WorldWideScience

Sample records for two-particle transfer reactions

  1. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  2. Relativistic effects in two-particle emission for electron and neutrino reactions

    CERN Document Server

    Simo, I Ruiz; Amaro, J E; Barbaro, M B; Caballero, J A; Donnelly, T W

    2014-01-01

    Two-particle two-hole contributions to electroweak response functions are computed in a fully relativistic Fermi gas, assuming that the electroweak current matrix elements are independent of the kinematics. We analyze the genuine kinematical and relativistic effects before including a realistic meson-exchange current (MEC) operator. This allows one to study the mathematical properties of the non-trivial seven-dimensional integrals appearing in the calculation and to design an optimal numerical procedure to reduce the computation time. This is required for practical applications to CC neutrino scattering experiments, where an additional integral over the neutrino flux is performed. A check of the feasibility of this model using a more realistic current operator is presented for the case of the contact term of the electroweak MEC.

  3. Mass Transfer with Chemical Reaction.

    Science.gov (United States)

    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)

  4. Mass Transfer with Chemical Reaction.

    Science.gov (United States)

    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)

  5. Pairing interaction and two-nucleon transfer reactions

    CERN Document Server

    Potel, Gregory; Barranco, Francisco; Vigezzi, Enrico; Broglia, Ricardo A

    2014-01-01

    Making use of the fact that the collective modes associated with the spontaneous (static and dynamic) violation of gauge invariance in atomic nuclei (pairing rotations and pairing vibrations) are amenable to a simple, quite accurate nuclear structure description (BCS and QRPA respectively), it is possible to quantitatively test the reaction mechanism which is at the basis of two-nucleon transfer reactions, specific probe of pairing in nuclei. With the help of the static and dynamic mean field spectroscopic amplitudes, taking into account successive and simultaneous transfer channels properly corrected because of non-orthogonality effects, as well as describing the associated elastic channels in terms of experimentally determined optical potentials, one obtains absolute, two-particle transfer differential cross sections which provide an overall account of the data within experimental errors. One of the first results connected with such quantitative studies of pairing correlations in nuclei is the observation o...

  6. Recent Developments in Electron Transfer Reactions

    OpenAIRE

    Marcus, Rudolph A.

    1987-01-01

    Earlier results and more recent developments in electron transfer reactions are reviewed. The more recent results include inverted behavior, electronic orientation effects on reaction rates, solvent dynamics, early steps in photosynthesis, and light emission from metal electrodes.

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

    Science.gov (United States)

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

    2015-10-14

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

  8. Isospin effects on two-particle correlation functions in E/A=61 MeV Ar-36+Sn-112,Sn-124 reactions

    NARCIS (Netherlands)

    Ghetti, R; Avdeichikov, [No Value; Jakobsson, B; Golubev, P; Helgesson, J; Colonna, N; Tagliente, G; Wilschut, HW; Kopecky, S; Kravchuk, VL; Anderson, EW; Nadel-Turonski, P; Westerberg, L; Bellini, [No Value; Sperduto, ML; Sutera, C

    2004-01-01

    Small-angle, two-particle correlation functions have been measured for Ar-36+Sn-112,Sn-124 collisions at E/A=61 MeV. Total momentum gated neutron-proton (np) and proton-proton (pp) correlations are stronger for the Sn-124 target. Some of the correlation functions for particle pairs involving deutero

  9. Transfer reactions as a doorway to fusion

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, P.R.S.; Maciel, A.M.M.; Anjos, R.M.; Moraes, S.B.; Liguori Neto, R.; Cabezas, R.; Muri, C.; Santos, G.M. [Instituto de Fisica, Universidade Federal Fluminense, Av. Litoranea s/n, Gragoata, Niteroi, RJ, 24210-340 (Brazil); Liang, J.F. [Nuclear Physics Laboratory, University of Washington, Seattle, WA 98195 (United States)

    1997-10-01

    This paper discusses the role played by transfer reactions on the sub-barrier fusion enhancement. A semiclassical formalism is used to derive the transfer form factors, that are used in coupled-channel calculations. It is shown that transfer reactions that take place at small distances may be an important doorway to fusion. The relation between this formalism and the long-range absorptive fusion potential is also discussed. Results of calculations for the {sup 16}O+{sup A}Sm, {sup 32}S+{sup 100}Mo and {sup 16}O+{sup 59}Co systems are presented. (author)

  10. Iridium-Catalyzed Hydrogen Transfer Reactions

    Science.gov (United States)

    Saidi, Ourida; Williams, Jonathan M. J.

    This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

  11. Transfer reaction code with nonlocal interactions

    CERN Document Server

    Titus, L J; Nunes, F M

    2016-01-01

    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 $E_d=10-70$ MeV, and provides cross sections with $4\\%$ accuracy.

  12. Transfer reaction code with nonlocal interactions

    Science.gov (United States)

    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.

  13. Multinucleon transfer reactions: Present status and perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Corradi, L., E-mail: corradi@lnl.infn.it [INFN – Laboratori Nazionali di Legnaro, Viale dell’Università 2, I-35020 Legnaro (Padova) (Italy); Szilner, S. [Ruđer Bošković Institute, Bijenicka cesta 54, HR-10000 Zagreb (Croatia); Pollarolo, G. [INFN and Università di Torino, Via P. Giuria 1, I-10125 Torino (Italy); Montanari, D. [INFN and Università di Padova, Via Marzolo 8, I-35131 Padova (Italy); Fioretto, E.; Stefanini, A.M.; Valiente-Dobón, J.J. [INFN – Laboratori Nazionali di Legnaro, Viale dell’Università 2, I-35020 Legnaro (Padova) (Italy); Farnea, E.; Michelagnoli, C.; Montagnoli, G.; Scarlassara, F.; Ur, C.A. [INFN and Università di Padova, Via Marzolo 8, I-35131 Padova (Italy); Mijatović, T.; Jelavić Malenica, D.; Soić, N. [Ruđer Bošković Institute, Bijenicka cesta 54, HR-10000 Zagreb (Croatia); Haas, F. [IPHC, CNRS/IN2P3, Université de Strasbourg, 23 rue du loess, F-67037 Strasbourg (France)

    2013-12-15

    Highlights: • The last generation large solid angle magnetic spectrometers for very heavy ions. • Transfer of multiple pairs, providing valuable information on nucleon-nucleon correlations. • The study of the properties of the heavy binary partner via transfer reactions. -- Abstract: Significant advances have been achieved in the last years in the field of multinucleon transfer reactions. The advent of the last generation large solid angle magnetic spectrometers pushed the detection efficiency more than an order of magnitude above previous limits, with a significant gain in mass resolution for very heavy ions. Further, the coupling of these spectrometers to large gamma arrays allowed to perform gamma-particle coincidences. One can thus detect the transfer strength to the lowest excited levels of binary products and perform gamma spectroscopy for nuclei moderately far from stability, especially in the neutron-rich region. Via transfer of multiple pairs valuable information on nucleon-nucleon correlations can also be derived, especially from measurements performed below the Coulomb barrier. There is growing interest in the study of the properties of the heavy binary partner, since the transfer mechanism may allow the production of (moderately) neutron rich nuclei in the Pb and in the actinides regions, crucial also for astrophysics. Present studies are relevant for future studies with radioactive beams.

  14. Intramolecular energy transfer reactions in polymetallic

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, J.

    1990-11-01

    This report is concerned with intramolecular, energy-transfer reactions. The concept of preparing synthetically a complex molecular species, capable of absorbing a photon at one metal center (antenna fragment), transferring that energy to a second metal center (reactive fragment) via a bridging ligand was first reported by our group in 1979. It is now apparent that a major emphasis in inorganic chemistry in the future will involve these types of molecular ensembles. Complexes discussed include Rh, Ru, and Cu complexes. 23 refs., 14 tabs.

  15. Transfer to the continuum and Breakup reactions

    CERN Document Server

    Moro, A M

    2006-01-01

    A standard approach for the calculation of breakup reactions of exotic nuclei into two fragments is to consider inelastic excitations into the single particle continuum of the projectile. Alternatively one can also consider the transfer to the continuum of a system composed of the light fragment and the target. In this work we make a comparative study of the two approaches, underline the different inputs, and identify the advantages and disadvantages of each approach. Our test cases consist of the breakup of $^{11}$Be on a proton target at intermediate energies, and the breakup of $^8$B on $^{58}$Ni at energies around the Coulomb barrier.

  16. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... to show general (or expected) properties. Properties such as in the physical and (semi-)chemical interface between classical and quantum systems and the effects of molecular bond length constraints on the temperature during simulations. As a second step the methodology is applied to the symmetric...

  17. Effects of Nonlocality on Transfer Reactions

    CERN Document Server

    Titus, Luke J

    2016-01-01

    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, 127Sn, 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, 20, and 50 MeV. We found that for bound states the Perry corrected wave functions resulting from the local equation agreed well with that from the nonlocal equation in the interior region, but discrepancies were found in the surface and peripheral regions. Overall, the Perey correction factor was adequate for scattering states, with the exception for a few partial waves. Nonlocality...

  18. Marcus Electron Transfer Reactions with Bulk Metallic Catalysis

    CERN Document Server

    Widom, A; Srivastava, Y N

    2015-01-01

    Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such electron transfer chemical reaction events occur in the neighborhood of metallic plates, then electrodynamic interface fields must also be considered in addition to mechanical oscillations. Such electrodynamic interfacial electric fields in principle strongly effect the chemical reaction rates. The thermodynamic states of the metal are unchanged by the reaction which implies that metallic plates are purely catalytic chemical agents.

  19. Liquid drop effects in subbarrier transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kim, H.J.

    1990-08-01

    Reaction products from a multitude of binary channels are observed to emerge at large c.m. angles at subbarrier energies for the {sup 50}Ti {plus} {sup 93}Nb system. The energy spectra of these products and the distance where they first emerge indicate that these reaction products result from the neck which is formed outside the Coulomb barrier. 9 refs., 5 figs.

  20. Heavy ion transfer reactions: Status and perspectives

    Indian Academy of Sciences (India)

    L Corradi

    2010-07-01

    With the large solid angle magnetic spectrometer (PRISMA) coupled to the -array (CLARA), extensive investigations of nuclear structure and reaction dynamics have been carried out. In the present paper aspects of these studies will be presented, focussing more closely on the reaction mechanism, in particular on the properties of quasielastic and deep inelastic processes and on measurements at energies far below the Coulomb barrier.

  1. Kinematical coincidence method in transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Acosta, L.; Amorini, F. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Auditore, L. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Berceanu, I. [Institute for Physics and Nuclear Engineering, Bucharest (Romania); Cardella, G., E-mail: cardella@ct.infn.it [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Chatterjiee, M.B. [Saha Institute for Nuclear Physics, Kolkata (India); De Filippo, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Francalanza, L.; Gianì, R. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); Grassi, L. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Rudjer Boskovic Institute, Zagreb (Croatia); Grzeszczuk, A. [Institut of Physics, University of Silesia, Katowice (Poland); La Guidara, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Centro Siciliano di Fisica Nucleare e Struttura della Materia, Catania (Italy); Lanzalone, G. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Facoltà di Ingegneria e Architettura, Università Kore, Enna (Italy); Lombardo, I. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Scienze Fisiche, Università Federico II and INFN Sezione di Napoli (Italy); Loria, D.; Minniti, T. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Pagano, E.V. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); and others

    2013-07-01

    A new method to extract high resolution angular distributions from kinematical coincidence measurements in binary reactions is presented. Kinematics is used to extract the center of mass angular distribution from the measured energy spectrum of light particles. Results obtained in the case of {sup 10}Be+p→{sup 9}Be+d reaction measured with the CHIMERA detector are shown. An angular resolution of few degrees in the center of mass is obtained. The range of applicability of the method is discussed.

  2. Probing cluster structures through sub-barrier transfer reactions

    Directory of Open Access Journals (Sweden)

    Rafferty D. C.

    2016-01-01

    Full Text Available Multinucleon transfer probabilities and excitation energy distributions have been measured in 16,18O, 19F + 208Pb at energies between 90% - 100% of the Coulomb barrier. A strong 2p2n enhancement is observed for all reactions, though most spectacularly in the 18O induced reaction. Results are interpreted in terms of the Semiclassical model, which seems to suggest α-cluster transfer in all studied systems. The relation to cluster-states in the projectile is discussed, with the experimental results consistent with previous structure studies. Dissipation of energy in the collisions of 18O is compared between different reaction modes, with cluster transfer associated with dissipation over a large number of internal states. Cluster transfer is shown to be a long range dissipation mechanism, which will inform the development of future models to treat these dynamic processes in reactions.

  3. One-nucleon transfer reactions and the optical potential

    CERN Document Server

    Nunes, F M; Ross, A; Titus, L J; Charity, R J; Dickhoff, W H; Mahzoon, M H; Sarich, J; Wild, S M

    2015-01-01

    We provide a summary of new developments in the area of direct reaction theory with a particular focus on one-nucleon transfer reactions. We provide a status of the methods available for describing (d,p) reactions. We discuss the effects of nonlocality in the optical potential in transfer reactions. The results of a purely phenomenological potential and the optical potential obtained from the dispersive optical model are compared; both point toward the importance of including nonlocality in transfer reactions explicitly. Given the large ambiguities associated with optical potentials, we discuss some new developments toward the quantification of this uncertainty. We conclude with some general comments and a brief account of new advances that are in the pipeline.

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

    NARCIS (Netherlands)

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

    2008-01-01

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

  5. Transfer reactions at the neutron dripline with triton target

    CERN Document Server

    Borge, M J G; Fynbo, H O U; Gomez Camacho, J; Johansen, J; Johansson, H T; Jonson, B; Krücken, R; Kurcewicz, J; Martel, I; Moro, A; Mücher, D; Nilsson, T; Nyman, G; Raabe, R; Randisi, G; Riisager, K; Sambi, S; Sanchez-Benitez, AM; Tengblad, O

    2012-01-01

    Two-neutron transfer to $^{9}$Li will populate the ground state of $^{11}$Li as well as low-lying resonances in a way that is complementary to studies of these states performed at higher beam energies. We aim at detecting the charged particles from the transfer reactions as well as neutrons coming from the decay of possible $^{11}$Li resonances.

  6. Transfer reactions at the neutron dripline with triton target

    CERN Multimedia

    Two-neutron transfer to $^{9}$Li will populate the ground state of $^{11}$Li as well as low-lying resonances in a way that is complementary to studies of these states performed at higher beam energies. We aim at detecting the charged particles from the transfer reactions as well as neutrons coming from the decay of possible $^{11}$Li resonances.

  7. Quantifying electron transfer reactions in biological systems

    DEFF Research Database (Denmark)

    Sjulstok, Emil Sjulstok; 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...

  8. Links between potential energy structures and quantum cumulative reaction probabilities of double proton transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Horsten, H.F. von [Institut fuer Physikalische Chemie, Christian-Albrechts-Universitaet, Olshausenstrasse 40, 24098 Kiel (Germany); Hartke, B. [Institut fuer Physikalische Chemie, Christian-Albrechts-Universitaet, Olshausenstrasse 40, 24098 Kiel (Germany)], E-mail: hartke@phc.uni-kiel.de

    2007-09-25

    Double proton transfer reactions of pyrazole-guanidine species exhibit unusual energy profiles of a plateau form, different from the standard single and double barrier shapes. We have demonstrated earlier that this leads to a characteristically different quantum dynamical behavior of plateau reactions, when measured appropriately. Here we show that these differences also carry over to traditional measures of reaction probability.

  9. Reactant-Product Quantum Coherence in Electron Transfer Reactions

    CERN Document Server

    Kominis, I K

    2012-01-01

    We investigate the physical meaning of quantum superposition states between reactants and products in electron transfer reactions. We show that such superpositions are strongly suppressed and to leading orders of perturbation theory do not pertain in electron transfer reactions. This is because of the intermediate manifold of states separating the reactants from the products. We provide an intuitive description of these considerations with Feynman diagrams. We also discuss the relation of such quantum coherences to understanding the fundamental quantum dynamics of spin-selective radical-ion-pair reactions.

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

    Indian Academy of Sciences (India)

    B Saritha; M Durga Prasad

    2012-01-01

    Recently, we had suggested that the motion along the promoter mode in the first part of the IRC of proton transfer reaction enhances the delocalization of electrons on the acceptor atom into the * orbital of the donor-hydrogen covalent bond, and as a consequence weakens it. This leads to a reduction of the barrier to the proton transfer as well as the stretching frequency of donor-hydrogen bond. An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence on three systems, (HF)3, formic acid dimer, and (H2O) clusters is provided to support this assertion.

  11. Intrinsic barriers for H-atom transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Franz, J.A.

    1994-08-01

    Hydrogen transfer reactions play a well-recognized role in coal liquefaction. While H-abstraction reactions between radicals and H-donors have been well-studied, understanding of structure-reactivity relationships remains surprisingly incomplete. Another form of hydrogen transfer known as radical hydrogen transfer (radical donation of H to an unsaturated compound) is currently the subject of much speculation. The barriers for identity reactions are key parameters in the Evans-Polanyi equation for estimating reaction barriers and are fundamentally significant for the insight they provide about bond reorganization energies for formation of transition state structures. Although knowable from experiment, relatively few H-abstraction identity barriers and no barriers for hydrocarbon radical hydrogen transfer reactions have been measured. This paper seeks to supplement and extend existing experimental data with results obtained by calculation. The authors have used ab initio and semiempirical molecular orbital methods (MNDO-PM3) to calculate barriers for a series of H-atom abstraction and radical-hydrogen-transfer identity reactions for alkyl, alkenyl, arylalkyl and hydroaryl systems. Details of this methodology and analyses of how barrier heights correlate with reactant and transition state properties will be presented and discussed.

  12. Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

    Science.gov (United States)

    Antoniou, P; Ma, Z; Zhang, P; Beratan, D N; Skourtis, S S

    2015-12-14

    Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer system or irreversibly change its molecular structure. For bridge-mediated electron-transfer reactions, infrared (vibrational) excitation of the bridge linking the electron donor to the electron acceptor was suggested as being capable of influencing the electron-transfer rate by modulating the bridge-mediated donor-to-acceptor electronic coupling. This kind of electron-transfer experiment has been realized, demonstrating that bridge-mediated electron-transfer rates can be changed by exciting vibrational modes of the bridge. Here, we use simple models and ab initio computations to explore the physical constraints on one's ability to vibrationally perturb electron-transfer rates using infrared excitation. These constraints stem from the nature of molecular vibrational spectra, the strengths of the electron-vibrational coupling, and the interaction between molecular vibrations and infrared radiation. With these constraints in mind, we suggest parameter regimes and molecular architectures that may enhance the vibrational control of electron transfer for fast coherent electron-transfer reactions.

  13. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Brus, Louis [Columbia Univ., New York, NY (United States)

    2017-01-31

    This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I3- and I5- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

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

    OpenAIRE

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

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using femtosecond midinfrared spectroscopy, we probe the vibrational responses of HPTS, its conjugate photobase, the hydrated proton/deuteron, and chloroacetate. The measurement of these four resonances allows ...

