus Theory of Electron Transfer in a Historical Perspective

    ERIC Educational Resources Information Center

    Di Giacomo, Francesco

    2015-01-01

    The RRKM Theory of Unimolecular Reactions and Marcus Theory of Electron Transfer are here briefly discussed in a historical perspective. In the final section, after a general discussion on the educational usefulness of teaching chemistry in a historical framework, hints are given on how some characteristics of Marcus' work could be introduced in…

  3. A review of proton transfer reactions between various carbon-acids and amine bases in aprotic solvents

    NASA Astrophysics Data System (ADS)

    Jarczewski, Arnold; Hubbard, Colin D.

    2003-04-01

    The subject of proton transfer between carbon acids and nitrogen bases in aprotic solvents is reviewed. Equilibrium and rate constants that characterize such reactions are most often determined utilizing UV-visible spectrophotometry. At ambient temperature reaction rates are sufficiently rapid that fast reaction methods, for example, the stopped-flow and temperature-jump techniques are required in many cases. Variation of the properties of the donor and acceptor reaction pairs enables electronic and steric effects upon thermodynamic and kinetic parameters of proton transfer to be assessed. Determination of the kinetic isotope effect (KIE), i.e. k(protium)/ k(deuterium) led to the conclusion that, under certain circumstances and when the KIE is greater than seven, the proton undergoes reaction with a significant degree of quantum mechanical tunneling, consistent with a theoretical prediction advanced several decades earlier. In fact this aspect may be one of the most significant outgrowths of these studies. Many reactions have been characterized (by tunneling) but rarely are the reacting systems experimentally amenable to obtaining all the experimental criteria that support tunneling. Controversy that has arisen regarding treatment of experimental data and resulting conclusions from them is visited in this review. The structural nature of the product state of reaction is formulated based on spectroscopic evidence, in favorable cases, and probable structures of the transition state can be inferred.

  4. Proton-coupled electron transfer versus hydrogen atom transfer in benzyl/toluene, methoxyl/methanol, and phenoxyl/phenol self-exchange reactions.

    PubMed

    Mayer, James M; Hrovat, David A; Thomas, Jennie L; Borden, Weston Thatcher

    2002-09-18

    Degenerate hydrogen atom exchange reactions have been studied using calculations, based on density functional theory (DFT), for (i) benzyl radical plus toluene, (ii) phenoxyl radical plus phenol, and (iii) methoxyl radical plus methanol. The first and third reactions occur via hydrogen atom transfer (HAT) mechanisms. The transition structure (TS) for benzyl/toluene hydrogen exchange has C(2)(h)() symmetry and corresponds to the approach of the 2p-pi orbital on the benzylic carbon of the radical to a benzylic hydrogen of toluene. In this TS, and in the similar C(2) TS for methoxyl/methanol hydrogen exchange, the SOMO has significant density in atomic orbitals that lie along the C-H vectors in the former reaction and nearly along the O-H vectors in the latter. In contrast, the SOMO at the phenoxyl/phenol TS is a pi symmetry orbital within each of the C(6)H(5)O units, involving 2p atomic orbitals on the oxygen atoms that are essentially orthogonal to the O.H.O vector. The transferring hydrogen in this reaction is a proton that is part of a typical hydrogen bond, involving a sigma lone pair on the oxygen of the phenoxyl radical and the O-H bond of phenol. Because the proton is transferred between oxygen sigma orbitals, and the electron is transferred between oxygen pi orbitals, this reaction should be described as a proton-coupled electron transfer (PCET). The PCET mechanism requires the formation of a hydrogen bond, and so is not available for benzyl/toluene exchange. The preference for phenoxyl/phenol to occur by PCET while methoxyl/methanol exchange occurs by HAT is traced to the greater pi donating ability of phenyl over methyl. This results in greater electron density on the oxygens in the PCET transition structure for phenoxyl/phenol, as compared to the PCET hilltop for methoxyl/methanol, and the greater electron density on the oxygens selectively stabilizes the phenoxyl/phenol TS by providing a larger binding energy of the transferring proton.

  5. Investigation of the ^{10}Li shell inversion by neutron continuum transfer reaction.

    PubMed

    Cavallaro, M; De Napoli, M; Cappuzzello, F; Orrigo, S E A; Agodi, C; Bondí, M; Carbone, D; Cunsolo, A; Davids, B; Davinson, T; Foti, A; Galinski, N; Kanungo, R; Lenske, H; Ruiz, C; Sanetullaev, A

    2017-01-06

    This Letter reports a study of the highly debated ^{10}Li structure through the d(^{9}Li,p)^{10}Li one-neutron transfer reaction at 100 MeV. The ^{10}Li energy spectrum is measured up to 4.6 MeV and angular distributions corresponding to different excitation energy regions are reported for the first time. The comparison between data and theoretical predictions, including pairing correlation effects, shows the existence of a p_{1/2} resonance at 0.45±0.03  MeV excitation energy, while no evidence for a significant s-wave contribution close to the threshold energy is observed. Moreover, two high-lying structures are populated at 1.5 and 2.9 MeV. The corresponding angular distributions suggest a significant s_{1/2} partial-wave contribution for the 1.5 MeV structure and a mixing of configurations at higher energy, with the d_{5/2} partial-wave contributing the most to the cross section.

  6. Reaction-diffusion systems in natural sciences and new technology transfer

    NASA Astrophysics Data System (ADS)

    Keller, André A.

    2012-12-01

    Diffusion mechanisms in natural sciences and innovation management involve partial differential equations (PDEs). This is due to their spatio-temporal dimensions. Functional semi-discretized PDEs (with lattice spatial structures or time delays) may be even more adapted to real world problems. In the modeling process, PDEs can also formalize behaviors, such as the logistic growth of populations with migration, and the adopters’ dynamics of new products in innovation models. In biology, these events are related to variations in the environment, population densities and overcrowding, migration and spreading of humans, animals, plants and other cells and organisms. In chemical reactions, molecules of different species interact locally and diffuse. In the management of new technologies, the diffusion processes of innovations in the marketplace (e.g., the mobile phone) are a major subject. These innovation diffusion models refer mainly to epidemic models. This contribution introduces that modeling process by using PDEs and reviews the essential features of the dynamics and control in biological, chemical and new technology transfer. This paper is essentially user-oriented with basic nonlinear evolution equations, delay PDEs, several analytical and numerical methods for solving, different solutions, and with the use of mathematical packages, notebooks and codes. The computations are carried out by using the software Wolfram Mathematica®7, and C++ codes.

  7. First Measurement of Transferred Polarization in the Exclusive e p --> e' K+ Lambda Reaction

    SciTech Connect

    Daniel S. Carman; Et. Al.

    2003-04-04

    The first measurements of the transferred polarization for the exclusive {rvec e}p {yields} e{prime}K{sup +}{rvec {Lambda}} reaction have been performed in Hall B at the Thomas Jefferson National Accelerator Facility using the CLAS spectrometer. A 2.567 GeV electron beam was used to measure the hyperon polarization over a range of Q{sup 2} from 0.3 to 1.5 (GeV/c){sup 2}, W from 1.6 to 2.15 GeV, and over the full center-of-mass angular range of the K{sup +} meson. Comparison with predictions of hadrodynamic models indicates strong sensitivity to the underlying resonance contributions. A non-relativistic quark model interpretation of our data suggests that the s{bar s} quark pair is produced with spins predominantly anti-aligned. Implications for the validity of the widely used {sup 3}P{sub o} quark-pair creation operator are discussed.

  8. Static and dynamic headspace analysis of instant coffee blends by proton-transfer-reaction mass spectrometry.

    PubMed

    Romano, Andrea; Gaysinsky, Sylvia; Czepa, Andreas; Del Pulgar, José Sanchez; Cappellin, Luca; Biasioli, Franco

    2015-09-01

    Instant coffee is a widespread product, generally related to a high consumer acceptability, also because of its ease of preparation. The present work addresses the characterization of the headspace of freshly brewed instant coffees resulting from different blends, during and immediately after preparation. The sample set consisted of 10 coffees, obtained by mixing three different blends in different proportions. The employment of Proton Transfer Reaction-Mass Spectrometry (PTR-MS) allowed for direct and real-time sampling from the headspace, under conditions that mimic those that are encountered above the cup during and right after brewing. Different coffee brews were separated on the basis of the respective volatile profiles, and data showed good consistency with the respective blend compositions. When the headspace evolution was monitored during preparation, similar results were obtained in terms of blend separation; moreover, different blends displayed different and reproducible 'signatures' in terms of time evolution. A straightforward method for the prediction of headspace composition is proposed, allowing to predict the volatile profiles of two-component and three-component blends on the basis of the respective parent components. Overall, the results constitute a successful example of the applicability of PTR-MS as a tool for product development in food science. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Characterization of an olfactometer by proton-transfer-reaction mass spectrometry

    NASA Astrophysics Data System (ADS)

    Beauchamp, J.; Frasnelli, J.; Buettner, A.; Scheibe, M.; Hansel, A.; Hummel, T.

    2010-02-01

    The performance of a commercial olfactometer instrument, which produces odorant pulses of defined duration and concentration, was characterized using proton-transfer-reaction mass spectrometry (PTR-MS). Direct coupling of the PTR-MS instrument with the olfactometer enabled on-line evaluation of the rapidly delivered aroma pulses. Tests were made with a selection of four odorous compounds: hydrogen sulfide, 2,3-butanedione, ethyl butanoate and ethyl hexanoate. Odour concentrations and stimulus durations for these compounds were monitored directly at the olfactometer delivery port via the respective PTR-MS signals. The performance of the olfactometer was found to be dependent on pulse duration. A decrease over time in maximum intensity for identical pulses over an extended duration showed headspace concentration depletions for compounds sourced from a water solution, indicative of gas/liquid partitioning. Such changes were not present using odours sourced from a cylinder or, presumably, when using liquid odours at neat concentrations. In conclusion, while an olfactometer provides stimuli with good reproducibility, the concept is subject to certain limitations that must be appreciated by the experimenter for accurate application of this technique.

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

    NASA Astrophysics Data System (ADS)

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

    2008-08-01

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

  11. Investigation of the 10Li shell inversion by neutron continuum transfer reaction

    NASA Astrophysics Data System (ADS)

    Cavallaro, M.; De Napoli, M.; Cappuzzello, F.; Orrigo, S. E. A.; Agodi, C.; Bondí, M.; Carbone, D.; Cunsolo, A.; Davids, B.; Davinson, T.; Foti, A.; Galinski, N.; Kanungo, R.; Lenske, H.; Ruiz, C.; Sanetullaev, A.

    2017-01-01

    This Letter reports a study of the highly debated 10Li structure through the d (9Li,p)10Li one-neutron transfer reaction at 100 MeV. The 10Li energy spectrum is measured up to 4.6 MeV and angular distributions corresponding to different excitation energy regions are reported for the first time. The comparison between data and theoretical predictions, including pairing correlation effects, shows the existence of a p1 /2 resonance at 0.45 ±0.03 MeV excitation energy, while no evidence for a significant s -wave contribution close to the threshold energy is observed. Moreover, two high-lying structures are populated at 1.5 and 2.9 MeV. The corresponding angular distributions suggest a significant s1 /2 partial-wave contribution for the 1.5 MeV structure and a mixing of configurations at higher energy, with the d5 /2 partial-wave contributing the most to the cross section.

  12. Fast fingerprinting of arson accelerants by proton transfer reaction time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Whyte, Christopher; Wyche, Kevin P.; Kholia, Mitesh; Ellis, Andrew M.; Monks, Paul S.

    2007-06-01

    Current techniques for the forensic analysis of fire debris as a means to detect the presence of arson accelerants normally use off-line sampling with the collection of accelerant vapours on activated charcoal strips and further pre-chemistry prior to analysis. An alternative method for the direct detection of arson accelerants that requires no sample pre-treatment is described here. The analysis uses proton transfer reaction mass spectrometry (PTR-MS), incorporating a time-of-flight mass spectrometer for rapid multichannel compound detection. It is demonstrated that using PTR-MS volatile organic compound (VOC) fingerprints of a given fire accelerant can be collected by simple head space analysis of accelerant burned materials. Using a set of the four most common arson accelerants and four common household building materials, characteristic VOC fingerprints are shown to provide successful identification of the accelerant used to burn each material. There is the potential to develop this methodology for the rapid screening of large numbers of samples.

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

    PubMed

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

    2013-11-05

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

  14. Polarizable solute in polarizable and flexible solvents: simulation study of electron transfer reaction systems.

    PubMed

    Ishida, Tateki

    2005-10-06

    A polarizable solute model, based on the empirical valence bond approach, is developed and applied to electron transfer (ET) reactions in polarizable and flexible water solvents. The polarization effect is investigated in comparison with a nonpolarizable solute and solvent model. With free energy curves constructed by a molecular dynamics simulation, the activation energy barrier and the reorganization energy related to ET processes are investigated. The present simulation results show that the activation energy barrier becomes larger in the polarizable model than in the nonpolarizable model and that this makes the ET rate slower than that with the nonpolarizable model. It is shown that the effect of the electronic energy difference of solute molecule on free energy profiles is remarkable and that, corresponding to this effect, the reorganization energy is significantly modified. These results indicate that the process of solvent polarization by the polarized solute to enhance the solute-solvent interaction is a key factor and that treating the polarization of both solute and solvent at the same time is essential. Also, the polarization effect on the diffusive motion of the solute molecule in the polarization solvent is studied. The polarized solute molecule shows slower diffusive motion compared with that in the nonpolarizable model.

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

    PubMed Central

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

    2013-01-01

    Proton-transfer-reaction time-of-flight mass-spectrometry (PTR-TOFMS) exhibits high selectivity with a resolution of around 5000 m/Δm. While isobars can be separated with this resolution, discrimination of isomeric compounds is usually not possible. The coupling of a multi-capillary column (MCC) with a PTR-TOFMS overcomes these problems as demonstrated in this paper for the ketone isomers 3-heptanone and 2-methyl-3-hexanone and for different aldehydes. Moreover, fragmentation of compounds can be studied in detail which might even improve the identification. LODs for compounds tested are in the range of low ppbv and peak positions of the respective separated substances show good repeatability (RSD of the peak positions <3.2%). Due to its special characteristics, such as isothermal operation, compact size, the MCC setup is suitable to be installed inside the instrument and the overall retention time for a complete spectrum is only a few minutes: this allows near real-time measurements in the optional MCC mode. In contrast to other methods that yield additional separation, such as the use of pre-cursor ions other than H3O+, this method yields additional information without increasing complexity. PMID:24119758

  16. Rapid tomato volatile profiling by using proton-transfer reaction mass spectrometry (PTR-MS).

    PubMed

    Farneti, Brian; Cristescu, Simona M; Costa, Guglielmo; Harren, Frans J M; Woltering, Ernst J

    2012-05-01

    The availability of rapid and accurate methods to assess fruit flavor is of utmost importance to support quality control especially in the breeding phase. Breeders need more information and analytical tools to facilitate selection for complex multigenic traits such as flavor quality. In this study, it is shown that proton-transfer reaction mass spectrometry (PTR-MS) is a suitable method to monitor at high sensitivity the emission of volatiles determining the tomato aromatic profile such as hexanal, hexenals, methanol, ethanol, and acetaldehyde. The volatiles emitted by 14 tomato varieties (at red stage) were analyzed by 2 solvent-free headspace methods: solid-phase microextraction/gas chromatography MS and PTR-MS. Multivariate statistics (principal component analysis and cluster analysis) of the PTR-MS results allow an unambiguous separation between varieties, especially with a clear fingerprinting separation between the different tomato types: round truss, cocktail, and cherry tomatoes. PTR-MS was also successfully used to monitor the changes in volatile profiles during postharvest ripening and storage.

  17. Limiting role of the mass transfer of gases in laser thermochemical reactions on the surface of solids

    NASA Astrophysics Data System (ADS)

    Sobol, Emil N.

    1990-10-01

    Growth kinetics of porous layers produced by gas-transfer controlled thermochemical reactions is described. The analysis of heat and mass-transfer problem allows to find the optimal regimes of laser treatment of solids. 1. GROWTH KINETICS OF SURFACE LAYERS The limiting role of gas transfer is characteristic of various processes in volved in the growth of solid layers of a new phase on the exposed surface'' in the course of laser oxidation and reduction of metals and laser synthesis and decomposition of nitrides and other compounds high-temperature superconductors included. When analyzing laser thermochemical reactions taking place in solids and involving the uptake or release of gases the absorbed energy flux q will be considered constant the thermooptical effects2 being disregarded. Let laser radiation incident on the surface of the original substance A give rise to a layer of a new phase B with a thickness of s through which a gas C migrates. We write the pertinent chemical decomposition and synthesis reactions in the form A 4 B + C and A + C ) B respectively. The direction of the reaction is determined by the sign of the Gibbs thermodynamic potential tG /H + TM where tH and tS are the changes of the enthalpy and entropy of the system respectively. According to the chemical equilibrium theory the pressure at the chemical reaction front is related to temperature by the Arrenius law:

  18. Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

    2016-01-01

    In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

  19. Rate-promoting vibrations and coupled hydrogen-electron transfer reactions in the condensed phase: A model for enzymatic catalysis

    NASA Astrophysics Data System (ADS)

    Mincer, Joshua S.; Schwartz, Steven D.

    2004-04-01

    A model is presented for coupled hydrogen-electron transfer reactions in condensed phase in the presence of a rate promoting vibration. Large kinetic isotope effects (KIEs) are found when the hydrogen is substituted with deuterium. While these KIEs are essentially temperature independent, reaction rates do exhibit temperature dependence. These findings agree with recent experimental data for various enzyme-catalyzed reactions, such as the amine dehydrogenases and soybean lipoxygenase. Consistent with earlier results, turning off the promoting vibration results in an increased KIE. Increasing the barrier height increases the KIE, while increasing the rate of electron transfer decreases it. These results are discussed in light of other views of vibrationally enhanced tunneling in enzymes.

  20. Solvent effects on the oxidation (electron transfer) reaction of [Fe(CN) 6] 4- by [Co(NH 3) 5pz] 3+

    NASA Astrophysics Data System (ADS)

    Muriel, F.; Jiménez, R.; López, M.; Prado-Gotor, R.; Sánchez, F.

    2004-03-01

    Solvent effects on the title reaction were studied in different reaction media constituted by water and organic cosolvents (methanol, tert-butyl alcohol, ethyleneglycol and glucose) at 298.2 K. The results are considered in light of the Marcus-Hush approach for electron transfer reactions. Variations of the electron transfer rate constant are shown to be mainly due to changes in the reaction free energy. On the other hand the energies of the MMCT band, corresponding to the optical electron transfer within the ion pair [Fe(CN) 6] 4-/[Co(NH 3) 5pz] 3+, in the different reaction media, have been obtained. The activation free energies of the thermal electron transfer process have been calculated from the band ( Eop) data, and compared with those obtained from the kinetic study. Quantitative agreement is found between the two series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from static (optical) measurements.

  1. Exploring excited-state hydrogen atom transfer along an ammonia wire cluster: Competitive reaction paths and vibrational mode selectivity

    NASA Astrophysics Data System (ADS)

    Tanner, Christian; Manca, Carine; Leutwyler, Samuel

    2005-05-01

    The excited-state hydrogen-atom transfer (ESHAT) reaction of the 7-hydroxyquinoline•(NH3)3 cluster involves a crossing from the initially excited π1π* to a π1σ* state. The nonadiabatic coupling between these states induces homolytic dissociation of the O-H bond and H-atom transfer to the closest NH3 molecule, forming a biradical structure denoted HT1, followed by two more Grotthus-type translocation steps along the ammonia wire. We investigate this reaction at the configuration interaction singles level, using a basis set with diffuse orbitals. Intrinsic reaction coordinate calculations of the enol→HT1 step predict that the H-atom transfer is preceded and followed by extensive twisting and bending of the ammonia wire, as well as large O -H⋯NH3 hydrogen bond contraction and expansion. The calculations also predict an excited-state proton transfer path involving synchronous proton motions; however, it lies 20-25kcal/mol above the ESHAT path. Higher singlet and triplet potential curves are calculated along the ESHAT reaction coordinate: Two singlet-triplet curve crossings occur within the HT1 product well and intersystem crossing to these Tn states branches the reaction back to the enol reactant side, decreasing the ESHAT yield. In fact, a product yield of ≈40% 7-ketoquinoline•(NH3)3 is experimentally observed. The vibrational mode selectivity of the enol→HT1 reaction step [C. Manca, C. Tanner, S. Coussan, A. Bach, and S. Leutwyler, J. Chem. Phys. 121, 2578 (2004)] is shown to be due to the large sensitivity of the diffuse πσ* state to vibrational displacements along the intermolecular coordinates.

  2. Cyclofunctionalization and free-radical-based hydrogen-transfer reactions. An iterative reaction sequence applied to the synthesis of the C(7)-C(16) subunit of zincophorin.

    PubMed

    Guindon, Y; Murtagh, L; Caron, V; Landry, S R; Jung, G; Bencheqroun, M; Faucher, A M; Guérin, B

    2001-08-10

    The strategy considered herein features an iodocyclofunctionalization/hydrogen-transfer reaction sequence for the elaboration of propionate motifs. Proceeding with excellent yield and diastereoselectivity, the synthetic sequence proposed gives access to the anti-anti dipropionate motif when the reduction step is performed under the control of the exocyclic effect. The tandem sequence is applied successfully to the synthesis of the C(7)-C(16) subunit of zincophorin, and iteration of the process gives the desired anti-anti-anti-anti polypropionate stereopentad. Modifications of the reaction sequence--including phenylselenocyclofunctionalization, carbonate hydrolysis, and chelation-controlled radical reduction reactions--lead to the formation of the anti-syn dipropionate motif with remarkable diastereocontrol.

  3. Study of all Reaction Channels in Deuteron-Deuteron Scattering

    NASA Astrophysics Data System (ADS)

    Ramazani-Moghaddam-Arani, A.; Amir-Ahmadi, H. R.; Bacher, A. D.; Bailey, C. D.; Biegun, A.; Eslami-Kalantari, M.; Gašparić, I.; Joulaeizadeh, L.; Kalantar-Nayestanaki, N.; Kistryn, St.; Kozela, A.; Mardanpour, H.; Messchendorp, J. G.; Micherdzinska, A. M.; Moeini, H.; Shende, S. V.; Stephan, E.; Stephenson, E. J.; Sworst, R.

    Few-nucleon systems can be used as fundamental laboratories for studying details of the nuclear force effects. We performed a series of deuteron-deuteron scattering experiments at intermediate energies. The experiments exploited BINA and BBS experimental setups and polarized deuteron beams with kinetic energies of 65 and 90 MeV/nucleon. These experiments aim to measure differential cross sections, vector and tensor analyzing powers of all available reaction channels in deuteron-deuteron scattering. With these data we will provide a systematic database, which will be used to test present theoretical approximations and upcoming ab-initio calculations in four-nucleon system.

  4. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    SciTech Connect

    Matsunaga, P.T.

    1991-11-01

    The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  5. Phosphoryl transfer is not rate-limiting for the ROCK I-catalyzed kinase reaction.

    PubMed

    Futer, Olga; Saadat, Ahmad R; Doran, John D; Raybuck, Scott A; Pazhanisamy, S

    2006-06-27

    Rho-associated coiled-coil kinase, ROCK, is implicated in Rho-mediated cell adhesion and smooth muscle contraction. Animal models suggest that the inhibition of ROCK can ameliorate conditions, such as vasospasm, hypertension, and inflammation. As part of our effort to design novel inhibitors of ROCK, we investigated the kinetic mechanism of ROCK I. Steady-state bisubstrate kinetics, inhibition kinetics, isotope partition analysis, viscosity effects, and presteady-state kinetics were used to explore the kinetic mechanism. Plots of reciprocals of initial rates obtained in the presence of nonhydrolyzable ATP analogues and the small molecule inhibitor of ROCK, Y-27632, against the reciprocals of the peptide concentrations yielded parallel lines (uncompetitive pattern). This pattern is indicative of an ordered binding mechanism, with the peptide adding first. The staurosporine analogue K252a, however, gave a noncompetitive pattern. When a pulse of (33)P-gamma-ATP mixed with ROCK was chased with excess unlabeled ATP and peptide, 0.66 enzyme equivalent of (33)P-phosphate was incorporated into the product in the first turnover. The presence of ATPase activity coupled with the isotope partition data is a clear evidence for the existence of a viable [E-ATP] complex in the kinase reaction and implicates a random binding mechanism. The k(cat)/K(m) parameters were fully sensitive to viscosity (viscosity effects of 1.4 +/- 0.2 and 0.9 +/- 0.3 for ATP and peptide 5, respectively), and therefore, the barriers to dissociation of either substrate are higher than the barrier for the phosphoryl transfer step. As a consequence, not all the binding steps are at fast equilibrium. The observation of a burst in presteady-state kinetics (k(b) = 10.2 +/- 2.1 s(-)(1)) and the viscosity effect on k(cat) of 1.3 +/- 0.2 characterize the phosphoryl transfer step to be fast and the release of product and/or the enzyme isomerization step accompanying it as rate-limiting at V(max) conditions. From

  6. Deuteron-induced nucleon transfer reactions within an ab initio framework: First application to p-shell nuclei

    DOE PAGES

    Raimondi, Francesco; Hupin, Guillaume; Navratil, Petr; ...