  15. Intrinsic barriers for H-atom transfer reactions involving hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Franz, J.A.

    1994-08-01

    Intrinsic barriers (formally the barrier in the absence of driving force) for H-atom transfer reactions are key parameters in Evans-Polyanyi and Marcus equations for estimating exothermic reaction barriers and are fundamentally significant for the insight they provide about bond reorganization energies for formation of transition state structures. Although knowable from experiment, relatively few of these barriers have been measured due to experimental difficulties in measuring rates for identity reactions. Thus, the authors have used semiempirical Molecular Orbital theoretical methods (MNDO/PM3) to calculate barriers for a series of H-atom transfer identity reactions involving alkyl, alkenyl, arylalkyl and hydroaryl radicals and donors. Briefly stated, they find that barriers decrease with the degree of alkyl substitution at the radical site whereas barriers increase with the degree of conjugation with the radical site. Details of the methodology and analyses of how these barrier heights correlate with reactant and transition state properties will be presented and discussed.

  16. Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions

    CERN Document Server

    Ramos, Pablo; Pavanello, Michele

    2015-01-01

    We have carried out a thorough benchmark of the FDE-ET method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 non-additive kinetic energy functionals and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE functional coupled with the PW91k non-additive Kinetic energy functional and a TZP basis set constitutes the most stable, and accurate level of theory for hole-transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.

  17. Potential Energy Diagrams: A Conceptual Tool in the Study of Electron Transfer Reactions.

    Science.gov (United States)

    Lewis, Nita A.

    1980-01-01

    Describes how the potential energy diagram may be used to theoretically describe the processes involved in a system undergoing electron transfer. Examines factors important in electron transfer reactions and discusses several classes of electron transfer reactions. (CS)

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

    Science.gov (United States)

    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.

  19. Mechanisms for control of biological electron transfer reactions.

    Science.gov (United States)

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

    2014-12-01

    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. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. On the slope anomaly in heavy-ion transfer reactions

    CERN Document Server

    Marta, H D; Fernández-Niello, J O; Pacheco, A J

    2002-01-01

    We discuss a semiclassical model of transfer reactions in heavy-ion collisions, in which the nuclei are assumed to move along classical trajectories governed by the Coulomb and the real part of the optical potential. The model, originally proposed for the case of spherical nuclei, is here extended to deformed ones. It takes into account tunneling around the point of closest approach of the collision partners, and the effect of other channels is included as an absorption due to the imaginary part of the optical potential. The interplay between absorption and tunneling effects explains both the observed energy dependence of the transfer probabilities at large distances, and the so-called 'slope anomaly' in neutron transfer reactions.

  1. Multinucleon transfer reactions in closed-shell nuclei

    CERN Document Server

    Szilner, S; Corradi, L; Marginean, N; Pollarolo, G; Stefanini, A M; Beghini, S; Behera, B R; Fioretto, E; Gadea, A; Guiot, B; Latina, A; Mason, P; Montagnoli, G; Scarlassara, F; Trotta, M; de Angelis, G; Della Vedova, F; Farnea, E; Haas, F; Lenzi, S; Lunardi, S; Marginean, R; Menegazzo, R; Napoli, D R; Nespolo, M; Pokrovsky, I V; Recchia, F; Romoli, M; Salsac, M -D; Soic, N; Valiente-Dobon, J J

    2007-01-01

    Multinucleon transfer reactions in 40Ca+96Zr and 90Zr+208Pb have been measured at energies close to the Coulomb barrier in a high resolution gamma-particle coincidence experiment. The large solid angle magnetic spectrometer PRISMA coupled to the CLARA gamma-array has been employed. Trajectory reconstruction has been applied for the complete identification of transfer products. Mass and charge yields, total kinetic energy losses, gamma transitions of the binary reaction partners, and comparison of data with semiclassical calculations are reported. Specific transitions in 95Zr populated in one particle transfer channels are discussed in terms of particle-phonon couplings. The gamma decays from states in 42Ca in the excitation energy region expected from pairing vibrations are also observed.

  2. Neutron transfer reactions in the fp-shell region

    Energy Technology Data Exchange (ETDEWEB)

    Mahgoub, Mahmoud

    2008-06-26

    Neutron transfer reactions were used to study the stability of the magic number N=28 near {sup 56}Ni. On one hand the one-neutron pickup (d,p) reaction was used for precision spectroscopy of single-particle levels in {sup 55}Fe. On the other hand we investigated the two-neutron transfer mechanism into {sup 56}Ni using the pickup reaction {sup 58}Ni((vector)p,t){sup 56}Ni. In addition the reliability of inverse kinematics reactions at low energy to study exotic nuclei was tested by the neutron transfer reactions t({sup 40}Ar,p){sup 42}Ar and d({sup 54}Fe,p){sup 55}Fe using tritium and deuterium targets, respectively, and by comparing the results with those of the normal kinematics reactions. The experimental data, differential cross-section and analyzing powers, are compared to DWBA and coupled channel calculations utilizing the code CHUCK3. By performing the single-neutron stripping reaction ((vector)d,p) on {sup 54}Fe the 1f{sub 7/2} shell in the ground state configuration was found to be partly broken. The instability of the 1f{sub 7/2} shell and the magic number N=28 was confirmed once by observing a number of levels with J{sup {pi}} = 7/2{sup -} at low excitation energies, which should not be populated if {sup 54}Fe has a closed 1f{sub 7/2} shell, and also by comparing our high precision experimental data with a large scale shell model calculation using the ANTOINE code [5]. Calculations including a partly broken 1f{sub 7/2} shell show better agreement with the experiment. The instability of the 1f{sub 7/2} shell was confirmed also by performing the two-neutron pick-up reaction ((vector)p,t) on {sup 58}Ni to study {sup 56}Ni, where a considerable improvement in the DWBA calculation was observed after considering 1f{sub 7/2} as a broken shell. To prove the reliability of inverse kinematics transfer reactions at low energies ({proportional_to} 2 AMeV), the aforementioned single-neutron transfer reaction (d,p) was repeated using a beam of {sup 54}Fe ions and a

  3. Quenching of Cross Sections in Nucleon Transfer Reactions

    CERN Document Server

    Kay, B P; Freeman, S J

    2013-01-01

    Cross sections for proton knockout observed in (e,e'p) reactions are apparently quenched by a factor of ~0.5, an effect attributed to short-range correlations between nucleons. Here we demonstrate that such quenching is not restricted to proton knockout, but a more general phenomenon associated with any nucleon transfer. Measurements of absolute cross sections on a number of targets between 16O and 208Pb were analyzed in a consistent way, with the cross sections reduced to spectroscopic factors through the distorted-wave Born approximation with global optical potentials. Across the 124 cases analyzed here, induced by various proton- and neutron-transfer reactions and with angular momentum transfer l=0-7, the results are consistent with a quenching factor of 0.55. This is an apparently uniform quenching of single-particle motion in the nuclear medium. The effect is seen not only in (d,p) reactions but also in reactions with A=3 and 4 projectiles, when realistic wave functions are used for the projectiles.

  4. Tem holder for sample transfer under reaction conditions

    DEFF Research Database (Denmark)

    Damsgaard, Christian Danvad; Zandbergen, Henny W.; Wagner, Jakob Birkedal

    and temperature, which usually are far from the operando conditions of e.g. heterogeneous catalysis. Our efforts focus on bridging these gaps by establishing in situ sample transfer between complementary measurement techniques. To fully exploit the capabilities of ETEM complementary experiments...... and characterization techniques are beneficial. Normally, the complementary measurements are done in parallel with experiments separated in time and space [3] or by mimicking a reactor bed by changing the feed gas composition according to reactivity and conversion measured in dedicated catalyst set-ups [4...... (XRD) setup and subsequently successfully transferred under reaction conditions to the ETEM....

  5. Laser controlled charge-transfer reaction at low temperatures

    CERN Document Server

    Petrov, Alexander; Kotochigova, Svetlana

    2016-01-01

    We study the low-temperature charge transfer reaction between a neutral atom and an ion under the influence of near-resonant laser light. By setting up a multi-channel model with field-dressed states we demonstrate that the reaction rate coefficient can be enhanced by several orders of magnitude with laser intensities of $10^6$ W/cm$^2$ or larger. In addition, depending on laser frequency one can induce a significant enhancement or suppression of the charge-exchange rate coefficient. For our intensities multi-photon processes are not important.

  6. Investigation of the unbound 21C nucleus via transfer reaction

    Directory of Open Access Journals (Sweden)

    Fukui Tokuro

    2014-03-01

    Full Text Available The cross section of the transfer reaction 20C(d,p21C at 30.0 MeV is investigated. The continuum-discretized coupled-channels method (CDCC is used in order to obtain the final state wave function. The smoothing procedure of the transition matrix and the channel-coupling effect on the cross section are discussed.

  7. Analysis of transfer reactions: determination of spectroscopic factors

    Energy Technology Data Exchange (ETDEWEB)

    Keeley, N. [CEA Saclay, Dept. d' Astrophysique, de Physique des Particules de Physique Nucleaire et de l' Instrumentation Associee (DSM/DAPNIA/SPhN), 91- Gif sur Yvette (France); The Andrzej So an Institute for Nuclear Studies, Dept. of Nuclear Reactions, Warsaw (Poland)

    2007-07-01

    An overview of the most popular models used for the analysis of direct reaction data is given, concentrating on practical aspects. The 4 following models (in order of increasing sophistication): the distorted wave born approximation (DWBA), the adiabatic model, the coupled channels born approximation, and the coupled reaction channels are briefly described. As a concrete example, the C{sup 12}(d,p)C{sup 13} reaction at an incident deuteron energy of 30 MeV is analysed with progressively more physically sophisticated models. The effect of the choice of the reaction model on the spectroscopic information extracted from the data is investigated and other sources of uncertainty in the derived spectroscopic factors are discussed. We have showed that the choice of the reaction model can significantly influence the nuclear structure information, particularly the spectroscopic factors or amplitudes but occasionally also the spin-parity, that we wish to extract from direct reaction data. We have also demonstrated that the DWBA can fail to give a satisfactory description of transfer data but when the tenets of the theory are fulfilled DWBA can work very well and will yield the same results as most sophisticated models. The use of global rather than fitted optical potentials can also lead to important differences in the extracted spectroscopic factors.

  8. Neutron Transfer reactions induced by 8Li on 9Be

    CERN Document Server

    Guimarães, V; Amro, H; Assunção, M; Barioni, A; Becchetti, F D; Carmargo, O; Garcia, H; Jiang, H; Kolata, J J; Lichtenthäler, R; Lizcano, D; Martines-Quiroz, E; Jiang, Hao

    2007-01-01

    Angular distributions for the elastic scattering of 8Li on 9Be and the neutron transfer reactions 9Be(8Li,7Li)10Be and 9Be(8Li,9Li)8Be have been measured with a 27 MeV 8Li radioactive nuclear beam. Spectroscopic factors for 8Li|n=9Li and 7Li|n=8Li bound systems were obtained from the comparison between the experimental differential cross section and finite-range DWBA calculations with the code FRESCO. The spectroscopic factors obtained are 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 7Li(n,g)8Li and 8Li(n,g)9Li were calculated in the framework of a potential model.

  9. Electron Transfer Reactions: Generalized Spin-Boson Approach

    CERN Document Server

    Merkli, Marco

    2012-01-01

    We introduce a mathematically rigorous analysis of a generalized spin-boson system for the treatment of a donor-acceptor (reactant-product) quantum system coupled to a thermal quantum noise. The donor/acceptor probability dynamics describes transport reactions in chemical processes in presence of a noisy environment -- such as the electron transfer in a photosynthetic reaction center. Besides being rigorous, our analysis has the advantages over previous ones that (1) we include a general, non energy-conserving system-environment interaction, and that (2) we allow for the donor or acceptor to consist of multiple energy levels lying closely together. We establish explicit expressions for the rates and the efficiency (final donor-acceptor population difference) of the reaction. In particular, we show that the rate increases for a multi-level acceptor, but the efficiency does not.

  10. Two particles on a star graph II

    CERN Document Server

    Harmer, M

    2007-01-01

    We consider a two particle system on a star graph with delta-function interaction. A complete description of the eigensolutions with real momenta is given; specifically it is shown that all eigensolutions can be written as integrals in the momentum plane of sums of products of appropriate one particle solutions.

  11. Two particles on a star graph

    CERN Document Server

    Harmer, M

    2007-01-01

    We consider a two particle system on a star graph with delta-function repulsive interaction. Given a natural class of one particle solutions, all possible eigensolutions of the problem are enumerated which include a family of solutions with discontinuous derivative on the diagonal.

  12. Effects of delocalization on intrinsic barriers for H-atom transfer: Implications for the radical hydrogen transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Ferris, K.F.; Franz, J.A.

    1992-08-01

    PM3 calculations of transition states (TS) for both normal H-atom transfer and radical hydrogen transfer (RHT) reactions of a a wide-variety of hydrocarbon structures have enabled development of quantitative structure-reactivity relationships. Results indicate that activation barriers for RHT reactions are large enough that thermoneutral and endothermic reactions should not compete with alternative multistep pathways.

  13. Consistency in Quenching of ``Absolute'' Spectroscopic Factors from Transfer Reactions

    Science.gov (United States)

    Schiffer, J. P.; Kay, B. P.; Freeman, S. J.

    2013-04-01

    The strengths of single-particle transitions in (e,e'p) knockout reactions on closed-shell nuclei are lower than expected,footnotetextG. J. Kramer et al., Nucl. Phys. A679, 267 (2001). due to limitations of the mean-field description imposed by correlations. This quenching of single-particle strength by ˜0.5 appeared to be a general property of nuclei from ^16O to ^208Pb. In our work, the combined sums of neutron-adding and neutron-removing strengths from (d,p) and (p,d) transfer reactions on four Ni isotopes yield very similar quenching factors of ˜0.53 (varying by ˜10% with reasonable choices of optical-model parameters).footnotetextJ. P. Schiffer et al., Phys. Rev. Lett. 108, 022501 (2012). Recently, spectroscopic overlaps between ^4He and ^3He were extracted from GFMC calculations.footnotetextI. Brida et al., Phys. Rev. C 84, 024319 (2011). With these, our data on (α,^3He) and (^3He,α) on the Ni isotopes yields ˜0.62. Additional data for proton transfer on Ni and transfer on other nuclei are also being analyzed. This work was supported by the U.S. Department of Energy, Office of Nuclear Physics, under Contract No. DE-AC02-06CH11357 and the U.K. Science and Technology Facilities Council.

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

    Science.gov (United States)

    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.

  15. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  16. A New Reaction-controlled Phase-transfer Catalyst System

    Institute of Scientific and Technical Information of China (English)

    Ming Qiang LI; Xi Gao JIAN; Gui Mei WANG; Yan YU

    2004-01-01

    A new reaction-controlled phase-transfer catalyst system was designed and synthesized. In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.

  17. Quantum Transition State Theory for proton transfer reactions in enzymes

    CERN Document Server

    Bothma, Jacques P; McKenzie, Ross H

    2009-01-01

    We consider the role of quantum effects in the transfer of hyrogen-like species in enzyme-catalysed reactions. This study is stimulated by claims that the observed magnitude and temperature dependence of kinetic isotope effects imply that quantum tunneling below the energy barrier associated with the transition state significantly enhances the reaction rate in many enzymes. We use a path integral approach which provides a general framework to understand tunneling in a quantum system which interacts with an environment at non-zero 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 $T_0$ which is determined by the curvature of potential energy surface near the top of the barrier. We argue that for most enzymes this temperature is less than room temperature. For physically reasonable parameters quantum transition state theory gives a quantitative descr...

  18. Electron transfer pathway analysis in bacterial photosynthetic reaction center

    CERN Document Server

    Kitoh-Nishioka, Hirotaka

    2016-01-01

    A new computational scheme to analyze electron transfer (ET) pathways in large biomolecules is presented with applications to ETs in bacterial photosynthetic reaction center. It consists of a linear combination of fragment molecular orbitals and an electron tunneling current analysis, which enables an efficient first-principles analysis of ET pathways in large biomolecules. The scheme has been applied to the ET from menaquinone to ubiquinone via nonheme iron complex in bacterial photosynthetic reaction center. It has revealed that not only the central Fe$^{2+}$ ion but also particular histidine ligands are involved in the ET pathways in such a way to mitigate perturbations that can be caused by metal ion substitution and depletion, which elucidates the experimentally observed insensitivity of the ET rate to these perturbations.

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

    Science.gov (United States)

    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 Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  20. Three-Body Model Analysis of Subbarrier alpha Transfer Reaction

    CERN Document Server

    Fukui, Tokuro; Yahiro, Masanobu

    2011-01-01

    Subbarrier alpha transfer reaction 13C(6Li,d)17O(6.356 MeV, 1/2+) at 3.6 MeV is analyzed with a alpha + d + 13C three-body model, and the asymptotic normalization coefficient (ANC) for alpha + 13C --> 17O(6.356 MeV, 1/2+), which essentially determines the reaction rate of 13C(alpha,n)16O, is extracted. Breakup effects of 6Li in the initial channel and those of 17O in the final channel are investigated with the continuum-discretized coupled-channels method (CDCC). The former is found to have a large back-coupling to the elastic channel, while the latter turns out significantly small. The transfer cross section calculated with Born approximation to the transition operator, including breakup states of 6Li, gives (C_{alpha 13C}{17O*})^2 =1.03 \\pm 0.29 fm^{-1}. This result is consistent with the value obtained by the previous DWBA calculation.

  1. Transfer reactions in inverse kinematics at REX-ISOLDE

    CERN Document Server

    Tengborn, E

    Research on the structure of exotic nuclei is one of the most intriguing topics in present day nuclear physics. With the use of facilities for isotope separation on-line, such as ISOLDE at CERN, short-lived isotopes can be studied experimentally. Since 2002, the REX-ISOLDE facility enables radioactive ions produced by ISOLDE to be post-accelerated, increasing the energy of the ions enough to do nuclear transfer reactions in inverse kinematics. In this thesis, transfer reactions are used to study the structure of neutron-rich lithium isotopes through a series of experiments at REX-ISOLDE. The first experiment used a 9Li beam at 2.36 MeV/u impinging on a deuterated polyethylene target to study 10Li, 9Li and 8Li. For the (d,p)-channel the resonance ground state and a first excited state are observed and the results agree with theoretical calculations. The elastic channel agrees with Optical Model, OM, calculations. For the (d,t)-channel the shape of the angular distribution agrees with Distorted Wave Born Approx...

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

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, J.J. [Columbia Univ., New York, NY (United States)

    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.

  3. Probing the pairing interaction through two-neutron transfer reactions

    Directory of Open Access Journals (Sweden)

    Margueron J.

    2012-12-01

    Full Text Available The treatment of the pairing interaction in mean-field-based models is addressed. In particular, the possibility to use pair transfers as A tool to better constrain this interaction is discussed. First, pairing inter-actions with various density dependencies (surface/volume mixing are used in the microscopic Hartree-Fock-Bogoliubov + quasiparticle random-phase approximation model to generate the form factors to be used in reaction calculations. Cross sections for (p,t two-neutron transfer reactions are calculated in the one-step zero-range distorted-wave Born approximation for some Tin isotopes and for incident proton energies from 15 to 35 MeV. Three different surface/volume mixings of A zero-range density-dependent pairing interaction are employed in the microscopic calculations and the sensitivity of the cross sections to the different mixings is analyzed. Differences among the three different theoretical predictions are found espacially for the nucleus 136Sn and they are more important at the incident proton energy of 15 MeV. We thus indicate (p,t two-neutron transfer reactions with very neutron-rich Sn isotopes and at proton energies around 15 MeV as good experimental cases where the surface/volume mixing of the pairing interaction may be probed. In the second part of the manuscript, ground-state to ground-state transitions are investigated. Approximations made to estimate two-nucleon transfer probabilities in ground-state to ground-state transitions and the physical interpretation of these probabilities are discussed. Probabilities are often calculated by approximating both ground states of the initial nucleus A and of the final nucleus A±2 by the same quasiparticle vacuum. We analyze two improvements of this approach. First, the effect of using two different ground states with average numbers of particles A and A±2 is quantified. Second, by using projection techniques, the role of particle number restoration is analyzed. Our analysis

  4. Determination of the Astrophysical S(E) Factors or Rates for Radiative Capture Reaction with One Nucleon Transfer Reaction%Determination of the Astrophysical S(E) Factors or Rates for Radiative Capture Reaction with One Nucleon Transfer Reaction

    Institute of Scientific and Technical Information of China (English)

    李志宏; 郭冰; 李云居; 苏俊; 李二涛; 白希祥; 王友宝; 曾晟; 王宝祥; 颜胜权; 李志常; 刘建成; 连钢; 金孙均; 刘鑫; 柳卫平

    2012-01-01

    The radiative capture reaction plays an important role in nuclear astrophysics. We have indirectly measured the astrophysical S(E) factors for some proton capture reactions and reaction rates for several neutron capture reactions with one nucleon transfer reactions at HI-13 tandem accelerator in recent years. Some of them are compiled into IAEA EXFOR database and JINA REACLIB project, and used in the network calculations of Big Bang nucleosynthesis and type-I X-ray bursts.

  5. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  6. Mass transfer in porous media with heterogeneous chemical reaction

    Directory of Open Access Journals (Sweden)

    Souza S.M.A.G.Ulson de

    2003-01-01

    Full Text Available In this paper, the modeling of the mass transfer process in packed-bed reactors is presented and takes into account dispersion in the main fluid phase, internal diffusion of the reactant in the pores of the catalyst, and surface reaction inside the catalyst. The method of volume averaging is applied to obtain the governing equation for use on a small scale. The local mass equilibrium is assumed for obtaining the one-equation model for use on a large scale. The closure problems are developed subject to the length-scale constraints and the model of a spatially periodic porous medium. The expressions for effective diffusivity, hydrodynamic dispersion, total dispersion and the Darcy's law permeability tensors are presented. Solution of the set of final equations permits the variations of velocity and concentration of the chemical species along the packed-bed reactors to be obtained.

  7. Exclusive photon-induced hadronic reactions at large momentum transfers

    CERN Document Server

    Schweiger, W

    1995-01-01

    It is generally assumed that due to factorization of long- and short-distance dynamics perturbative QCD can be applied to exclusive hadronic reactions at large momentum transfers. Within such a perturbative approach diquarks turn out to be a useful phenomenological device to model non-perturbative effects still observable in the kinematic range accessible by present-days experiments. The basic ingredients of the perturbative formalism with diquarks, i.e. Feynman rules for diquarks and quark-diquark wave functions of baryons, are briefly summarized. Applications of the diquark model to the electromagnetic form factors of the proton in the space- as well as time-like region, Compton-scattering off protons, gamma-gamma -> p-pbar, and photoproduction of Kaons are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Suria, Sabartanty [Iowa State Univ., Ames, IA (United States)

    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.

  9. Two-particle correlation via Bremsstrahlung

    Science.gov (United States)

    Cho, Soyeon; Park, Kayoung; Yoon, Jin-Hee

    2017-04-01

    Ridge is the well-known structure in two-particle angular correlations at highenergy heavy-ion collisions. This structure is physically understood through elliptic and higher-order flows at nucleus-nucleus collisions. This behavior is also found in small systems, such as proton-proton collisions, recently. However, Ridge structure in small system is hard to be understood using hydrodynamics, since small systems are not dense enough to produce the Quark-Gluon plasma. Thus, we try to describe this phenomena through kinematic interaction between jets and medium partons. In high-energy heavy-ion collision, the energetic particles called jets go out in specific direction and lose their energy while passing through the medium. During such process, photons/gluons are emitted from interaction between jets and medium partons. We concentrate on energy loss via photon radiations, known as Bremsstrahlung. Recently, two symmetric double scattering processes between jet particle and medium parton are reported to be able to produce certain constructive interference, which gives collective motion and medium partons are aligned along incoming jet particles. We conjecture that similar behavior might happen in Bremsstrahlung processes, and therefore we consider the two symmetric diagrams of photon emission and medium parton scattering. We expect these two amplitudes to give constructive interference leading to the collective motion of medium. We check the correlation between emitted photon and final jet, and those between medium parton and final jet for high-energy jet. To describe parton momentum distribution in medium, we use the Maxwell-Boltzmann distribution. We discover collective motion in both angular correlations. We also check the tendency of the angular correlation for two particles according to the incident angle of jet particle, energy of emitted photon and temperature of systems, respectively. We can conclude that collective motion is able to be understood through

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

    Energy Technology Data Exchange (ETDEWEB)

    Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

    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 ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 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

  11. Stereoselectivity in electron-transfer reactions in chiral media.

    Science.gov (United States)

    Olmstead, Deborah; Hua, Xaio; Osvath, Peter; Lappin, A Graham

    2010-02-07

    The oxidation of [Co(edta)](2-) by [IrCl(6)](2-) proceeds by both inner-sphere and outer-sphere electron-transfer pathways. In the presence of added [Co(en)(3)](3+), the outer-sphere pathway is enhanced. When optically active [Co(en)(3)](3+) is used, the [Co(edta)](-) formed is optically active, reflecting a 1.5% DeltaLambda selectivity. It is proposed that the selectivity arises from preferential formation and reactivity of the DeltaLambda ion pair, {[Co(edta)](2-),[Co(en)(3)](3+)}. Direct reaction of [Co(edta)](-) with [Co(en)(3)](2+) has also been investigated in the optically active solvent, (S)-(-)-1,2-propylene carbonate. The induction is small, forming 0.75% Delta-[Co(en)(3)](3+), consistent with the important role for hydrogen bonding in determining the precursor stereoselectivity to the exclusion of solvent.

  12. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    Science.gov (United States)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  13. Fine-Tuning Two-Particle Interferometry; 2, Opacity Effects

    CERN Document Server

    Tomasik, Boris; Tomasik, Boris; Heinz, Ulrich

    1998-01-01

    We present a model study of single-particle spectra and two-particle Bose-Einstein correlations for opaque sources. We study the transverse mass dependence of the correlation radii R_\\perp, R_\\parallel and R_0 in the YKP parametrization and find a strong sensitivity of the temporal radius parameter R_0^2 to the source opacity. A simple comparison with the published data from 158 A GeV/c Pb+Pb collisions at CERN indicates that the pion source created in these collisions emits particles from the whole reaction volume and is not opaque. For opaque sources we find certain regions of inapplicability of the YKP parametrization which can be avoided by a slightly different parametrization for the correlator. The physical meaning of the modified parameters is briefly discussed.

  14. The $^{136}$Xe + $^{208}$Pb reaction: A test of models of multi-nucleon transfer reactions

    CERN Document Server

    Barrett, J S; Loveland, W; Zhu, S; Ayangeakaa, A D; Carpenter, M P; Greene, J P; Janssens, R V F; Lauritsen, T; McCutchan, E A; Sonzogni, A A; Chiara, C J; Harker, J L; Walters, W B

    2015-01-01

    The yields of over 200 projectile-like fragments (PLFs) and target-like fragments (TLFs) from the interaction of (E$_{c.m.}$=450 MeV) $^{136}$Xe with a thick target of $^{208}$Pb were measured using Gammasphere and off-line $\\gamma$-ray spectroscopy, giving a comprehensive picture of the production cross sections in this reaction.The measured yields were compared to predictions of the GRAZING model and the predictions of Zagrebaev and Greiner using a quantitative metric, the theory evaluation factor, {\\bf tef}. The GRAZING model predictions are adequate for describing the yields of nuclei near the target or projectile but grossly underestimate the yields of all other products. The predictions of Zagrebaev and Greiner correctly describe the magnitude and maxima of the observed TLF transfer cross sections for a wide range of transfers ($\\Delta$Z = -8 to $\\Delta$Z = +2). However for $\\Delta$Z =+4, the observed position of the maximum in the distribution is four neutrons richer than the predicted maximum. The pre...

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

    DEFF Research Database (Denmark)

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

    Proton-coupled electron-transfer (PCET) is found in a range of oxidation-reduction reactions in biology.1 This mechanism is of interest for applications in energy conversion processes. The PCET reaction has been shown to be facilitated when the proton is transferred to an intramolecular basic sit...

  16. Coupled-channels description of the 40Ca+58,64Ni transfer and fusion reactions

    CERN Document Server

    Scamps, G; Hagino, K; Haas, F; Courtin, S

    2016-01-01

    Preliminary experimental data for nucleon transfer reactions of the 40Ca+58Ni and 40Ca+64Ni systems are analyzed with the coupled- channels approach. It is shown that a simple treatment for the transfer in the coupled-channels method cannot reproduce simultaneously the transfer probabilities and the sub-barrier enhancement of fusion cross sections.

  17. Role of transfer reactions in heavy-ion collisions at the Coulomb barrier

    Directory of Open Access Journals (Sweden)

    Pollarolo Giovanni

    2011-10-01

    Full Text Available One and two neutron transfer reactions are discussed in the semiclassical formalism. The twoneutrons transfer cross sections are calculated in the successive approximation. Comparisons with new experimental data below the Coulomb barrier are discussed in term of transfer probabilities as a function of the distance of closest approach for Coulomb scattering.

  18. Neutron Transfer Reactions for Deformed Nuclei Using Sturmian Basis

    CERN Document Server

    Gueorguiev, V G; Escher, J E; Dietrich, F S

    2007-01-01

    We study the spin-parity distribution P(J$^{\\pi}$,E) of $^{156}$Gd excited states above the neutron separation energy that are expected to be populated via the neutron pickup reaction $^{157}$Gd($^{3}$He,$^{4}$He)$^{156}$Gd. In general, modeling of the spin-parity distribution is important for the applicability of the surrogate reaction technique as a method of deducing reaction cross sections. We model excited states in $^{156}$Gd as rotational states built on intrinsic states consisting of a hole in the core where the hole represents neutron removal form a deformed single particle state. The reaction cross section to each excited state is calculated using standard reaction code that uses spherical reaction form-factor input. The spectroscopic factor associated with each form-factor is the expansion coefficient of the deformed neutron state in a spherical Sturmian basis consisting of the spherical reaction form-factors.

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

    Science.gov (United States)

    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

  20. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive ...... vibrational frequency changes, local mode anharmonicity, and rotational reorganization, in both diabatic and adiabatic limits. Systems for which this formalism is appropriate are discussed....

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

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, C.L.; Rehm, K.E.; Gehring, J. [and others

    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.

  2. Final state interactions in two-particle interferometry

    CERN Document Server

    Anchishkin, D V; Renk, P

    1998-01-01

    We reconsider the influence of two-particle final state interactions (FSI) on two-particle Bose-Einstein interferometry. We concentrate in particular on the problem of particle emission at different times. Assuming chaoticity of the source, we derive a new general expression for the symmetrized two-particle cross section. We discuss the approximations needed to derive from the general result the Koonin-Pratt formula. Introducing a less stringent version of the so-called smoothness approximation we also derive a more accurate formula. It can be implemented into classical event generators and allows to calculate FSI corrected two-particle correlation functions via modified Bose-Einstein "weights".

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

    Science.gov (United States)

    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.

  4. Examining the effect of nonlocality in (d ,n ) transfer reactions

    Science.gov (United States)

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

    2016-07-01

    Background: In the past year we have been exploring the effect of the explicit inclusion of nonlocality in (d ,p ) reactions. Purpose: The goal of this paper is to extend previous studies to (d ,n ) reactions, which, although similar to (d ,p ) reactions, have specific properties that merit inspection. Method: 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. Results: We look separately at the modifications introduced by nonlocality in the final bound and scattering states as well as the consequences reflected 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 ) reactions. Due to the particular role of the Coulomb force in the bound state, often we found the effects of nonlocality to be larger in (d ,n ) than in (d ,p ) reactions. Conclusions: Our results confirm the importance of including nonlocality explicitly in deuteron-induced reactions.

  5. Photoinduced electron transfer reactions of ruthenium(II)-complexes containing amino acid with quinones.

    Science.gov (United States)

    Eswaran, Rajkumar; Kalayar, Swarnalatha; Paulpandian, Muthu Mareeswaran; Seenivasan, Rajagopal

    2014-05-01

    With the aim of mimicking, at basic level the photoinduced electron transfer process in the reaction center of photosystem II, ruthenium(II)-polypyridyl complexes, carrying amino acids were synthesized and studied their photoinduced electron transfer reactions with quinones by steady state and time resolved measurements. The reaction of quinones with excited state of ruthenium(II)-complexes, I-V in acetonitrile has been studied by luminescence quenching technique and the rate constant, k(q), values are close to the diffusion controlled rate. The detection of the semiquinone anion radical in this system using time-resolved transient absorption spectroscopy confirms the electron transfer nature of the reaction. The semiclassical theory of electron transfer has been successfully applied to the photoluminescence quenching of Ru(II)-complexes with quinones.

  6. Charge-Transfer Reaction of Cediranib with 2,3-Dichloro- 3,5 ...

    African Journals Online (AJOL)

    Abstract. Purpose: To investigate the charge-transfer (CT) reaction between cediranib (CRB) and 2, 3 - dichloro- ... Conclusion: The developed assay has high throughput and consumed minimum volume of organic solvent ..... radical ions…

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

    CERN Document Server

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

    2016-01-01

    [Background:] Recent work found that core excitation 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 understand the origin of the dynamical effects. [Method:] Based on the particle-rotor model of $n+^{10}$Be, we generate a number of models with a range of separation energies ($S_n=0.1-5.0$ 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 $^{10}$Be(d,p)$^{11}$Be like reactions, and study the excitation effects for beam energies from $E_d=15-90$ 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, to that of the original structure model. We al...

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

    Science.gov (United States)

    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.

  9. Electron transfer reactions, cyanide and O2 binding of truncated hemoglobin from Bacillus subtilis

    DEFF Research Database (Denmark)

    Fernandez, Esther; Larsson, Jonas T.; McLean, Kirsty J.

    2013-01-01

    in trHb-Bs shifted −59 mV per pH unit at pH higher than 7, consistently with a 1e−/1 H+ – transfer reaction. The heterogeneous rate constant ks for a quasi-reversible 1e− – 1H+ – transfer reaction between graphite and trHb-Bs was 10.1 ± 2.3 s−1. Upon reversible cyanide binding the ks doubled, while...

  10. Recyclable Polystyrene-Supported Siloxane-Transfer Agent for Palladium-Catalyzed Cross-Coupling Reactions

    Science.gov (United States)

    2015-01-01

    The rational design, synthesis, and validation of a significantly improved insoluble polymer-supported siloxane-transfer agent has been achieved that permits efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling. Drawbacks of a previous polymer-supported siloxane-transfer agent, relating to reaction efficiency and polymer stability after repeated cycles, have been addressed. PMID:24661113

  11. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Frutos, Luis Manuel, E-mail: luisma.frutos@uah.es [Departamento de Química Física, Universidad de Alcalá, 28871 Alcalá de Henares, Madrid (Spain); Acuña, A. Ulises [Instituto de Química Física “Rocasolano”, C.S.I.C., Serrano 119, 28006 Madrid (Spain)

    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.

  13. Studies on electron transfer reactions of Keggin-type mixed addenda heteropolytungstovanadophosphates with NADH

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Kasi Rajasekaran

    2009-03-01

    The coenzyme nicotinamide adenine dinucleotide (NADH) undergoes facile electron transfer reaction with vanadium (V) substituted Keggin-type heteropolyanions (HPA) [PVVW11O40]4- (PV1) and [PV$^{V}_{2}$W10O40]5- (PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1 : 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one electron reduced heteropoly blues (HPB), viz. [PVIVW11O40]5- and [PVIVVVW10O40]6-. Oxygraph measurements show that there is no uptake of molecular oxygen during the course of reaction. The reaction proceeds through multi-step electron-proton-electron transfer mechanism, with rate limiting initial one electron transfer from NADH to HPA by outer sphere electron transfer process. Bimolecular rate constant for electron transfer reaction between NADH and PV2 in phosphate buffer of pH = 6 has been determined spectrophotometrically.

  14. A semiclassical theory of electron transfer reactions in Condon approximation and beyond

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Sokolov, V. V.; Ulstrup, Jens

    2001-01-01

    The effect of the modulation of the electronic wave functions by configurational fluctuations of the molecular environment on the kinetic parameters of electron transfer reactions is discussed. A self-consistent algorithm for the calculation of the potential profile along the reaction coordinate...

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

    Science.gov (United States)

    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.

  16. Two-neutron transfer reactions investigating shell stability and inverse kinematics capability

    Energy Technology Data Exchange (ETDEWEB)

    Mahgoub, Mahmoud; Bildstein, Vinzenz; Faestermann, Thomas; Gernhaeuser, Roman; Kroell, Thorsten; Kruecken, Reiner; Maier, Ludwig; Wirth, Hans [Physik-Department E12, TU Muenchen, Garching (Germany); Bohlen, Hans-Gerhard; Kokalova, Tzanka; Oertzen, Wolfram von; Wheldon, Carl [HMI, Berlin (Germany); Bucurescu, Dorel [NIPNE, Bucharest (Romania); Dorsch, Tatiana [Physik-Department E12, TU Muenchen, Garching (Germany); HMI, Berlin (Germany); Hertenberger, Ralf [Sektion Physik, LMU Muenchen (Germany)

    2008-07-01

    Neutron transfer reactions were used to study the stability of the magic number N=28. We investigated neutron pairing correlations using the two-neutron pickup reaction {sup 58}Ni((vector)p,t){sup 56}Ni depending on the fact that nuclei with high neutron pairing are good magic nuclei. The capability of inverse kinematics reactions to study exotic nuclei was tested by the neutron transfer reactions t({sup 40}Ar,p){sup 42} Ar using a tritium target and comparing the results and conclusions with the normal kinematics reactions. The results for the reactions on Ni and Ar compared to DWBA calculations will be presented. Future possibilities for the use of inverse kinematics to study exotic nuclei with radioactive beams are discussed.