    2016-05-10

    Low-energy transfer reactions in which a proton is stripped from a deuteron projectile and dropped into a target play a crucial role in the formation of nuclei in both primordial and stellar nucleosynthesis, as well as in the study of exotic nuclei using radioactive beam facilities and inverse kinematics. Here, ab initio approaches have been successfully applied to describe the 3H(d,n)4He and 3He(d,p)4He fusion processes. An ab initio treatment of transfer reactions would also be desirable for heavier targets. In this work, we extend the ab initio description of (d,p) reactions to processes with light p-shell nuclei. As a firstmore » application, we study the elastic scattering of deuterium on 7Li and the 7Li(d,p)8Li transfer reaction based on a two-body Hamiltonian. We use the no-core shell model to compute the wave functions of the nuclei involved in the reaction, and describe the dynamics between targets and projectiles with the help of microscopic-cluster states in the spirit of the resonating group method. The shapes of the excitation functions for deuterons impinging on 7Li are qualitatively reproduced up to the deuteron breakup energy. The interplay between d–7Li and p–8Li particle-decay channels determines some features of the 9Be spectrum above the d+7Li threshold. Our prediction for the parity of the 17.298 MeV resonance is at odds with the experimental assignment. Deuteron stripping reactions with p-shell targets can now be computed ab initio, but calculations are very demanding. Finally, a quantitative description of the 7Li(d,p)8Li reaction will require further work to include the effect of three-nucleon forces and additional decay channels and to improve the convergence rate of our calculations.« less

  7. Transient kinetics of electron transfer reactions of flavodoxin: ionic strength dependence of semiquinone oxidation by cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic acid and computer modeling of reaction complexes.

    PubMed

    Simondsen, R P; Weber, P C; Salemme, F R; Tollin, G

    1982-12-07

    Electron transfer reactions between Clostridum pasteurianum flavodoxin semiquinone and various oxidants [horse heart cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic [horse heart cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic acid (EDTA)] have been studied as a function of ionic strength by using stopped-flow spectrophotometry. The cytochrome c reaction is complicated by the existence of two cytochrome species which react at different rates and whose relative concentrations are ionic strength dependent. Only the faster of these two reactions is considered here. At low ionic strength, complex formation between cytochrome c and flavodoxin is indicated by a leveling off of the pseudo-first-order rate constant at high cytochrome c concentration. This is not observed for either ferricyanide or ferric EDTA. For cytochrome c, the rate and association constants for complex formation were found to increase with decreasing ionic strength, consistent with negative charges on flavodoxin interacting with the positively charged cytochrome electron transfer site. Both ferricyanide and ferric EDTA are negatively charged oxidants, and the rate data respond to ionic strength changes as would be predicted for reactants of the same charge sign. These results demonstrate that electrostatic interactions involving negatively charged groups are important in orienting flavodoxin with respect to oxidants during electron transfer. We have also carried out computer modeling studies of putative complexes of flavodoxin with cytochrome c and ferricyanide, which relate their structural properties to both the observed kinetic behavior and some more general features of physiological electron transfer processes. The results of this study are consistent with the ionic strength behavior described above.

  8. Effect of micellar environment on Marcus correlation curves for photoinduced bimolecular electron transfer reactions

    SciTech Connect

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2005-07-15

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amine has been investigated in two cationic micelles, namely, cetyltrimethyl ammonium bromide (CTAB) and dodecyltrimethyl ammonium bromide (DTAB), and the results have been compared with those observed earlier in sodium dodecyl sulphate (SDS) and triton-X-100 (TX-100) micelles for similar donor-acceptor pairs. Due to a reasonably high effective concentration of the amines in the micellar Stern layer, the steady-state fluorescence results show significant static quenching. In the time-resolved (TR) measurements with subnanosecond time resolution, contribution from static quenching is avoided. Correlations of the dynamic quenching constants (k{sub q}{sup TR}), as estimated from the TR measurements, show the typical bell-shaped curves with the free-energy changes ({delta}G{sup 0}) of the ET reactions, as predicted by the Marcus outersphere ET theory. Comparing present results with those obtained earlier for similar coumarin-amine systems in SDS and TX-100 micelles, it is seen that the inversion in the present micelles occurs at an exergonicity (-{delta}G{sup 0}>{approx}1.2-1.3 eV) much higher than that observed in SDS and TX-100 micelles (-{delta}G{sup 0}>{approx}0.7 eV), which has been rationalized based on the relative propensities of the ET and solvation rates in different micelles. In CTAB and DTAB micelles, the k{sub q}{sup TR} values are lower than the solvation rates, which result in the full contribution of the solvent reorganization energy ({lambda}{sub s}) towards the activation barrier for the ET reaction. Contrary to this, in SDS and TX-100 micelles, k{sub q}{sup TR} values are either higher or comparable with the solvation rates, causing only a partial contribution of {lambda}{sub s} in these cases. Thus, Marcus inversion in present cationic micelles is inferred to be the true inversion, whereas that in the anionic SDS and neutral TX-100 micelles are understood to be the apparent

  9. Digallane with redox-active diimine ligand: dualism of electron-transfer reactions.

    PubMed

    Fedushkin, Igor L; Skatova, Alexandra A; Dodonov, Vladimir A; Chudakova, Valentina A; Bazyakina, Natalia L; Piskunov, Alexander V; Demeshko, Serhiy V; Fukin, Georgy K

    2014-05-19

    The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands. Treatment of compound 3 with B(C6F5)3 leads to removal of pyridine and restores compound 2. The reaction of compound 1 with 3,6-di-tert-butyl-ortho-benzoquinone (3,6-Q) proceeds with oxidation of all the redox-active centers in 1 (the Ga-Ga bond and two dpp-Bian dianions) and results in mononuclear catecholate (dpp-Bian)Ga(Cat) (4) (Cat = [3,6-Q](2-)). Treatment of 4 with AgBF4 gives a mixture of [(dpp-Bian)2Ag][BF4] (5) and (dpp-Bian)GaF(Cat) (6), which both consist of neutral dpp-Bian ligands. The reduction of benzylideneacetone (BA) with 1 generates the BA radical-anions, which dimerize, affording (dpp-Bian)Ga-(BA-BA)-Ga(dpp-Bian) (7). In this case the Ga-Ga bond remains unchanged. Within 10 min at 95 °C in solution compound 7 undergoes transformation to paramagnetic complex (dpp-Bian)Ga(BA-BA) (8) and metal-free compound C36H40N2 (9). The latter is a product of intramolecular addition of the C-H bond of one of the iPr groups to the C═N bond in dpp-Bian. Diamagnetic compounds 3, 5, 6, and 9 have been characterized by NMR spectroscopy, and paramagnetic complexes 2, 4, 7, and 8 by ESR spectroscopy. Molecular structures of 2-7 and 9 have been established by single-crystal X-ray analysis.

  10. Steric effect for proton, hydrogen-atom, and hydride transfer reactions with geometric isomers of NADH-model ruthenium complexes.

    PubMed

    Cohen, Brian W; Polyansky, Dmitry E; Achord, Patrick; Cabelli, Diane; Muckerman, James T; Tanaka, Koji; Thummel, Randolph P; Zong, Ruifa; Fujita, Etsuko

    2012-01-01

    Two isomers, [Ru(1)]2+ (Ru = Ru(bpy)2, bpy = 2,2'-bipyridine, 1 = 2-(pyrid-2'-yl)-1-azaacridine) and [Ru(2)]2+ (2 = 3-(pyrid-2'-yl)-4-azaacridine), are bioinspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C1 complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]2+ and [Ru(2)]2+ have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]2+ and [Ru(2HH)]2+, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2*-)] in aprotic and even protic media is slow compared to that of [Ru(1*-)]+. The net hydrogen-atom transfer between *[Ru(1)]2+ and hydroquinone (H2Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]2+ because the non-coordinated N atom is not easily available for an interaction with H2Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]2+ to [Ph3C]+ is significantly slower than that of [Ru (2HH)]2+ owing to steric congestion at the donor site.

  11. First-principles computation of electron transfer and reaction rate at a perovskite cathode for hydrogen production.

    PubMed

    Liu, C T; Chu, J F; Lin, C K; Hong, C W

    2017-03-22

    The focus of this research is on the electron transfer and its reaction rate at the perovskite cathode of a photoelectrochemical cell for hydrogen production. By employing the density functional theory (DFT), the electron density, projected density of states (PDOS), electron distribution and electron transfer path between [Fe-Fe] hydrogenase and the perovskite cathode can be obtained. Simulation results show that the perovskite cathode is better than traditional cathodes for hydrogen production. Before transmission to the [Fe-Fe] hydrogenase, electron clouds mainly aggregate at the periphery of amine molecules. Simulations also show that the key to hydrogen production at the perovskite structure lies in the organic molecules. Electrons are transferred to the hydrocarbon structural chain before reaching the Fe atoms. The Rice, Ramsperger, Kassel and Marcus (RRKM) theory was used to predict the reaction rates at different temperatures. It was found that the reaction rates are in good agreement with the experimental results. This research provides more physical insight into the electron transfer mechanism during the hydrogen production process.

  12. Energetics of charge transfer reactions in solvents of dipolar and higher order multipolar character. II. Results

    NASA Astrophysics Data System (ADS)

    Perng, Baw-Ching; Newton, Marshall D.; Raineri, Fernando O.; Friedman, Harold L.

    1996-05-01

    We apply the theories developed in the preceding paper (paper I) to calculate various energy quantities of charge transfer (CT) reactions in nine solvents that cover a wide range of polarity, and for which interaction site models (ISM's) may be found in the literature. Besides the two surrogate Hamiltonian theories developed in paper I, the renormalized site-density theory (RST) and the renormalized dielectric theory (RDT), we also investigate a simple harmonic approximation (HXA) for the diabatic free energy profiles, whose characteristic parameters are calculated taking specific advantage of the expression given by the extended reference interaction site method (XRISM) for the free energy of solvation. For each CT process we analyze (a) the solvent reorganization energy λ, (b) the shift of the absorption transition energy due to the solvatochromic effect, and (c) the solvent contribution to the free energy change ΔA. In addition, for a few selected examples, we also report the detailed diabatic free energy profiles. The calculations reported rely on solute-solvent and solvent-solvent pair correlation functions obtained with the XRISM integral equation method applied to nonpolarizable (with fixed mean partial charges) ISM representations of the solute and solvent molecules. To rectify the omission of the solvent electronic degrees of freedom, we correct the dielectric part of the solvent reorganization energy with an additive term designed to compensate for the use of fixed charge ISM models. Contact with theories in which the solvent is represented as a dielectric continuum medium (with or without spatial dispersion) and the solute as a set of charges inside spherical cavities carved out of the dielectric is made straightforwardly within the RDT theory by considering a particularly simple form of the solute-solvent RISM site-site direct correlation functions. Using simple ISM models for several solute species, including Reichardt's betaine-30 dye and a

  13. Advanced online monitoring of cell culture off-gas using proton transfer reaction mass spectrometry.

    PubMed

    Schmidberger, Timo; Gutmann, Rene; Bayer, Karl; Kronthaler, Jennifer; Huber, Robert

    2014-01-01

    Mass spectrometry has been frequently applied to monitor the O₂ and CO₂ content in the off-gas of animal cell culture fermentations. In contrast to classical mass spectrometry the proton transfer reaction mass spectrometry (PTR-MS) provides additional information of volatile organic compounds by application of a soft ionization technology. Hence, the spectra show less fragments and can more accurately assigned to particular compounds. In order to discriminate between compounds of non-metabolic and metabolic origin cell free experiments and fed-batch cultivations with a recombinant CHO cell line were conducted. As a result, in total eight volatiles showing high relevance to individual cultivation or cultivation conditions could be identified. Among the detected compounds methanethiol, with a mass-to-charge ratio of 49, qualifies as a key candidate in process monitoring due to its strong connectivity to lactate formation. Moreover, the versatile and complex data sets acquired by PTR MS provide a valuable resource for statistical modeling to predict non direct measurable parameters. Hence, partial least square regression was applied to the complete spectra of volatiles measured and important cell culture parameters such as viable cell density estimated (R²  = 0.86). As a whole, the results of this study clearly show that PTR-MS provides a powerful tool to improve bioprocess-monitoring for mammalian cell culture. Thus, specific volatiles emitted by cells and measured online by the PTR-MS and complex variables gained through statistical modeling will contribute to a deeper process understanding in the future and open promising perspectives to bioprocess control.

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

    USGS Publications Warehouse

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

    2012-01-01

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

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

    SciTech Connect

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-11-21

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

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

    SciTech Connect

    Soudackov, Alexander; Hammes-Schiffer, Sharon

    2015-11-17

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approach in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy

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

    PubMed Central

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

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

  18. Nuclear transfer reaction measurements at the ESR—for the investigation of the astrophysical 15O(α,γ)19Ne reaction

    NASA Astrophysics Data System (ADS)

    Doherty, D. T.; Woods, P. J.; Litvinov, Yu A.; Najafi, M. Ali; Bagchi, S.; Bishop, S.; Bo, M.; Brandau, C.; Davinson, T.; Dillmann, I.; Estrade, A.; Egelhof, P.; Evdokimov, A.; Gumberidze, A.; Heil, M.; Lederer, C.; Litvinov, S. A.; Lotay, G.; Kalantar-Nayestanaki, N.; Kiselev, O.; Kozhuharov, C.; Kröll, T.; Mahjour-Shafei, M.; Mutterer, M.; Nolden, F.; Petridis, N.; Popp, U.; Reifarth, R.; Rigollet, C.; Roy, S.; Steck, M.; Stöhlker, Th; Streicher, B.; Trotsenko, S.; von Schmid, M.; Yan, X. L.; Zamora, J. C.

    2015-11-01

    Astrophysical x-ray bursts are thought to be a result of thermonuclear explosions on the atmosphere of an accreting neutron star. Between these bursts, energy is thought to be generated by the hot CNO cycles. The 15O(α,γ)19Ne reaction is one reaction that allows breakout from these CNO cycles and into the rp-process to fuel outbursts. The reaction is expected to be dominated by a single 3/2+ resonance at 4.033 MeV in 19Ne, however, limited information is available on this key state. This work reports on a pioneering study of the 20Ne(p,d)19Ne reaction, performed in inverse kinematics at the experimental storage ring (ESR) as a means of accessing the astrophysically important 4.033 MeV state in 19Ne. The unique, background free, high luminosity conditions of the storage ring were utilized for this, the first transfer reaction performed at the ESR. The results of this pioneering test experiment are presented along with suggestions for future measurements at storage ring facilities.

  19. Polarization Transfer in the {sup 4}He({rvec E},E{prime}{rvec P}){sup 3}H Reaction

    SciTech Connect

    Steffen Strauch

    2003-05-01

    Polarization transfer in the {sup 4}He({rvec E},E{prime}{rvec P}){sup 3}H reaction was measured in Jefferson Lab experiment 93-049. The ratio of the polarization transfer coefficients, (P{prime}{sub x}/P{prime}{sub z}){sub He}, is on average significantly reduced as compared to the same ratio in elastic ep scattering. This is so far unaccounted for by relativistic DWIA calculations, and favors the inclusion of a predicted medium modification of the proton form factor.

  20. Discovery of the Shape Coexisting 0{sup +} State in {sup 32}Mg by a Two Neutron Transfer Reaction

    SciTech Connect

    Wimmer, K.; Kroell, T.; Kruecken, R.; Bildstein, V.; Gernhaeuser, R.; Bastin, B.; Bree, N.; Diriken, J.; Van Duppen, P.; Huyse, M.; Patronis, N.; Vermaelen, P.; Voulot, D.; Van de Walle, J.; Wenander, F.; Fraile, L. M.; Chapman, R.; Hadinia, B.; Orlandi, R.; Smith, J. F.

    2010-12-17

    The ''island of inversion'' nucleus {sup 32}Mg has been studied by a (t, p) two neutron transfer reaction in inverse kinematics at REX-ISOLDE. The shape coexistent excited 0{sup +} state in {sup 32}Mg has been identified by the characteristic angular distribution of the protons of the {Delta}L=0 transfer. The excitation energy of 1058 keV is much lower than predicted by any theoretical model. The low {gamma}-ray intensity observed for the decay of this 0{sup +} state indicates a lifetime of more than 10 ns. Deduced spectroscopic amplitudes are compared with occupation numbers from shell-model calculations.

  1. Time-resolved and steady-state fluorescence studies of excited-state proton-transfer reactions of proflavine

    NASA Astrophysics Data System (ADS)

    De Silvestri, S.; Laporta, P.

    1984-01-01

    Time-resolved and steady-state fluorescence studies of proflavine in aqueous solution are presented. The observation of a monoexponential fluorescence decay with a time constant decreasing with increasing pH and the presence of an anomalous red-shift in the fluorescence spectrum as a function of pH indicate the existence of a complex proton-transfer mechanism in the excited state. A reaction scheme is proposed and the corresponding proton-transfer rates are evaluated. An excited-state pK value of 12.85 is obtained for the equilibrium between the cationic form of proflavine and the same form dissociated at an amino group.

  2. Transition-metal-catalyzed group transfer reactions for selective C-H bond functionalization of artemisinin.

    PubMed

    Liu, Yungen; Xiao, Wenbo; Wong, Man-Kin; Che, Chi-Ming

    2007-10-11

    Three types of novel artemisinin derivatives have been synthesized through transition-metal-catalyzed intramolecular carbenoid and nitrenoid C-H bond insertion reactions. With rhodium complexes as catalysts, lactone 11 was synthesized via carbene insertion reaction at the C16 position in 90% yield; oxazolidinone 13 was synthesized via nitrene insertion reaction at the C10 position in 87% yield based on 77% conversion; and sulfamidate 14 was synthesized via nitrene insertion reaction at the C8 position in 87% yield.

  3. Spin-Transfer Measurements for the Pion Deuteron Going to Proton Proton Reaction at Energies Spanning the Delta Resonance

    NASA Astrophysics Data System (ADS)

    Feltham, Andrew G.

    1992-01-01

    We describe the first spin-transfer experiment performed for the pi{vec d} to{vec p}p reaction. Three spin-transfer parameters were measured: K_sp {LS}{'}; K _sp{SS}{'}; and K_sp{NN}{' }, each at a single angle for a number of energies spanning the Delta resonance of this system. The apparatus employed in this experiment consisted of established systems, including a dynamically polarized deuteron target and a proton polarimeter which utilized the well known proton-carbon analyzing powers. Two arms of detectors were used to minimize the background contribution by preferentially selecting those two-body final states corresponding to the pi dto pp reaction kinematics. We compare our results with the predictions of published partial wave amplitude fits pertaining to existing data on the time-reversed ppto dpi reaction, and demonstrate the inadequacy of these established fits in providing a complete description of this fundamental process. In addition, our data are compared with the predictions of two current theories. The failure of these theories to describe the fundamental features of this reaction clearly demonstrates the need for further theoretical work in this area. The data presented in this thesis are essential for the unique determination of the partial wave amplitudes characterizing the pprightleftharpoons d pi reaction. The accurate experimental determination of these amplitudes will provide an important framework for testing further theoretical developments.

  4. Evidencing an inner-sphere mechanism for NHC-Au(I)-catalyzed carbene-transfer reactions from ethyl diazoacetate

    PubMed Central

    Fructos, Manuel R; Urbano, Juan

    2015-01-01

    Summary Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA) and styrene or methanol catalyzed by the [IPrAu]+ core (IPr = 1,3-bis(diisopropylphenyl)imidazole-2-ylidene) have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol) takes place in the coordination sphere of Au(I) by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechanisms for Au(I)-catalyzed reactions. PMID:26664649

  5. Thermodynamic Integration Networks and Their Application to Charge Transfer Reactions within the AauDyPI Fungal Peroxidase.

    PubMed

    Bauß, Anna; Langenmaier, Michael; Strittmatter, Eric; Plattner, Dietmar A; Koslowski, Thorsten

    2016-06-09

    We present a computer simulation study of the thermodynamics and kinetics of charge transfer reactions within the fungal peroxidase AauDyPI from Auricularia auriculae-judae. Driving forces and reorganization energies are obtained from a thermodynamic integration scheme based upon molecular dynamics simulations. To enhance the numerical accuracy, the free energies are analyzed within a least-squares scheme of a closely knit thermodynamic network. We identify Tyr147, Tyr229, and Trp105 as oxidative agents, and find Trp377 to be a long-lived reaction intermediate. The results are compared to recent experimental findings.

  6. Neutron Transfer Reactions on Neutron-Rich N=50 and N=82 Nuclei Near the r-Process Path

    SciTech Connect

    Cizewski, J. A.; Jones, K. L.; Kozub, R. L.; Pain, S. D.; Thomas, J. S.; Arbanas, Goran; Adekola, Aderemi S; Bardayan, Daniel W; Blackmon, Jeff C; Chae, K. Y.; Chipps, K.; Dean, David Jarvis; Erikson, Luke; Gaddis, A. L.; Harlin, Christopher W; Hatarik, Robert; Howard, Joshua A; Johnson, Micah; Kapler, R.; Krolas, W.; Liang, J Felix; Livesay, Jake; Ma, Zhanwen; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D; O'Malley, Patrick; Paulauskas, Stanley V; Shapira, Dan; ShrinerJr., J. F.; Sissom, D. J.; Smith, Michael Scott; Swan, T. P.; Wilson, Gemma L

    2009-01-01

    Neutron transfer (d,p) reaction studies on the N = 50 isotones, 82Ge and 84Se, and A{approx}130 nuclei, 130,132Sn and 134Te, have been measured. Direct neutron capture cross sections for 82Ge and 84Se (n,?) have been calculated and are combined with Hauser-Feshbach expectations to estimate total (n,?) cross sections. The A{approx}130 studies used an early implementation of the ORRUBA array of position-sensitive silicon strip detectors for reaction proton measurements. Preliminary excitation energy and angular distribution results from the A{approx}130 measurements are reported.

  7. Nuclear spectroscopy study of the isotopes populated via multinucleon transfer in the 90Zr + 208Pb reaction

    SciTech Connect

    Ur, C. A.; Corradi, L.; Stefanini, A. M.; Behera, B. R.; Fioretto, E.; Gadea, A.; Latina, A.; Szilner, S.; Beghini, S.; Farnea, E.; Montagnoli, G.; Scarlassara, F.; Haas, F.; Pollarolo, G.

    2006-08-14

    The present work takes advantage of the multinucleon transfer mechanism between heavy reaction partners to study the population pattern of excited nuclear states in near spherical Zirconium isotopes following the 90Zr + 208Pb reaction at an energy closed to the Coulomb barrier. Both the projectile and the target are well known closed shell nuclei offering an optimum situation for clean experimental and theoretical conditions. Total kinetic energy loss (TKEL) distributions were compared with calculations performed with the GRAZING code. The ability to use the TKEL as a selection tool for the states at different excitation energies was shown.

  8. Non-covalent π-π stacking interactions turn off non-adiabatic effects in proton-coupled electron transfer reactions.

    PubMed

    Muñoz-Rugeles, Leonardo; Galano, Annia; Raúl Alvarez-Idaboy, J

    2017-03-08

    π-π stacking interactions do not necessarily change the mechanism involved in the H transfer reaction between phenol and phenoxyl radicals. We propose that, in such cases, the e(-) is transferred between the π delocalized moieties, while the H(+) is transferred between the donor and acceptor atoms.

  9. Novel concept microarray enabling PCR and multistep reactions through pipette-free aperture-to-aperture parallel transfer

    PubMed Central

    2010-01-01

    Background The microarray has contributed to developing the omic analysis. However, as it depends basically on the surface reaction, it is hard to perform bulk reactions and sequential multistep reactions. On the other hand, the popular microplate technology, which has a great merit of being able to perform parallel multistep reactions, has come to its limit in increasing the number of wells (currently, up to 9600) and reducing the volume to deal with due to the difficulty in operations. Results Here, we report a novel microarray technology which enables us to explore advanced applications, termed microarray-with-manageable volumes (MMV). The technical essence is in the pipette-free direct parallel transfer from well to well performed by centrifugation, evading the evaporation and adsorption-losses during handling. By developing the MMV plate, accompanying devices and techniques, generation of multiple conditions (256 kinds) and performance of parallel multistep reactions, including PCR and in vitro translation reactions, have been made possible. These were demonstrated by applying the MMV technology to searching lysozyme-crystallizing conditions and selecting peptides aimed for Aβ-binding or cathepsin E-inhibition. Conclusions With the introduction of a novel concept microarray (MMV) technology, parallel and multistep reactions in sub-μL scale have become possible. PMID:20923572

  10. Proton-coupled electron transfer in tyrosine and a β-hairpin maquette: reaction dynamics on the picosecond time scale.