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

    Directory of Open Access Journals (Sweden)

    H.M. Devaraja

    2015-09-01

    Full Text Available 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.

  18. Neutron Transfer Reactions: Surrogates for Neutron Capture for Basic and Applied Nuclear Science

    Science.gov (United States)

    Cizewski, J. A.; Jones, K. L.; Kozub, R. L.; Pain, S. D.; Peters, W. A.; Adekola, A.; Allen, J.; Bardayan, D. W.; Becker, J. A.; Blackmon, J. C.; Chae, K. Y.; Chipps, K. A.; Erikson, L.; Gaddis, A.; Harlin, C.; Hatarik, R.; Howard, J.; Jandel, M.; Johnson, M. S.; Kapler, R.; Krolas, W.; Liang, F.; Livesay, R. J.; Ma, Z.; Matei, C.; Matthews, C.; Moazen, B.; Nesaraja, C. D.; O'Malley, P.; Patterson, N.; Paulauskas, S. V.; Pelham, T.; Pittman, S. T.; Radford, D.; Rogers, J.; Schmitt, K.; Shapira, D.; Shriner, J. F.; Sissom, D. J.; Smith, M. S.; Swan, T.; Thomas, J. S.; Vieira, D. J.; Wilhelmy, J. B.; Wilson, G. L.

    2009-03-01

    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 130,132Sn, 134Te and 75As are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cizewski, J. A. [Rutgers University; Jones, K. L. [University of Tennessee; Kozub, R. L. [Tennessee Technological University; Pain, Steven D [ORNL; Peters, W. A. [Rutgers University; Adekola, Aderemi S [ORNL; Allen, J. [Rutgers University; Bardayan, Daniel W [ORNL; Becker, J. [Lawrence Livermore National Laboratory (LLNL); Blackmon, Jeff C [ORNL; Chae, K. Y. [University of Tennessee; Chipps, K. [Colorado School of Mines, Golden; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; Jandel, M. [Los Alamos National Laboratory (LANL); Johnson, Micah [ORNL; Kapler, R. [University of Tennessee; Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Livesay, Jake [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Matthews, C. [Rutgers University; Moazen, Brian [University of Tennessee; Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Patterson, N. P. [University of Surrey, UK; Paulauskas, Stanley [University of Tennessee; Pelham, T. [University of Surrey, UK; Pittman, S. T. [University of Tennessee, Knoxville (UTK); Radford, David C [ORNL; Rogers, J. [Tennessee Technological University; Schmitt, Kyle [University of Tennessee; Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Thomas, J. S. [Rutgers University; Vieira, D. J. [Los Alamos National Laboratory (LANL); Wilhelmy, J. B. [Los Alamos National Laboratory (LANL); Wilson, Gemma L [ORNL

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Heinz, S.; Beliuskina, O. [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt (Germany); Justus-Liebig-Universitaet Giessen, II. Physikalisches Institut, Giessen (Germany); Devaraja, H.M.; Gupta, M. [Manipal University, Manipal Centre for Natural Sciences, Manipal, Karnataka (India); Comas, V.; Hofmann, S.; Muenzenberg, G.; Ackermann, D.; Kindler, B.; Lommel, B.; Mann, R.; Maurer, J. [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt (Germany); Hornung, C. [Justus-Liebig-Universitaet Giessen, II. Physikalisches Institut, Giessen (Germany); Henderson, R.A.; Moody, K.J.; Shaughnessy, D.A.; Stoyer, M.A. [Lawrence Livermore National Laboratory, Livermore, CA (United States); Hessberger, F.P. [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt (Germany); Helmholtz-Institut Mainz, Mainz (Germany); Nishio, K. [Japan Atomic Energy Agency, Tokai Ibaraki (Japan); Popeko, A.G.; Yeremin, A.V. [Joint Institute for Nuclear Research, Dubna (Russian Federation)

    2016-09-15

    Recently, we reported the observation of several new isotopes with proton numbers Z ≥ 92 in low-energy collisions of {sup 48}Ca + {sup 248}Cm. 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. (orig.)

  1. 9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions.

    Science.gov (United States)

    Boutaghou, M Nazim; Cole, Richard B

    2012-08-01

    The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume.

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

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)

    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

  3. Reaction dynamics and proton coupled electron transfer: studies of tyrosine-based charge transfer in natural and biomimetic systems.

    Science.gov (United States)

    Barry, Bridgette A

    2015-01-01

    In bioenergetic reactions, electrons are transferred long distances via a hopping mechanism. In photosynthesis and DNA synthesis, the aromatic amino acid residue, tyrosine, functions as an intermediate that is transiently oxidized and reduced during long distance electron transfer. At physiological pH values, oxidation of tyrosine is associated with a deprotonation of the phenolic oxygen, giving rise to a proton coupled electron transfer (PCET) reaction. Tyrosine-based PCET reactions are important in photosystem II, which carries out the light-induced oxidation of water, and in ribonucleotide reductase, which reduces ribonucleotides to form deoxynucleotides. Photosystem II contains two redox-active tyrosines, YD (Y160 in the D2 polypeptide) and YZ (Y161 in the D1 polypeptide). YD forms a light-induced stable radical, while YZ functions as an essential charge relay, oxidizing the catalytic Mn₄CaO₅ cluster on each of four photo-oxidation reactions. In Escherichia coli class 1a RNR, the β2 subunit contains the radical initiator, Y122O•, which is reversibly reduced and oxidized in long range electron transfer with the α2 subunit. In the isolated E. coli β2 subunit, Y122O• is a stable radical, but Y122O• is activated for rapid PCET in an α2β2 substrate/effector complex. Recent results concerning the structure and function of YD, YZ, and Y122 are reviewed here. Comparison is made to recent results derived from bioengineered proteins and biomimetic compounds, in which tyrosine-based charge transfer mechanisms have been investigated. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Hydrodynamics: Fluctuating initial conditions and two-particle correlations

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, R.P.G.; Grassi, F. [Instituto de Fisica, Universidade de Sao Paulo (Brazil); Hama, Y., E-mail: hama@fma.if.usp.b [Instituto de Fisica, Universidade de Sao Paulo (Brazil); Qian, W.-L. [Instituto de Fisica, Universidade de Sao Paulo (Brazil)

    2011-03-15

    Event-by-event hydrodynamics (or hydrodynamics with fluctuating initial conditions) has been developed in the past few years. Here we discuss how it may help to understand the various structures observed in two-particle correlations.

  5. Probabilistic Teleportation of Two-Particle State of General Formation

    Institute of Scientific and Technical Information of China (English)

    YAN Feng-Li; TAN Hong-Ge; YANG Lin-Guang

    2002-01-01

    A scheme for probabilistic teleporting an unknown two-particle state of general formation by partly pure entangled four-particle state is proposed. It is shown that after performing two Bell state measurements, proper unitary transformation and the measurement on an auxiliary qubit, the unknown two-particle state of general formation, which was destroyed at one place, can be reconstructed at another place with certain probability.

  6. Significance Of Deuteron Breakup In A Halo Transfer Reaction

    CERN Document Server

    Yilmaz, M; Yilmaz, Mustafa; Gonul, Bulent

    2000-01-01

    We discuss the quasi-adiabatic approximations to the three-body wavefunction in breakup processes, clarifying the assumptions underlying the model. This suggests alternative approximation schemes. Using different theoretical three-body models, calculated differential cross section angular distributions for the Be-11(p,d) reaction,for which new preliminary data have been reported at 35 MeV, are presented. We show that calculations are sensitive to the inclusion of deuteron breakup and to the breakup model used, particularly if used to deduce absolute spectroscopic information on the 0{+} and 2{+} Be-10 core state parentages. There is also considerable sensitivity to the model used in calculations of the relative cross sections to the two states.

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

    Science.gov (United States)

    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

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

    Indian Academy of Sciences (India)

    Alireza Najafi Chermahini; Abbas Teimouri

    2014-01-01

    The inter and intra molecular proton transfer reactions of a series of pyrazole derivatives have been studied by using density functional theory (DFT) andMP2 methods implementing 6-311++G(d,p) atomic basis set. The substituents have been selected to cover a wide range of electronic effects. Proton transfer process was studied for mechanisms including single proton transfer, double proton transfer and proton transfer assisted by a water or ammonia molecule. The results showed single proton transfer reactions for interconversion pyrazole derivatives need highest activation energies in the range of 45.7−51.59 and 49.4−53.96 kcal/mol at B3LYP and MP2 levels, respectively. It was found that for the 3-substituted pyrazoles, electron withdrawing groups form stronger dimers but in the 5-substituted tautomers electron donating groups form stronger hydrogen bond. The double proton transfer reactions between dimers were studied and transition states calculated. The ranges of activation energies were found to be 17.51−19.36 and 17.02−17.80 kcal/mol for the C → E and D → D reactions respectively. In addition, the activation energies for the proton transfer reaction assisted by water or ammonia molecules were found to be in the range of 26.62−31.78 and 17.25−22.46 kcal/mol, respectively, calculated at MP2/6-311++G(d,p) level of theory.

  9. Removal of Hg~0 with sodium chlorite solution and mass transfer reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The absorption behavior of Hg0 was studied experimentally by using sodium chlorite solution(NaClO2) as the absorbent in a bubble reactor.Primary influencing factors on removal efficiency of Hg0 such as NaClO2 concentration,pH,reaction temperature and the concentration of Hg0 were investigated.The results indicated that 72.91% of Hg0 removal efficiency could be achieved in acidic NaClO2 solution.The removal mechanism of Hg0 was proposed by analyzing of Hg2+ concentration in ab-sorption solution after reaction and comparing the electrode potentials between NaClO2 species and Hg2+/Hg0.The experimental results of mass transfer-reaction kinetics on oxidation of Hg0 by NaClO2 solution showed that with the increase of NaClO2 concentration and the decrease of pH value,the enhancement factor(E) and ratio of KG(Hg0)/kG(Hg0) increased and the liquid phase mass transfer resistance decreased,which is benefit to the mass transfer adsorption reaction.Although the increase of reaction temperature could improve the enhancement factor(E),but the ratio of KG(Hg0)/kG(Hg0) decreased;as a result,the liquid phase mass transfer resistance increased,therefore,the reaction rate for removal of Hg0 decreased.

  10. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  11. Disentangling the transfer and breakup contributions from the inclusive ^{8}Li+ ^{208}Pb reaction

    CERN Document Server

    Moro, A M; García-Martínez, H; Aguilera, E F; Martínez-Quiroz, E; Gómez-Camacho, J

    2003-01-01

    An analysis of the elastic and one-neutron removal channel for the reaction (^{8})Li+(^{208})Pb reaction at energies around the Coulomb barrier is presented. For the elastic scattering, an optical model analysis of the experimental data is performed. The observed (^{7})Li is interpreted as the superposition of the one-neutron transfer reaction, (^{208})Pb((^{8})Li,(^{7} )Li)(^{209})Pb, and the breakup reaction. The separate contribution of each one of these processes has been calculated within the DWBA formalism. The sum of both contributions explains adequately the experimental angular distribution of (^{7})Li.

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

    Science.gov (United States)

    Mirabelli, Mario F.; Zenobi, Renato

    2017-08-01

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

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

    Science.gov (United States)

    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.

  14. Quantum Coherence as a Witness of Vibronically Hot Energy Transfer in Bacterial Reaction Centre

    CERN Document Server

    Paleček, David; Westenhoff, Sebastian; Zigmantas, Donatas

    2016-01-01

    Photosynthetic proteins have evolved over billions of years so as to undergo optimal energy transfer to the sites of charge separation. Based on spectroscopically detected quantum coherences, it has been suggested that this energy transfer is partially wavelike. This conclusion critically depends on assignment of the coherences to the evolution of excitonic superpositions. Here we demonstrate for a bacterial reaction centre protein that long-lived coherent spectroscopic oscillations, which bear canonical signatures of excitonic superpositions, are essentially vibrational excited state coherences shifted to the ground state of the chromophores . We show that appearance of these coherences is brought about by release of electronic energy during the energy transfer. Our results establish how energy migrates on vibrationally hot chromophores in the reaction centre and they call for a re-examination of claims of quantum energy transfer in photosynthesis.

  15. Deceleration of the electron transfer reaction in the photosynthetic reaction centre as a manifestation of its structure fluctuations

    Directory of Open Access Journals (Sweden)

    Knox P. P.

    2010-07-01

    Full Text Available Aim. To extract information on the nature of protein structural relaxation from the kinetics of electron transfer reaction in the photosynthetic reaction centre (RC. Methods. The kinetic curves obtained by absorption spectroscopy are processed by a maximum entropy method to get the spectrum of relaxation times. Results. A series of distinctive peaks of this spectrum in the interval from 0.1 s to hundreds of seconds is revealed. With the time of exposure of the sample to actinic light increasing, the positions of the peak maxima grow linearly. Conclusions. Theoretical analysis of these results reveals the formation of several structural states of the RC protein. Remarkably, in each of these states the slow reaction kinetics follow the same fractional power law that reflects the glass-like properties of the protein.

  16. Selective Hydrogen Transfer Reaction in FCC Process:Characterization and Application

    Institute of Scientific and Technical Information of China (English)

    Chen Beiyan; He Mingyuan; Da Zhijian

    2003-01-01

    The product distribution and gasoline quality of FCC process, especially the olefin content,heavily depends on the catalyst performance in terms of selective/non-selective hydrogen transfer reaction selectivity. A reliable experimental protocol has been established by using n-dodecane as a probe molecule to characterize the selective hydrogen transfer ability of catalytic materials. The results obtained have been correlated with the performance of the practical catalysts.

  17. Adiabatic criteria for outer-sphere bimolecular electron-transfer reactions

    Science.gov (United States)

    Onuchic, Jose Nelson; Beratan, David N.

    1988-01-01

    A model is presented for outer-sphere bimolecular electron-transfer reactions which is correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. From this model, the conditions for the transfer to be adiabatic or nonadiabatic are deduced. The time-scale separations needed to adequately describe the process as an average over (distant dependent) unimolecular rates are described.

  18. The 2H(e, e' p)n reaction at large energy transfers

    NARCIS (Netherlands)

    Willering, Hendrik Willem

    2003-01-01

    At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron "breakup" reaction 2H(e,e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the quasielast

  19. Construction of cyclic enones via gold-catalyzed oxygen transfer reactions

    Directory of Open Access Journals (Sweden)

    Gerald B. Hammond

    2011-05-01

    Full Text Available During the last decade, gold-catalyzed reactions have become a tour de force in organic synthesis. Recently, the gold-, Brønsted acid- or Lewis acid-catalyzed oxygen transfer from carbonyl to carbon–carbon triple bond, the so-called alkyne–carbonyl metathesis, has attracted much attention because this atom economical transformation generates α,β-unsaturated carbonyl derivatives which are of great interest in synthetic organic chemistry. This mini-review focuses on the most recent achievements on gold-catalyzed oxygen transfer reactions of tethered alkynones, diynes or alkynyl epoxides to cyclic enones. The corresponding mechanisms for the transformations are also discussed.

  20. A Novel Micro-hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between ferro/ferricyanide in aqueous phase (W) and ferrocene in 1, 2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

  1. A Novel Micro—hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    DongPingZHAN; BingLiangWU

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between feero/ferricyanide in aqueous phase(W) and ferrocene in 1,2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

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

    Science.gov (United States)

    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.

  3. Theoretical Study on the NO2 + NO2- Electron Transfer Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Zheng-Yu(周正宇); GAO,Hong-Wei(高洪伟); XING,Yu-Mei(邢玉梅); GUO,Li(郭丽); QU,Yu-Hui(曲玉辉)

    2002-01-01

    The NO2 + NO2- electron transfer reaction was studied with DFT-B3LYP method at 6-311 + G* basis set level for the eight selected structures: four species favor the strucure of "head to head". The geometry of transition state was obtained by the linear coordinate method. Three parameters, non-adiahatic activation energy (Ead), coupling matrix element (Hif) and reorganization energy (λ) for electron transfer reaction can be calculated. According to the reorganization energy of the ET reaction, the values obtained from George-Griffith-Marcus (GGM) method (the contribution only from diagonal elements of force constant matrix) are larger than those obtained from Hessian matrix method (including the contribution from both diagonal and off-diagonal elements), which suggests that the coupling interactions between different vibrational modes are important to the inner-sphere reogrganization energy for the ET reactions in gaseous phase. The value of rate constant was obtained by using above three activation parameters.

  4. Quantum Secret Sharing with Two-Particle Entangled States

    Institute of Scientific and Technical Information of China (English)

    LIU Wei-Tao; LIANG Lin-Mei; LI Cheng-Zu; YUAN Jian-Min

    2006-01-01

    We present a new protocol for the quantum secret sharing (QSS) task among multiparties with two-particle entangled states. In our scheme, the secret is split among a number of participating partners and the reconstruction requires collaboration of all the authorized partners. Instead of multiparticle Greenberger-Horne-Zeilinger states,only two-particle entangled states are employed in this scheme. By local operations and individual measurements on either of the two entangled particles, each authorized partner obtains a sequence of secret bits shared with other authorized partners. This protocol can be experimentally realized using only linear optical elements and simple entanglement source. It is scalable in practice.

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

    NARCIS (Netherlands)

    Timkovsky, J.; Dusek, U.; Henzing, J. S.; Kuipers, T. L.; Röckmann, T.; Holzinger, R.

    2015-01-01

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

  6. Phthalimides as exceptionally efficient single electron transfer acceptors in reductive coupling reactions promoted by samarium diiodide.

    Science.gov (United States)

    Vacas, Tatiana; Alvarez, Eleuterio; Chiara, Jose Luis

    2007-12-20

    Experimental and theoretical evidence shows that phthalimides are highly efficient single electron transfer acceptors in reactions promoted by samarium diiodide, affording ketyl radical anion intermediates, which participate in high-yielding inter- and intramolecular reductive coupling processes with different radicophiles including imides, oxime ethers, nitrones, and Michael acceptors.

  7. Multinucleon transfer reactions studied with the heavy-ion magnetic spectrometer PRISMA

    Energy Technology Data Exchange (ETDEWEB)

    Corradi, L.; Stefanini, A.M.; Behera, B.R.; Gadea, A.; Fioretto, E.; Latina, A.; Marginean, N. [INFN, Laboratori Nazionali di Legnaro, Legnaro (Padova) (Italy); Szilner, S. [INFN, Laboratori Nazionali di Legnaro, Legnaro (Padova) (Italy); Boskovic Institute, Zagreb (Croatia); Beghini, S.; Farnea, E.; Montagnoli, G.; Scarlassara, F.; Ur, C. [Universita di Padova and INFN, Sezione di Padova, Dipartimento di Fisica, Padova (Italy); Haas, F. [IN2P3-CNRS-Universite Louis Pasteur, Institut de Recherches Subatomiques, Strasbourg (France); Pollarolo, G. [Universita di Torino and INFN, Sezione di Torino, Dipartimento di Fisica Teorica, Torino (Italy); Trotta, M. [INFN - Sezione di Napoli and Dipartimento di Fisica, Universita di Napoli, Napoli (Italy)

    2005-09-01

    Recent inclusive measurements on multinucleon transfer reactions reveal important information on the interplay between single-particle and nucleon pair degrees of freedom. More detailed studies are being performed with the new magnetic spectrometer PRISMA, coupled to the CLARA {gamma}-array. (orig.)

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

    Science.gov (United States)

    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…

  9. Proton transfer reactions in carbon nanotubes endohedrally functionalized with selected polar amino acid sidechains

    Energy Technology Data Exchange (ETDEWEB)

    Abi, T.G. [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India); Taraphder, Srabani, E-mail: srabani@chem.iitkgp.ernet.in [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India)

    2012-09-11

    Graphical abstract: Free Energies of activation and reaction for intramolecular proton transfer between polar amino acid sidechains and hydroxyl groups inside the core of endohedrally functionalized single walled carbon nanotubes. Highlights: Black-Right-Pointing-Pointer EVB based free energy simulation of proton transfer in hydrophobic confinement. Black-Right-Pointing-Pointer Aminoacid sidechain and OH group suspended within carbon nanotube act as reactants. Black-Right-Pointing-Pointer Donors like His and Glu are efficient in confinement aided by local hydrogen bonds. -- Abstract: We use the empirical-valence-bond (EVB) theory to investigate intramolecular proton transfer reactions between a selected set of polar amino acid sidechains and hydroxyl groups suspended inside carbon nanotubes to model the effect of hydrophobic confinement on the energetics of proton transfer involving (i) translocation of an excess protonic charge (with protonated histidine sidechain as donor) and (ii) transformation of a neutral reactant state to a charge-separated product state (with sidechains of Asp, Glu, Ser and Thr as donor). In both the cases, confinement in hydrophobic medium is found to change the associated free energies compared to their respective values in the bulk solution phase. Presence of stable hydrogen bonding within the pore is found to have a significant effect on both free energies of reaction and activation and thus governs the thermodynamic and kinetic feasibilities of these intramolecular reactions in hydrophobic confinement.

  10. Synthesis, characterisation, and oxygen atom transfer reactions involving the first gold(I)-alkylperoxo complexes.

    Science.gov (United States)

    Collado, Alba; Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Slawin, Alexandra M Z; Nolan, Steven P

    2013-11-25

    The synthesis of a new class of organogold species containing a peroxo moiety is reported. Complexes [Au(IPr)(OO(t)Bu)] and [Au(SIPr)(OO(t)Bu)] have been synthesised via a straightforward methodology using the parent gold(I) hydroxide complexes as synthons. These complexes have been successfully used in oxygen-transfer reactions to triphenylphosphine.

  11. Long-range proton transfer in aqueous acid-base reactions

    NARCIS (Netherlands)

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

    2008-01-01

    We study the mechanism of proton transfer (PT) in the aqueous acid−base reaction between the photoacid 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS) and acetate by probing the vibrational resonances of HPTS, acetate, and the hydrated proton with femtosecond mid-infrared laser pulses. We find that PT

  12. Beyond frontier molecular orbital theory: a systematic electron transfer model (ETM) for polar bimolecular organic reactions.

    Science.gov (United States)

    Cahill, Katharine J; Johnson, Richard P

    2013-03-01

    Polar bimolecular reactions often begin as charge-transfer complexes and may proceed with a high degree of electron transfer character. Frontier molecular orbital (FMO) theory is predicated in part on this concept. We have developed an electron transfer model (ETM) in which we systematically transfer one electron between reactants and then use density functional methods to model the resultant radical or radical ion intermediates. Sites of higher reactivity are revealed by a composite spin density map (SDM) of odd electron character on the electron density surface, assuming that a new two-electron bond would occur preferentially at these sites. ETM correctly predicts regio- and stereoselectivity for a broad array of reactions, including Diels-Alder, dipolar and ketene cycloadditions, Birch reduction, many types of nucleophilic additions, and electrophilic addition to aromatic rings and polyenes. Conformational analysis of radical ions is often necessary to predict reaction stereochemistry. The electronic and geometric changes due to one-electron oxidation or reduction parallel the reaction coordinate for electrophilic or nucleophilic addition, respectively. The effect is more dramatic for one-electron reduction.

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

    Science.gov (United States)

    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 eVc.m.. This may be due to formation of a long-lived collision complex (Ar-HCl)+.

  14. Mechanism of the Primary Charge Transfer Reaction in the Cytochrome bc1 Complex

    DEFF Research Database (Denmark)

    Barragan, Angela M; Schulten, Klaus; Solov'yov, Ilia A

    2016-01-01

    , the quinol-protein interaction, which initiates the Q-cycle, has not yet been completely described. Furthermore, the initial charge transfer reactions of the Q-cycle lack a physical description. The present investigation utilizes classical molecular dynamics simulations in tandem with quantum density...

  15. Cluster-transfer reactions with radioactive beams: a spectroscopic tool for neutron-rich nuclei

    CERN Document Server

    AUTHOR|(CDS)2086156; Raabe, Riccardo; Bracco, Angela

    In this thesis work, an exploratory experiment to investigate cluster-transfer reactions with radioactive beams in inverse kinematics is presented. The aim of the experiment was to test the potential of cluster-transfer reactions at the Coulomb barrier, as a possible mean to perform $\\gamma$ spectroscopy studies of exotic neutron-rich nuclei at medium-high energies and spins. The experiment was performed at ISOLDE (CERN), employing the heavy-ion reaction $^{98}$Rb + $^{7}$Li at 2.85 MeV/A. Cluster-transfer reaction channels were studied through particle-$\\gamma$ coincidence measurements, using the MINIBALL Ge array coupled to the charged particle Si detectors T-REX. Sr, Y and Zr neutron-rich nuclei with A $\\approx$ 100 were populated by either triton- or $\\alpha$ transfer from $^{7}$Li to the beam nuclei and the emitted complementary charged fragment was detected in coincidence with the $\\gamma$ cascade of the residues, after few neutrons evaporation. The measured $\\gamma$ spectra were studied in detail and t...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  18. Photoinduced Electron Transfer Reaction between Poly-guanylic Acid (5`) with Anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The electron transfer reaction between triplet anthraquinone-2-sulfonate with poly-guanylic acid (5) (poly[G]) in acetonitrile-H2O has been investigated by 248 nm laser flash photolysis. The transient absorption spectra of radical cation of poly[G] and radical anion of anthraqunione-2-sulfonate(AQS) arising from electron transfer reaction has been observed simultaneously for the first time. The formation processes of radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate as well as the decay processes of triplet anthraquinone-2-sulfonate have also been observed, the apparent rate constants for the formation and decay of transient species have been determined. The free energy changes in the process of the electron transfer was also calculated.

  19. Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

    Science.gov (United States)

    Wang, Changhua; Zhang, Xintong; Liu, Yichun

    2015-12-01

    Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

  20. Structure and mechanism of styrene monooxygenase reductase: new insight into the FAD-transfer reaction.

    Science.gov (United States)

    Morrison, Eliot; Kantz, Auric; Gassner, George T; Sazinsky, Matthew H

    2013-09-03

    The two-component flavoprotein styrene monooxygenase (SMO) from Pseudomonas putida S12 catalyzes the NADH- and FAD-dependent epoxidation of styrene to styrene oxide. In this study, we investigate the mechanism of flavin reduction and transfer from the reductase (SMOB) to the epoxidase (NSMOA) component and report our findings in light of the 2.2 Å crystal structure of SMOB. Upon rapidly mixing with NADH, SMOB forms an NADH → FADox charge-transfer intermediate and catalyzes a hydride-transfer reaction from NADH to FAD, with a rate constant of 49.1 ± 1.4 s(-1), in a step that is coupled to the rapid dissociation of NAD(+). Electrochemical and equilibrium-binding studies indicate that NSMOA binds FADhq ∼13-times more tightly than SMOB, which supports a vectoral transfer of FADhq from the reductase to the epoxidase. After binding to NSMOA, FADhq rapidly reacts with molecular oxygen to form a stable C(4a)-hydroperoxide intermediate. The half-life of apoSMOB generated in the FAD-transfer reaction is increased ∼21-fold, supporting a protein-protein interaction between apoSMOB and the peroxide intermediate of NSMOA. The mechanisms of FAD dissociation and transport from SMOB to NSMOA were probed by monitoring the competitive reduction of cytochrome c in the presence and absence of pyridine nucleotides. On the basis of these studies, we propose a model in which reduced FAD binds to SMOB in equilibrium between an unreactive, sequestered state (S state) and more reactive, transfer state (T state). The dissociation of NAD(+) after the hydride-transfer reaction transiently populates the T state, promoting the transfer of FADhq to NSMOA. The binding of pyridine nucleotides to SMOB-FADhq shifts the FADhq-binding equilibrium from the T state to the S state. Additionally, the 2.2 Å crystal structure of SMOB-FADox reported in this work is discussed in light of the pyridine nucleotide-gated flavin-transfer and electron-transfer reactions.

  1. TELEPORTATION OF A TWO-PARTICLE ENTANGLED STATE

    Institute of Scientific and Technical Information of China (English)

    叶柳; 姚春梅; 郭光灿

    2001-01-01

    A scheme for teleporting a two-particle entangled state via a three-particle entangled state is proposed. It is shown that the probability of successful teleportation is twice the modulus square of the smaller Schmidt coefficient of the entangled three-particle state.

  2. Canonical Quantum Teleportation of Two-Particle Arbitrary State

    Institute of Scientific and Technical Information of China (English)

    HAO Xiang; ZHU Shi-Qun

    2005-01-01

    The canonical quantum teleportation of two-particle arbitrary state is realized by means of phase operator and number operator. The maximally entangled eigenstates between the difference of phase operators and the sum of number operators are considered as the quantum channels. In contrast to the standard quantum teleportation, the different unitary local operation of canonical teleportation can be simplified by a general expression.

  3. Teleportation of Two-Particle Entangled State via Cluster State

    Institute of Scientific and Technical Information of China (English)

    LI Da-Chuang; CAO Zhuo-Liang

    2007-01-01

    In this paper,two schemes for teleporting an unknown two-particle entangled state from the sender (Alice)to the receiver (Bob) via a four-particle entangled cluster state are proposed.In these two schemes,the unknown twoparticle entangled state can be teleported perfectly.The successful probabilities and fidelities of the schemes can reach unity.

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

    Science.gov (United States)

    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. © 2017 Wiley Periodicals, Inc.

  5. Controlling an electron-transfer reaction at a metal surface by manipulating reactant motion and orientation.

    Science.gov (United States)

    Bartels, Nils; Krüger, Bastian C; Auerbach, Daniel J; Wodtke, Alec M; Schäfer, Tim

    2014-12-08

    The loss or gain of vibrational energy in collisions of an NO molecule with the surface of a gold single crystal proceeds by electron transfer. With the advent of new optical pumping and orientation methods, we can now control all molecular degrees of freedom important to this electron-transfer-mediated process, providing the most detailed look yet into the inner workings of an electron-transfer reaction and showing how to control its outcome. We find the probability of electron transfer increases with increasing translational and vibrational energy as well as with proper orientation of the reactant. However, as the vibrational energy increases, translational excitation becomes unimportant and proper orientation becomes less critical. One can understand the interplay of all three control parameters from simple model potentials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

    Science.gov (United States)

    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. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    Science.gov (United States)

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-08

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex.

  9. Probing surface distribution of $\\alpha$-cluster in $^{20}$Ne via $\\alpha$-transfer reaction

    CERN Document Server

    Fukui, Tokuro; Suhara, Tadahiro; Kanada-En'yo, Yoshiko; Ogata, Kazuyuki

    2015-01-01

    Direct evidence of the $\\alpha$-cluster development in bound states has not been obtained yet although a number of experimental studies were carried out to extract the information of the clustering. In particular in conventional analyses of $\\alpha$-transfer reactions, there exist a few significant problems on reaction models, which are insufficient to qualitatively discuss the cluster structure. We aim to verify the development of the $\\alpha$-cluster structure from observables. As the first application, it is argued to extract the spatial information of the cluster structure of the $^{20}$Ne nucleus in its ground state through the cross section of the $\\alpha$-transfer reaction $^{16}$O($^6$Li,~$d$)$^{20}$Ne. For the analysis of the transfer reaction, we work with the coupled-channels Born approximation (CCBA) approach, in which the breakup effect of $^6$Li is explicitly taken into account by means of the continuum-discretized coupled-channels method (CDCC) based on the three-body $\\alpha + d + {}^{16}$O mo...

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

    Science.gov (United States)

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

    Science.gov (United States)

    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.

  12. Minor actinide fission induced by multi-nucleon transfer reaction in inverse kinematics

    Directory of Open Access Journals (Sweden)

    Taieb J.

    2010-03-01

    Full Text Available In the framework of nuclear waste incineration and design of new generation nuclear reactors, experimental data on fission probabilities and on fission fragment yields of minor actinides are crucial to design prototypes. Transfer-induced fission has proven to be an efficient method to study fission probabilities of actinides which cannot be investigated with standard techniques due to their high radioactivity. We report on the preliminary results of an experiment performed at GANIL that investigates fission probabilities with multi-nucleon transfer reactions in inverse kinematics between a 238U beam on a 12C target. Actinides from U to Cm were produced with an excitation energy range from 0 to 30 MeV. In addition, inverse kinematics allowed to characterize the fission fragments in mass and charge. A key point of the analysis resides in the identification of the actinides produced in the different transfer channels. The new annular telescope SPIDER was used to tag the target-like recoil nucleus of the transfer reaction and to determine the excitation energy of the actinide. The fission probability for each transfer channel is accessible and the preliminary results for 238U are promising.

  13. Studies on electron transfer reactions: Reduction of heteropoly 10-tungstodivanadophosphate by thioglycolic acid in aqueous medium

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Natarajan Mariselvi; Kandasamy Venkateshwari; Arunachalam Sarathi; Kasi Rajasekaran

    2010-05-01

    Rates of electron transfer reaction of thioglycolic acid with vanadium(V) substituted Keggintype heteropolyanion, [PVVVVW10O40]5-, in acetate-acetic acid buffers have been measured spectrophotometrically at 25°C. The order of the reaction with respect to substrate and oxidant is unity. The reaction shows simple second order kinetics at constant pH. The rate of the reaction increases with increase of pH of the medium. The mono-anion HSCH2COO- and di-anion -SCH2COO- are found to be the reactive species. Rate constants for mono-anion and di-anion are evaluated from rate law derived from the mechanism. By applying Rehm-Weller relationship, self exchange rate constant for the -SCH2COO-/S$^{\\bullet}$ CH2COO- couple was evaluated as 3.3 × 103 dm3 mol-1 s-1 at 25°C.

  14. Theoretical Study on the Kinetics of Electron Transfer for Bond-breaking Reaction

    Institute of Scientific and Technical Information of China (English)

    XING,Yu-Mei(邢玉梅); ZHOU,Zheng-Yu(周正宇); GAO,Hong-Wei(高洪伟)

    2002-01-01

    To test the theory of dissociative electron transfer, a simple model describing the kinetics of electron transfer bond-breaking reactions was used. The Hamiltonian of the system was given.The homogeneous and heterogeneous kinetic data fit reasonably well with an activation-driving force relatiobship derived from the Marcus quadratic theory. In the heterogeneous case, there is a good agreement between the theoretical calculation amd the experimental result, while in the homogeneous case, a good a greement is only observed for the tertiary halides. This is due to the stability of tertiary radical resulting from the sterical effect.

  15. Discovery of the shape coexisting 0$^{+}$ state in $^{32}$Mg by a two neutron transfer reaction

    CERN Document Server

    Wimmer, K; Krücken, R; Bildstein, V; Gernhäuser, 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; Lutter, R; Thirolf, P G; Labiche, M; Blazhev, A; Kalkühler, M; Reiter, P; Seidlitz, M; Warr, N; Macchiavelli, A O; Jeppesen, H B; Fiori, E; Georgiev, G; Schrieder, G; Gupta, S Das; Bianco, G Lo; Nardelli, S; Butterworth, J; Johansen, J; Riisager, K

    2010-01-01

    The Island of Inversion nucleus $^{32}$Mg has been studied by a (t,p) two neutron transfer reaction in inverse kinematics at REX-ISOLDE. The shape coexistent excited 0$^{+}$ state in $^{32}$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$^{+}$ state indicates a lifetime of more than 10 ns. Deduced spectroscopic amplitudes are compared with occupation numbers from shell model calculations.

  16. GALS - setup for production and study of multinucleon transfer reaction products: present status

    Science.gov (United States)

    Zemlyanoy, S.; Zagrebaev, V.; Kozulin, E.; Kudryavtsev, Yu; Fedosseev, V.; Bark, R.; Janas, Z.

    2016-06-01

    This is a brief report on the current status of the new GAs cell based Laser ionization Setup (GALS) at Flerov Laboratory for Nuclear Reactions (FLNR) - JINR, Dubna. GALS is planned to exploit available beams from the U-400M cyclotron in low energy multi-nucleon transfer reactions to study exotic neutron-rich nuclei located in the "north-east" region of nuclear map. Products from 4.5 to 9 MeV/nucleon heavy-ion collisions, such as 136Xe on 208Pb, are to be captured in a gas cell and selectively laser-ionized in a sextupole (quadrupole) ion guide extraction system.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A. A. [National Research Center Kurchatov Institute (Russian Federation); Zhang, H. Q.; Lin, C. J.; Jia, H. M. [China Institute of Atomic Energy (China); Khlebnikov, S. V. [Khlopin Radium Institute (Russian Federation); Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S. [National Research Center Kurchatov Institute (Russian Federation); Trzaska, W. H. [University of Jyväskylä, Department of Physics (Finland); Xu, X. X. [China Institute of Atomic Energy (China); Yang, F. [National Research Center Kurchatov Institute (Russian Federation); Sargsyan, V. V., E-mail: sargsyan@theor.jinr.ru; Adamian, G. G.; Antonenko, N. V. [Joint Institute for Nuclear Research (Russian Federation); Scheid, W. [Institüt für Theoretische Physik der Justus-Liebig-Universität (Germany)

    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.

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

    Directory of Open Access Journals (Sweden)

    Yang Qu

    2017-03-01

    Full Text Available 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.

  20. Energy momentum conservation effects on two-particle correlation functions

    CERN Document Server

    Bock, Nicolas

    2011-01-01

    Two particle correlations are used to extract information about the characteristic size of the system in proton-proton and heavy ion collisions. The size of the system can be extracted from the Bose-Einstein quantum mechanical effect for identical particles. However there are also long range correlations that shift the baseline of the correlation function from the expected flat behavior. A possible source of these correlations is the conservation of energy and momentum, especially for small systems, where the energy available for particle production is limited. A new technique, first used by the STAR collaboration, of quantifying these long range correlations using energy-momentum conservation considerations is presented in this talk. Using Monte Carlo simulations of proton-proton collisions at 900 GeV, it is shown that the baseline of the two particle correlation function can be described using this technique.