    PubMed

    Pagba, Cynthia V; Chi, San-Hui; Perry, Joseph; Barry, Bridgette A

    2015-02-12

    In proteins, proton-coupled electron transfer (PCET) can involve the transient oxidation and reduction of the aromatic amino acid tyrosine. Due to the short life time of tyrosyl radical intermediates, transient absorption spectroscopy provides an important tool in deciphering electron-transfer mechanisms. In this report, the photoionization of solution tyrosine and tyrosinate was investigated using transient, picosecond absorption spectroscopy. The results were compared to data acquired from a tyrosine-containing β-hairpin peptide. This maquette, peptide A, is an 18-mer that exhibits π-π interaction between tyrosine (Y5) and histidine (H14). Y5 and H14 carry out an orthogonal PCET reaction when Y5 is oxidized in the mid-pH range. Photolysis of all samples (280 nm, instrument response: 360 fs) generated a solvated electron signal within 3 ps. A signal from the S1 state and a 410 nm signal from the neutral tyrosyl radical were also formed in 3 ps. Fits to S1 and tyrosyl radical decay profiles revealed biphasic kinetics with time constants of 10-50 and 400-1300 ps. The PCET reaction at pH 9 was associated with a significant decrease in the rate of tyrosyl radical and S1 decay compared to electron transfer (ET) alone (pH 11). This pH dependence was observed both in solution and peptide samples. The pH 9 reaction may occur with a sequential electron-transfer, proton-transfer (ETPT) mechanism. Alternatively, the pH 9 reaction may occur by coupled proton and electron transfer (CPET). CPET would be associated with a reorganization energy larger than that of the pH 11 reaction. Significantly, the decay kinetics of S1 and the tyrosyl radical were accelerated in peptide A compared to solution samples at both pH values. These data suggest either an increase in electronic coupling or a specific, sequence-dependent interaction, which facilitates ET and PCET in the β hairpin.

  11. Probing ‘Spin-Forbidden’ Oxygen Atom Transfer: Gas-Phase Reactions of Chromium-Porphyrin Complexes

    PubMed Central

    Fornarini, Simonetta; Lanucara, Francesco; Warren, Jeffrey J.

    2010-01-01

    Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a ‘two-state’ reactivity model has been extensively applied especially in iron-porphyrin systems. Herein we explore the gas phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)CrIII]+ (1) and [(TPFPP)CrVO]+ (2). These are an attractive system to examine the effects of spin state change on oxygen atom transfer because the d1 CrV species are doublets while the CrIII complexes have quartet ground states with high-lying doublet excited states. In the gas phase, [(TPFPP)CrIII]+ forms adducts with a variety of neutral donors but O-atom transfer is only observed for NO2. Pyridine N-oxide adducts of 1 do yield 2 upon collision induced dissociation (CID), but the ethylene oxide, DMSO, and TEMPO analogs do not. [(TPFPP)CrVO]+ is shown by its reactivity and by CID experiments to be a terminal metal-oxo with a single vacant coordination site. It also displays limited reaction chemistry, being deoxygenated only by the very potent reductant P(OMe)3. In general, [(TPFPP)CrVO]+ species are much less reactive than the Fe and Mn analogs. Thermochemical analysis of the reactions points towards the involvement of spin issues in the lower observed reactivity of the chromium complexes. PMID:20218631

  12. Long-term mass transfer and mixing-controlled reactions of a DNAPL plume from persistent residuals

    NASA Astrophysics Data System (ADS)

    Liu, Yuan; Illangasekare, Tissa H.; Kitanidis, Peter K.

    2014-02-01

    Understanding and being able to predict the long-term behavior of DNAPL (i.e., PCE and TCE) residuals after active remediation has ceased have become increasingly important as attention at many sites turns from aggressive remediation to monitored natural attenuation and long-term stewardship. However, plume behavior due to mass loading and reactions during these later phases is less studied as they involve large spatial and temporal scales. We apply both theoretical analysis and pore-scale simulations to investigate mass transfer from DNAPL residuals and subsequent reactions within the generated plume, and, in particular, to show the differences between early- and late-time behaviors of the plume. In the zone of entry of the DNAPL entrapment zone where the concentration boundary layer in the flowing groundwater has not fully developed, the pore-scale simulations confirm the past findings based on laboratory studies that the mass transfer increases as a power-law function of the Peclét number, and is enhanced due to reactions in the plume. Away from the entry zone and further down gradient, the long-term reactions are limited by the available additive and mixing in the porous medium, thereby behave considerably differently from the entry zone. For the reaction between the contaminant and an additive with intrinsic second-order bimolecular kinetics, the late-time reaction demonstrates a first-order decay macroscopically with respect to the mass of the limiting additive, not with respect to that of the contaminant. The late-time decay rate only depends on the intrinsic reaction rate and the solubility of the entrapped DNAPL. At the intermediate time, the additive decays exponentially with the square of time (t2), instead of time (t). Moreover, the intermediate decay rate also depends on the initial conditions, the spatial distribution of DNAPL residuals, and the effective dispersion coefficient.

  13. Ground and excited state intramolecular proton transfer controlled intramolecular charge separation and recombination: A new type of charge and proton transfer reaction

    NASA Astrophysics Data System (ADS)

    Nie, Daobo; Bian, Zuqiang; Yu, Anchi; Chen, Zhuqi; Liu, Zhiwei; Huang, Chunhui

    2008-06-01

    A novel β-diketone 1-(4-(9-carbazol)phenyl)-3-phenyl-1,3-propanedione (CDBM) has been synthesized. When excited at 380 nm, this molecule shows single fluorescence. However, when excited at 338 nm, it shows dual fluorescence. A Al 3+ complex Al(CDBM) 3 has been synthesized to investigate the dual fluorescence of CDBM. It is found that this complex shows single fluorescence under all excitation. This result indicated that the dual fluorescence of CDBM may relate to the intramolecular proton transfer reaction. Based on the experimental and theoretical studies of CDBM, N-(4-cyanophenyl)carbazole (CBN) and Al(CDBM) 3, a "ground and excited state intramolecular proton transfer controlled intramolecular charge separation and recombination" mechanism is proposed to explain the unusual excitation-dependent dual fluorescence of CDBM.

  14. A novel salt of antidiabetic drug metformin resulting from a proton transfer reaction: Synthesis, characterization, crystal structure and solution studies

    NASA Astrophysics Data System (ADS)

    Ghasemi, Fatemeh; Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Refahi, Masoud; García-Granda, Santiago; Mendoza-Meroño, Rafael

    2017-03-01

    Reaction between N,N-dimethylebiguanidine, Met = Metformin, and 4-hydroxy-2,6-pyridinedicarboxylic acid, HO-dipicH2, results in the formation of a novel proton transfer compound, [MetH2][HO-dipicH]2·H2O, 1. The characterization was performed using FTIR, UV-Vis, 1H and 13C NMR spectroscopy and X-ray crystallography. The crystal system is triclinic with space group P 1 bar and two molecules per unit cell. The protonation constants of O-dipic and Met, in all of probability protonated forms, and the equilibrium constants for the O-dipic-Met proton transfer system were investigated by the potentiometric pH titration method using the Hyperquad2008 program. The stoichiometry of the proton transfer species in solution were in agreement with the solid state result.

  15. Dynamic protein conformations preferentially drive energy transfer along the active chain of the photosystem II reaction centre

    NASA Astrophysics Data System (ADS)

    Zhang, Lu; Silva, Daniel-Adriano; Zhang, Houdao; Yue, Alexander; Yan, Yijing; Huang, Xuhui

    2014-06-01

    One longstanding puzzle concerning photosystem II, a core component of photosynthesis, is that only one of the two symmetric branches in its reaction centre is active in electron transfer. To investigate the effect of the photosystem II environment on the preferential selection of the energy transfer pathway (a prerequisite for electron transfer), we have constructed an exciton model via extensive molecular dynamics simulations and quantum mechanics/molecular mechanics calculations based on a recent X-ray structure. Our results suggest that it is essential to take into account an ensemble of protein conformations to accurately compute the site energies. We identify the cofactor CLA606 of active chain as the most probable site for the energy excitation. We further pinpoint a number of charged protein residues that collectively lower the CLA606 site energy. Our work provides insights into the understanding of molecular mechanisms of the core machinery of the green-plant photosynthesis.

  16. Dynamic protein conformations preferentially drive energy transfer along the active chain of the photosystem II reaction centre.

    PubMed

    Zhang, Lu; Silva, Daniel-Adriano; Zhang, Houdao; Yue, Alexander; Yan, YiJing; Huang, Xuhui

    2014-06-23

    One longstanding puzzle concerning photosystem II, a core component of photosynthesis, is that only one of the two symmetric branches in its reaction centre is active in electron transfer. To investigate the effect of the photosystem II environment on the preferential selection of the energy transfer pathway (a prerequisite for electron transfer), we have constructed an exciton model via extensive molecular dynamics simulations and quantum mechanics/molecular mechanics calculations based on a recent X-ray structure. Our results suggest that it is essential to take into account an ensemble of protein conformations to accurately compute the site energies. We identify the cofactor CLA606 of active chain as the most probable site for the energy excitation. We further pinpoint a number of charged protein residues that collectively lower the CLA606 site energy. Our work provides insights into the understanding of molecular mechanisms of the core machinery of the green-plant photosynthesis.

  17. Dynamic protein conformations preferentially drive energy transfer along the active chain of the photosystem II reaction centre

    PubMed Central

    Zhang, Lu; Silva, Daniel-Adriano; Zhang, Houdao; Yue, Alexander; Yan, YiJing; Huang, Xuhui

    2014-01-01

    One longstanding puzzle concerning photosystem II, a core component of photosynthesis, is that only one of the two symmetric branches in its reaction centre is active in electron transfer. To investigate the effect of the photosystem II environment on the preferential selection of the energy transfer pathway (a prerequisite for electron transfer), we have constructed an exciton model via extensive molecular dynamics simulations and quantum mechanics/molecular mechanics calculations based on a recent X-ray structure. Our results suggest that it is essential to take into account an ensemble of protein conformations to accurately compute the site energies. We identify the cofactor CLA606 of active chain as the most probable site for the energy excitation. We further pinpoint a number of charged protein residues that collectively lower the CLA606 site energy. Our work provides insights into the understanding of molecular mechanisms of the core machinery of the green-plant photosynthesis. PMID:24954746

  18. Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O + 232Th reaction

    NASA Astrophysics Data System (ADS)

    Léguillon, R.; Nishio, K.; Hirose, K.; Makii, H.; Nishinaka, I.; Orlandi, R.; Tsukada, K.; Smallcombe, J.; Chiba, S.; Aritomo, Y.; Ohtsuki, T.; Tatsuzawa, R.; Takaki, N.; Tamura, N.; Goto, S.; Tsekhanovich, I.; Petrache, C. M.; Andreyev, A. N.

    2016-10-01

    It is shown that the multinucleon transfer reactions is a powerful tool to study fission of exotic neutron-rich actinide nuclei, which cannot be accessed by particle-capture or heavy-ion fusion reactions. In this work, multinucleon transfer channels of the 18O + 232Th reaction are used to study fission of fourteen nuclei 231,232,233,234Th, 232,233,234,235,236Pa, and 234,235,236,237,238U. Identification of fissioning nuclei and of their excitation energy is performed on an event-by-event basis, through the measurement of outgoing ejectile particle in coincidence with fission fragments. Fission fragment mass distributions are measured for each transfer channel, in selected bins of excitation energy. In particular, the mass distributions of 231,234Th and 234,235,236Pa are measured for the first time. Predominantly asymmetric fission is observed at low excitation energies for all studied cases, with a gradual increase of the symmetric mode towards higher excitation energy. The experimental distributions are found to be in general agreement with predictions of the fluctuation-dissipation model.

  19. Lung cancer detection by proton transfer reaction mass-spectrometric analysis of human breath gas

    NASA Astrophysics Data System (ADS)

    Wehinger, Andreas; Schmid, Alex; Mechtcheriakov, Sergei; Ledochowski, Maximilian; Grabmer, Christoph; Gastl, Guenther A.; Amann, Anton

    2007-08-01

    Background Determination of the diagnostic usefulness of proton transfer reaction mass spectrometry (PTR-MS) for detecting primary lung cancer through analysis of volatile organic compounds (VOCs) in exhaled human breath was demonstrated in this investigation. Unlike, for example, gas-chromatographic analyses, PTR-MS can be used without time-consuming preconcentration of the gas samples.Methods By means of PTR-MS, exhaled breath samples from primary lung cancer patients (n = 17) were analyzed and compared with both an overall control collective (controls total, n = 170) and three sub-collectives: hospital personnel (controls hospital, n = 35), age-matched persons (controls age, n = 25), and smokers (controls s, n = 60), respectively.Results Among the VOCs present at reasonably high concentrations, the ones leading to the product ion at m/z = 31 (VOC-31, tentatively protonated formaldehyde) and m/z = 43 (VOC-43, tentatively a fragment of protonated iso-propanol), were found at significantly higher concentrations in the breath gas of the primary lung cancer patients as compared to the healthy controls at the following median concentrations (with interquartile distance, iqr): For VOC-31 the median concentrations were 7.0 ppb (iqr, 15.5 ppb) versus 3.0 ppb (iqr, 1.9 ppb) with P < 10-4. For VOC-43 the median concentrations were 244.1 ppb (iqr, 236.2 ppb) versus 94.1 ppb (iqr, 55.2 ppb) with P < 10-6. The discriminative power between the two collectives was further assessed by ROC-curves obtained upon variation of the chosen threshold concentration and by Fisher's Quadratic Discriminant Method.Conclusions Within the limits of pilot study, VOC-31 and -43 were found to best discriminate between exhaled breath of primary lung cancer cases and healthy controls. Simple and time-saving breath gas analysis by PTR-MS makes this method attractive for a larger clinical evaluation. It may become a new valuable tool for diagnosing primary lung cancer.

  20. Using intramolecular energy transfer to transform non-photoactive, visible-light-absorbing chromophores into sensitizers for photoredox reactions.

    PubMed

    Gu, Jing; Chen, Jin; Schmehl, Russell H

    2010-06-02

    This work discusses the synthesis, photophysical behavior, and photoinduced electron-transfer reactivity of multichromophoric molecules having a visible-light-absorbing MLCT component coupled to a ligand with a localized excited state of the same spin multiplicity that serves to lengthen the excited-state lifetime of the complex significantly. The appropriate ligands were prepared by Wittig coupling of a bipyridine derivative with pyrenecarboxaldehyde. The modified ligand, a pyrene-vinyl-bipyridyl ensemble (pyrv-bpy), was then reacted with RuCl(3) to yield [(pyrv-bpy)(2)RuCl(2)]. The complex has MLCT absorption out to 800 nm, and excitation results in the formation of a ligand-localized excited state with a lifetime long enough to undergo bimolecular electron-transfer reactions. The pyrenylvinyl "localized" excited state of the complex reacts via photoinduced electron transfer with a variety of viologen and diquat electron acceptors. The remarkable aspect of the electron-transfer process is that whereas the excited state can be considered to be ligand-localized the photoredox reaction almost certainly involves the direct formation of the one-electron-oxidized metal center.

  1. Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

    PubMed

    Mukherjee, Tamal; Ito, Naoki; Gould, Ian R

    2011-03-17

    The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

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

    SciTech Connect

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

    2014-05-07

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

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

    PubMed

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

    2014-05-07

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

  4. N-Heterocyclic olefins as ancillary ligands in catalysis: a study of their behaviour in transfer hydrogenation reactions.

    PubMed

    Iturmendi, Amaia; García, Nestor; Jaseer, E A; Munárriz, Julen; Sanz Miguel, Pablo J; Polo, Victor; Iglesias, Manuel; Oro, Luis A

    2016-08-09

    The Ir(i) complexes [Ir(cod)(κP,C,P'-NHO(PPh2))]PF6 and [IrCl(cod)(κC-NHO(OMe))] (cod = 1,5-cyclooctadiene, NHO(PPh2) = 1,3-bis(2-(diphenylphosphanyl)ethyl)-2-methyleneimidazoline) and NHO(OMe) = 1,3-bis(2-(methoxyethyl)-2-methyleneimidazoline), both featuring an N-heterocyclic olefin ligand (NHO), have been tested in the transfer hydrogenation reaction; this representing the first example of the use of NHOs as ancillary ligands in catalysis. The pre-catalyst [Ir(cod)(κP,C,P'-NHO(PPh2))]PF6 has shown excellent activities in the transfer hydrogenation of aldehydes, ketones and imines using (i)PrOH as a hydrogen source, while [IrCl(cod)(κC-NHO(OMe))] decomposes throughout the reaction to give low yields of the hydrogenated product. Addition of one or two equivalents of a phosphine ligand to the latter avoids catalyst decomposition and significantly improves the reaction yields. The reaction mechanism has been investigated by means of stoichiometric studies and theoretical calculations. The formation of the active species ([Ir(κP,C,P'-NHO(PPh2))((i)PrO)]) has been proposed to occur via isopropoxide coordination and concomitant COD dissociation. Moreover, throughout the catalytic cycle the NHO moiety behaves as a hemilabile ligand, thus allowing the catalyst to adopt stable square planar geometries in the transition states, which reduces the energetic barrier of the process.

  5. TDDFT study of the polarity controlled ion-pair separation in an excited-state proton transfer reaction.

    PubMed

    Liu, Yu-Hui; Mehata, Mohan Singh; Lan, Sheng-Cheng

    2014-07-15

    6-Hydroxyquinoline (6HQ) is an ideal photoacid system for exploring excited-state proton transfer (ESPT) reactions. We have previously (Mahata et al. (2002)) shown that the ESPT reaction between 6HQ and trimethylamine (TMA) leads to an "unusual" emission in the 440-450 nm range, containing two decay components (∼5 ns and ∼12 ns). The observed results suggest the presence of a contact ion-pair and a solvent separated ion-pair. In this work, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been employed to study the nature of the contact ion-pair formed between 6HQ and TMA and to determine why the decay component ∼12 ns is absent in a non-polar solvent. Calculations of the hydrogen-bonded complexes formed between 6HQ and TMA and its ESPT reaction product, namely 6HQ-TMA and 6HQ-TMA-PT, respectively, have been carried out, both in the electronic ground and excited states. Moreover, by using the CPCM model, different dielectric constants have been introduced into the calculations. On increasing the dielectric constant, the hydrogen bond in 6HQ-TMA-PT becomes weaker and the hydrogen bond length becomes larger; this effectively facilitates the proton transfer reaction and formation of separated ion-pair. Thus, the separation and diffusion of the contact ion-pair can be controlled by changing the polarity of the surroundings.

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

    SciTech Connect

    Dixon, David Adams

    2013-07-02

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

  7. Skin reactions triggered by the use of cosmetic products in nonspecific lipid transfer protein-sensitive patients.

    PubMed

    Giani, M; Pirotta, L; Locanto, M; Cadoni, S; Puddu, P; De Pità, O

    2010-01-01

    Nonspecific lipid transfer proteins (nsLTPs) are members of the prolamine superfamily and they are found in pollen and food, as well as in latex. Due to the strong stability both against pepsin digestion and thermal denaturation, sensitisation towards these proteins is often associated with severe systemic reactions (angioedema, urticaria, asthma, anaphylaxis, etc.) following the ingestion of both raw or fresh food and cooked or preserved food. Many studies have shown reactivity towards nsLTPs both via inhalation and orally and in this study we present two cases of nsLTPs-sensitive patients who manifested the immediate onset of skin reactions following the use of cosmetic products containing these proteins. Thus, in order to prevent immediate reactions linked to their use, it is necessary to recommend nsLTPssensitive patients to avoid the topical use of products containing these proteins (and obviously the ingestion of foods containing these proteins).

  8. DNA‐Accelerated Catalysis of Carbene‐Transfer Reactions by a DNA/Cationic Iron Porphyrin Hybrid

    PubMed Central

    Rioz‐Martínez, Ana; Oelerich, Jens; Ségaud, Nathalie

    2016-01-01

    Abstract A novel DNA‐based hybrid catalyst comprised of salmon testes DNA and an iron(III) complex of a cationic meso‐tetrakis(N‐alkylpyridyl)porphyrin was developed. When the N‐methyl substituents were placed at the ortho position with respect to the porphyrin ring, high reactivity in catalytic carbene‐transfer reactions was observed under mild conditions, as demonstrated in the catalytic enantioselective cyclopropanation of styrene derivatives with ethyl diazoacetate (EDA) as the carbene precursor. A remarkable feature of this catalytic system is the large DNA‐induced rate acceleration observed in this reaction and the related dimerization of EDA. It is proposed that high effective molarity of all components of the reaction in or near the DNA is one of the key contributors to this unique reactivity. This study demonstrates that the concept of DNA‐based asymmetric catalysis can be expanded into the realm of organometallic chemistry. PMID:27730731

  9. The {sup 9}Be({sup 8}Li,{sup 9}Be){sup 8}Li elastic-transfer reaction

    SciTech Connect

    Camargo, O.; Guimaraes, V.; Lichtenthaeler, R.; Scarduelli, V.; Kolata, J. J.; Bertulani, C. A.; Amro, H.; Becchetti, F. D.; Jiang Hao; Aguilera, E. F.; Lizcano, D.; Martinez-Quiroz, E.; Garcia, H.

    2008-09-15

    Angular distributions for the {sup 9}Be({sup 8}Li,{sup 9}Be){sup 8}Li elastic-transfer reaction have been measured with a 27-MeV {sup 8}Li radioactive nuclear beam. Spectroscopic factors for the <{sup 9}Be|{sup 8}Li+p> bound system were obtained from the comparison between the experimental differential cross sections and finite-range distorted-wave Born approximation calculations made with the code FRESCO. The spectroscopic factors so obtained are compared with shell-model calculations and other experimental values. Using the present value for the spectroscopic factors, cross sections and reaction rates for the {sup 8}Li(p,{gamma}){sup 9}Be direct proton-capture reaction of astrophysical interest were calculated in the framework of the potential model.

  10. Use of Neutron Transfer Reactions to Indirectly Determine Neutron Capture Cross Sections on Neutron-Rich Nuclei

    SciTech Connect

    McCleskey, M.; Mukhamedzhanov, A. M.; Tribble, R. E.; Simmons, E.; Spiridon, A.; Banu, A.; Roeder, B.; Goldberg, V.; Trache, L.; Chen, X. F.; Lui, Y.-W.

    2010-03-01

    {sup 14}C(n,gamma){sup 15}C is being used as a test case in the development of an indirect method to determine neutron capture cross sections on neutron-rich unstable nuclei at astrophysical energies. Our approach makes use of two reactions: one peripheral used to find the asymptotic normalization coefficient (ANC) and a second non-peripheral reaction to determine the spectroscopic factor. The ANC for {sup 15}C has been determined using a HI neutron transfer reaction with a 12 MeV/nucleon {sup 14}C beam on a {sup 13}C target. The spectroscopic factor will be determined using {sup 14}C(d,p) in forward kinematics with an incident deuteron energy of 60 MeV. Both experiments were performed using the MDM high-resolution spectrometer at Texas A and M University.

  11. Synthetic scope and mechanistic studies of Ru(OH)x/Al2O3-catalyzed heterogeneous hydrogen-transfer reactions.

    PubMed

    Yamaguchi, Kazuya; Koike, Takeshi; Kotani, Miyuki; Matsushita, Mitsunori; Shinachi, Satoshi; Mizuno, Noritaka

    2005-11-04

    Three kinds of hydrogen-transfer reactions, namely racemization of chiral secondary alcohols, reduction of carbonyl compounds to alcohols using 2-propanol as a hydrogen donor, and isomerization of allylic alcohols to saturated ketones, are efficiently promoted by the easily prepared and inexpensive supported ruthenium catalyst Ru(OH)x/Al2O3. A wide variety of substrates, such as aromatic, aliphatic, and heterocyclic alcohols or carbonyl compounds, can be converted into the desired products, under anaerobic conditions, in moderate to excellent yields and without the need for additives such as bases. A larger scale, solvent-free reaction is also demonstrated: the isomerization of 1-octen-3-ol with a substrate/catalyst ratio of 20,000/1 shows a very high turnover frequency (TOF) of 18,400 h(-1), with a turnover number (TON) that reaches 17,200. The catalysis for these reactions is intrinsically heterogeneous in nature, and the Ru(OH)x/Al2O3 recovered after the reactions can be reused without appreciable loss of catalytic performance. The reaction mechanism of the present Ru(OH)x/Al2O3-catalyzed hydrogen-transfer reactions were examined with monodeuterated substrates. After the racemization of (S)-1-deuterio-1-phenylethanol in the presence of acetophenone was complete, the deuterium content at the alpha-position of the corresponding racemic alcohol was 91%, whereas no deuterium was incorporated into the alpha-position during the racemization of (S)-1-phenylethanol-OD. These results show that direct carbon-to-carbon hydrogen transfer occurs via a metal monohydride for the racemization of chiral secondary alcohols and reduction of carbonyl compounds to alcohols. For the isomerization, the alpha-deuterium of 3-deuterio-1-octen-3-ol was selectively relocated at the beta-position of the corresponding ketones (99% D at the beta-position), suggesting the involvement of a 1,4-addition of ruthenium monohydride species to the alpha,beta-unsaturated ketone intermediate. The

  12. Three-carbon Dowd-Beckwith ring expansion reaction versus intramolecular 1,5-hydrogen transfer reaction: a theoretical study.