  1. Splitting the wavefunctions of two particles in two boxes

    CERN Document Server

    Van Enk, S J

    2008-01-01

    I consider two identical quantum particles in two boxes. We can split each box, and thereby the wavefunction of each particle, into two parts. When two half boxes are interchanged and combined with the other halves, where do the two particles end up? I solve this problem for two identical bosons and for two identical fermions. The solution can be used to define a measurement that yields some information about the relative phase between the two parts of a split wavefunction.

  2. Probabilistic Teleportation of an Arbitrary Two-particle State

    Institute of Scientific and Technical Information of China (English)

    顾永建; 郑亦庄; 郭光灿

    2001-01-01

    A scheme for the teleportation of an arbitrary two-particle state via two non-maximally entangled particle pairsis proposed. We show that teleportation can be successfully realized with a certain probability if the receiveradopts an appropriate unitary-reduction strategy. A specific strategy is provided in detail The probability of successful teleportation is determined by the smaller coefficients of the two entangled pairs.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  6. Dynamic Solvent Effects in Alcohol Solutions for Electron Transfer Reactions Involving the Metallocenes

    Science.gov (United States)

    1990-05-15

    Transfer Reactions Involving the Metallocenes by W.R. Fawcett and C.A. Foss, Jr. Prepared for Presentation at The Electrochemical Society Meeting...Technical 800 N. Quincy Arlington, VA 22217-5000 &UL OWaep "W" Prepared for presentation at The" Electrochemical Society Meeting, Montreal Canada, tlay...Extended Abstract must be submitted with the 75-Ward Abstract by December 1, 1969 Montreal, Quebec, Canada-May 6-11, 1990 Submit to: The Electrochemical

  7. Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

    KAUST Repository

    Chen, Tao

    2012-08-01

    Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

  8. Transfer reactions on light exotic nuclei studied with CHIMERA detector at LNS

    Directory of Open Access Journals (Sweden)

    Cardella Giuseppe

    2014-03-01

    Full Text Available The kinematical coincidence method is used to extract angular distribution of elastic scattering and transfer reactions. The detected light particle energy spectra are used to extract the angular distribution with around 1° resolution in the Center of Mass (CM system. Examples with 10Be beam are presented. In the case of proton scattering, γ-ray coincidences are used to discriminate excited levels population from elastic scattering.

  9. Solvent Effects on Simple Electron Transfer Reactions. A Comparison of Results for Homogeneous and Heterogeneous Systems

    Science.gov (United States)

    1989-05-01

    Electroanalytical Chemistry Department of Chemistry University of California . Davis, CA 95616 \\ JUN2 0 1989 May 1, 1989 C2 E Reproduction in whole or in...0541 Davis, CA 95616 . O 0 Office of Naval Research 800 N. Quincy Arlington, VA 22217-5000 Prepared for Publication in: Journal of Electroanalytical ... Chemistry 1& A (U fm M Solvent effects on the rate constants for both homogeneous and hetero- geneous electron transfer reactions have been analyzed on

  10. Mechanism of electron transfer reaction for xanthene dye-sensitized formation of methyl viologen radical

    Energy Technology Data Exchange (ETDEWEB)

    Usui, Y.; Misawa, H.; Sakuragi, H.; Tokumaru, K.

    1987-05-01

    Sensitized reduction of methyl viologen, MV/sup 2 +/, occurs efficiently through electron transfer from triplet xanthene dyes to MV/sup 2 +/ followed by electron transfer to the resulting semioxidized dyes from a reductant like triethanolamine. Unreactive ion pair complexes between these dyes and MV/sup 2 +/ are formed (formation constant: 1.2 x 10/sup 3/ M/sup -1/ for Eosine Y and MV/sup 2 +/ in 50% aqueous ethanol solution). The quantum yield for the reduced methyl viologen radical depends on the concentrations of MV/sup 2 +/ and the amine and on the ionic strength of solution. The efficiency of the electron transfer from triplet dyes to MV/sup 2 +/ is increased by addition of alcohol, and solvent effects on the reaction mechanism are discussed. 38 references, 5 figures, 2 tables.

  11. Spectroscopy of $^{46}$Ar by the (t,p) two-neutron transfer reaction

    CERN Document Server

    Nowak, K.; Hellgartner, S.; Mücher, D.; Bildstein, V.; Diriken, J.; Elseviers, J.; Gaffney, L.P.; Gernhäuser, R.; Iwanicki, J.; Johansen, J.G.; Huyse, M.; Konki, J.; Kröll, T.; Krücken, T.; Lutter, R.; Orlandi, R.; Pakarinen, J.; Raabe, R.; Reiter, P.; Roger, T.; Schrieder, G.; Seidlitz, M.; Sorlin, O.; Van Duppen, P.; Warr, N.; De Witte, H.; Zielinska, M.

    2016-01-01

    States in the $N=28$ nucleus $^{46}$Ar have been studied by a two-neutron transfer reaction at REX-ISOLDE (CERN). A beam of radioactive $^{44}$ at an energy of 2.16~AMeV and a tritium loaded titanium target were used to populate $^{46}$ by the t($^{44}$,p) two-neutron transfer reaction. Protons emitted from the target were identified in the T-REX silicon detector array. The excitation energies of states in $^{46}$ have been reconstructed from the measured angles and energies of recoil protons. Angular distributions for three final states were measured and based on the shape of the differential cross section an excited state at 3695~keV has been identified as $J^\\pi = 0^+$. The angular differential cross section for the population of different states are compared to calculations using a reaction model employing both sequential and direct transfer of two neutrons. Results are compared to shell model calculations using state-of-the-art effective interactions.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Transient W-band EPR study of sequential electron transfer in photosynthetic bacterial reaction centers

    Energy Technology Data Exchange (ETDEWEB)

    Tang, J.; Utschig, L.M.; Poluektov, O.; Thurnauer, M.C. [Argonne National Lab., IL (United States). Chemistry Div.

    1999-06-17

    The key reaction of photosynthetic solar energy conversion involves the photoexcitation of a primary donor (P) followed by rapid, sequential electron transfer to a series of acceptors resulting in charge separation. Electron-spin polarized (ESP) EPR spectra at W-band (95 GHz) were obtained for deuterated Fe-removed/Zn-substituted photosynthetic bacterial reaction centers (RCs) to investigate the influence of the rate of charge separation on the observed P{sup +}Q{sub A}{sup {minus}} charge separated state. Temperature dependent ESP EPR spectra for kinetically characterized Zn-substituted RCs from Rb. sphaeroides R-26 having different rates (k{sub Q}) of the electron transfer from the bacteriopheophytin to the quinone acceptor were obtained. The Zn-RCs exhibited either the native fast (200 ps){sup {minus}1} k{sub Q} or a slow (3--6 ns){sup {minus}1} k{sub Q} at 298 K as determined from transient optical measurements. Sequential electron-transfer polarization modeling of the polarized W-band EPR spectra obtained with these samples was used to address the reason for the differences in the electron-transfer rates. Here, the authors report the k{sub Q} rate constant, the temperature dependence of k{sub Q}, and the reorganization energy for the P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}} electron-transfer step determined from SETP modeling of the experimental spectra. The reorganization energy for the electron-transfer process between P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}}, and not structural changes in the donor or acceptor, was found to be the dominant factor that is altered during Fe-removal procedures.

  14. Application of Magnetic Dicationic Ionic Liquid Phase Transfer Catalyst in Nuclophilic Substitution Reactions of Benzyl Halids in Water

    OpenAIRE

    Manouchehr Aghajeri; Ali Reza Kiasat; Bijan Mombeni Goodajdar

    2016-01-01

    magnetic dicationic ionic liquid (MDIL) was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions. The reactions was occurred in water and furnished the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.

  15. Simulations of two-particle interactions with 2D quantum walks in time

    Energy Technology Data Exchange (ETDEWEB)

    Schreiber, A.; Laiho, K.; Silberhorn, C. [University of Paderborn, Applied Physics, Warburger Str. 100, 33098 Paderborn, Germany and Max Planck Institute for the Science of Light, Günther-Scharowsky-str. 1 / Bau 24, 91058 Erlangen (Germany); Gábris, A. [Department of Physics, FNSPE, Czech Technical University in Prague, Břehová 7, 115 19 Praha, Czech Republic and Wigner Research Centre for Physics, Hungarian Academy of Sciences, H-1525 Budapest, P. O. Box 49 (Hungary); Rohde, P. P. [University of Paderborn, Applied Physics, Warburger Str. 100, 33098 Paderborn, Germany and Centre for Engineered Quantum Systems, Department of Physics and Astronomy, Macquarie University, Sydney NSW 2113 (Australia); Štefaňak, M.; Potoček, V.; Hamilton, C.; Jex, I. [Department of Physics, FNSPE, Czech Technical University in Prague, Břehová 7, 115 19 Praha (Czech Republic)

    2014-12-04

    We present the experimental implementation of a quantum walk on a two-dimensional lattice and show how to employ the optical system to simulate the quantum propagation of two interacting particles. Our quantum walk in time transfers the spatial spread of a quantum walk into the time domain, which guarantees a high stability and scalability of the setup. We present with our device quantum walks over 12 steps on a 2D lattice. By changing the properties of the driving quantum coin, we investigate different kinds of two-particle interactions and reveal their impact on the occurring quantum propagation.

  16. Angular distribution in two-particle emission induced by neutrinos and electrons

    CERN Document Server

    Simo, I Ruiz; Amaro, J E; Barbaro, M B; Caballero, J A; Donnelly, T W

    2014-01-01

    The angular distribution of the phase space arising in two-particle emission reactions induced by electrons and neutrinos is computed in the laboratory (Lab) system by boosting the isotropic distribution in the center of mass (CM) system used in Monte Carlo generators. The Lab distribution has a singularity for some angular values, coming from the Jacobian of the angular transformation between CM and Lab systems. We recover the formula we obtained in a previous calculation for the Lab angular distribution. This is in accordance with the Monte Carlo method used to generate two-particle events for neutrino scattering~\\cite{Sob12}. Inversely, by performing the transformation to the CM system, it can be shown that the phase-space function, which is proportional to the two particle-two hole (2p-2h) hadronic tensor for a constant current operator, can be computed analytically in the frozen nucleon approximation, if Pauli blocking is absent. The results in the CM frame confirm our previous work done using an alterna...

  17. Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Chu, Kuan Yu; Lee, Sheng; Tsai, Ming-Tsang; Lu, I-Chung; Dyakov, Yuri A; Lai, Yin Hung; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-03-01

    One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.

  18. Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

    Institute of Scientific and Technical Information of China (English)

    Kun-hui Liu; Li-dan Wu; Xiao-ran Zou; Wen Yang; Qian Du; Hong-mei Su

    2011-01-01

    Pentachlorophenol,a widespread environmental pollutant that is possibly carcinogenic to humans,is metabolically oxidized to tetrachloroquinone (TCBQ) which can result in DNA damage.We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases (thymine and uracil) upon UVA (355 nm) excitation using the technique of nanosecond time-resolved laser flash photolysis.It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ*,which are highly reactive towards thymine or uracil and undergo two parallel reactions,the hydrogen abstraction and electron transfer,leading to the observed photoproducts of TCBQH.and TCBQ.- in transient absorption spectra.The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards.By characterizing the photochemical hydrogen abstraction and electron transfer reactions,our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

  19. Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

    KAUST Repository

    Dehury, Niranjan

    2016-07-18

    Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

  20. Effects of acid concentration on intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile in solution

    Indian Academy of Sciences (India)

    Biswajit Guchhait; Tuhin Pradhan; Ranjit Biswas

    2014-01-01

    Effects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques. While absorption and fluorescence bands of P4C have been found to be shifted towards higher energy with increasing acid concentration in acetonitrile and ethyl acetate, no significant dependence has been observed in ethanolic solutions. Reaction rate becomes increasingly slower with acid concentration in acetonitrile and ethyl acetate. In contrast, acid in ethanolic solutions does not produce such an effect on reaction rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results.

  1. Charge-transfer reactions between C{sub 60} and hydrophilic solutes

    Energy Technology Data Exchange (ETDEWEB)

    Dimitrijevic, N.M.; Nedeljkovic, J.M.; Saponjic, Z.V. [Institute for Nuclear Sciences ``Vinca``, Belgrade (Yugoslavia)

    1998-10-01

    Two different procedures for dissolving fullerene molecule C{sub 60} into aqueous solutions have been developed. Embedding C{sub 60} clusters into a water-soluble host molecule of {gamma}-cyclodextrin resulted in relatively low concentration of C{sub 60} (5-10 {mu}M). Prepare of a stable ionic surfactant/water/oil microemulsion provided a method for dissolving C{sub 60} in relatively high concentrations (1 mM). In both cases charge-transfer reactions between hydrophobic molecule of C{sub 60} and hydrophilic solutes were examined. Anion radical C{sub 60}{sup -} was detected in reaction with radiolytically produced radicals (e{sub aq}{sup -}, (CH{sub 3}){sub 2}COH or MV{sup +}), and in reaction with excess electrons stored onto nanometer-sized metal (Ag) or quantized semiconductor (TiO{sub 2}) particles. (orig.) 33 refs.

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

    Science.gov (United States)

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-01

    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. Proton and charge transfer reactions dynamics of a hydroxyflavone derivative in a polar solvent and in a cyclodextrin nanocavity

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, M.; Organero, J.A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain); Douhal, A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain)], E-mail: Abderrazzak.douhal@uclm.es

    2007-09-25

    In this work, we report on the observation of ultrafast intramolecular charge- and proton-transfer reactions of 4'-dimethylaminoflavonol (DMAF) in N,N-dimethyl formamide and in {gamma}-cyclodextrin ({gamma}-CD) solution. Upon femtosecond excitation an intramolecular charge transfer (ICT) reaction takes place to produce an ICT structure in {approx}200 fs. This structure may undergo a proton transfer reaction to generate a zwitterionic (Z) form in 2-3 ps, or relaxes in its potential energy well, to later equilibrate with that of Z in hundreds of ps. Addition of {gamma}-CD does not significantly affect the fast dynamics of the formed anion. The fs-emission signals of the parent molecule, 3-hydroxyflavone, indicate that the dimethyl amino group in DMAF enhances the rate constant of intermolecular proton-transfer and intramolecular charge-transfer reactions.

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

    Science.gov (United States)

    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. Evidence of coupled photoinduced proton transfer and intramolecular charge transfer reaction in para-N,N-dimethylamino orthohydroxy benzaldehyde: Spectroscopic and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Mahanta, Subrata; Singh, Rupashree Balia; Kar, Samiran [Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700009 (India); Guchhait, Nikhil [Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700009 (India)], E-mail: nguchhait@yahoo.com

    2008-12-10

    Steady state and time resolved fluorescence spectroscopy and quantum chemical calculations have been used to study excited state properties of para-N,N-dimethylamino orthohydroxy benzaldehyde (PDOHBA). Spectral characteristics of PDOHBA support the existence of both donor-acceptor charge transfer (CT) and proton transfer (PT) reaction in the excited state. Structural calculations at Hartree Fock and Density Functional Theory (DFT) levels and theoretical potential energy surfaces (PESs) along the proton transfer and donor twisting coordinates using DFT and Time Dependent Density Functional Theory point towards the possibility of barrierless PT and CT reaction in the first excited state of PDOHBA.

  6. pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kouta [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Matsumura, Hirotoshi; Ishida, Takuya [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Yoshida, Makoto [Department of Environmental and Natural Resource Science, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509 (Japan); Igarashi, Kiyohiko; Samejima, Masahiro [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Ohno, Hiroyuki [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Nakamura, Nobuhumi, E-mail: nobu1@cc.tuat.ac.jp [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)

    2016-08-26

    A pyranose dehydrogenase from Coprinopsis cinerea (CcPDH) is an extracellular quinohemoeprotein, which consists a b-type cytochrome domain, a pyrroloquinoline-quinone (PQQ) domain, and a family 1-type carbohydrate-binding module. The electron transfer reaction of CcPDH was studied using some electron acceptors and a carbon electrode at various pH levels. Phenazine methosulfate (PMS) reacted directly at the PQQ domain, whereas cytochrome c (cyt c) reacted via the cytochrome domain of intact CcPDH. Thus, electrons are transferred from reduced PQQ in the catalytic domain of CcPDH to heme b in the N-terminal cytochrome domain, which acts as a built-in mediator and transfers electron to a heterogenous electron transfer protein. The optimal pH values of the PMS reduction (pH 6.5) and the cyt c reduction (pH 8.5) differ. The catalytic currents for the oxidation of L-fucose were observed within a range of pH 4.5 to 11. Bioelectrocatalysis of CcPDH based on direct electron transfer demonstrated that the pH profile of the biocatalytic current was similar to the reduction activity of cyt c characters. - Highlights: • pH dependencies of activity were different for the reduction of cyt c and DCPIP. • DET-based bioelectrocatalysis of CcPDH was observed. • The similar pH-dependent profile was found with cyt c and electrode. • The present results suggested that IET reaction of CcPDH shows pH dependence.

  7. Lifetimes and sizes from two-particle correlation functions

    CERN Document Server

    Heinz, Ulrich W; Wiedemann, Urs Achim; Wu Yuang Fang

    1996-01-01

    We discuss the Yano-Koonin-Podgoretsky (YKP) parametrization of the two-particle correlation function for azimuthally symmetric expanding sources. We derive model-independent expressions for the YKP fit parameters and discuss their physical interpretation. We use them to evaluate the YKP fit parameters and their momentum dependence for a simple model for the emission function and propose new strategies for extracting the source lifetime. Longitudinal expansion of the source can be seen directly in the rapidity dependence of the Yano-Koonin velocity.

  8. Two-particle Anderson localization at low energies

    CERN Document Server

    Ekanga, Trésor

    2012-01-01

    We prove exponential spectral localization in a two-particle lattice Anderson model, with a short-range interaction and external random i.i.d. potential, at sufficiently low energies. The proof is based on the multi-particle multi-scale analysis developed earlier by Chulaevsky and Suhov (2009) in the case of high disorder. Our method applies to a larger class of random potentials than in Aizenman and Warzel (2009) where dynamical localization was proved with the help of the fractional moment method.

  9. Multinucleon transfer reactions for the sup 50 Ti+ sup 93 Nb system at sub- and near-barrier energies

    Energy Technology Data Exchange (ETDEWEB)

    Kim, H.J.; Gomez del Campo, J.; Shapira, D.; Stelson, P.H. (Oak Ridge National Lab., TN (USA)); Napoli, D.; Scarlassara, F. (Istituto Nazionale di Fisica Nucleare, Legnaro (Italy). Lab. Nazionale di Legnaro); D' Onofrio, A. (Istituto Nazionale di Fisica Nucleare, Naples (Italy)); Wieleczko, J.P. (Oak Ridge National Lab., TN (USA) CEA Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France))

    1990-06-01

    A significant yield of multinucleon-transfer products is observed at back angles in quasielastic reactions between {sup 50}Ti and {sup 93}Nb at sub- and near-barrier energies. A variety of nuclidic species that require transfers of up to four nucleons are observed for E{sub c.m.} {ge} 103.9 MeV. The internuclear separation distance where the multinucleon-transfer products first emerge nearly coincides with the closest approach distance of the experimentally established fusion threshold energy, indicating a common origin for the fusion enhancement and multinucleon-transfer reactions.

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

    Science.gov (United States)

    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.

  11. Effect of positive Q-value neutron transfers on sub-barrier fusion reactions

    Science.gov (United States)

    Wen, Pei-Wei; Feng, Zhao-Qing; Zhang, Fan; Li, Cheng; Lin, Cheng-Jian; Zhang, Feng-Shou

    2017-06-01

    The role of positive Q-value neutron transfers in sub-barrier fusion reactions has been studied with a modified quantum coupled channels model with all order couplings (CCFULL model). Neutron rearrangement related only to the dynamical matching condition with no free parameters is implemented in the model, which provides a way to understand especially the Q-value dependence of sub-barrier fusion reactions. The fusion cross sections of the collision systems 40Ca+94, 96Zr have been calculated and analyzed. The general trend of experimental data can be reproduced well with additional channels for neutron rearrangement. We find that enhancement of sub-barrier fusion cross sections is closely related to the Q-value of the transferred neutrons, in particular for channels with sequential even number transferred neutrons. Supported by National Natural Science Foundation of China (11635003, 11025524, 11161130520, 11175218, U1332207) National Basic Research Program of China (2010CB832903) European Commission’s 7th Framework Programme (Fp7-PEOPLE-2010-IRSES) Agreement Project (269131)

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

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Benjamin Joel [Univ. of California, Berkeley, CA (United States)

    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 ~240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH2I2 and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a ~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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  15. Gamma ray spectroscopy of neutron-rich actinides after multi-nucleon transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, Andreas; Birkenbach, Benedikt; Reiter, Peter; Hess, Herbert; Lewandowski, Lars; Steinbach, Tim [Institut fuer Kernphysik, Universitaet zu Koeln (Germany); Collaboration: LNL 11.22-Collaboration

    2014-07-01

    Excited states in neutron-rich Th and U nuclei were investigated after multi-nucleon transfer reactions employing the AGATA demonstrator and PRISMA setup at LNL (INFN, Italy). A primary {sup 136}Xe beam of 1 GeV hitting a {sup 238}U target was used to produce the nuclei of interest in the actinide region. Beam-like reaction products in the Xe-Ba-region were identified and selected by the PRISMA spectrometer. Kinematic coincidences between the binary reaction products of beam-like and target-like nuclei are detected with an additional MCP detector. Those coincidences allow clean conditions for in-beam γ-ray spectroscopy. Background contributions from excited fission fragments are successfully discriminated. γ-rays from excited states in beam- and target-like particles were measured with the position sensitive AGATA HPGe detectors. Improved energy resolution after Doppler correction is based on the novel γ-ray tracking technique which was successfully exploited to increase the quality of the γ-spectra. γ-ray spectra of the produced beam-like isotopes in the one-proton and two-proton transfer channels will be presented. Corresponding results from the hard-to-reach neutron-rich isotopes beyond {sup 232}Th will focus on their collective properties and cross section limits for their production.

  16. Mechanism of electron transfer reaction of ternary dipicolinatochromium(III) complex involving oxalate as secondary ligand

    Indian Academy of Sciences (India)

    Hassan Amroun Ewais; Iqbal Mohamed Ibrhium Ismail

    2013-09-01

    Mechanism of electron transfer reaction of ternary Mechanism of the oxidation of [CrIII(DPA)(OX)(H2O)]− (DPA = dipicolinate and OX = oxalate) by periodate in aqueous acidic medium has been studied spectrophotometrically over the pH range of 4.45-5.57 at different temperatures. The reaction is first order with respect to both [IO$^{−}_{4}$] and the complex concentration, and it obeys the following rate law: $$d[{\\text Cr}^{\\text{VI}}]/dt = k_6K_4K_6[{\\text IO}^−_4][{\\text{Cr}}^{\\text{III}}]_{\\text{T}}/\\{([H^+] + K_4) + (K_5[H+] + K_6K_4)[{\\text{IO}}^{−}_{4}]\\}.$$ The rate of the reaction increases with increasing pH due to the deprotonation equilibria of the complex. The experimental rate law is consistent with a mechanism in which the deprotonated form [CrIII(DPA)(OX)(OH)]2− is more reactive than the conjugated acid. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO$^{−}_{4}$ to chromium(III). Thermodynamic activation parameters were calculated using the transition state theory equation.dipicolinatochromium(III) complex involving oxalate as secondary ligand

  17. Self-similar two-particle separation model

    DEFF Research Database (Denmark)

    Lüthi, Beat; Berg, Jacob; Ott, Søren

    2007-01-01

    We present a new stochastic model for relative two-particle separation in turbulence. Inspired by material line stretching, we suggest that a similar process also occurs beyond the viscous range, with time scaling according to the longitudinal second-order structure function S2(r), e.g.; in the i......We present a new stochastic model for relative two-particle separation in turbulence. Inspired by material line stretching, we suggest that a similar process also occurs beyond the viscous range, with time scaling according to the longitudinal second-order structure function S2(r), e.......g.; in the inertial range as epsilon−1/3r2/3. Particle separation is modeled as a Gaussian process without invoking information of Eulerian acceleration statistics or of precise shapes of Eulerian velocity distribution functions. The time scale is a function of S2(r) and thus of the Lagrangian evolving separation....... The model predictions agree with numerical and experimental results for various initial particle separations. We present model results for fixed time and fixed scale statistics. We find that for the Richardson-Obukhov law, i.e., =gepsilont3, to hold and to also be observed in experiments, high Reynolds...

  18. Two-particle correlations in pseudorapidity in a hydrodynamic model

    CERN Document Server

    Bozek, Piotr; Olszewski, Adam

    2015-01-01

    Two-particle pseudorapidity correlations of hadrons produced in Pb+Pb collisions at 2.76 TeV at the CERN Large Hadron Collider are analyzed in the framework of a model based on viscous 3+1-dimensional hydrodynamics with the Glauber initial condition. Based on our results, we argue that the correlation from resonance decays, formed at a late stage of the evolution, produce significant effects. In particular, their contribution to the event averages of the coefficients of the expansion in the Legendre basis explain 60-70% of the experimental values. We have proposed an accurate way to compute these coefficients, independent of the binning in pseudorapidity, and tested a double expansion of the two-particle correlation function in the azimuth and pseudorapidity, which allows us to investigate the pseudorapidity correlations between harmonics of the collective flow. In our model, these quantities are also dominated by non-flow effects from the resonance decays. Finally, our method can be used to compute higher-o...

  19. Propagating two-particle reduced density matrices without wavefunctions

    CERN Document Server

    Lackner, Fabian; Sato, Takeshi; Ishikawa, Kenichi L; Burgdörfer, Joachim

    2014-01-01

    Describing time-dependent many-body systems where correlation effects play an important role remains a major theoretical challenge. In this paper we develop a time-dependent many-body theory that is based on the two-particle reduced density matrix (2-RDM). We develop a closed equation of motion for the 2-RDM employing a novel reconstruction functional for the three-particle reduced density matrix (3-RDM) that preserves norm, energy, and spin symmetries during time propagation. We show that approximately enforcing $N$-representability during time evolution is essential for achieving stable solutions. As a prototypical test case which features long-range Coulomb interactions we employ the one-dimensional model for lithium hydride (LiH) in strong infrared laser fields. We probe both one-particle observables such as the time-dependent dipole moment and two-particle observables such as the pair density and mean electron-electron interaction energy. Our results are in very good agreement with numerically exact solu...

  20. Theoretical predictions on production of neutron-deficient nuclei with Z ≥ 93 in multinucleon transfer reactions

    Science.gov (United States)

    Zhu, Long; Su, Jun; Zhang, Feng-Shou

    2017-08-01

    Within the framework of dinuclear system model, the transfer reactions 58Ni + 233U, 58Ni + 238U, and 64Ni + 238U are investigated. The influences of projectile and target neutron numbers on cross sections of producing neutron-deficient actinide nuclei in transfer reactions are studied. It is found that the system 58Ni + 233U with smaller neutron excess is favorable to produce neutron-deficient nuclei. We predict the production cross sections of neutron-deficient nuclei with Z = 93- 98 in transfer reactions 58Ni + 233U and 40Ca + 245Cm with different incident energies. We find the transfer reactions 58Ni + 233U and 40Ca + 245Cm are feasible for producing neutron-deficient actinide nuclei in future experiments.

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

    Directory of Open Access Journals (Sweden)

    Nathalie Peira

    Full Text Available 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.

  2. On the theory of electron transfer reactions at semiconductor electrode/liquid interfaces

    Science.gov (United States)

    Gao, Yi Qin; Georgievskii, Yuri; Marcus, R. A.

    2000-02-01

    Electron transfer reaction rate constants at semiconductor/liquid interfaces are calculated using the Fermi Golden Rule and a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the electronic structures of semiconductors with surfaces and are compared. The maximum electron transfer rate constants at Si/viologen2+/+ and InP/Me2Fc+/0 interfaces are computed using the tight-binding type calculations for the solid and the extended-Hückel for the coupling to the redox agent at the interface. These results for the bulk states are compared with the experimentally measured values of Lewis and co-workers, and are in reasonable agreement, without adjusting parameters. In the case of InP/liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  6. On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

    Energy Technology Data Exchange (ETDEWEB)

    Slavov, Chavdar Lyubomirov

    2009-07-09

    The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

  7. Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.

    Directory of Open Access Journals (Sweden)

    Faiz G Awad

    Full Text Available 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.

  8. Effects of mass transfer on MHD flow of casson fluid with chemical reaction and suction

    Directory of Open Access Journals (Sweden)

    S. A. Shehzad

    2013-03-01

    Full Text Available Effect of mass transfer in the magnetohydrodynamic flow of a Casson fluid over a porous stretching sheet is addressed in the presence of a chemical reaction. A series solution for the resulting nonlinear flow is computed. The skin friction coefficient and local Sherwood number are analyzed through numerical values for various parameters of interest. The velocity and concentration fields are illustrated for several pertinent flow parameters. We observed that the Casson parameter and Hartman number have similar effects on the velocity in a qualitative sense. We further analyzed that the concentration profile decreases rapidly in comparison to the fluid velocity when we increased the values of the suction parameter.

  9. Luminescence from low-energy He/sup +//Xe charge-transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, E.G.; Hughes, B.M.; Fee, D.C.; Tiernan, T.O.

    1977-04-01

    Optical emissions produced by collision of 100-eV He/sup +/ ions with Xe atoms have been studied over the spectral range from 40 to 900 nm. All of the major lines in the emission spectrum can be assigned to transitions in Xe II resulting from charge-transfer reactions. Emission cross sections for the major lines in the vacuum-ultraviolet and visible spectral regions are reported and the importance of cascading is assessed. The kinetic energy dependence is discussed for several of these lines.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L. [University of Tennessee, Knoxville (UTK); Pain, S. D. [Rutgers University; Kozub, R. L. [Tennessee Technological University; Adekola, Aderemi S [ORNL; Bardayan, Daniel W [ORNL; Blackmon, Jeff C [ORNL; Catford, Wilton N [ORNL; Chae, K. Y. [University of Tennessee, Knoxville (UTK); Chipps, K. [Colorado School of Mines, Golden; Cizewski, J. A. [Rutgers University; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Greife, U. [Colorado School of Mines, Golden; Grzywacz, R. K. [University of Tennessee, Knoxville (UTK); Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; James, J. [Colorado School of Mines, Golden; Kapler, R. [University of Tennessee, Knoxville (UTK); Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Moazen, Brian [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Patterson, N. P. [University of Surrey, UK; Paulauskas, Stanley [University of Tennessee, Knoxville (UTK); Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sikora, M. [Rutgers University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Thomas, J. S. [Rutgers University; Wilson, Gemma L [ORNL

    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.

  11. Relayed 13C magnetization transfer: Detection of malate dehydrogenase reaction in vivo

    Science.gov (United States)

    Yang, Jehoon; Shen, Jun

    2007-02-01

    Malate dehydrogenase catalyzes rapid interconversion between dilute metabolites oxaloacetate and malate. Both oxaloacetate and malate are below the detection threshold of in vivo MRS. Oxaloacetate is also in rapid exchange with aspartate catalyzed by aspartate aminotransferase, the latter metabolite is observable in vivo using 13C MRS. We hypothesized that the rapid turnover of oxaloacetate can effectively relay perturbation of magnetization between malate and aspartate. Here, we report indirect observation of the malate dehydrogenase reaction by saturating malate C2 resonance at 71.2 ppm and detecting a reduced aspartate C2 signal at 53.2 ppm due to relayed magnetization transfer via oxaloacetate C2 at 201.3 ppm. Using this strategy the rate of the cerebral malate dehydrogenase reaction was determined to be 9 ± 2 μmol/g wet weight/min (means ± SD, n = 5) at 11.7 Tesla in anesthetized adult rats infused with [1,6- 13C 2]glucose.

  12. Characterization of ferritin core on redox reactions as a nanocomposite for electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Kwang Min [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Watt, Richard K.; Watt, Gerald D. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Choi, Sang H. [Advanced Materials and Processing Branch, NASA Langley Research Center, Hampton, VA 23681 (United States); Kim, Hyug-Han [Department of Chemistry, School of Advanced Science, Dankook University, Chonan 330-180 (Korea, Republic of); Kim, Sun I. [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Kim, Seon Jeong, E-mail: sjk@hanyang.ac.k [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2010-04-01

    The kinetics of the change in mass related to the release from and deposition onto the cavities of a ferritin in the SWCNT nanocomposite by electrochemical redox reactions, and the effects of the SWCNT on the kinetics of the variation in mass of the ferritin nanocomposite were characterized using an electrochemical quartz crystal microbalance. The change in mass of reconstituted ferritin in the SWCNT nanocomposite shows reversible variation and stability of the ferritin/SWCNT nanocomposite on redox reactions was confirmed by using a coreless apoferritin and a Fe{sup 2+} chelating agent. The ferritin/SWCNT nanocomposite is a good candidate for applications based on electron transfer, such as biosensor, biobatteries and electrodes for biofuel cell.

  13. Lifetime and g-factor measurements of excited states using Coulomb excitation and alpha transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Guevara, Z. E., E-mail: zjguevaram@unal.edu.co; Torres, D. A., E-mail: datorresg@unal.edu.co [Physics Department, Universidad Nacional de Colombia, Bogotá D.C. (Colombia)

    2016-07-07

    In this contribution the challenges in the use of a setup to simultaneously measure lifetimes and g-factor values will be presented. The simultaneous use of the transient field technique and the Doppler Shift Attenuation Method, to measure magnetic moments and lifetimes respectively, allows to obtain a complete characterization of the currents of nucleons and the deformation in excited states close to the ground state. The technique is at the moment limited to Coulomb excitation and alpha-transfer reactions, what opens an interesting perspective to consider this type of experiments with radioactive beams. The use of deep-inelastic and fusion-evaporation reactions will be discussed. An example of a setup that makes use of a beam of {sup 106}Cd to study excited states of {sup 110}Sn and the beam nuclei itself will be presented.

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

    Science.gov (United States)

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

  16. A Stefan model for mass transfer in a rotating disk reaction vessel

    KAUST Repository

    BOHUN, C. S.

    2015-05-04

    Copyright © Cambridge University Press 2015. In this paper, we focus on the process of mass transfer in the rotating disk apparatus formulated as a Stefan problem with consideration given to both the hydrodynamics of the process and the specific chemical reactions occurring in the bulk. The wide range in the reaction rates of the underlying chemistry allows for a natural decoupling of the problem into a simplified set of weakly coupled convective-reaction-diffusion equations for the slowly reacting chemical species and a set of algebraic relations for the species that react rapidly. An analysis of the chemical equilibrium conditions identifies an expansion parameter and a reduced model that remains valid for arbitrarily large times. Numerical solutions of the model are compared to an asymptotic analysis revealing three distinct time scales and chemical diffusion boundary layer that lies completely inside the hydrodynamic layer. Formulated as a Stefan problem, the model generalizes the work of Levich (Levich and Spalding (1962) Physicochemical hydrodynamics, vol. 689, Prentice-Hall Englewood Cliffs, NJ) and will help better understand the natural limitations of the rotating disk reaction vessel when consideration is made for the reacting chemical species.

  17. Conformity between IBM and TQM (SU(6) quadrupole phonon model) in treating two-nucleon transfer reactions

    Science.gov (United States)

    Kyrchev, G.; Paar, V.

    1983-03-01

    It is shown that TQM is capable of treating two-nucleon transfer (TNT) reactions in an analogous manner to IBM. A proof that the IBM two-nucleon transfer amplitudes can be identically converted into standard matrix elements for TQM, is presented, using the relation between the Schwinger and Holstein-Primakoff representations of the SU(6) generators.

  18. Conformational gating of the electron transfer reaction QA−⋅QB → QAQB−⋅ in bacterial reaction centers of Rhodobacter sphaeroides determined by a driving force assay

    Science.gov (United States)

    Graige, M. S.; Feher, G.; Okamura, M. Y.

    1998-01-01

    The mechanism of the electron transfer reaction, QA−⋅QB → QAQB−⋅, was studied in isolated reaction centers from the photosynthetic bacterium Rhodobacter sphaeroides by replacing the native Q10 in the QA binding site with quinones having different redox potentials. These substitutions are expected to change the intrinsic electron transfer rate by changing the redox free energy (i.e., driving force) for electron transfer without affecting other events that may be associated with the electron transfer (e.g., protein dynamics or protonation). The electron transfer from QA−⋅ to QB was measured by three independent methods: a functional assay involving cytochrome c2 to measure the rate of QA−⋅ oxidation, optical kinetic spectroscopy to measure changes in semiquinone absorption, and kinetic near-IR spectroscopy to measure electrochromic shifts that occur in response to electron transfer. The results show that the rate of the observed electron transfer from QA−⋅ to QB does not change as the redox free energy for electron transfer is varied over a range of 150 meV. The strong temperature dependence of the observed rate rules out the possibility that the reaction is activationless. We conclude, therefore, that the independence of the observed rate on the driving force for electron transfer is due to conformational gating, that is, the rate limiting step is a conformational change required before electron transfer. This change is proposed to be the movement, controlled kinetically either by protein dynamics or intermolecular interactions, of QB by ≈5 Å as observed in the x-ray studies of Stowell et al. [Stowell, M. H. B., McPhillips, T. M., Rees, D. C., Soltis, S. M., Abresch, E. & Feher, G. (1997) Science 276, 812–816]. PMID:9751725

  19. Topology Studies of Hydrodynamics Using Two-Particle Correlation Analysis

    Science.gov (United States)

    Takahashi, J.; Tavares, B. M.; Qian, W. L.; Andrade, R.; Grassi, F.; Hama, Y.; Kodama, T.; Xu, N.