    PubMed

    Ardura, Diego; Sordo, Tomás L

    2005-11-11

    [Reaction: see text]. The evolution of the primary radicals formed by addition of AIBN/HSnBu3 to methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate, methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate, and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate in benzene has been theoretically investigated by ROMP2/6-311++G(2d,2p)//UB3LYP/6-31G(d,p) calculations taking into account the effect of solvent through a PCM-UAHF model. According to the theoretical results, for methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is the cyclooctane derivative from the three-carbon ring expansion, whereas for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is that corresponding to the 1,5-H transposition in agreement with the experimental findings. This different behavior is a consequence of several factors determining the relative energy barriers. The methyl substituent destabilizes the ring expansion process for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate because of steric repulsion but favors it in the case of the beta-trans-substituted substrate because it makes possible the evolution of the system along more favorable conformations. The methyl group also favors the 1,5-H transposition rendering the transposed product a tertiary radical. The second stage of the ring expansion process is stabilized by resonance.

  13. Energy, Electron Transfer and Photocatalytic Reactions of Visible Light Absorbing Transition Metal Complexes

    SciTech Connect

    Schmehl, Russell H.

    2016-03-02

    This is the final technical report for a project carried out at Tulane University of New Orleans that describes the development of light induced (solar) reactions geared toward decomposing water into its component elements : hydrogen and oxygen. Much of the work involved optimizing systems for absorbing visible light and undergoing light promoted reactions to generate very strong reducing agents that are capable of reacting with water to produce hydrogen. Additional portions of the research were collaborative efforts to put the strong reducing agents to work in reaction with hydrogen generation catalysts prepared elsewhere. Time resolved laser spectroscopic methods were used to evaluate the light induced reactions and characterize very reactive intermediate substances formed during the reactions.

  14. An Uncharged Amine in the Transition State of the Ribosomal Peptidyl Transfer Reaction

    PubMed Central

    Kingery, David A.; Pfund, Emmanuel; Voorhees, Rebecca M.; Okuda, Kensuke; Wohlgemuth, Ingo; Kitchen, David E.; Rodnina, Marina V.; Strobel, Scott A.

    2010-01-01

    SUMMARY The ribosome has an active site comprised of RNA that catalyzes peptide bond formation. To understand how RNA promotes this reaction requires a detailed understanding of the chemical transition state. Here, we report the Brønsted coefficient of the α-amino nucleophile (βnuc) using a series of puromycin derivatives. Both 50S subunit and 70S ribosome catalyzed reactions displayed linear free-energy relationships with slopes close to zero under conditions where chemistry is rate limiting. These results indicate that at the transition state the nucleophile is neutral in the ribosome catalyzed reaction, in contrast to the substantial positive charge reported for typical uncatalyzed aminolysis reactions. This suggests that the ribosomal transition state involves deprotonation to a degree commensurate with nitrogen-carbon bond formation. Such a transition state is significantly different from that of uncatalyzed aminolysis reactions in solution. PMID:18482701

  15. Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

    PubMed

    Markle, Todd F; Tenderholt, Adam L; Mayer, James M

    2012-01-12

    The oxidation of three phenols, which contain an intramolecular hydrogen bond to a pendent pyridine or amine group, has been shown, in a previous experimental study, to undergo concerted proton-electron transfer (CPET). In this reaction, the electron is transferred to an outer-sphere oxidant, and the proton is transferred from the oxygen to nitrogen atom. In the present study, this reaction is studied computationally using a version of Hammes-Schiffer's multistate continuum theory where CPET is formulated as a transmission frequency between neutral and cation vibrational-electronic states. The neutral and cation proton vibrational wave functions are computed from one-dimensional potential energy surfaces (PESs) for the transferring proton in a fixed heavy atom framework. The overlap integrals for these neutral/cation wave functions, considering several initial (i.e., neutral) and final (i.e., cation) vibrational states, are used to evaluate the relative rates of oxidation. The analysis is extended to heavy atom configurations with various proton donor-acceptor (i.e., O-N) distances to assess the importance of heavy atom "gating". Such changes in d(ON) dramatically affect the nature of the proton PESs and wave functions. Surprisingly, the most reactive configurations have similar donor-acceptor distances despite the large (~0.2 Å) differences in the optimized structures. These theoretical results qualitatively reproduce the experimental faster reactivity of the reaction of the pyridyl derivative 1 versus the CH(2)-pyridyl 2, but the computed factor of 5 is smaller than the experimental 10(2). The amine derivative is calculated to react similarly to 1, which does not agree with the experiments, likely due to some of the simplifying assumptions made in applying the theory. The computed kinetic isotope effects (KIEs) and their temperature dependence are in agreement with experimental results.

  16. Does the pressure dependence of kinetic isotope effects report usefully on dynamics in enzyme H-transfer reactions?

    PubMed

    Hoeven, Robin; Heyes, Derren J; Hay, Sam; Scrutton, Nigel S

    2015-08-01

    The temperature dependence of kinetic isotope effects (KIEs) has emerged as the main experimental probe of enzymatic H-transfer by quantum tunnelling. Implicit in the interpretation is a presumed role for dynamic coupling of H-transfer chemistry to the protein environment, the so-called 'promoting motions/vibrations hypothesis'. This idea remains contentious, and others have questioned the importance and/or existence of promoting motions/vibrations. New experimental methods of addressing this problem are emerging, including use of mass-modulated enzymes and time-resolved spectroscopy. The pressure dependence of KIEs has been considered as a potential probe of quantum tunnelling reactions, because semi-classical KIEs, which are defined by differences in zero-point vibrational energy, are relatively insensitive to kbar changes in pressure. Reported combined pressure and temperature (p-T) dependence studies of H-transfer reactions are, however, limited. Here, we extend and review the available p-T studies that have utilized well-defined experimental systems in which quantum mechanical tunnelling is established. These include flavoproteins, quinoproteins, light-activated enzymes and chemical model systems. We show that there is no clear general trend between the p-T dependencies of the KIEs in these systems. Given the complex nature of p-T studies, we conclude that computational simulations using determined (e.g. X-ray) structures are also needed alongside experimental measurements of reaction rates/KIEs to guide the interpretation of p-T effects. In providing new insight into H-transfer/environmental coupling, combined approaches that unite both atomistic understanding with experimental rate measurements will require careful evaluation on a case-by-case basis. Although individually informative, we conclude that p-T studies do not provide the more generalized insight that has come from studies of the temperature dependence of KIEs.

  17. Intramolecular energy transfer reactions in polymetallic complexes.. Progress report, 1991--1992

    SciTech Connect

    Petersen, J.

    1992-12-01

    (1) Excited-state energy transfer: The major effort was an attempt to sensitize the photoelimination of H{sub 2} from a bimetallic, metal-dihydride complex. These complexes have involved Fe, Ru, and Co complexes. (2) Excited-state electron transfer (charge separation): A series of diad and triad complexes were prepared in order to sustain charge separation in an artificial photosynthetic system.

  18. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    PubMed

    Adamovich, Igor V; Li, Ting; Lempert, Walter R

    2015-08-13

    This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

  19. Combined Quantum Mechanical and Molecular Mechanics Studies of the Electron-Transfer Reactions Involving Carbon Tetrachloride in Solution

    SciTech Connect

    Valiev, Marat; Bylaska, Eric J.; Dupuis, Michel; Tratnyek, Paul G.

    2008-03-27

    The reductive dechlorination of carbon tetrachloride, CC₄, was investigated using combined high level quantum mechanical and molecular mechanics (QM/MM) approach. The first electron transfer process was assumed to proceed by a concerted electron transfer-bond breaking mechanism, and reaction barriers for the first electron reduction were estimated by using the crossing point of the free energy profiles of CCl₃-Cl and CCl₃-Cl•- as a function of the CCl₃-Cl distance. The results of these calculations showed that the activation barriers for this reaction are reachable under a wide range of reduction potentials. In the gas-phase, the barrier to reduction varied from 0.8 kcal/mol for reducing agent with a -5 kcal/mol work function to 24.7 kcal/mol for a reducing agent with a 40 kcal/mol work function at the CCSD(T)/aug-cc-pVDZ level. In the aqueous phase, QM/MM calculations at the CCSD(T)/aug-cc-pVDZ level predicted that the barrier to reduction varied from 0.7 kcal/mol to 35.2 kcal/mol for -2.32 V and 0.93 V reduction potentials respectively. COSMO continuum solvation calculations were also performed for comparison. For strong reducing agents (EH < -1.5V) very little difference was seen between the QM/MM and COSMO activation barriers. For weak reducing agents (EH > 0V) the activation barriers differed by as much as 6 kcal/mol between the QM/MM and COSMO calculations. These results demonstrate that ab initio electronic structure methods coupled with explicit molecular mechanics representation of the aqueous environment offer an efficient and accurate way to calculate the free energy reaction barriers for dissociative electron transfer reactions of organochlorine compounds to identify the potentially important environmental degradation processes.

  20. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path.

    PubMed

    Daschakraborty, Snehasis; Kiefer, Philip M; Miller, Yifat; Motro, Yair; Pines, Dina; Pines, Ehud; Hynes, James T

    2016-03-10

    The protonation of methylamine base CH3NH2 by carbonic acid H2CO3 within a hydrogen (H)-bonded complex in aqueous solution was studied via Car-Parrinello dynamics in the preceding paper (Daschakraborty, S.; Kiefer, P. M.; Miller, Y.; Motro, Y.; Pines, D.; Pines, E.; Hynes, J. T. J. Phys. Chem. B 2016, DOI: 10.1021/acs.jpcb.5b12742). Here some important further details of the reaction path are presented, with specific emphasis on the water solvent's role. The overall reaction is barrierless and very rapid, on an ∼100 fs time scale, with the proton transfer (PT) event itself being very sudden (<10 fs). This transfer is preceded by the acid-base H-bond's compression, while the water solvent changes little until the actual PT occurrence; this results from the very strong driving force for the reaction, as indicated by the very favorable acid-protonated base ΔpKa difference. Further solvent rearrangement follows immediately the sudden PT's production of an incipient contact ion pair, stabilizing it by establishment of equilibrium solvation. The solvent water's short time scale ∼120 fs response to the incipient ion pair formation is primarily associated with librational modes and H-bond compression of water molecules around the carboxylate anion and the protonated base. This is consistent with this stabilization involving significant increase in H-bonding of hydration shell waters to the negatively charged carboxylate group oxygens' (especially the former H2CO3 donor oxygen) and the nitrogen of the positively charged protonated base's NH3(+).

  1. Elastic scattering and transfer reactions for the system 7Be + 58Ni at Coulomb barrier energies

    NASA Astrophysics Data System (ADS)

    Mazzocco, M.; Torresi, D.; Acosta, L.; Boiano, A.; Boiano, C.; Glodariu, T.; Guglielmetti, A.; Keeley, N.; La Commara, M.; Lay, J. A.; Martel, I.; Mazzocchi, C.; Molini, P.; Parascandolo, C.; Parkar, V. V.; Pierroutsakou, D.; Romoli, M.; Rusek, K.; Sanchez-Benitez, A. M.; Sandoli, M.; Signorini, C.; Silvestri, R.; Soramel, F.; Strano, E.; Stroe, L.

    2015-09-01

    We investigated the reaction induced by the Radioactive Ion Beam 7Be on the closed proton shell nucleus 58Ni at 22.0 MeV bombarding energy. The 7Be beam was produced by means of the in-flight technique with the facility EXOTIC at INFN-LNL (Italy). Charged reaction products were mass and charge identified in a rather wide angular range and their energy distributions were analyzed to infer some information on the production mechanism. The relevance of direct processes, especially 3He- and 4He-stripping, as well as compound nucleus reactions is critically reviewed.

  2. The all-Cartesian reaction plane Hamiltonian: formulation and application to the H-atom transfer in tropolone.

    PubMed

    Giese, Kai; Kühn, Oliver

    2005-08-01

    In this work we present an all-Cartesian reaction surface approach, where the large amplitude coordinates span the so-called reaction plane, that is, the unique plane defined by the two minima and the saddle-point structure of an isomerization reaction. Orthogonal modes are treated within harmonic approximation which gives the total Hamiltonian an almost separable form that is suitable for multidimensional quantum dynamics calculations. The reaction plane Hamiltonian is constructed for the H-atom transfer in tropolone as an example for a system with an intramolecular O...H-O hydrogen bond. We find ground-state tunneling splittings of 3.5 and 0.16 cm(-1) for the normal and deuterated species, respectively. We calculated infrared-absorption spectra for a four-dimensional model focusing on the low-frequency region. Here, we identify a reaction mode which is closely connected to the tautomerization that is reflected in the increase of tunneling splitting to 18 cm(-1) upon excitation.

  3. Time-dependent Hartree-Fock calculations for multinucleon transfer and quasifission processes in the 238U+64Ni reaction

    NASA Astrophysics Data System (ADS)

    Sekizawa, Kazuyuki; Yabana, Kazuhiro

    2016-05-01

    Background: Multinucleon transfer (MNT) and quasifission (QF) processes are dominant processes in low-energy collisions of two heavy nuclei. They are expected to be useful to produce neutron-rich unstable nuclei. Nuclear dynamics leading to these processes depends sensitively on nuclear properties such as deformation and shell structure. Purpose: We elucidate reaction mechanisms of MNT and QF processes involving heavy deformed nuclei, making detailed comparisons between microscopic time-dependent Hartree-Fock (TDHF) calculations and measurements for the 238U+64Ni reaction. Methods: Three-dimensional Skyrme-TDHF calculations are performed. Particle-number projection method is used to evaluate MNT cross sections from the TDHF wave function after collision. Results: Fragment masses, total kinetic energy (TKE), scattering angle, contact time, and MNT cross sections are investigated for the 238U+64Ni reaction. They show reasonable agreements with measurements. At small impact parameters, collision dynamics depends sensitively on the orientation of deformed 238U. In tip (side) collisions, we find a larger (smaller) TKE and a shorter (longer) contact time. In tip collisions, we find a strong influence of quantum shells around 208Pb. Conclusions: It is confirmed that the TDHF calculations reasonably describe both MNT and QF processes in the 238U64Ni reaction. Analyses of this system indicate the significance of the nuclear structure effects such as deformation and quantum shells in nuclear reaction dynamics at low energies.

  4. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation. [Spiropyrans

    SciTech Connect

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in [approximately]240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH[sub 2]I[sub 2] and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a [approximately]350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  5. Importance of polarization transfer in reaction products for interpreting and analyzing CIDNP at low magnetic fields.

    PubMed

    Pravdivtsev, Andrey N; Yurkovskaya, Alexandra V; Ivanov, Konstantin L; Vieth, Hans-Martin

    2015-05-01

    The magnetic field dependence of Chemically Induced Dynamic Nuclear Polarization (CIDNP) was studied for the amino acids N-acetyl histidine, N-acetyl tryptophan and N-acetyl tyrosine. It is demonstrated that at low field CIDNP is strongly affected by polarization redistribution in the diamagnetic molecules. Such a polarization transfer is of coherent nature and is due to spin coherences formed together with non-equilibrium population of the spin states. These coherences clearly manifest themselves in an oscillatory time dependence of polarization. Polarization transfer effects are most pronounced at nuclear spin Level Anti-Crossings (LACs), which also result in sharp features in the CIDNP field dependence. Thus, polarization transfer is an important factor, which has to be taken into account in order to interpret low-field CIDNP data on both qualitative and quantitative level. Possible applications of polarization transfer phenomena are also discussed in the paper. In particular, the role of LACs in spin order transfer is highlighted: LACs provide a new tool for precise manipulation of spin hyperpolarization and NMR enhancement of selected target spins.

  6. Synthesis of branched cores by poly-O-alkylation reaction under phase transfer conditions. A systematic study

    NASA Astrophysics Data System (ADS)

    Landeros, José M.; Silvestre, Hugo A.; Guadarrama, Patricia

    2013-04-01

    In the present paper is described a systematic study of poly-O-alkylation reactions of pentaerythritol (PE) and 1,1,1-tris(hydroxymethyl)ethane (TME) by 1,4 Michael addition, under phase transfer catalysis (PTC), considering the effect of: (1) the organophilicity of PTC (three different catalysts were tested), (2) PTC concentration (from catalytic to equimolar conditions), and (3) the regime of addition of reactants coexisting in the aqueous phase of the heterogeneous reaction system. The less organophilic transfer agent showed the best performance on these reactions. In our case, benzyltriethylammonium chloride (TEBAC) gathers the best features. The presence of NaOH as base, promotes the interfacial mechanism and not the bulk one. Out of the optimal range of concentration of NaOH (35-40%), competition between nucleophiles can occur, due to the saturation of the medium. Regarding the regime of addition of reactants, the scenario where NaOH and TEBAC are less time in contact, favors the formation of the desired products. Finally, the deprotection of tert-butyl groups of the poly-O-alkylated compounds is described, to get branched cores with terminal carboxylic acid groups in good yields (90-94%). Spectroscopic properties, such as IR, 1H and 13C NMR, of the synthesized compounds are also described.

  7. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    SciTech Connect

    Koretsky, A.P.

    1984-01-01

    /sup 31/P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP.

  8. Studying 10BE and 11BE Halo States Through The (P,D) Single-Neutron Transfer Reaction

    NASA Astrophysics Data System (ADS)

    Kuhn, Keri; Sarazin, Fred; Tigress Collaboration; (Pcb)2 Collaboration

    2016-09-01

    One-neutron transfer reactions are being used to study single-particle neutron states in nuclei. For one-neutron halo nuclei, such as 11Be, the (p,d) reaction enables the removal of the halo neutron or of one of the core neutrons. This way, it is possible to simultaneously study the halo wavefunction of the 11Be ground-state but also a possible excited halo state in 10Be. The 11Be(p, d)10Be transfer reaction at 10 MeV/nucleon is being investigated at the TRIUMF-ISAC II facility with the Printed Circuit Board Based Charged Particle ((PCB)2) array inside the TRIUMF ISAC Gamma-Ray Escape-Suppressed Spectrometer (TIGRESS). The ground state and first excited state of 10Be can be directly identified using deuteron identification and kinematics from the charged particle array, while the four excited states in10Be around 6 MeV, including the suspected halo state (2- state), are identified using coincident gamma rays from TIGRESS with the identified deuterons. Angular distributions for the 10Be populated states will be shown along with their FRESCO fits. This work is partially supported by the US Department of Energy through Grant/Contract No. DE-FG03- 93ER40789.

  9. Studying 10Be and 11Be Halo States through the (p,d) Single-Neutron Transfer Reaction

    NASA Astrophysics Data System (ADS)

    Kuhn, Keri; Sarazin, Fred; (Pcb)2 Collaboration; Tigress Collaboration

    2015-10-01

    One-neutron transfer reactions are being used to study single-particle neutron states in nuclei. For one-neutron halo nuclei, such as 11Be, the (p,d) reaction enables the removal of the halo neutron or of one of the core neutrons. This way, it is possible to simultaneously study the halo wavefunction of the 11Be ground-state but also a possible excited halo state in 10Be. The 11Be(p, d)10Be transfer reaction at 10 MeV/nucleon is being investigated at the TRIUMF-ISAC II facility with the Printed Circuit Board Based Charged Particle ((PCB)2) array inside the TRIUMF ISAC Gamma-Ray Escape-Suppressed Spectrometer (TIGRESS). The ground state and first excited state of 10Be can be directly identified using deuteron identification and kinematics from the charged particle array, while the four excited states in10Be around 6 MeV, including the suspected halo state (2- state), are identified using coincident gamma rays from TIGRESS with the identified deuterons. Angular distributions for the 10Be populated states will be shown along with their FRESCO fits. This work is partially supported by the US Department of Energy through Grant/Contract No. DE-FG03-93ER40789 (Colorado School of Mines).

  10. On the reaction mechanism of the complete intermolecular O2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands.

    PubMed

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J; Liakos, Dimitrios G; Neese, Frank

    2014-10-06

    The recently described intermolecular O2 transfer between the side-on Ni-O2 complex [(12-TMC)Ni-O2](+) and the manganese complex [(14-TMC)Mn](2+), where 12-TMC and 14-TMC are 12- and 14-membered macrocyclic ligands, 12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 14-TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long-range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two-step reaction, with a first rate-determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ-η(1):η(1)-O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.

  11. Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

    NASA Technical Reports Server (NTRS)

    Blankenship, R. E.

    1994-01-01

    Photosynthetic reaction centers from a variety of organisms have been isolated and characterized. The groups of prokaryotic photosynthetic organisms include the purple bacteria, the filamentous green bacteria, the green sulfur bacteria and the heliobacteria as anoxygenic representatives as well as the cyanobacteria and prochlorophytes as oxygenic representatives. This review focuses on structural and functional comparisons of the various groups of photosynthetic reaction centers and considers possible evolutionary scenarios to explain the diversity of existing photosynthetic organisms.

  12. 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

  13. Influence of zeolite pore structure on product selectivities for protolysis and hydride transfer reactions in the cracking of n-pentane.

    PubMed

    Miyaji, Akimitsu; Iwase, Yasuyoshi; Nishitoba, Toshiki; Long, Nguyen Quang; Motokura, Ken; Baba, Toshihide

    2015-02-21

    The conversion of n-pentane was carried out to examine the effects of reaction conditions on changes in product selectivities at 823 K, using zeolites with 10- and 12-membered rings. We also investigated the influence of the pore structure of these zeolites on their catalytic activities for both protolysis and hydride transfer reactions. In the first half of this work, we examined the influence of acidic proton concentration and n-pentane pressure on the reaction rates for protolysis and hydride transfer reactions using ZSM-5 zeolites. The rates of hydride transfer reactions were more influenced by pentane pressure compared to protolysis reactions, and were proportional to the square of n-pentane pressure and the concentration of acidic protons. In the second half of this work, the influence of the zeolite pore structure on changes in product selectivities with n-pentane conversion and that on the rates of protolysis and the hydride transfer reactions were revealed using various zeolites with 10- and 12-membered rings. The catalytic activities of zeolites for the protolysis and hydride transfer reactions were influenced more by the spatial volume of the zeolite cavity than the acid strength of protons on the zeolite.

  14. Hydrogen Atom Transfer Reactions of a Ruthenium Imidazole Complex: Hydrogen Tunneling and the Applicability of the Marcus Cross Relation

    PubMed Central

    Wu, Adam; Mayer, James M.

    2009-01-01

    The reaction of RuII(acac)2(py-imH) (RuIIimH) with TEMPO• (2,2,6,6-tetramethyl-piperidine-1-oxyl radical) in MeCN quantitatively gives RuIII(acac)2(py-im) (RuIIIim) and the hydroxylamine TEMPO-H by transfer of H• (H+ + e−) (acac = 2,4-pentanedionato, py-imH = 2-(2′-pyridyl)imidazole). Kinetic measurements of this reaction by UV-vis stopped-flow techniques indicate a bimolecular rate constant k3H = 1400 ± 100 M−1 s−1 at 298 K. The reaction proceeds via a concerted hydrogen atom transfer (HAT) mechanism, as shown by ruling out the stepwise pathways of initial proton or electron transfer due to their very unfavorable thermochemistry (ΔG°). Deuterium transfer from RuII(acac)2(py-imD) (RuIIimD) to TEMPO• is surprisingly much slower at k3D = 60 ± 7 M−1 s−1, with k3H/k3D = 23 ± 3 at 298 K. Temperature dependent measurements of this deuterium kinetic isotope effect (KIE) show a large difference between the apparent activation energies, Ea3D − Ea3H = 1.9 ± 0.8 kcal mol−1. The large k3H/k3D and ΔEa values appear to be greater than the semi-classical limits and thus suggest a tunneling mechanism. The self-exchange HAT reaction between RuIIimH and RuIIIim, measured by 1H NMR line broadening, occurs with k4H = (3.2 ± 0.3) × 105 M−1 s−1 at 298 K and k4H/k4D = 1.5 ± 0.2. Despite the small KIE, tunneling is suggested by the ratio of Arrhenius pre-exponential factors, log(A4H/A4D) = −0.5 ± 0.3. These data provide a test of the applicability of the Marcus cross relation for H and D transfers, over a range of temperatures, for a reaction that involves substantial tunneling. The cross relation calculates rate constants for RuIIimH(D) + TEMPO• that are greater than those observed: k3H,calc/k3H = 31 ± 4 and k3D,calc/k3D = 140 ± 20 at 298 K. In these rate constants and in the activation parameters, there is a better agreement with the Marcus cross relation for H than for D transfer, despite the greater prevalence of tunneling for H. The cross

  15. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    SciTech Connect

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-10-08

    Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.

  16. The Metal or the Ligand? The Preferred Locus for Redox Changes in Oxygen Atom Transfer Reactions of Rhenium Amidodiphenoxides.

    PubMed

    Hoffman, Justin M; Oliver, Allen G; Brown, Seth Nathaniel

    2017-03-03

    The rhenium(V) oxo complex oxo(triphenylphosphine)(bis(3,5-di-tert-butyl-2-phenoxo)amido)rhenium(V), (ONO(Cat))ReO(PPh3), reacts with molecular oxygen to give triphenylphosphine oxide and the dimeric rhenium(VII) complex fac,anti-(ONO(Cat))Re(O)(μ-O)2Re(O)(ONO(Cat)). The ONO ligand adopts an unusual fac geometry, presumably to maximize π donation to rhenium; strong π donation is substantiated by the intraligand bond distances (metrical oxidation state = -2.24(9)). Addition of the N-heterocyclic carbene ligand IMes to fac,anti-(ONO(Cat))Re(O)(μ-O)2Re(O)(ONO(Cat)) cleaves the dimer into monomeric C1-symmetric fac-(ONO(Cat))ReO2(IMes). The monorhenium(VII) complex is deoxygenated by PMe2Ph to give the rhenium(V) compound (ONO(Cat))ReO(IMes), which can be independently prepared by ligand substitution of (ONO(Cat))ReO(PPh3). The degree of stereochemical rigidity exhibited by the dioxo compound, as established by dynamic NMR spectroscopy, excludes the intermediacy of mer-(ONO(Q))Re(V)O2(IMes) in this oxygen atom transfer reaction. Thus, oxygen atom transfer takes place preferentially by direct reduction of the oxorhenium(VII) moiety (classical oxygen atom transfer) rather than through initial internal electron transfer and ligand-centered reduction of an oxorhenium(V)-iminoquinone.

  17. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    PubMed Central

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-01-01

    The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

  18. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    DOE PAGES

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; ...

    2014-10-08

    Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We concludemore » that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.« less

  19. Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions of mono-, di-, and tri-aryl-substituted donors, models for hydrogen atom transfers in polyunsaturated fatty acid radicals.

    PubMed

    DeZutter, Christopher B; Horner, John H; Newcomb, Martin

    2008-03-06

    Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions in models of polyunsaturated fatty acid radicals were measured via laser flash photolysis methods. Photolyses of PTOC (pyridine-2-thioneoxycarbonyl) ester derivatives of carboxylic acids gave primary alkyl radicals that reacted by 1,5-hydrogen transfer from mono-, di-, and tri-aryl-substituted positions or 1,6-hydrogen transfer from di- and tri-aryl-substituted positions to give UV-detectable products. Rate constants for reactions in acetonitrile at room temperature ranged from 1 x 10(4) to 4 x 10(6) s(-1). The activation energies for a matched pair of 1,5- and 1,6-hydrogen atom transfers giving tri-aryl-substituted radicals were approximately equal, as were the primary kinetic isotope effects, but the 1,5-hydrogen atom transfer reaction was 1 order of magnitude faster at room temperature than the 1,6-hydrogen atom transfer reaction due to a less favorable entropy of activation for the 1,6-transfer reaction. Solvent effects on the rate constants for the 1,5-hydrogen atom transfer reaction of the 2-[2-(diphenylmethyl)phenyl]ethyl radical at ambient temperature were as large as a factor of 2 with the reaction increasing in rate in lower polarity solvents. Hybrid density functional theory computations for the 1,5- and 1,6-hydrogen atom transfers of the tri-aryl-substituted donors were in qualitative agreement with the experimental results.

  20. Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.

    PubMed

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jahn, Ullrich

    2014-09-08

    Oxidative single-electron transfer-catalyzed tandem reactions consisting of a conjugate addition and a radical cyclization are reported, which incorporate the mandatory terminal oxidant as a functionality into the product.

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

    PubMed

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

    2010-05-07

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

  2. The Study of the D(e,e'p)n Reaction at High Four-Momentum Transfer

    NASA Astrophysics Data System (ADS)

    Khanal, Hari

    2014-09-01

    A study of the D (e ,e' p) reaction has been carried out at the Thomas Jefferson National Accelerator Facility (Jefferson Lab) for a set of fixed values of four-momentum transfers Q2 = 2.1 and 0.8 (GeV/c)2 and for missing momenta pm ranging from pm = 0.03 to pm = 0.65 GeV/c. The analysis resulted in the determination of absolute D (e ,e' p) n cross sections as a function of the recoiling neutron momentum and it's scattering angle with respect to the momentum transfer q-> . The experimental momentum distribution of the bound proton inside the deuteron has been determined for the first time at a set of fixed neutron recoil angle. A study of the D (e ,e' p) reaction has been carried out at the Thomas Jefferson National Accelerator Facility (Jefferson Lab) for a set of fixed values of four-momentum transfers Q2 = 2.1 and 0.8 (GeV/c)2 and for missing momenta pm ranging from pm = 0.03 to pm = 0.65 GeV/c. The analysis resulted in the determination of absolute D (e ,e' p) n cross sections as a function of the recoiling neutron momentum and it's scattering angle with respect to the momentum transfer q-> . The experimental momentum distribution of the bound proton inside the deuteron has been determined for the first time at a set of fixed neutron recoil angle. Department of Energy (DOE).

  3. Improving the Convergence of Chiral EFT for Few-Nucleon Systems

    SciTech Connect

    Epelbaum, Evgeny; Glockle, W.; Meissner, Ulf-G.

    2003-11-01

    In the past decade chiral EFT has been applied by several groups to study the properties of fewâ nucleon systems based on the original idea of Weinberg [1], see [2] for a recent review. It is of utmost importance for all these applications to verify the convergence of the lowâ momentum expansion. As pointed out by Kaiser et al. [3], nucleonâ nucleon peripheral scattering provides an excellent ground to test the convergence of the chiral expansion. Indeed, the high angular momentum scattering states are dominated by the longâ range part of the nuclear force, where chiral dynamics is important. For example, no shortâ range contact interactions (with, in general, unknown coupling constants) contribute to Dâ and higher partial waves at nextâ nextâ toâ leading order (NNLO), which allows for parameterâ free calculations. In addition, the interaction between two nucleons becomes weak due to the centrifugal barrier, so that the Sâ matrix can be obtained using perturbative methods. It was found in [3

  4. A precise few-nucleon size difference by isotope shift measurements of helium

    NASA Astrophysics Data System (ADS)

    Rezaeian, Nima Hassan

    We perform high precision measurements of an isotope shift between the two stable isotopes of helium. We use laser excitation of the 23 S1 -- 23P0 transition at 1083 .... in a metastable beam of 3He and 4He atoms. A newly developed tunable laser frequency selector along with our previous electro-optic frequency modulation technique provides extremely reliable, adaptable, and precise frequency and intensity control. The intensity control contributes negligibly to overall experimental uncertainty by selecting (t selection < 50 ) and stabilizing the intensity of the required sideband and eliminating (˜10-5) the unwanted frequencies generated during the modulation of 1083 nm laser carrier frequency. The selection technique uses a MEMS based fiber switch (tswitch ≈ 10 ms) and several temperature stabilized narrow band (˜3 GHz) fiber gratings. A fiber based optical circulator and an inline fiber amplifier provide the desired isolation and the net gain for the selected frequency. Also rapid (˜2 sec.) alternating measurements of the 23 S1 -- 23P0 interval for both species of helium is achieved with a custom fiber laser for simultaneous optical pumping. A servo-controlled retro-reflected laser beam eliminates residual Doppler effects during the isotope shift measurement. An improved detection design and software control makes negligible subtle potential biases in the data collection. With these advances, combined with new internal and external consistency checks, we are able to obtain results consistent with the best previous measurements, but with substantially improved precision. Our measurement of the 23S 1 -- 23P0 isotope shift between 3He and 4He is 31 097 535.2 (5)kHz. The most recent theoretic calculation combined with this measuremen. yields a new determination for nuclear size differences between 3He and 4He: Deltarc = 0.292 6 (1)exp (8)th(52)expfm, with a precision of less than a part in 104 coming from the experimental uncertainty (first parenthesis), and a part in 10 3 coming from theory. This value is consistent with electron scattering measurement, but a factor of 10 more precise. It is inconsistent (4 sigma) with a recent isotope shift measurement on another helium transition (2 1S0 -- 23 S1). Comparisons with ongoing muonic helium measurements may provide clues to the origin of what is currently called the proton puzzle: electronic and muonic measurements of the proton size do not agree. In the future, the experimental improvements described here can be used for higher precision tests of atomic theory and quantum electrodynamics, as well as an important atomic physics source of the fine structure constant.

  5. Few-nucleon systems with state-of-the-art chiral nucleon-nucleon forces

    NASA Astrophysics Data System (ADS)

    Binder, S.; Calci, A.; Epelbaum, E.; Furnstahl, R. J.; Golak, J.; Hebeler, K.; Kamada, H.; Krebs, H.; Langhammer, J.; Liebig, S.; Maris, P.; Meißner, Ulf-G.; Minossi, D.; Nogga, A.; Potter, H.; Roth, R.; Skibiński, R.; Topolnicki, K.; Vary, J. P.; Witała, H.; Lenpic Collaboration

    2016-04-01

    We apply improved nucleon-nucleon potentials up to fifth order in chiral effective field theory, along with a new analysis of the theoretical truncation errors to study nucleon-deuteron (N d ) scattering and selected low-energy observables in 3H,4He , and 6Li. Calculations beyond second order differ from experiment well outside the range of quantified uncertainties, providing truly unambiguous evidence for missing three-nucleon forces within the employed framework. The sizes of the required three-nucleon-force contributions agree well with expectations based on Weinberg's power counting. We identify the energy range in elastic N d scattering best suited to study three-nucleon-force effects and estimate the achievable accuracy of theoretical predictions for various observables.

  6. Invited Reaction: Informal Learning and the Transfer of Learning--How Managers Develop Proficiency

    ERIC Educational Resources Information Center

    Marsick, Victoria J.

    2003-01-01

    Enos, Kehrhahn, and Bell have made an important contribution to measuring informal learning and its transfer as proficiency in a set of company-identified managerial skills. Measurement of informal learning is at the crux of research that seeks to link learning outcomes to other indicators of effective performance. The ability to show how informal…

  7. A monolith immobilised iridium Cp* catalyst for hydrogen transfer reactions under flow conditions.

    PubMed

    Rojo, Maria Victoria; Guetzoyan, Lucie; Baxendale, Ian R

    2015-02-14

    An immobilised iridium hydrogen transfer catalyst has been developed for use in flow based processing by incorporation of a ligand into a porous polymeric monolithic flow reactor. The monolithic construct has been used for several redox reductions demonstrating excellent recyclability, good turnover numbers and high chemical stability giving negligible metal leaching over extended periods of use.

  8. Polarization transfer in the {sup 4}He({rvec e}, e'{rvec p}){sup 3}H reaction

    SciTech Connect

    Sonja Dieterich; et. al

    2001-02-15

    Polarization transfer in the {sup 4}He({rvec e}, e'{rvec p}){sup 3}H reaction at a Q{sup 2} of 0.4 (GeV/c){sup 2} was measured at the Mainz Microtron MAMI. The ratio of the transverse to the longitudinal polarization components of the ejected protons was compared with the same ratio for elastic ep scattering. The results are consistent with a recent fully relativistic calculation which includes a predicted medium modification of the proton form factor based on a quark-meson coupling model.

  9. Effect of viscosity on photoinduced electron transfer reaction: An observation of the Marcus inverted region in homogeneous solvents

    NASA Astrophysics Data System (ADS)

    Saini, Rajesh Kumar; Kuchlyan, Jagannath; Sarkar, Nilmoni

    2016-09-01

    The viscosity effect of homogeneous solvents on the dynamics of photoinduced electron transfer (PET) reaction among the coumarins and N,N-dimethylaniline (DMA) is investigated using steady-state and time-resolved fluorescence spectroscopy. A bell shape Marcus inversion in the ET rates has been detected in the plot of ET rate constant (kq) with free energy change (ΔG0) in viscous solvents decanol and EG, but it is not observed in DMSO like low viscous solvent. We have also reported that there is no complex formation between the coumarin dye and DMA molecule by using fluorescence correlation spectroscopy.

  10. Description of nucleon-transfer and fusion reactions within time-dependent approaches and coupled-channel method

    SciTech Connect

    Samarin, V. V.

    2015-01-15

    The time-dependent Schrödinger equation and the method of perturbed stationary states that is based on the expansion of the total wave function for the system of two nuclear cores and a nucleon in a set of nucleon two-center functions are used to describe nucleon transfers and fusion in low-energy nuclear reactions. A set of multichannel equations that couple the relative motion of nuclei to the motion of the nucleon is obtained. The kinetic-energy coupling matrix is similar to the coupling matrix for collective excitations of nuclei.

  11. 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.

  12. Ultrafast twisting motions and intramolecular charge-transfer reaction in a cyanine dye trapped in molecular nanocavities

    NASA Astrophysics Data System (ADS)

    Fayed, T. A.; Organero, J. A.; Garcia-Ochoa, I.; Tormo, L.; Douhal, A.

    2002-09-01

    Emission properties of the cyanine dye, 1-(2-naphthyl)-2-ethenyl-(2-benzothiazolium) iodide, in aqueous nanocavities offered by cyclodextrins and in a film of a polymeric matrix were studied by means of steady-state and picosecond time-resolved emission spectroscopy. The results show the occurrence of a fast twisting motion and a subsequent intramolecular charge-transfer reaction. The initial step can be prevented by the size of the nanocavity which governs the spectral position of the fluorescence band and lifetime of the excited encapsulated host.

  13. Relevance of single-particle and collective excitations in zirconium isotopes populated by neutron transfer reactions in the {sup 90}Zr+{sup 208}Pb system

    SciTech Connect

    Pajtler, M. Varga; Szilner, S.; Malenica, D. Jelavić; Mijatović, T.; Soić, N.; Corradi, L.; Angelis, G. de; Fioretto, E.; Montanari, D.; Stefanini, A. M.; Valiente-Dobón, J. J.; Gadea, A.; Haas, F.; Lunardi, S.; Mengoni, D.; Montagnoli, G.; Recchia, F.; Scarlassara, F.; Märginean, N.; Pollarolo, G.; and others

    2015-10-15

    Multineutron transfer reaction {sup 90}Zr+{sup 208}Pb has been studied at the energy close to the Coulomb barrier energy by using the PRISMA + CLARA set-up. In this fragment-γ coincidence measurement, the selective properties of the reaction mechanism in the population of the specific states have been discussed. Based on the observed γ transitions of neutron transfer channels, namely {sup 89–94}Zr isotopes, their level schemes have been constructed and updated.

  14. The role of quantum effects in proton transfer reactions in enzymes: quantum tunneling in a noisy environment?

    NASA Astrophysics Data System (ADS)

    Bothma, Jacques P.; Gilmore, Joel B.; McKenzie, Ross H.

    2010-05-01

    We consider the role of quantum effects in the transfer of hydrogen-like species in enzyme-catalyzed reactions. This review is stimulated by claims that the observed magnitude and temperature dependence of kinetic isotope effects (KIEs) implies that quantum tunneling below the energy barrier associated with the transition state significantly enhances the reaction rate in many enzymes. We review the path integral approach and the Caldeira-Leggett model, which provides a general framework to describe and understand tunneling in a quantum system that interacts with a noisy environment at nonzero temperature. Here the quantum system is the active site of the enzyme, and the environment is the surrounding protein and water. Tunneling well below the barrier only occurs for temperatures less than a temperature T0, which is determined by the curvature of the potential energy surface near the top of the barrier. We argue that for most enzymes this temperature is less than room temperature. We review typical values for the parameters in the Caldeira-Leggett Hamiltonian, including the frequency-dependent friction and noise due to the environment. For physically reasonable parameters, we show that quantum transition state theory gives a quantitative description of the temperature dependence and magnitude of KIEs for two classes of enzymes that have been claimed to exhibit signatures of quantum tunneling. The only quantum effects are those associated with the transition state, both reflection at the barrier top and tunneling just below the barrier. We establish that the friction and noise due to the environment are weak and only slightly modify the reaction rate. Furthermore, at room temperature and for typical energy barriers environmental fluctuations with frequencies much less than 1000 cm-1 do not have a significant effect on quantum corrections to the reaction rate. This is essentially because the time scales associated with the dynamics of proton transfer are faster than

  15. Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction.

    PubMed

    Li, Ji-Lai; Mata, Ricardo A; Ryde, Ulf

    2013-03-12

    The oxygen-atom transfer reaction catalyzed by the mononuclear molybdenum enzyme dimethyl sulfoxide reductase (DMSOR) has attracted considerable attention through both experimental and theoretical studies. We show here that this reaction is more sensitive to details of quantum mechanical calculations than what has previously been appreciated. Basis sets of at least triple-ζ quality are needed to obtain qualitatively correct results. Dispersion has an appreciable effect on the reaction, in particular the binding of the substrate or the dissociation of the product (up to 34 kJ/mol). Polar and nonpolar solvation effects are also significant, especially if the enzyme can avoid cavitation effects by using a preformed active-site cavity. Relativistic effects are considerable (up to 22 kJ/mol), but they are reasonably well treated by a relativistic effective core potential. Various density-functional methods give widely different results for the activation and reaction energy (differences of over 100 kJ/mol), mainly reflecting the amount of exact exchange in the functional, owing to the oxidation of Mo from +IV to +VI. By calibration toward local CCSD(T0) calculations, we show that none of eight tested functionals (TPSS, BP86, BLYP, B97-D, TPSSH, B3LYP, PBE0, and BHLYP) give accurate energies for all states in the reaction. Instead, B3LYP gives the best activation barrier, whereas pure functionals give more accurate energies for the other states. Our best results indicate that the enzyme follows a two-step associative reaction mechanism with an overall activation enthalpy of 63 kJ/mol, which is in excellent agreement with the experimental results.

  16. An analysis of model proton-coupled electron transfer reactions via the mixed quantum-classical Liouville approach.

    PubMed

    Shakib, Farnaz A; Hanna, Gabriel

    2014-07-28

    The nonadiabatic dynamics of model proton-coupled electron transfer (PCET) reactions is investigated for the first time using a surface-hopping algorithm based on the solution of the mixed quantum-classical Liouville equation (QCLE). This method provides a rigorous treatment of quantum coherence/decoherence effects in the dynamics of mixed quantum-classical systems, which is lacking in the molecular dynamics with quantum transitions surface-hopping approach commonly used for simulating PCET reactions. Within this approach, the protonic and electronic coordinates are treated quantum mechanically and the solvent coordinate evolves classically on both single adiabatic surfaces and on coherently coupled pairs of adiabatic surfaces. Both concerted and sequential PCET reactions are studied in detail under various subsystem-bath coupling conditions and insights into the dynamical principles underlying PCET reactions are gained. Notably, an examination of the trajectories reveals that the system spends the majority of its time on the average of two coherently coupled adiabatic surfaces, during which a phase enters into the calculation of an observable. In general, the results of this paper demonstrate the applicability of QCLE-based surface-hopping dynamics to the study of PCET and emphasize the importance of mean surface evolution and decoherence effects in the calculation of PCET rate constants.

  17. Computation of Accurate Activation Barriers for Methyl-Transfer Reactions of Sulfonium and Ammonium Salts in Aqueous Solution.

    PubMed

    Gunaydin, Hakan; Acevedo, Orlando; Jorgensen, William L; Houk, K N

    2007-05-01

    The energetics of methyl-transfer reactions from dimethylammonium, tetramethylammonium, and trimethylsulfonium to dimethylamine were computed with density functional theory, MP2, CBS-QB3, and quantum mechanics/molecular mechanics (QM/MM) Monte Carlo methods. At the CBS-QB3 level, the gas-phase activation enthalpies are computed to be 9.9, 15.3, and 7.9 kcal/mol, respectively. MP2/6-31+G(d,p) activation enthalpies are in best agreement with the CBS-QB3 results. The effects of aqueous solvation on these reactions were studied with polarizable continuum model, generalized Born/surface area (GB/SA), and QM/MM Monte Carlo simulations utilizing free-energy perturbation theory in which the PDDG/PM3 semiempirical Hamiltonian for the QM and explicit TIP4P water molecules in the MM region were used. In the aqueous phase, all of these reactions proceed more slowly when compared to the gas phase, since the charged reactants are stabilized more than the transition structure geometries with delocalized positive charges. In order to obtain the aqueous-phase activation free energies, the gas-phase activation free energies were corrected with the solvation free energies obtained from single-point conductor-like polarizable continuum model and GB/SA calculations for the stationary points along the reaction coordinate.

  18. A chromium(III)-superoxo complex in oxygen atom transfer reactions as a chemical model of cysteine dioxygenase.

    PubMed

    Cho, Jaeheung; Woo, Jaeyoung; Nam, Wonwoo

    2012-07-11

    Metal-superoxo species are believed to play key roles in oxygenation reactions by metalloenzymes. One example is cysteine dioxygenase (CDO) that catalyzes the oxidation of cysteine with O(2), and an iron(III)-superoxo species is proposed as an intermediate that effects the sulfoxidation reaction. We now report the first biomimetic example showing that a chromium(III)-superoxo complex bearing a macrocyclic TMC ligand, [Cr(III)(O(2))(TMC)(Cl)](+), is an active oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of phosphine and sulfides. The electrophilic character of the Cr(III)-superoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles. A Cr(IV)-oxo complex, [Cr(IV)(O)(TMC)(Cl)](+), formed in the OAT reactions by the chromium(III)-superoxo complex, is characterized by X-ray crystallography and various spectroscopic methods. The present results support the proposed oxidant and mechanism in CDO, such as an iron(III)-superoxo species is an active oxidant that attacks the sulfur atom of the cysteine ligand by the terminal oxygen atom of the superoxo group, followed by the formation of a sulfoxide and an iron(IV)-oxo species via an O-O bond cleavage.

  19. Measurement of proton transfer reaction rates in a microwave cavity discharge flowing afterglow

    NASA Astrophysics Data System (ADS)

    Brooke, George M., IV

    The reaction rate coefficients between the hydronium ion and the molecules ethene (C2H4), propene (C 3H6), 1-butene (C4H8) and hydrogen sulfide (H2S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is spatially separated from the flow tube, eliminating many of the problems inherent with the original FA devices. In addition to measuring reaction rate coefficients, the MCD-FA was shown to be an effective tool for measuring trace compounds in atmospheric air. This method has many advantages over current detection techniques since compounds can be detected in almost real time, large mass ranges can be scanned quickly, and repeated calibration is not required. Preliminary measurements were made of car exhaust and exhaled alveolar air. Car exhaust showed the presence of numerous hydrocarbons, such as butene, benzene and toluene while the exhaled alveolar air showed the presence of various volatile organic compounds such as methanol and acetone.

  20. The Use of Conjugate Charts in Transfer Reactions: A Unified Approach

    ERIC Educational Resources Information Center

    Allnutt, Michael I.

    2007-01-01

    Redox reactions can be conveniently discussed in terms of the relative strengths of the oxidant, the reductant, and their conjugates; a conjugate chart is a most convenient and useful way of doing this. A similar chart for acids and bases is proposed, which can be applied in the same manner. (Contains 7 figures and 2 tables.)

  1. Examining the effect of nonlocality in (d,n) transfer reactions

    DOE PAGES

    Ross, A.; Titus, L. J.; Nunes, F. M.

    2016-07-13

    In the last year we have been exploring the effect of the explicit inclusion of nonlocality in (d,p) reactions. The goal of this work is to extend previous studies to (d,n) reactions, which, although similar to (d,p), have specific properties that merit inspection. We apply our methods (both the distorted wave Born approximation and the adiabatic wave approximation) to (d; n) reactions on 16O, 40Ca, 48Ca, 126Sn, 132Sn, and 208Pb at 20 and 50 MeV. As a result, we look separately at the modifications introduced by nonlocality in the final bound and scattering states, as well as the consequences reflectedmore » on the differential angular distributions. The cross sections obtained when using nonlocality explicitly are significantly different than those using the local approximation, just as in (d,p). Due to the particular role of Coulomb in the bound state, often we found the effects of nonlocality to be larger in (d,n) than in (d,p). In conclusion, our results con rm the importance of including nonlocality explicitly in deuteron-induced reactions.« less

  2. Charge transfer reactions at interfaces between neutral gas and plasma: Dynamical effects and X-ray emission

    NASA Astrophysics Data System (ADS)

    Provornikova, E.; Izmodenov, V. V.; Lallement, R.

    2012-04-01

    Charge-transfer is the main process linking neutrals and charged particles in the interaction regions of neutral (or partly ionized) gas with a plasma. In this paper we illustrate the importance of charge-transfer with respect to the dynamics and the structure of neutral gas-plasma interfaces. We consider the following phenomena: (1) the heliospheric interface - region where the solar wind plasma interacts with the partly-ionized local interstellar medium (LISM) and (2) neutral interstellar clouds embedded in a hot, tenuous plasma such as the million degree gas that fills the so-called ``Local Bubble". In (1), we discuss several effects in the outer heliosphere caused by charge exchange of interstellar neutral atoms and plasma protons. In (2) we describe the role of charge exchange in the formation of a transition region between the cloud and the surrounding plasma based on a two-component model of the cloud-plasma interaction. In the model the cloud consists of relatively cold and dense atomic hydrogen gas, surrounded by hot, low density, fully ionized plasma. We discuss the structure of the cloud-plasma interface and the effect of charge exchange on the lifetime of interstellar clouds. Charge transfer between neutral atoms and minor ions in the plasma produces X-ray emission. Assuming standard abundances of minor ions in the hot gas surrounding the cold interstellar cloud, we estimate the X-ray emissivity consecutive to the charge transfer reactions. Our model shows that the charge-transfer X-ray emission from the neutral cloud-plasma interface may be comparable to the diffuse thermal X-ray emission from the million degree gas cavity itself.

  3. Optimizing the Electron Transfer Reactions at the Cathode of Microbial Fuel Cells

    DTIC Science & Technology

    2015-05-15

    suspension of live, intact bacteria to monitor the in situ absorbance changes in bacteria as they respired aerobically on soluble ferrous ions. Our prior...observations suggested the following hypothesis: acidophilic bacteria that belong to different phyla express different types of electron transfer...autotrophic bacteria , itegrating cavity absorption meter REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR/MONITOR’S ACRONYM(S

  4. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    NASA Astrophysics Data System (ADS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-11-01

    Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH2) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such zwitterion modified PP surface.

  5. Effect on the parameters of the high-heel shoe and transfer time of ground reaction force during level walking

    PubMed Central

    Hyun, Seung-Hyun; Kim, Young-Pyo; Ryew, Che-Cheong

    2016-01-01

    This study aimed to analyze an effect on the parameters of high-heel shoe and transfer time of ground reaction force during level walking and subjects participated were composed of adult female subjects (n=13) of 20s with height of high heel (0 cm, 9 cm, respectively). Instrument used for the study was 1 set force plate (AMTI-OR9-7) and sampling rate for data collection of analysis parameters was set-up at 1,000 Hz. The revelation of required coefficient of friction (RCOF) maximum showed significant difference with more rapid than that of 1st peak vertical force (1 PVF). Transfer time of body weight showed significant difference with more delay at 9 cm than that of 0 cm. RCOF required more frictional force required because PVF showed significant difference with larger value on 9 cm than that of 3 cm at 1 PVF. Both center of pressure (COP) x and COPy showed rather less displacement on 9 cm than that of 0 cm. In addition, level walking by high heel shoe did not control efficiently the ground reaction force due to restricted control capacity of coefficient of frictional force and therefore could suggest an inducement of muscle fatigue, heightening a possibility of sliding and falling due to decrease of frictional force. PMID:27807524

  6. Hybrid approach for including electronic and nuclear quantum effects in molecular dynamics simulations of hydrogen transfer reactions in enzymes

    NASA Astrophysics Data System (ADS)

    Billeter, Salomon R.; Webb, Simon P.; Iordanov, Tzvetelin; Agarwal, Pratul K.; Hammes-Schiffer, Sharon

    2001-04-01

    A hybrid approach for simulating proton and hydride transfer reactions in enzymes is presented. The electronic quantum effects are incorporated with an empirical valence bond approach. The nuclear quantum effects of the transferring hydrogen are included with a mixed quantum/classical molecular dynamics method in which the hydrogen nucleus is described as a multidimensional vibrational wave function. The free energy profiles are obtained as functions of a collective reaction coordinate. A perturbation formula is derived to incorporate the vibrationally adiabatic nuclear quantum effects into the free energy profiles. The dynamical effects are studied with the molecular dynamics with quantum transitions (MDQT) surface hopping method, which incorporates nonadiabatic transitions among the adiabatic hydrogen vibrational states. The MDQT method is combined with a reactive flux approach to calculate the transmission coefficient and to investigate the real-time dynamics of reactive trajectories. This hybrid approach includes nuclear quantum effects such as zero point energy, hydrogen tunneling, and excited vibrational states, as well as the dynamics of the complete enzyme and solvent. The nuclear quantum effects are incorporated during the generation of the free energy profiles and dynamical trajectories rather than subsequently added as corrections. Moreover, this methodology provides detailed mechanistic information at the molecular level and allows the calculation of rates and kinetic isotope effects. An initial application of this approach to the enzyme liver alcohol dehydrogenase is also presented.

  7. Use of proton transfer reaction time-of-flight mass spectrometry for quantitative monitoring of toxic nitramines in the environment

    NASA Astrophysics Data System (ADS)

    Wisthaler, A.; Zhu, L.; Stenstrøm, Y.; Nielsen, C. J.

    2014-12-01

    Naturally occurring aliphatic amines and industrially emitted aromatic amines and alkanolamines produce toxic nitramines, (R1R2)-N-NO2, when photo-oxidized in the atmosphere in the presence of nitrogen oxides (NOx). Particular concerns arise from amine-based CO2 capture where the amine solution may get nitrated by NOx in the flue gas. An on-line analytical technique for measuring nitramines in industrial emissions and in ambient air is thus in high demand. Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) is a state-of-the-art technique for on-line measurements of volatile organic compounds (VOCs) in air. Herein, we report on the use of high mass resolution proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) for on-line analysis of nitramines. We generated a mass spectral library from a series of nitramines and investigated the analytical performance of PTR-ToF-MS in terms of sensitivity, precision, accuracy and detection limit. We will discuss limitations of the innovative technique and propose measurement strategies for future emission and ambient measurements.

  8. Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method.

    PubMed

    Warneke, Carsten; De Gouw, Joost A; Kuster, William C; Goldan, Paul D; Fall, Ray

    2003-06-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.

  9. Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.

    PubMed

    Reiser, Oliver

    2016-09-20

    Visible-light photoredox catalysis offers exciting opportunities to achieve challenging carbon-carbon bond formations under mild and ecologically benign conditions. Desired features of photoredox catalysts are photostability, long excited-state lifetimes, strong absorption in the visible region, and high reduction or oxidation potentials to achieve electron transfer to substrates, thus generating radicals that can undergo synthetic organic transformations. These requirements are met in a convincing way by Ru(II)(phenanthroline)3- and Ir(III)(phenylpyridine)3-type complexes and, as a low-cost alternative, by organic dyes that offer a metal-free catalyst but suffer in general from lower photostability. Cu(I)(phenanthroline)2 complexes have been recognized for more than 30 years as photoresponsive compounds with highly negative Cu(I)* → Cu(II) oxidation potentials, but nevertheless, they have not been widely considered as suitable photoredox catalysts, mainly because their excited lifetimes are shorter by a factor of 5 to 10 compared with Ru(II) and Ir(III) complexes, their absorption in the visible region is weak, and their low Cu(II) → Cu(I) reduction potentials might impede the closure of a catalytic cycle for a given process. Contrasting again with Ru(II)L3 and Ir(III)L3 complexes, Cu(I)L2 assemblies undergo more rapid ligand exchange in solution, thus potentially reducing the concentration of the photoactive species. Focusing on atom transfer radical addition (ATRA) reactions and related processes, we highlight recent developments that show the utility of Cu(I)(phenanthroline)2 complexes as photoredox catalysts, demonstrating that despite their short excited-state lifetimes and weak absorption such complexes are efficient at low catalyst loadings. Moreover, some of the inherent disadvantages stated above can even be turned to advantages: (1) the low Cu(II) → Cu(I) reduction potential might efficiently promote reactions via a radical chain pathway, and (2

  10. Elastic scattering and neutron transfer of the 26Mg + 13C reaction

    NASA Astrophysics Data System (ADS)

    McCleskey, Matthew; Alharby, A.; Banu, A.; Goldberg, V. Z.; McCleskey, E.; Roeder, B. T.; Spiridon, A.; Trache, L.; Tribble, R. E.

    2013-10-01

    Direct proton capture on 26Si is of interest for its role in the destruction of 26Si that would otherwise be available to β+ decay into 26mAl. This is part of the network of reactions that influence the production and destruction of the important astrophysical observable 26Al. The 13C(26Mg,27Mg)12C reaction at 12 MeV/nucleon has been measured at Texas A &M University Cyclotron Institute with the aim to determine ANC for 27P <--> p + 26Si via mirror symmetry. Details of the experiment as well as preliminary results will be presented. Present address: Faculty of Sciences, Physics Department, Princess Nora University Riyadh, Saudi Arabia.

  11. Temperature effect on back electron-transfer reactions within a geminate radical pair: The influence of the solvent on the adiabaticity of the process

    NASA Astrophysics Data System (ADS)

    Vauthey, Eric; Suppan, Paul

    1989-12-01

    A study of the temperature dependence (from 233 to 353 K) of the rate of back electron-transfer reactions within geminate radical pairs by measurement of the free radical yield is reported. The radical pair is generated by photoinduced electron transfer with rhodamine 6G and oxazine 118 cations as electron acceptors and aromatic amines and methoxy-benzene derivatives as electron donors in acetonitrile, methanol and ethanol. In acetonitrile, the back electron transfer is non-adiabatic and apparent negative activation energies are observed for barrierless reactions. In alcohol solvents, an anomalously large temperature dependence is observed, which is attributed to a solvent-controlled adiabatic behaviour.

  12. Electrostatic calculations of amino acid titration and electron transfer, Q-AQB-->QAQ-B, in the reaction center.

    PubMed Central

    Beroza, P; Fredkin, D R; Okamura, M Y; Feher, G

    1995-01-01

    The titration of amino acids and the energetics of electron transfer from the primary electron acceptor (QA) to the secondary electron acceptor (QB) in the photosynthetic reaction center of Rhodobacter sphaeroides are calculated using a continuum electrostatic model. Strong electrostatic interactions between titrating sites give rise to complex titration curves. Glu L212 is calculated to have an anomalously broad titration curve, which explains the seemingly contradictory experimental results concerning its pKa. The electrostatic field following electron transfer shifts the average protonation of amino acids near the quinones. The pH dependence of the free energy between Q-AQB and QAQ-B calculated from these shifts is in good agreement with experiment. However, the calculated absolute free energy difference is in severe disagreement (by approximately 230 meV) with the observed experimental value, i.e., electron transfer from Q-A to QB is calculated to be unfavorable. The large stabilization energy of the Q-A state arises from the predominantly positively charged residues in the vicinity of QA in contrast to the predominantly negatively charged residues near QB. The discrepancy between calculated and experimental values for delta G(Q-AQB-->QAQ-B) points to limitations of the continuum electrostatic model. Inclusion of other contributions to the energetics (e.g., protein motion following quinone reduction) that may improve the agreement between theory and experiment are discussed. PMID:7647231

  13. B-branch electron transfer in reaction centers of Rhodobacter sphaeroides assessed with site-directed mutagenesis.

    PubMed

    de Boer, Arjo L; Neerken, Sieglinde; de Wijn, Rik; Permentier, Hjalmar P; Gast, Peter; Vijgenboom, Erik; Hoff, Arnold J

    2002-01-01

    Mutants of Rhodobacter (Rba.) sphaeroides are described which were designed to study electron transfer along the so-called B-branch of reaction center (RC) cofactors. Combining the mutation L(M214)H, which results in the incorporation of a bacteriochlorophyll, beta, for H(A) [Kirmaier et al. (1991) Science 251: 922-927] with two mutations, G(M203)D and Y(M210)W, near B(A), we have created a double and a triple mutant with long lifetimes of the excited state P(*) of the primary donor P, viz. 80 and 160 ps at room temperature, respectively. The yield of P(+)Q(A) (-) formation in these mutants is reduced to 50 and 30%, respectively, of that in wildtype RCs. For both mutants, the quantum yield of P(+)H(B) (-) formation was less than 10%, in contrast to the 15% B-branch electron transfer demonstrated in RCs of a similar mutant of Rba. capsulatus with a P(*) lifetime of 15 ps [Heller et al. (1995) Science 269: 940-945]. We conclude that the lifetime of P(*) is not a governing factor in switching to B-branch electron transfer. The direct photoreduction of the secondary quinone, Q(B), was studied with a triple mutant combining the G(M203)D, L(M214)H and A(M260)W mutations. In this triple mutant Q(A) does not bind to the reaction center [Ridge et al. (1999) Photosynth Res 59: 9-26]. It is shown that B-branch electron transfer leading to P(+)Q(B) (-) formation occurs to a minor extent at both room temperature and at cryogenic temperatures (about 3% following a saturating laser flash at 20 K). In contrast, in wildtype RCs P(+)Q(B) (-) formation involves the A-branch and does not occur at all at cryogenic temperatures. Attempts to accumulate the P(+)Q(B) (-) state under continuous illumination were not successful. Charge recombination of P(+)Q(B) (-) formed by B-branch electron transfer in the new mutant is much faster (seconds) than has been previously reported for charge recombination of P(+)Q(B) (-) trapped in wildtype RCs (10(5) s) [Kleinfeld et al. (1984b) Biochemistry 23

  14. Influence of psychical trauma through transgenerational transfer on the development of traumatic reactions in women with diagnosed breast cancer.

    PubMed

    Anton, Sanda; Tomanović, Katarina; Mrdenović, Slobodan; Katinić, Krizo; Gugić, Damir; Topić, Jelena

    2011-09-01

    Earlier experience of psychological trauma of a close person can through a transgenerational transfer influence traumatic reactions of a person going through a trauma at present, resulting in a repetition of earlier traumatic experiences and a development of a variety of mental disturbances. Purpose of our study was to evaluate the influence of transgenerational transfer on the development of Posttraumatic stress disorder (PTSD) in women with diagnosed breast cancer that had a family member with diagnosed cancer. The sample mainly consisted of 120 women treated in a Department of Oncology, Osijek University Hospital Center with diagnosis of newly discovered breast cancer, during the conduction of radio therapy having values Hamilton depression scale (HAM-D) from > or = 8 to < or = 24 or values Hamilton anxiety scale (HAM-A) from > or = 17 to < or = 30. Psychotherapeutic interview with a detailed clinical overview and with applying diagnostic criteria according to DSM-IV for mental disorders, specially structured non-standardized questionnaire for etiologic factors evaluation of the beginning of examinees' mental disorder, Los Angeles Symptom Checklist of PTSD symptoms (LASC), Hamilton's scale for anxiety evaluation (HAM-A) and Hamilton's scale for depression evaluation (HAM-D) were used. Results show that 61 (51%) of patients have a family member with diagnosed cancer. The average total value on LASC for examinees that had a family member with diagnosed cancer was slightly higher (22.92) in comparison to those who had no such family member (20.88). No statistically significant connection was found between having a family member with diagnosed cancer and the average total value on LASC. Although no connection was established between having a family member with diagnosed cancer and the average value on LASC in women with diagnosed breast cancer, transgenerational transfer of emotions seems to be important in their traumatic reactions, but it is still insufficiently

  15. Solvent Dynamical Effects in Electron Transfer: Molecular Dynamics Simulations of Reactions in Methanol

    DTIC Science & Technology

    1993-04-01

    Lennard - Jones (LJ) spheres in contact, of varying diameter (4 or 5 A), and containing a univalent charge (cation or anion) on one site so to probe possible effects of the ionic charge sign. Following equilibration, the collective solvent response to a sudden charge transfer between the spherical sites is followed, and described in terms of the response function C(t), describing the difference in the solvent-induced electrostatic potential between the initial and final solute states. In all cases, the C(t) curves exhibit a very rapid (50-100 fs) initial decay component

  16. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS).

    PubMed

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-03-17

    Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH(-) as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H](+) [mass-to-charge ratio (m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H](-) (m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones. Graphical Abstract ᅟ.

  17. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

    NASA Astrophysics Data System (ADS)

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-03-01

    Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio (m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- (m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones.

  18. Quantitative kinetic analysis of hydrogen transfer reactions from dietary polyphenols to the DPPH radical.

    PubMed

    Goupy, Pascale; Dufour, Claire; Loonis, Michele; Dangles, Olivier

    2003-01-29

    Diphenylpicrylhydrazyl (DPPH) is widely used for quickly assessing the ability of polyphenols to transfer labile H atoms to radicals, a likely mechanism of antioxidant protection. This popular test generally pays no attention to the kinetics of H atom transfer, which however could be even more important than the total H-atom-donating capacities (stoichiometry, EC50) typically evaluated. In the present work, a series of dietary polyphenols belonging to the most representative families (flavonols from onion, flavanol monomers and oligomers from barley, and caffeic acid and caffeoyl esters from artichoke and endive) are characterized not only by their total stoichiometries (n(tot)) but also by their rate constants of first H atom abstraction by DPPH (k(1)), deduced from the kinetic analysis of the decay of the DPPH visible band following addition of the antioxidant. The mildly reactive DPPH radical allows a good discrimation between polyphenols, as demonstrated by the relatively large ranges of k(1) (ca. 400-5000 M(-)(1) s(-)(1)) and n(tot) (ca. 1-5) values typically measured with antioxidants having a single polyphenolic nucleus. With antioxidants displaying more than one polyphenolic nucleus (procyanidin oligomers, dicaffeoyl esters), the kinetic analysis makes it possible to demonstrate significant differences in reactivity between the subunits (two distinct k(1) values whose ratio lies in the range 3-10) and nonadditive stoichiometries.

  19. Reorganization of intramolecular high frequency vibrational modes and dynamic solvent effect in electron transfer reactions.

    PubMed

    Yudanov, Vladislav V; Mikhailova, Valentina A; Ivanov, Anatoly I

    2012-04-26

    The possibility of the multichannel stochastic model to adequately describe all principal regularities observed in thermal electron transfer kinetics has been demonstrated. The most important are as follows: (i) the model predicts the solvent controlled regime in the Marcus normal region and its almost full suppression in the Marcus inverted region as well as a continuous transition between them in the vicinity of the activationless region; (ii) the suppression of dynamic solvent effect (DSE) is principally caused by the reorganization of high frequency vibrational modes; (iii) an additional factor of the DSE suppression stems from fast solvent relaxation component; (iv) in the inverted region, the multichannel stochastic model predicts the apparent activation energy to be much less than that calculated with Marcus equation. The exploration of the multichannel stochastic model has allowed one to conclude that the reorganization of high frequency vibrational modes can (i) raise the maximum rate constant above the solvent controlled limit by 2 and more orders of magnitude, (ii) shift the rate constant maximum to larger values of the free energy gap, and (iii) approach the electron transfer kinetics to the nonadiabatic regime.

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

    NASA Astrophysics Data System (ADS)

    Amador-Muñoz, Omar; Misztal, Pawel K.; Weber, Robin; Worton, David R.; Zhang, Haofei; Drozd, Greg; Goldstein, Allen H.

    2016-11-01

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

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

    PubMed

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

    2015-12-17

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

  2. Domino rhodium/palladium-catalyzed dehydrogenation reactions of alcohols to acids by hydrogen transfer to inactivated alkenes.

    PubMed

    Trincado, Mónica; Grützmacher, Hansjörg; Vizza, Francesco; Bianchini, Claudio

    2010-03-01

    The combination of the d(8) Rh(I) diolefin amide [Rh(trop(2)N)(PPh(3))] (trop(2)N=bis(5-H-dibenzo[a,d]cyclohepten-5-yl)amide) and a palladium heterogeneous catalyst results in the formation of a superior catalyst system for the dehydrogenative coupling of alcohols. The overall process represents a mild and direct method for the synthesis of aromatic and heteroaromatic carboxylic acids for which inactivated olefins can be used as hydrogen acceptors. Allyl alcohols are also applicable to this coupling reaction and provide the corresponding saturated aliphatic carboxylic acids. This transformation has been found to be very efficient in the presence of silica-supported palladium nanoparticles. The dehydrogenation of benzyl alcohol by the rhodium amide, [Rh]N, follows the well established mechanism of metal-ligand bifunctional catalysis. The resulting amino hydride complex, [RhH]NH, transfers a H(2) molecule to the Pd nanoparticles, which, in turn, deliver hydrogen to the inactivated alkene. Thus a domino catalytic reaction is developed which promotes the reaction R-CH(2)-OH+NaOH+2 alkene-->R-COONa+2 alkane.

  3. Application of a BOSS – Gaussian Interface for QM/MM Simulations of Henry and Methyl Transfer Reactions

    PubMed Central

    Vilseck, Jonah Z.; Kostal, Jakub; Tirado-Rives, Julian; Jorgensen, William L.

    2015-01-01

    Hybrid quantum mechanics and molecular mechanics (QM/MM) computer simulations have become an indispensable tool for studying chemical and biological phenomena for systems too large to treat with quantum mechanics alone. For several decades, semi-empirical QM methods have been used in QM/MM simulations. However, with increased computational resources, the introduction of ab initio and density function methods into on-the-fly QM/MM simulations is being increasingly preferred. This adaptation can be accomplished with a program interface that tethers independent QM and MM software packages. This report introduces such an interface for the BOSS and Gaussian programs, featuring modification of BOSS to request QM energies and partial atomic charges from Gaussian. A customizable C-shell linker script facilitates the inter-program communication. The BOSS–Gaussian interface also provides convenient access to Charge Model 5 (CM5) partial atomic charges for multiple purposes including QM/MM studies of reactions. In this report, the BOSS–Gaussian interface is applied to a nitroaldol (Henry) reaction and two methyl transfer reactions in aqueous solution. Improved agreement with experiment is found by determining free-energy surfaces with MP2/CM5 QM/MM simulations than previously reported investigations employing semiempirical methods. PMID:26311531

  4. Assessment of theoretical procedures for calculating barrier heights for a diverse set of water-catalyzed proton-transfer reactions.

    PubMed

    Karton, Amir; O'Reilly, Robert J; Radom, Leo

    2012-04-26

    Accurate electronic barrier heights are obtained for a set of nine proton-transfer tautomerization reactions, which are either (i) uncatalyzed, (ii) catalyzed by one water molecule, or (iii) catalyzed by two water molecules. The barrier heights for reactions (i) and (ii) are obtained by means of the high-level ab initio W2.2 thermochemical protocol, while those for reaction (iii) are obtained using the W1 protocol. These three sets of benchmark barrier heights allow an assessment of the performance of more approximate theoretical procedures for the calculation of barrier heights of uncatalyzed and water-catalyzed reactions. We evaluate initially the performance of the composite G4 procedure and variants thereof (e.g., G4(MP2) and G4(MP2)-6X), as well as that of standard ab initio procedures (e.g., MP2, SCS-MP2, and MP4). We find that the performance of the G4(MP2)-type thermochemical procedures deteriorates with the number of water molecules involved in the catalysis. This behavior is linked to deficiencies in the MP2-based basis-set-correction term in the G4(MP2)-type procedures. This is remedied in the MP4-based G4 procedure, which shows good performance for both the uncatalyzed and the water-catalyzed reactions, with mean absolute deviations (MADs) from the benchmark values lying below the threshold of "chemical accuracy" (arbitrarily defined as 1 kcal mol(-1) ≈ 4.2 kJ mol(-1)). We also examine the performance of a large number of density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. We find that, with few exceptions (most notably PW6-B95 and B97-2), the performance of the DFT procedures that give good results for the uncatalyzed reactions deteriorates with the number of water molecules involved in the catalysis. The DHDFT procedures, on the other hand, show excellent performance for both the uncatalyzed and catalyzed reactions. Specifically, almost all of them afford MADs below the "chemical accuracy" threshold, with ROB2-PLYP and B2K

  5. Multinucleon transfer reactions for the {sup 28}Si+{sup 90,94}Zr systems in the region below and near the Coulomb barrier

    SciTech Connect

    Kalkal, Sunil; Mandal, S.; Garg, Ritika; Saxena, Mansi; Goyal, Savi; Verma, S.; Kumar, Suresh; Singh, R.; Madhavan, N.; Jhingan, A.; Nath, S.; Gehlot, J.; Mohanto, Gayatri; Prasad, E.; Sandal, Rohit; Behera, B. R.; Pramanik, U. D.; Sinha, A. K.

    2011-05-15

    Measurements on multinucleon transfer reactions for {sup 28}Si+{sup 90,94}Zr systems were performed at sub- and near-barrier energies. The fact that {sup 90}Zr has a closed neutron shell (N = 50) and {sup 94}Zr has four neutrons outside the closed shell, allows us to investigate the effects of shell closure and pairing correlation on multinucleon transfer mechanism. The experiment was performed with pulsed {sup 28}Si beam using the Heavy Ion Reaction Analyzer (HIRA) at Inter University Accelerator Centre (IUAC), New Delhi. Based on the Q-value considerations, it turned out that pickup channels were neutron transfer whereas stripping channels were proton transfer. For the {sup 28}Si+{sup 90}Zr system, the values of the slope parameter for two-neutron pickup turned out to be less than that for one-neutron pickup. The values of the slope parameter were almost the same for two-, three-, and four-neutron pickup channels in the case of the {sup 28}Si+{sup 94}Zr system. The transfer probabilities in the case of the {sup 28}Si+{sup 94}Zr system were much larger than those for the {sup 28}Si+{sup 90}Zr system, further supporting the fact that there is a correlation between the transfer channels and sub-barrier fusion cross-section enhancement. An odd-even staggering was observed in the extracted transfer probabilities at the barrier radius implying the role of pairing correlation in transfer reactions.

  6. Study of 11Be on 9Be one neutron transfer reactions at TRIUMF ISAC-II

    NASA Astrophysics Data System (ADS)

    Braid, Ryan; (Pcb)2 Collaboration; Tigress Collaboration

    2016-09-01

    The structure of neutron-rich Beryllium isotopes displays interesting properties arising from the interplay of alpha clustering and valence neutrons, leading in some cases to halo nuclei. In this presentation, preliminary results of the 11Be on 9Be reaction at 55 MeV and 30.14 MeV leading to two interesting exit channels will be shown, the first one enabling the study of 12Be and the second the study of 10Be. This reaction has advantages over the traditional (d,p) or (d,t) methods, since the reactants are equal in mass they both scatter in a detectable angular range. Additionally, TIGRESS allows precise γ-tagging for the excited states. Some challenges in analysis include the 10Be degeneracy, a large n breakup signature, and multiple particle excitation. The data and ongoing analysis will be presented. This work is partially supported by the US Department of Energy through Grant/Contract No. DE-FG03- 93ER40789 (Colorado School of Mines).

  7. One- and two-electron-transfer reactions of (dpp-Bian)Sm(dme)3.

    PubMed

    Fedushkin, Igor L; Maslova, Olga V; Hummert, Markus; Schumann, Herbert

    2010-03-15

    The reduction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian) with an excess of samarium in 1,2-dimethoxyethane (dme) affords the Sm(II) complex (dpp-Bian)Sm(dme)(3) (1). The reaction of 1 with 0.5 mol equiv of 1,2-dibromostilbene proceeds with the formation of the dimeric Sm(III) complex [(dpp-Bian)SmBr(dme)](2) (2). Oxidation of both the metal and the dpp-Bian ligand takes place if 1 is reacted with equimolar amounts of 1,2-dibromostilbene or iodine, yielding the monomeric Sm(III) derivatives (dpp-Bian)SmBr(2)(dme) (3) and (dpp-Bian)SmI(2)(THF)(2) (4; THF = tetrahydrofuran), respectively. The reaction of 1 with 0.5 mol equiv of iodine followed by 0.5 mol equiv of tetramethylthiuram disulfide gives the Sm(III) complex (dpp-Bian)SmI[SC(S)NMe(2)](dme) (5). Compound 4 and tBuOK react with the formation of the iodine-bridged dimer [(dpp-Bian)SmI(OtBu)(THF)](2) (6). Complexes 1 and 2 have been characterized by (1)H NMR spectroscopy and complexes 2-6 by their molecular structures, which were determined by single-crystal X-ray diffraction.

  8. Intramolecular energy- and electron-transfer reactions in polymetallic complexes. Annual report

    SciTech Connect

    Peterson, J.D.

    1991-12-01

    The complexes (tpy)Ru(II)(tpp)Co(III)(PPhEt{sub 2})H{sub 2}{sup 3+}, (NC){sub 3}Fe(II)(tpp)Co(III)(PPhEt{sub 2})H{sub 2} and (NC){sub 3}Fe(II)(tpp)Co(III)(PPh{sub 3})H{sub 2} (where tpp = 2,3,5,6-tetrakis(2{prime}-pyridyl)pyrazine), were prepared and their photochemistry studied. Reasons for the low quantum yields for H{sub 2} production are discussed briefly. A series of FeRuRh complexes is being prepared. Plans for the coming year on intramolecular energy transfer and charge separation are discussed.

  9. Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

    PubMed

    Carducci, Tessa M; Blackwell, Raymond E; Murray, Royce W

    2015-04-16

    Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

  10. Donor–acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions

    PubMed Central

    Stergiou, Anastasios; Pagona, Georgia

    2014-01-01

    Summary Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor–acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor–acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor–acceptor graphene-based hybrids, will be discussed. PMID:25247140

  11. Electron transfer reactions in microporous solids. Progress report, June 1991--May 1992

    SciTech Connect

    Mallouk, T.E.

    1992-05-01

    We have studied electron transfer quenching of the excited state of Ru(bpy){sub 3}{sup 2+} in aqueous suspensions of zeolites Y, L, and mordenite. The internal pore network of the zeolite is ion-exchanged with methylviologen cations, which quench the excited state of the surface-bound sensitizer. A detailed study of the quenching and charge recombination kinetics, using time-resolved luminescence quenching and transient diffuse reflectance spectroscopies, shows to remarkable effects: first, the excited state quenching is entirely dynamic is large-pore zeolites (L and Y), even when they are prepared as apparently ``dry`` powders (which still contain significant amounts of internally sited water). Second, a lower limit for the diffusion coefficient of the MV{sup 2+} ion in these zeolites, determined by this technique, is 10{sup {minus}7} cm{sup 2}sec, i.e., only about one order of magnitude slower than a typical ion in liquid water, and 2--3 orders of magnitude faster than charge transfer diffusion of cations in polyelectrolyte films or membranes such as Nafion. Surface sensitization of internally platinized layered oxide semiconductors such as K{sub 4-x}H{sub x}Nb{sub 6}O{sub 17}{center_dot}nH{sub 2}O (x {approx} 2.5) yields photocatalysts for the production of H{sub 2} and I{sub 3{minus}} in aqueous iodide solutions. Layered alkali niobates and titanates form a class of zeolitic wide-bandap semiconductors, and are the first examples of photocatalysts that evolve hydrogen from an electrochemically reversible (i.e., non-sacrificial) electron donor with visible light excitation.

  12. Studies on the mechanisms of phosphorothioyl transfer in enzymatic and nonenzymatic reactions

    SciTech Connect

    Domanico, P.L.

    1986-01-01

    The stereochemical course of rabbit liver fructose bisphosphatase (E.C.3.1.3.11) was determined by hydrolyzing a substrate analog (Sp)-(1-/sup 18/O)-fructose 1-phosphorothioate 6-phosphate in H/sub 2//sup 17/O, incorporating the chiral, inorganic phosphorothioate product into ATP..beta..S, and analyzing the isotopic distribution of /sup 18/O in ATP..beta..S by /sup 31/P NMR. The results indicate that the 1-phosphoryl group is transferred with inversion of configuration. A series of /sup 18/O-enrichment and exchange, single-turnover experiments rule out an enzyme acylphosphate intermediate in the hydrolysis. Consequently, fructose bisphosphatase catalyzes the hydrolysis of fructose 1,6-bisphosphate via a direct transfer of the phosphoryl moiety to water. To determine whether a monomeric metaphosphorothioate intermediate is formed during the hydrolysis of phosphorothioate monoesters, the stereochemical course of the hydrolysis of chiral (Rp)- and (Sp)-(/sup 18/O) O-p-nitrophenyl phosphorothioate in H/sub 2//sup 17/O was determined as per rabbit liver fructose bisphosphatase. /sup 31/P NMR analysis of the isotopic distribution of the ..beta..-P species of (Rp)-(..beta..-/sup 17/O,..beta..-/sup 18/O) ATP..beta..S for both isomers showed the monoester hydrolysis to proceed with inversion of configuration implying that if the metaphosphorothioate intermediate was formed, it did not exist long enough to become symmetrically solvated and, subsequently, suffered nucleophilic attack on the face opposing that occupied by the leaving group, p-nitrophenol.

  13. Non-adiabatic processes in the charge transfer reaction of O{sub 2} molecules with potassium surfaces without dissociation

    SciTech Connect

    Krix, David; Nienhaus, Hermann

    2014-08-21

    Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K{sub 2}O{sub 2} is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period.

  14. Extracting the Asymptotic Normalization Coefficients in Neutron Transfer Reactions to Determine the Astrophysical Reaction Rates for {sup 22}Mg(p,{gamma}){sup 23}Al and {sup 17}F(p,{gamma}){sup 18}Ne

    SciTech Connect

    Al-Abdullah, T.; Chen, X.; Clark, H.; Fu, C.; Gagliardi, C. A.; Lui, Y.-W.; Mukhamedzhanov, A. M.; Tabacaru, G.; Tokimoto, Y.; Trache, L.; Tribble, R. E.; Zhai, Y.; Carstoiu, F.

    2008-01-24

    It was expected that {gamma} rays from {sup 18}F and {sup 22}Na would be observed in massive One novae, but neither has been to date. The {sup 17}F(p,{gamma}){sup 18}Ne and {sup 22}Mg(p,{gamma}){sup 23}Al reactions may play important roles in the production and destruction of {sup 18}F and {sup 22}Na. We have determined the asymptotic normalization coefficients for {sup 18}Ne and {sup 23}Al through measurements of peripheral neutron transfer reactions in the mirror nuclear systems. We use the ANCs to calculate the astrophysical S-factors and reaction rates for these two reactions.

  15. The selective reaction of methoxyamine with cytidine residues in mammalian initiator transfer ribonucleic acid

    PubMed Central

    Piper, Peter W.; Clark, Brian F.C.

    1974-01-01

    Methoxyamine reacts selectively with tRNA molecules at certain exposed cytosine residues usually located in non base-paired regions of the two dimensional clover leaf structure. Here methoxyamine is used for the first time in a study of a mammalian tRNA structure. One of the sequence abnormalities of myeloma initiator tRNA is a cytosine instead of the usual uracil immediately preceding the anticodon. A study of the reaction of the cytosine residues with methoxyamine indicates that the accessibility of bases to chemical reagents in the anticodon loop of this mammalian initiator tRNA is very similar to that observed for the bacterial initiator tRNA. Images PMID:10793658

  16. 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

  17. Effect of moisture conditions and transfers on alkali silica reaction damaged structures

    SciTech Connect

    Multon, Stephane; Toutlemonde, Francois

    2010-06-15

    The aim of this paper is to point out the water driving effect on the alkali silica reaction (ASR) expansion and particularly when modifications of moisture conditions occur. After being submitted to a unidirectional moisture gradient during 14 months, the upper faces of ASR reactive beams were covered by water for 9 months. This late water supply on the upper face rapidly produced large expansions, which mainly occurred along the transverse and the vertical directions resulting in large longitudinal cracks. Companion nonreactive specimens were kept in the same environmental conditions in order to quantify the basic characteristics of moisture-dependent expansive behaviour of the material. The paper focuses on the effects of late water supply or late drying on already ASR-damaged concrete, which is a significant concern for real-life structures. Both structural effects of late water supply on ASR progress in already damaged structures and interpretation of such phenomena are described.

  18. Vibrational population distributions of the product of the chemiluminescent charge transfer reaction: O + (2D)+HCl --> O+HCl + (A 2Sigma + )

    NASA Astrophysics Data System (ADS)

    Shiraishi, Yasushi; Kusunoki, Isao

    1987-12-01

    The chemiluminescent charge transfer reaction of O+ (2 D)ions with HCl has been studied in the energy range of 7 to 100 eVc.m. . The vibrational population distributions of the HCl+(A 2 Σ+,v') product have been analyzed from the emission spectra of the A→X transition. At low collision energy the distribution has a peak at v'=3. The partial reaction cross section σ(3) for this level increases with decreasing collision energy. The features of the reaction are very similar to the F+ +CO→ F+CO+ (A) reaction reported previously. The mechanism has been discussed on the basis of curve crossing between the initial and final states along the HCl vibrational coordinate in the asymptotic region of the [O-HCl]+ system. The projectile ions C+ and N+ have also been tested for the charge transfer reaction of HCl(X)→HCl+(A).

  19. Characterization of alternate reductant binding and electron transfer in the dopamine. beta. -monooxygenase reaction

    SciTech Connect

    Stewart, L.C.; Klinman, J.P.

    1987-08-25

    The steady-state limiting kinetic parameters V/sub max/, V/K/sub DA/, and V/K/sub O/sub 2//, together with deuterium isotope effects on these parameters, have been determined for the dopamine ..beta..-monooxygenase (D..beta..M) reaction in the presence of structurally distinct reductants. The results show the one-electron reductant ferrocyanide to be nearly as kinetically competent as the presumed in vivo reductant ascrobate. Further, a reductant system of ferricyanide plus substrate dopamine yields steady-state kinetic parameters and isotope effects very similar to those measured solely in the presence of ferrocyanide, indicating a role for catecholamine in the rapid recycling of oxidized ferrocyanide. Use of substrate dopamine as the sole reductant is found to lead to a highly unusual kinetic independence of oxygen concentration, as well as significantly reduced values of V/sub max/ and V/K/sub DA/, and the authors conclude that dopamine reduces enzymic copper in a rate-limiting step that is 40-fold slower than with ascorbate. The near-identical kinetic parameters measured in the presence of either ascorbate or ferrocyanide, together with markedly reduced rates with dopamine, are interpreted in terms of a binding site for reductant that is physically distinct from the substrate binding site. This view is supported by molecular modeling, which reveals ascorbate and ferrocyanide to possess an unexpected similarity in potential sites for interaction with enzymic residues. With regard to electron flux, identical values of V/K/sub O/sub 2// have been measured with (2,2-/sup 2/H/sub 2/)dopamine as substrate both in the presence and in the absence of added ascorbate. This key result unambiguously rules out an entry of electrons to enzyme forms leading from the enzyme-dopamine complex to enzyme-bound product and, hence, reaction mechanisms involving a reductive activation of the putative Cu(II)-OOH prior to substrate hydroxylation.

  20. Ion/Ion Reactions with "Onium" Reagents: An Approach for the Gas-phase Transfer of Organic Cations to Multiply-Charged Anions

    NASA Astrophysics Data System (ADS)

    Gilbert, Joshua D.; Prentice, Boone M.; McLuckey, Scott A.

    2015-05-01

    The use of ion/ion reactions to effect gas-phase alkylation is demonstrated. Commonly used fixed-charge "onium" cations are well-suited for ion/ion reactions with multiply deprotonated analytes because of their tendency to form long-lived electrostatic complexes. Activation of these complexes results in an SN2 reaction that yields an alkylated anion with the loss of a neutral remnant of the reagent. This alkylation process forms the basis of a general method for alkylation of deprotonated analytes generated via electrospray, and is demonstrated on a variety of anionic sites. SN2 reactions of this nature are demonstrated empirically and characterized using density functional theory (DFT). This method for modification in the gas phase is extended to the transfer of larger and more complex R groups that can be used in later gas-phase synthesis steps. For example, N-cyclohexyl- N'-(2-morpholinoethyl)carbodiimide (CMC) is used to transfer a carbodiimide functionality to a peptide anion containing a carboxylic acid. Subsequent activation yields a selective reaction between the transferred carbodiimide group and a carboxylic acid, suggesting the carbodiimide functionality is retained through the transfer process. Many different R groups are transferable using this method, allowing for new possibilities for charge manipulation and derivatization in the gas phase.

  1. Ion/ion reactions with "onium" reagents: an approach for the gas-phase transfer of organic cations to multiply-charged anions.

    PubMed

    Gilbert, Joshua D; Prentice, Boone M; McLuckey, Scott A

    2015-05-01

    The use of ion/ion reactions to effect gas-phase alkylation is demonstrated. Commonly used fixed-charge "onium" cations are well-suited for ion/ion reactions with multiply deprotonated analytes because of their tendency to form long-lived electrostatic complexes. Activation of these complexes results in an SN2 reaction that yields an alkylated anion with the loss of a neutral remnant of the reagent. This alkylation process forms the basis of a general method for alkylation of deprotonated analytes generated via electrospray, and is demonstrated on a variety of anionic sites. SN2 reactions of this nature are demonstrated empirically and characterized using density functional theory (DFT). This method for modification in the gas phase is extended to the transfer of larger and more complex R groups that can be used in later gas-phase synthesis steps. For example, N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide (CMC) is used to transfer a carbodiimide functionality to a peptide anion containing a carboxylic acid. Subsequent activation yields a selective reaction between the transferred carbodiimide group and a carboxylic acid, suggesting the carbodiimide functionality is retained through the transfer process. Many different R groups are transferable using this method, allowing for new possibilities for charge manipulation and derivatization in the gas phase.

  2. Monte Carlo simulation of transfer reactions using extended R-matrix theory picturing surrogate-type WFCF features

    NASA Astrophysics Data System (ADS)

    Bouland, Olivier H.

    2016-03-01

    This article supplies an overview of issues related to the interpretation of surrogate measurement results for neutron-incident cross section predictions; difficulties that are somehow masked by the historical conversion route based on Weisskopf-Ewing approximation. Our proposal is to handle the various difficulties by using a more rigorous approach relying on Monte Carlo simulation of transfer reactions with extended R-matrix theory. The multiple deficiencies of the historical surrogate treatment are recalled but only one is examined in some details here; meaning the calculation of in-out-going channel Width Fluctuation Correction Factors (WFCF) which behavior witness partly the failure of Niels Bohr's compound nucleus theoretical landmark. Relevant WFCF calculations according to neutron-induced surrogate- and cross section-types as a function of neutron-induced fluctuating energy range [0 - 2.1 MeV] are presented and commented in the case of the 240Pu* and 241Pu* compound nucleus isotopes.

  3. Mediation of donor–acceptor distance in an enzymatic methyl transfer reaction

    PubMed Central

    Zhang, Jianyu; Kulik, Heather J.; Martinez, Todd J.; Klinman, Judith P.

    2015-01-01

    Enzymatic methyl transfer, catalyzed by catechol-O-methyltransferase (COMT), is investigated using binding isotope effects (BIEs), time-resolved fluorescence lifetimes, Stokes shifts, and extended graphics processing unit (GPU)-based quantum mechanics/molecular mechanics (QM/MM) approaches. The WT enzyme is compared with mutants at Tyr68, a conserved residue that is located behind the reactive sulfur of cofactor. Small (>1) BIEs are observed for an S-adenosylmethionine (AdoMet)-binary and abortive ternary complex containing 8-hydroxyquinoline, and contrast with previously reported inverse (<1) kinetic isotope effects (KIEs). Extended GPU-based computational studies of a ternary complex containing catecholate show a clear trend in ground state structures, from noncanonical bond lengths for WT toward solution values with mutants. Structural and dynamical differences that are sensitive to Tyr68 have also been detected using time-resolved Stokes shift measurements and molecular dynamics. These experimental and computational results are discussed in the context of active site compaction that requires an ionization of substrate within the enzyme ternary complex. PMID:26080432

  4. Side chain effects in reactions of the potassium-tyrosine charge transfer complex

    NASA Astrophysics Data System (ADS)

    da Silva, F. Ferreira; Meneses, G.; Ingólfsson, O.; Limão-Vieira, P.

    2016-10-01

    Fragmentation of transient negative ions of tyrosine formed through electron transfer in collisions with neutral potassium atoms is presented in the collision energy range from 30 to 75 eV. At low collision energies the dominating side chain channel observed corresponds to the cleavage of the bond from the para-position of the phenyl ring to the β-C of the remaining moiety, but cleavage of the Cαsbnd Cβ bond is also observed. Further fragments are formed through cleavage of the Cα bond to the carbonyl group, through decomposition of the carboxyl group or through significant decomposition of the backbone. The dehydrogenated molecular anion is also observed with appreciable intensity. These results are discussed in the context of earlier studies on dissociative electron attachment to tyrosine and other amino acids, as well as within the role of the side chain in electron induced decomposition of this aromatic amino acid. Stabilization of the temporary molecular anion in the transient collision complex is discussed and we argue that this may have significant influence on the branching ratios observed.

  5. The reaction of an iridium PNP complex with parahydrogen facilitates polarisation transfer without chemical change.

    PubMed

    Holmes, Arthur J; Rayner, Peter J; Cowley, Michael J; Green, Gary G R; Whitwood, Adrian C; Duckett, Simon B

    2015-01-21

    The short lived pincer complex [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(py)]BF4 is shown to be active for signal amplification by reversible exchange. This catalyst formulation enables the efficient transfer of polarization from parahydrogen to be placed into just a single molecule of the hyperpolarisation target, pyridine. When the catalysts (1)H nuclei are replaced by (2)H, increased levels of substrate hyperpolarization result and when the reverse situation is examined the catalyst itself is clearly visible through hyperpolarised signals. The ligand exchange pathways of [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(py)]BF4 that are associated with this process are shown to involve the formation of 16-electron [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2]BF4 and the 18-electron H2 addition product [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(H2)]BF4.

  6. Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers: volume change, enthalpy, and entropy of electron-transfer reactions in the intact cells of the cyanobacterium Synechocystis PCC 6803.

    PubMed

    Boichenko, V A; Hou, J M; Mauzerall, D

    2001-06-19

    The volume and enthalpy changes for charge transfer in the 0.1-10 micros time window in photosynthetic reaction centers of the intact cells of Synechocystis PCC 6803 were determined using pulsed, time-resolved photoacoustics. This required invention of a method to correct for the cell artifact at the temperature of maximum density of water caused by the heterogeneous system. Cells grown under either white or red light had different PS I/PS II molar ratios, approximately 3 and approximately 1.7, respectively, but invariable action spectra and effective antenna sizes of the photosystems. In both cultures, the photoacoustic measurements revealed that their thermodynamic parameters differed strongly in the spectral regions of predominant excitation of PS I (680 nm) and PS II (625 nm). On correcting for contribution of the two photosystems at these wavelengths, the volume change was determined to be -27 +/- 3 and -2 +/- 3 A3 for PS I and PS II, respectively. The energy storage on the approximately 1 micros time scale was estimated to be 80 +/- 15% and 45 +/- 10% per trap in PS I and PS II, respectively. These correspond to enthalpies of -0.33 +/- 0.2 and -1 +/- 0.2 eV for the assumed formation of ion radical pairs P700+F(AB-) and Y(Z*)P680Q(A-), respectively. Taking the free energy of the above reactions as the differences of their redox potentials in situ, apparent entropy changes were estimated to be +0.4 +/- 0.2 and -0.2 +/- 0.2 eV for PS I and PS II, respectively. These values are similar to that obtained in vitro for the purified reaction center complexes on the microsecond time scale [Hou et al. (2001) Biochemistry 40, 7109-7116, 7117-7125]. The constancy of these thermodynamic values over a 2-fold change of the ratio of PS I/PS II is support for this method of in vivo analysis. Our pulsed PA method can correct the "cell" or heterogeneous artifact and thus opens a new route for studying the thermodynamics of electron transfer in vivo.

  7. Electron transfer kinetics in photosynthetic reaction centers embedded in trehalose glasses: trapping of conformational substates at room temperature.

    PubMed Central

    Palazzo, Gerardo; Mallardi, Antonia; Hochkoeppler, Alejandro; Cordone, Lorenzo; Venturoli, Giovanni

    2002-01-01

    We report on room temperature electron transfer in the reaction center (RC) complex purified from Rhodobacter sphaeroides. The protein was embedded in trehalose-water systems of different trehalose/water ratios. This enabled us to get new insights on the relationship between RC conformational dynamics and long-range electron transfer. In particular, we measured the kinetics of electron transfer from the primary reduced quinone acceptor (Q(A)(-)) to the primary photo oxidized donor (P(+)), by time-resolved absorption spectroscopy, as a function of the matrix composition. The composition was evaluated either by weighing (liquid samples) or by near infrared spectroscopy (highly viscous or solid glasses). Deconvolution of the observed, nonexponential kinetics required a continuous spectrum of rate constants. The average rate constant ( = 8.7 s(-1) in a 28% (w/w) trehalose solution) increases smoothly by increasing the trehalose/water ratio. In solid glasses, at trehalose/water ratios > or = 97%, an abrupt increase is observed ( = 26.6 s(-1) in the driest solid sample). A dramatic broadening of the rate distribution function parallels the above sudden increase. Both effects fully revert upon rehydration of the glass. We compared the kinetics observed at room temperature in extensively dried water-trehalose matrices with the ones measured in glycerol-water mixtures at cryogenic temperatures and conclude that, in solid trehalose-water glasses, the thermal fluctuations among conformational substates are inhibited. This was inferred from the large broadening of the rate constant distribution for electron transfer obtained in solid glasses, which was due to the free energy distribution barriers having become quasi static. Accordingly, the RC relaxation from dark-adapted to light-adapted conformation, which follows primary charge separation at room temperature, is progressively hindered over the time scale of P(+)Q(A)(-) charge recombination, upon decreasing the

  8. "Abnormal" salt and solvent effects on anion/cation electron-transfer reactions: an interpretation based on Marcus-Hush treatment.

    PubMed

    Garcia-Fernandez, E; Prado-Gotor, R; Sanchez, F

    2005-08-11

    Salt and solvent effects on the kinetics of the reactions [Fe(CN)6]3- + [Ru(NH3)5pz](2+) right arrow over left arrow [Fe(CN)6]4- + [Ru(NH3)5pz]3+ (pz = pyrazine) have been studied through T-jump measurements. The forward and reverse reactions show different behaviors: "abnormal" salt and solvent effects in the first case and normal effects in the second one. These facts imply an asymmetric behavior of anion/cation reactions depending on the charge of the oxidant. The results can be rationalized by using the Marcus-Hush treatment for electron-transfer reactions.

  9. Determination of the neutron electric form factor from the reaction 3He(e,e'n) at medium momentum transfer

    NASA Astrophysics Data System (ADS)

    Becker, J.; Andresen, H. G.; Annand, J. R. M.; Aulenbacher, K.; Beuchel, K.; Blume-Werry, J.; Dombo, Th.; Drescher, P.; Ebert, M.; Eyl, D.; Frey, A.; Grabmayr, P.; Großmann, T.; Hartmann, P.; Hehl, T.; Heil, W.; Herberg, C.; Hoffmann, J.; Kellie, J. D.; Klein, F.; Livingston, K.; Leduc, M.; Meyerhoff, M.; Möller, H.; Nachtigall, Ch.; Natter, A.; Ostrick, M.; Otten, E. W.; Owens, R. O.; Plützer, S.; Reichert, E.; Rohe, D.; Schäfer, M.; Schmieden, H.; Sprengard, R.; Steigerwald, M.; Steffens, K.-H.; Surkau, R.; Walcher, Th.; Watson, R.; Wilms, E.

    The electric form factor of the neutron GEn has been determined in double polarized exclusive 3He(e,e'n) scattering in quasi-elastic kinematics by measuring asymmetries A⊥, A∥ of the cross section with respect to helicity reversal of the electron, with the nuclear spin being oriented perpendicular to the momentum transfer q in case of A⊥ and parallel in case of A∥. The experiment was performed at the 855 MeV c. w. microtron MAMI at Mainz. The degree of polarization of the electron beam and of the gaseous 3He target were each about 50%. Scattered electrons and neutrons were detected in coincidence by detector arrays covering large solid angles. Quasi-elastic scattering events were reconstructed from the measured electron scattering angles ϑe, φe and the neutron momentum vector pn' in the plane wave impulse approximation. We obtain the result (0.27 < Q2c2/GeV2 < 0.5)= 0.0334 +/- 0.0033stat+/- 0.0028syst which is averaged over the indicated range of Q2, the squared momentum transfer. This GEn value is significantly smaller than measured from the D(e,e'n) reaction under similar kinematical conditions. To what extent final state interactions in 3He quench the GEn result is subject of calculations currently in progress elsewhere.

  10. Spectroscopy of 7He using the 9Be(6He,8Be) transfer reaction

    NASA Astrophysics Data System (ADS)

    Renzi, F.; Raabe, R.; Randisi, G.; Smirnov, D.; Angulo, C.; Cabrera, J.; Casarejos, E.; Keutgen, Th.; Ninane, A.; Charvet, J. L.; Gillibert, A.; Lapoux, V.; Nalpas, L.; Obertelli, A.; Skaza, F.; Sida, J. L.; Orr, N. A.; Sidorchuk, S. I.; Wolski, R.; Borge, M. J. G.; Escrig, D.

    2016-08-01

    The unbound nucleus 7He has been investigated via the reaction of a 16.8 MeV 6He radioactive ion beam on a 9Be target. The measurement of the outgoing 8Be through its well characterized two-α decay permitted the energy of the 6He+n system to be reconstructed. Through comparison with a complete Monte Carlo simulation incorporating R -matrix lineshapes, the 7He ground state was determined to lie 0.380(28) MeV above the neutron decay with a width of Γ =0.179 (21 ) MeV. A neutron spectroscopic factor SF=0.608 (18 ) was extracted in agreement with the most recent calculations. Significant evidence was found for a broad resonance lying at 2.6(2) MeV above threshold with a ΓFWHM=2.3 (3 ) MeV. These parameters are fully consistent with the properties of 1 /2- state reported by Wuosmaa et al. [Phys. Rev. C 72, 061301(R) (2005), 10.1103/PhysRevC.72.061301]. Limits were also put on the presence of narrow resonances seen in earlier experiments.

  11. High yield of B-branch electron transfer in a quadruple reaction center mutant of the photosynthetic bacterium Rhodobacter sphaeroides.

    PubMed

    de Boer, Arjo L; Neerken, Sieglinde; de Wijn, Rik; Permentier, Hjalmar P; Gast, Peter; Vijgenboom, Erik; Hoff, Arnold J

    2002-03-05

    A new reaction center (RC) quadruple mutant, called LDHW, of Rhodobacter sphaeroides is described. This mutant was constructed to obtain a high yield of B-branch electron transfer and to study P(+)Q(B)(-) formation via the B-branch. The A-branch of the mutant RC contains two monomer bacteriochlorophylls, B(A) and beta, as a result of the H mutation L(M214)H. The latter bacteriochlorophyll replaces bacteriopheophytin H(A) of wild-type RCs. As a result of the W mutation A(M260)W, the A-branch does not contain the ubiquinone Q(A); this facilitates the study of P(+)Q(B)(-) formation. Furthermore, the D mutation G(M203)D introduces an aspartic acid residue near B(A). Together these mutations impede electron transfer through the A-branch. The B-branch contains two bacteriopheophytins, Phi(B) and H(B), and a ubiquinone, Q(B.) Phi(B) replaces the monomer bacteriochlorophyll B(B) as a result of the L mutation H(M182)L. In the LDHW mutant we find 35-45% B-branch electron transfer, the highest yield reported so far. Transient absorption spectroscopy at 10 K, where the absorption bands due to the Q(X) transitions of Phi(B) and H(B) are well resolved, shows simultaneous bleachings of both absorption bands. Although photoreduction of the bacteriopheophytins occurs with a high yield, no significant (approximately 1%) P(+)Q(B)(-) formation was found.

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

    PubMed

    Ringer, Joachim M

    2013-01-01

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

  13. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    SciTech Connect

    Koretsky, A.P.

    1984-08-01

    This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. Chronically implanted detection coils, employing a balanced matching configuration of capacitors in the tuned circuit, were used to obtain /sup 31/P NMR spectra from heart, kidney, and liver in situ. Gated spectra of heart obtained at systole and diastole and the effects of fructose on kidney and liver were studied. The ability to observe other nuclei using implanted coils is illustrated with /sup 39/K NMR spectra from kidney and muscle. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate (13 ..mu..mol/min/gm tissue) were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O (0.8 to 1.7) and Na/sup +//ATP (4 to 10) values. The problems associated with ATP synthesis rate measurements in kidney, e.g., the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed.

  14. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

    SciTech Connect

    Zheng, Haiyan; Li, Kuo; Cody, George D.; Tulk, Christopher A.; Dong, Xiao; Gao, Guoying; Molaison, Jamie J.; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N.; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-kwang

    2016-08-25

    Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH···N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3 bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

  15. Corrosion of ferritic steels by molten lithium: Influence of competing thermal gradient mass transfer and surface product reactions

    SciTech Connect

    Tortorelli, P.F.

    1987-10-01

    An Fe-12Cr-1MoVW steel was exposed to thermally convective lithium for 6962 h. Results showed that the weight change profile of Fe-12Cr-1MoVW steel changed substantially as the maximum loop temperature was raised from 500 to 600/sup 0/C. Furthermore, for a particular loop experiment, changes in the structure and composition of the exposed surfaces did not reflect typical thermal gradient mass transfer effects for all elements: the surface concentration of chromium was often a maximum at intermediate temperatures, while nickel (present at low concentrations in the starting material) tended to be transported to the coldest part of the loop. Such data were interpreted in terms of a qualitative model in which there are different dominant reactions or the various constituents of the ferritic steels (surface product formation involving nitrogen and/or carbon and solubility-driven elemental transport). This competition among different reactions is important in evaluating overall corrosion behavior and the effects of temperature. The overall corrosion rate of the 12Cr-1MoVW steel was relatively low when compared to that for austenitic stainless steel exposed under similar conditions.

  16. An Adsorptive Transfer Technique Coupled with Brdicka Reaction to Reveal the Importance of Metallothionein in Chemotherapy with Platinum Based Cytostatics

    PubMed Central

    Krizkova, Sona; Fabrik, Ivo; Huska, Dalibor; Adam, Vojtech; Babula, Petr; Hrabeta, Jan; Eckschlager, Tomas; Pochop, Pavel; Darsova, Denisa; Kukacka, Jiri; Prusa, Richard; Trnkova, Libuse; Kizek, Rene

    2010-01-01

    The drugs based on platinum metals represent one of the oldest, but also one of the most effective groups of chemotherapeutic agents. Thanks to many clinical studies it is known that resistance of tumor cells to drugs is a frequent cause of chemotherapy failure. With regard to platinum based drugs, multidrug resistance can also be connected with increased expression of low-molecular weight protein metallothionein (MT). This study aimed at investigating the interactions of MT with cisplatin or carboplatin, using the adsorptive transfer technique coupled with differential pulse voltammetry Brdicka reaction (AdTS DPV Brdicka reaction), and a comparison of in vitro results with results obtained in vivo. The results obtained from the in vitro study show a strong affinity between platinum based drugs and MT. Further, we analyzed extracts of neuroblastoma cell lines treated with cisplatin or carboplatin. It is clear that neuroblastoma UKF-NB-4 cisplatin-resistant and cisplatin-sensitive cell lines unlikely respond to the presence of the platinum-based cytostatics cisplatin and carboplatin. Finally, we determined the level of MT in samples from rabbits treated with carboplatin and patients with retinoblastoma treated with the same drug. PMID:21614176

  17. Synthesis, spectra, and electron-transfer reaction of aspartic acid-functionalized water-soluble perylene bisimide in aqueous solution.

    PubMed

    Zhong, Lina; Xing, Feifei; Shi, Wei; Yan, Liuming; Xie, Liqing; Zhu, Shourong

    2013-04-24

    An aspartic acid-functionalized water-soluble perylene bisimide, N,N'-di(2-succinic acid)-perylene-3,4,9,10-tetracarboxylic bisimide (PASP) was synthesized and characterized. It has absorbance maximum A(0-0) and A(0-1) at 527 and 498 nm (ε ≈ 1.7 × 10(4) L cm(-1) mol(-1)) respectively in pH 7.20 HEPES buffer. Two quasi-reversible redox processes with E1/2 at -0.17 and -0.71 V (vs Ag/AgCl) respectively in pH 7-12.5 aqueous solutions. PASP can react with Na2S in pure aqueous solution to form monoanion radical and dianion species consecutively. PASP(-•) has EPR signal with g = 1.998 in aqueous solution, whereas PASP(2-) is EPR silent. The monoanion radical formation is a first-order reaction with k = 8.9 × 10(-2) s(-1). Dianion species formation is a zero-order reaction and the rate constant is 4.3 × 10(-8) mol L(-1) s(-1). The presence of H2O2 greatly increases the radical formation rate constant. PASP as a two-electron transfer reagent is expected to be used in the water photolysis.

  18. B-side electron transfer promoted by absorbance of multiple photons in Rhodobacter sphaeroides R-26 reaction centers

    SciTech Connect

    Lin, S.; Jackson, J.A.; Taguchi, A.K.W.; Woodbury, N.W.

    1999-06-03

    Femtosecond transient absorbance spectra of quinone-depleted Rhodobacter sphaeroides R-26 reaction centers in the Q{sub X} transition region have been measured at 15 K under various excitation conditions. This study focuses on the excitation wavelength dependence and excitation intensity dependence of the formation of charge-separated states on the A- and B-side of the reaction center, judging from the bleaching of the 533 nm (B-side) and 544 nm (A-side) ground-state transitions of the reaction center bacteriopheophytins (H{sub A} and H{sub B}). Upon low-intensity selective excitation directly into the bacteriopheophytin Q{sub Y} transitions (near 760 nm), bleaching of both ground-state bacteriopheophytin Q{sub X} transitions appeared immediately, showing that initially either the A- or B-side bacteriopheophytin could be excited. However, both excited states ultimately resulted in P{sup +}H{sub A}{sup {minus}} formation under these conditions. Low-intensity excitation at any of the various wavelengths showed no difference in the kinetics of the A-side charge separation forming P{sup +}H{sub A}{sup {minus}} and no substantial formation of the B-side charge-separated state, P{sup +}H{sub B}{sup {minus}}. In contrast, high-intensity 595 nm excitation resulted in substantial long-lived bleaching of the B-side bacteriopheophytin ground-state transition at 533 nm. This 533 nm bleaching was formed with essentially the same time constant as the bleaching at 544 nm due to A-side charge separation. Both bleaching bands persisted at the longest times measured in quinone-removed reaction centers. The long-lived bleaching at 533 nm using high-intensity excitation most likely represents the formation of P{sup +}H{sub B}{sup {minus}} with a relative yield of nearly 40%. One possible mechanism for B-side electron transfer is that two-photon excitation of the reaction center resulting in the state P{sup *}B{sub B}{sup *} makes P{sup +}B{sub B}{sup {minus}} thermodynamically

  19. Chlorine transfer between glycine, taurine, and histamine: reaction rates and impact on cellular reactivity.

    PubMed

    Peskin, Alexander V; Midwinter, Robyn G; Harwood, David T; Winterbourn, Christine C

    2005-02-01

    Hypochlorous acid formed by activated neutrophils reacts with amines to produce chloramines. Chloramines vary in stability, reactivity, and cell permeability. We have examined whether chloramine exchange occurs between physiologically important amines or amino acids and if this affects interactions of chloramines with cells. We have demonstrated transchlorination reactions between histamine, glycine, and taurine chloramines by measuring chloramine decay rates with mixtures as well as by mass spectrometry. Kinetic analysis suggested the formation of an intermediate complex with a high Km. Apparent second-order rate constants, determined for concentrations

  20. Chlorine transfer between glycine, taurine, and histamine: reaction rates and impact on cellular reactivity.

    PubMed

    Peskin, Alexander V; Midwinter, Robyn G; Harwood, David T; Winterbourn, Christine C

    2004-11-15

    Hypochlorous acid formed by activated neutrophils reacts with amines to produce chloramines. Chloramines vary in stability, reactivity, and cell permeability. We have examined whether chloramine exchange occurs between physiologically important amines or amino acids and if this affects interactions of chloramines with cells. We have demonstrated transchlorination reactions between histamine, glycine, and taurine chloramines by measuring chloramine decay rates with mixtures as well as by mass spectrometry. Kinetic analysis suggested the formation of an intermediate complex with a high K(m). Apparent second-order rate constants, determined for concentrations

  1. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach.

    PubMed

    Amorati, Riccardo; Menichetti, Stefano; Mileo, Elisabetta; Pedulli, Gian Franco; Viglianisi, Caterina

    2009-01-01

    The role of intramolecular hydrogen bonding (HB) on the bond-dissociation enthalpy (BDE) of the phenolic O-H and on the kinetics of H-atom transfer to peroxyl radicals (k(inh)) of several 2-alkoxyphenols was experimentally quantified by the EPR equilibration technique and by inhibited autoxidation studies. These compounds can be regarded as useful models for studying the H-atom abstraction from 2-OR phenols, such as many lignans, reduced coenzyme Q and curcumin. The effects of the various substituents on the BDE(O-H) of 2-methoxy, 2-methoxy-4-methyl, 2,4-dimethoxyphenols versus phenol were measured in benzene solution as -1.8; -3.7; -5.4 kcal mol(-1), respectively. In the case of polymethoxyphenols, significant deviations from the BDE(O-H) values predicted by the additive effects of the substituents were found. The logarithms of the k(inh) constants in cumene were inversely related to the BDE(O-H) values, obeying a linear Evans-Polanyi plot with the same slope of other substituted phenols and a y-axis intercept slightly smaller than that of 2,6-dimethyl phenols. In the cases of phenols having the 2-OR substituent included in a five-membered condensed ring (i.e, compounds 9-11), both conformational isomers in which the OH group points toward or away from the oxygen in position 2 were detected by FTIR spectroscopy and the intramolecular HB strength was thus estimated. The contribution to the BDE(O-H) of the ortho-OR substituent in 9, corrected for intramolecular HB formation, was calculated as -5.6 kcal mol(-1). The similar behaviour of cyclic and non-cyclic ortho-alkoxy derivatives clearly showed that the preferred conformation of the OMe group in ortho-methoxyphenoxyl radicals is that in which the methyl group points away from the phenoxyl oxygen, in contrast to the geometries predicted by DFT calculations.

  2. Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

    NASA Astrophysics Data System (ADS)

    Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

    2016-03-01

    A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

  3. MPW1K Performs Much Better than B3LYP in DFT Calculations on Reactions that Proceed by Proton-Coupled Electron Transfer (PCET)

    PubMed Central

    Lingwood, Mark; Hammond, Jeff R.; Hrovat, David A.; Mayer, James M.; Borden, Weston Thatcher

    2008-01-01

    DFT calculations have been performed with the B3LYP and MPW1K functional on the hydrogen atom abstraction reactions of ethenoxyl with ethenol and of phenoxyl with both phenol and α-naphthol. Comparison with the results of G3 calculations shows that B3LYP seriously underestimates the barrier heights for the reaction of ethenoxyl with ethenol by both proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms. The MPW1K functional also underestimates the barrier heights, but by much less than B3LYP. Similarly, comparison with the results of experiments on the reaction of phenoxyl radical with α-naphthol indicates that the barrier height for the preferred PCET mechanism is calculated more accurately by MPW1K than by B3LYP. These findings indicate that the MPW1K functional is much better suited than B3LYP for calculations on hydrogen abstraction reactions by both HAT and PCET mechanisms. PMID:18725967

  4. Spectroscopic investigation on kinetics, thermodynamics and mechanism for electron transfer reaction of iron(III) complex with sulphur centered radical in stimulated biological system.

    PubMed

    Deepalakshmi, S; Sivalingam, A; Kannadasan, T; Subramaniam, P; Sivakumar, P; Brahadeesh, S T

    2014-04-24

    Electron transfer reactions of biological organic sulphides with several metal ions to generate sulphide radical cations are a great concern in biochemical process. To understand the mechanism, a stimulated biological system having model compounds, iron(III)-bipyridyl complex with thio-diglycolic acid (TDGA) was investigated. Spectroscopic study reveals the kinetics and thermodynamics of the reaction in aqueous perchloric acid medium. The reaction follows first and fractional order of 0.412 with respect to [Fe(bpy)3](3+) and TDGA, respectively. The oxidation is insensitive to variation in [H(+)] but slightly decreases with increase in ionic strength ([I]). Addition of acrylamide, a radical scavenger has no effect on the rate of the reaction. The high negative value of ΔS(#) (-74.3±1.09 J K(-1) mol(-1)) indicates the complex formed has a definite orientation higher than the reactants. Based on the above results, a suitable reaction mechanism for this reaction is proposed.

  5. Reaction dynamics and energy transfer in ion/surface scattering: Oxygen(+)/silicon dioxide and neon(+)/silicon(001)

    NASA Astrophysics Data System (ADS)

    Quinteros, Cecilia Laura

    The scattering of hyperthermal ions on surfaces provides detailed information regarding physical and chemical processes of scientific and technological importance. In order to explore the dynamics of atomic ion-surface interactions with and without chemical transformations, two different systems have been studied. The scattering of hyperthermal Ne+ on Si(001) provides a critical test for the applicability of simple models for energy transfer. Angle-, energy-, and mass-resolved detection reveals that for Ne+ energies between 50--300 eV, a simple analytical model can provide a quantitative description of the energy transfer process. In contrast, the study of O+/SiOx exhibits a vast array of reaction channels. Not only are scattered and sputtered species found, but O2 - is formed through the abstraction of surface oxygen via two competing pathways. For low O+ energies, O 2- is produced exclusively by scattering-mediated abstraction, where an incident oxygen ion reacts with a surface O-atom. At higher energies, recoil-abstraction is also observed, in which a recoiling O- anion collides with a neighboring surface O-atom to form O2-. The two mechanisms are related in that scattering-mediated abstraction and recoil-abstraction both form O 2- products along the outgoing path of the trajectory. A simple barrier model for oxygen abstraction strongly suggests that the precursors for O2- formation are the scattered and recoiled O- species. This study represents the first experimental evidence of hyperthermal atomic ions abstracting oxygen atoms from an oxide surface.

  6. Mechanisms and kinetics of noncatalytic ether reaction in supercritical water. 2. Proton-transferred fragmentation of dimethyl ether to formaldehyde in competition with hydrolysis.

    PubMed

    Nagai, Yasuharu; Matubayasi, Nobuyuki; Nakahara, Masaru

    2005-04-28

    Noncatalytic reaction pathways and rates of dimethyl ether (DME) in supercritical water are determined in a tube reactor made of quartz according to liquid- and gas-phase 1H and 13C NMR observations. The reaction is studied at two concentrations (0.1 and 0.5 M) in supercritical water at 400 degrees C and over a water-density range of 0.1-0.6 g/cm3. The supercritical water reaction is compared with the neat one (in the absence of solvent) at 0.1 M and 400 degrees C. DME is found to decompose through (i) the proton-transferred fragmentation to methane and formaldehyde and (ii) the hydrolysis to methanol. Formaldehyde from reaction (i) is consecutively subjected to four types of redox reactions. Two of them proceed even without solvent: (iii) the unimolecular proton-transferred decarbonylation forming hydrogen and carbon monoxide and (iv) the bimolecular self-disproportionation generating methanol and carbon monoxide. When the solvent water is present, two additional paths are open: (v) the bimolecular self-disproportionation of formaldehyde with reactant water, producing methanol and formic acid, and (vi) the bimolecular cross-disproportionation between formaldehyde and formic acid, yielding methanol and carbonic acid. Methanol is produced through the three types of disproportionations (iv)-(vi) as well as the hydrolysis (ii). The presence of solvent water decelerates the proton-transferred fragmentation of DME; the rate constant is reduced by 40% at 0.5 g/cm3. This is caused by the suppression of low-frequency concerted motion corresponding to the reaction coordinate for the simultaneous C-O bond scission and proton transfer from one methyl carbon to the other. In contrast to the proton-transferred fragmentation, the hydrolysis of DME is markedly accelerated by increasing the water density. The latter becomes more important than the former in supercritical water at densities greater than 0.5 g/cm3.

  7. Teaching the fundamentals of electron transfer reactions in mitochondria and the production and detection of reactive oxygen species

    PubMed Central

    Mailloux, Ryan J.

    2015-01-01

    Mitochondria fulfill a number of biological functions which inherently depend on ATP and O2−•/H2O2 production. Both ATP and O2−•/H2O2 are generated by electron transfer reactions. ATP is the product of oxidative phosphorylation whereas O2−• is generated by singlet electron reduction of di-oxygen (O2). O2−• is then rapidly dismutated by superoxide dismutase (SOD) producing H2O2. O2−•/H2O2 were once viewed as unfortunately by-products of aerobic respiration. This characterization is fitting considering over production of O2−•/H2O2 by mitochondria is associated with range of pathological conditions and aging. However, O2−•/H2O2 are only dangerous in large quantities. If produced in a controlled fashion and maintained at a low concentration, cells can benefit greatly from the redox properties of O2−•/H2O2. Indeed, low rates of O2−•/H2O2 production are required for intrinsic mitochondrial signaling (e.g. modulation of mitochondrial processes) and communication with the rest of the cell. O2−•/H2O2 levels are kept in check by anti-oxidant defense systems that sequester O2−•/H2O2 with extreme efficiency. Given the importance of O2−•/H2O2 in cellular function, it is imperative to consider how mitochondria produce O2−•/H2O2 and how O2−•/H2O2 genesis is regulated in conjunction with fluctuations in nutritional and redox states. Here, I discuss the fundamentals of electron transfer reactions in mitochondria and emerging knowledge on the 11 potential sources of mitochondrial O2−•/H2O2 in tandem with their significance in contributing to overall O2−•/H2O2 emission in health and disease. The potential for classifying these different sites in isopotential groups, which is essentially defined by the redox properties of electron donator involved in O2−•/H2O2 production, as originally suggested by Brand and colleagues is also surveyed in detail. In addition, redox signaling mechanisms that control O2−•/H2O2

  8. Thermodynamic Studies and Hydride Transfer Reactions from a Rhodium Complex to BX3 Compounds

    SciTech Connect

    Mock, Michael T; Potter, Robert G; Camaioni, Donald M; Li, Jun; Dougherty, William G; Kassel, W S; Twamley, Brendan; DuBois, Daniel L

    2009-10-14

    This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H2 gas to form B–H bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX3 compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (ΔG°H-) were determined for HRh(dmpe)2 and HRh(depe)2, where dmpe = 1,2-bis(dimethylphosphinoethane) and depe = 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt3]⁻ on this scale. Isodesmic reactions between [HBEt3]⁻ and various BX3 complexes to form BEt3 and [HBX3]⁻ were examined computationally to determine the relative hydride affinities of various BX3 compounds. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX3 compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B-H bonds from B-X bonds, and the extent to which BX3 compounds are reduced by transition-metal hydride complexes forming species containing multiple B-H bonds depends on the heterolytic B-X bond energy. An example is the reduction of B(SPh)3 using HRh(dmpe)2 in the presence of triethylamine to form Et3N-BH3 in high yields. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  9. Predicted yields of new neutron-rich isotopes of nuclei with Z=64-80 in the multinucleon transfer reaction {sup 48}Ca+{sup 238}U

    SciTech Connect

    Adamian, G. G.; Antonenko, N. V.; Sargsyan, V. V.; Scheid, W.

    2010-05-15

    The production cross sections of new neutron-rich isotopes of nuclei with charge numbers Z=64-80 are estimated for future experiments in the multinucleon transfer reaction {sup 48}Ca+{sup 238}U at bombarding energy E{sub c.m.}=189 MeV close to the Coulomb barrier.

  10. SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

    EPA Science Inventory

    The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

  11. Influence