    2009-12-01

    The effects of fluctuating initial conditions are studied in the context of relativistic heavy ion collisions where a rapidly evolving system is formed. Two-particle correlation analysis is applied to events generated with the NEXSPHERIO hydrodynamic code, starting with fluctuating nonsmooth initial conditions (IC). The results show that the nonsmoothness in the IC survives the hydroevolution and can be seen as topological features of the angular correlation function of the particles emerging from the evolving system. A long range correlation is observed in the longitudinal direction and in the azimuthal direction a double peak structure is observed in the opposite direction to the trigger particle. This analysis provides clear evidence that these are signatures of the combined effect of tubular structures present in the IC and the proceeding collective dynamics of the hot and dense medium.

  20. Topology studies of hydrodynamics using two particle correlation analysis

    CERN Document Server

    Takahashi, J; Qian, W L; Grassi, F; Hama, Y; Kodama, T; Xu, N

    2009-01-01

    Two particle correlation analysis is applied to events generated with the NEXSPHERIO hydrodynamic evolution code starting with fluctuating non-smooth initial conditions. Results show that the non-smoothness in the initial distributions survives the hydro-evolution and can be seen as topological features in the correlation function. Long range angular correlation in the longitudinal direction and a double peak structure in the azimuthal direction opposite to the trigger particle direction were observed, similar to features observed in the experimental data. This analysis provides clear evidence that these are signatures of the combined effect of tubular structures present in initial conditions, originated from the interactions of the energetic particles, and the proceeding collective dynamics of the hot and dense medium created in heavy ion collisions.

  1. Pro duction of Exotic Nuclei in Low-Energy Multi-Nucleon Transfer Reactions

    Institute of Scientific and Technical Information of China (English)

    VI Zagrebaev; Walter Greiner

    2015-01-01

    Multinucleon transfer processes in low-energy heavy ion collisions open a new field of re-search in nuclear physics, namely, production and studying properties of heavy neutron rich nuclei. This not-yet-explored area of the nuclear map is extremely important for understanding the astrophysical nu-cleosynthesis and the origin of heavy elements. Beams of very heavy U-like ions are needed to produce new long-living isotopes of transfermium and superheavy elements located very close to the island of sta-bility. The calculated cross sections are high enough to perform the experiments at available accelerators. Beams of medium-mass ions (such as 136Xe, 192Os, 198Pt) can be used for the production of neutron rich nuclei located along the neutron closed shell N=126 (the last waiting point) having the largest impact on the astrophysical r-process. The Low-energy multinucleon transfer reactions is a very efficient tool also for the production and spectroscopic study of light exotic nuclei. The corresponding cross sections are 2 or 3 orders of magnitude larger as compared with high energy fragmentation reactions.

  2. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    Science.gov (United States)

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)], E-mail: yonghliang@hotmail.com; Tang, Zhen Q. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)

    2006-03-20

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO . (H{sub 2}O) {sub n} n = 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{sub 2} is the most stable isomer in the gas phase, and the tautomer K{sub 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 {sub cis} {r_reversible} 3WK{sub 1} and 2WE {sub trans} {r_reversible} 2WK{sub 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 {sub cis} and K{sub 1} cannot happen without solvent-assisted.

  4. Excited-state charge coupled proton transfer reaction in dipole-functionalized salicylideneaniline

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Kew-Yu, E-mail: kyuchen@fcu.edu.tw; Hu, Jiun-Wei

    2015-03-15

    Based on design and synthesis of salicylideneaniline derivatives 1–4, we demonstrate an exceedingly useful system to investigate the excited-state intramolecular charge transfer (ESICT) coupled with excited-state intramolecular proton transfer (ESIPT) reaction via the dipolar functionality of Schiff base salicylideneaniline. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess a strong intramolecular six-membered-ring hydrogen bond. Compounds 2–4 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 1 exhibits remarkable dual emission due to the different solvent-polarity environments between ESICT and ESIPT states. Moreover, the geometric structures, frontier molecular orbitals (MOs) and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT) and time-dependent DFT calculations. - Highlights: • A dipole-functionalized salicylideneaniline derivative was synthesized. • The Schiff base exhibits remarkable dual emission. • A novel ESICT/ESIPT coupled system was created.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-06-06

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

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

    Science.gov (United States)

    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 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 spectra with the spectra theoretically calculated for

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

    Science.gov (United States)

    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.

  8. Application of Magnetic Dicationic Ionic Liquid Phase Transfer Catalyst in Nuclophilic Substitution Reactions of Benzyl Halids in Water

    Directory of Open Access Journals (Sweden)

    Manouchehr Aghajeri

    2016-06-01

    Full Text Available magnetic dicationic ionic liquid (MDIL was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions. The reactions was occurred in water and furnished the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-31

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

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

    Science.gov (United States)

    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

  11. One nucleon transfer reactions around $^{68}$Ni at REX-ISOLDE

    CERN Multimedia

    Blazhev, A A; Kruecken, R; Mertzimekis, T; Darby, I G; Lagogiannis, A; Habs, D; Diriken, J V J; Patronis, N

    2008-01-01

    We intend to investigate the single particle properties of the neutron-rich Ni isotopes in the mass region around $^{68}$Ni and at a later stage towards the doubly-magic $^{78}$Ni. As a first experiment we propose to study the single particle character of the ground and first excited states of $^{67}$Ni. This nucleus will be the projectile-like reaction product for the one-neutron transfer reaction. A $^{66}$Ni beam at 3A MeV delivered from REX-ISOLDE will be directed on a CD$_{2}$ target. Protons produced from the (d,p) reaction will be detected either in singles or in coincidence with ${\\gamma}$-rays recorded by the MINIBALL array. The particles will be detected by the newly-built Si position-sensitive barrel configuration. The objectives of this work are the unambiguous determination of the spins and parities of the first excited states of $^{67}$Ni and measurement of the relative spectroscopic factors of those states as well as of the ground state. The experimental results will be compared with those from...

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

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

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

  13. Study of the Ne(^3P_2) + CH_3F Electron Transfer Reaction below 1 Kelvin

    CERN Document Server

    Jankunas, Justin; Osterwalder, Andreas

    2014-01-01

    Relatively little is known about the dynamics of electron transfer reactions at low collision energy. We present a study of Penning ionization of ground state methyl fluoride molecules by electronically excited neon atoms in the 13 $\\mu$eV--4.8 meV (150 mK--56 K) collision energy range, using a neutral-neutral merged beam setup. Relative cross sections have been measured for three Ne($^3P_2$)+ CH$_3$F reaction channels by counting the number of CH$_3$F$^+$, CH$_2$F$^+$, and CH$_3^+$ product ions, as a function of relative velocity between the neon and methyl fluoride molecular beams. Experimental cross sections markedly deviate from the Langevin capture model at collision energies above 20 K. The branching ratios are constant. In other words, the chemical shape of the CH$_3$F molecule, as seen by Ne($^3P_2$) atom, appears not to change as the collision energy is varied, in contrast to related Ne($^3P_J$) + CH$_3$X (X=Cl and Br) reactions at higher collision energies.

  14. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    Science.gov (United States)

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect.

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

    Science.gov (United States)

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  19. Soft symmetry improvement of two particle irreducible effective actions

    CERN Document Server

    Brown, Michael J

    2016-01-01

    Two particle irreducible effective actions (2PIEAs) are valuable non-perturbative techniques in quantum field theory; however, finite truncations of them violate the Ward identities (WIs) of theories with spontaneously broken symmetries. The symmetry improvement (SI) method of Pilaftsis and Teresi attempts to overcome this by imposing the WIs as constraints on the solution; however the method suffers from the non-existence of solutions in linear response theory and in certain truncations in equilibrium. Motivated by this, we introduce a new method called soft symmetry improvement (SSI) which relaxes the constraint. Violations of WIs are allowed but punished in a least-squares implementation of the symmetry improvement idea. A new parameter $\\xi$ controls the strength of the constraint. The method interpolates between the unimproved ($\\xi \\to \\infty$) and SI ($\\xi \\to 0$) cases and the hope is that practically useful solutions can be found for finite $\\xi$. We study the SSI-2PIEA for a scalar O(N) model in the...

  20. Two-Particle Correlations in Heavy-Light Ion Collisions

    CERN Document Server

    Wertepny, Douglas E

    2016-01-01

    We study the initial, high-energy scatterings in heavy ion collisions using the saturation/Color Glass Condensate framework. We focus on two-particle long-range rapidity correlations which are modeled as two-gluon correlations. We calculate the two-gluon production cross section using the saturation framework in the heavy-light ion regime, including all-order saturation effects in the heavy nucleus while considering only two-orders in the light ion. The two-gluon production cross section generates four types of long-range in rapidity correlations: (i) geometric correlations, (ii) Hanbury Brown and Twiss (HBT) like correlations accompanied by a back-to-back maximum, (iii) near-side correlations, and (iv) away-side azimuthal correlations. The geometric correlations (i) are due to the fact that nucleons are correlated by simply being confined within the same nucleus. Correlations (iii) and (iv) have exactly the same amplitudes along with azimuthal and rapidity shapes: one centered around $\\Delta \\phi =0$ and the...

  1. Pin-point chemical modification of RNA with diverse molecules through the functionality transfer reaction and the copper-catalyzed azide-alkyne cycloaddition reaction.

    Science.gov (United States)

    Onizuka, Kazumitsu; Shibata, Atsushi; Taniguchi, Yosuke; Sasaki, Shigeki

    2011-05-07

    The internal modification of RNA has been successfully achieved by the functionality transfer reaction (FTR) and following click chemistry with diverse azide compounds. The benefits of the FTR have been demonstrated by its specificity, rapidity, broad applicability, and procedure simplicity. © The Royal Society of Chemistry 2011

  2. Numerical simulation of ultrasonic enhancement on mass transfer in liquid-solid reaction by a new computational model.

    Science.gov (United States)

    Jiao, Qingbin; Bayanheshig; Tan, Xin; Zhu, Jiwei

    2014-03-01

    Mass transfer coefficient is an important parameter in the process of mass transfer. It can reflect the degree of enhancement of mass transfer process in liquid-solid reaction and in non-reactive systems like dissolution and leaching, and further verify the issues by experiments in the reaction process. In the present paper, a new computational model quantitatively solving ultrasonic enhancement on mass transfer coefficient in liquid-solid reaction is established, and the mass transfer coefficient on silicon surface with a transducer at frequencies of 40 kHz, 60 kHz, 80 kHz and 100 kHz has been numerically simulated. The simulation results indicate that mass transfer coefficient increases with the increasing of ultrasound power, and the maximum value of mass transfer coefficient is 1.467 × 10(-4) m/s at 60 kHz and the minimum is 1.310 × 10(-4) m/s at 80 kHz in the condition when ultrasound power is 50 W (the mass transfer coefficient is 2.384 × 10(-5) m/s without ultrasound). The extrinsic factors such as temperature and transducer diameter and distance between reactor and ultrasound source also influence the mass transfer coefficient on silicon surface. Mass transfer coefficient increases with the increasing temperature, with the decreasing distance between silicon and central position, with the decreasing of transducer diameter, and with the decreasing of distance between reactor and ultrasound source at the same ultrasonic power and frequency. The simulation results indicate that the computational model can quantitatively solve the ultrasonic enhancement on mass transfer coefficient.

  3. 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

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, H.; Yamada, A.; Okazaki, S., E-mail: okazaki@apchem.nagoya-u.ac.jp [Department of Applied Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    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.

  4. New recoil transfer chamber for thermalization of heavy ions produced in fusion–evaporation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Alfonso, M.C. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); Department of Chemistry, Texas A& M University, College Station, TX 77842 (United States); Tereshatov, E.E. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); DeVanzo, M.J. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); Department of Physics, Astronomy, and Geosciences, Towson University, Towson, MD 21252 (United States); Sefcik, J.A. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); Department of Physics and Geosciences, Angelo State University, San Angelo, TX 76909 (United States); Bennett, M.E. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); Mayorov, D.A.; Werke, T.A. [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States); Department of Chemistry, Texas A& M University, College Station, TX 77842 (United States); Folden, C.M., E-mail: Folden@comp.tamu.edu [Cyclotron Institute, Texas A& M University, College Station, TX 77843 (United States)

    2015-10-21

    A new Recoil Transfer Chamber (RTC) has been designed, fabricated, and characterized at the Cyclotron Institute at Texas A&M University. The design is based on a gas stopper that was previously in routine use at the National Superconducting Cyclotron Laboratory. This new RTC uses He gas to stop ions, and a combination of a static electric field and gas flow to maximize the extraction efficiency. In offline experiments, a {sup 228}Th source was used to produce {sup 216}Po which was successfully extracted even though it has a short half-life. In online experiments using the products of the {sup 118}Sn({sup 40}Ar, 6n){sup 152}Er reaction, an efficiency of several tens of percent was measured.

  5. Effect of phenol and halogenated phenols on energy transfer reactions of rat liver mitochondria.

    Directory of Open Access Journals (Sweden)

    Izushi,Fumio

    1988-02-01

    Full Text Available The in vitro effects of phenol and p-halogenated phenols on mitochondrial energy transfer reactions were examined using isolated rat liver mitochondria. The relationship between physiochemical properties of phenolic compounds and their effects on mitochondria were studied. Phenol and p-halogenated phenols induced the release of K+ ions from mitochondria, suggesting a change in permeability to K+ ions. A decrease in the respiratory control index, an increase in K+ release and stimulation of latent ATPase activity were observed with these compounds in the descending order of p-iodophenol, p-bromophenol, p-chlorophenol, p-fluorophenol and phenol. The concentrations of the phenolic compounds resulting in fifty percent inhibition of the respiratory control index and those resulting in fifty percent release of K+ ions significantly correlated with Hammett's substituent constant (sigma and the hydrophobic binding constant (pi of the compounds.

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

    Directory of Open Access Journals (Sweden)

    A. Sanetullaev

    2014-09-01

    Full Text Available 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,dNi55 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.

  7. Determination of Reactive Intermediates During Anodic Oxygen-transfer Reactions at Lead Dioxide

    Institute of Scientific and Technical Information of China (English)

    AI Shi-yun; ZHANG Wen; GAO Meng-nan; GU Fen-lin; WANG Qing-jiang; JIN Li-tong

    2004-01-01

    The anodic discharge of water to produce adsorbed hydroxyl free radicals(*OH) is considered to be a prerequisite to anodic O-transfer reactions at a PbO2 electrode. In this work, a method was studied by means of high-performance liquid chromatography(HPLC) combined with electrochemical detection(ED) so as to investigate the production of hydroxyl free radicals(*OH) in the process of the anodic discharge of H2O at a PbO2 electrode. The voltammetric data obtained at the PbO2 electrode for the oxidation of salicylic acid to salicylate hydroxylation products(DHBAs) and the detection of DHBAs by means of HPLC-ED confirm the proposed mechanism.

  8. Neutron spectroscopic factors of {sup 55}Ni hole-states from (p,d) transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sanetullaev, A. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Tsang, M.B., E-mail: tsang@nscl.msu.edu [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Lynch, W.G.; Lee, Jenny; Bazin, D. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Chan, K.P. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Physics Department, Hong Kong Chinese University, Shatin, Hong Kong (China); Coupland, D.; Henzl, V.; Henzlova, D.; Kilburn, M.; Rogers, A.M. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Sun, Z.Y. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Institute of Modern Physics, CAS, Lanzhou 730000 (China); Youngs, M. [National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Charity, R.J.; Sobotka, L.G. [Department of Chemistry, Washington University, St. Louis, MO 63130 (United States); Famiano, M. [Department of Physics, Western Michigan University, Kalamazoo, MI 49008 (United States); Hudan, S. [Department of Chemistry, Indiana University, Bloomington, IN 47405 (United States); Shapira, D. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Peters, W.A. [Rutgers University, Piscataway, NJ 08854 (United States); Barbieri, C. [Department of Physics, University of Surrey, Guildford GU2 7XH (United Kingdom); and others

    2014-09-07

    Spectroscopic information has been extracted on the hole-states of {sup 55}Ni, the least known of the quartet of nuclei ({sup 55}Ni, {sup 57}Ni, {sup 55}Co and {sup 57}Cu), one nucleon away from {sup 56}Ni, the N=Z=28 double magic nucleus. Using the {sup 1}H({sup 56}Ni,d){sup 55}Ni transfer reaction in inverse kinematics, neutron spectroscopic factors, spins and parities have been extracted for the f{sub 7/2}, p{sub 3/2} and the s{sub 1/2} hole-states of {sup 55}Ni. 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 s{sub 1/2} hole-state below Fermi energy.

  9. Neutron spectroscopic factors of $^{55}$Ni hole-states from (p,d) transfer reactions

    CERN Document Server

    Sanetullaev, A; 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

    2014-01-01

    Spectroscopic information has been extracted on the hole-states of $^{55}$Ni, the least known of the quartet of nuclei ($^{55}$Ni, $^{57}$Ni, $^{55}$Co and $^{57}$Co), one neutron away from $^{56}$Ni, the N=Z=28 double magic nucleus. Using the $^{1}$H($^{56}$Ni,d)$^{55}$Ni transfer reaction in inverse kinematics, neutron spectroscopic factors, spins and parities have been extracted for the f$_{7/2}$, p$_{3/2}$ and the s$_{1/2}$ hole-states of $^{55}$Ni. This new data provides 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 s$_{1/2}$ hole-state below Fermi energy.

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

    Science.gov (United States)

    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.

  11. First Measurement of Transferred Polarization in the Exclusive e→p→e'K+Λ→ Reaction

    Science.gov (United States)

    Carman, D. S.; Joo, K.; Mestayer, M. D.; Raue, B. A.; Adams, G.; Ambrozewicz, P.; Anciant, E.; Anghinolfi, M.; Armstrong, D. S.; Asavapibhop, B.; Audit, G.; Auger, T.; Avakian, H.; Bagdasaryan, H.; Ball, J. P.; Barrow, S. P.; Battaglieri, M.; Beard, K.; Bektasoglu, M.; Bellis, M.; Bennhold, C.; Bianchi, N.; Biselli, A. S.; Boiarinov, S.; Bonner, B. E.; Bouchigny, S.; Bradford, R.; Branford, D.; Briscoe, W. J.; Brooks, W. K.; Burkert, V. D.; Butuceanu, C.; Calarco, J. R.; Carnahan, B.; Cazes, A.; Cetina, C.; Ciciani, L.; Clark, R.; Cole, P. L.; Coleman, A.; Cords, D.; Corvisiero, P.; Crabb, D.; Crannell, H.; Cummings, J. P.; Desanctis, E.; Degtyarenko, P. V.; Denizli, H.; Dennis, L.; Devita, R.; Dharmawardane, K. V.; Dhuga, K. S.; Djalali, C.; Dodge, G. E.; Doughty, D.; Dragovitsch, P.; Dugger, M.; Dytman, S.; Dzyubak, O. P.; Eckhause, M.; Egiyan, H.; Egiyan, K. S.; Elouadrhiri, L.; Empl, A.; Eugenio, P.; Fatemi, R.; Fedotov, G.; Feuerbach, R. J.; Ficenec, J.; Forest, T. A.; Funsten, H.; Gaff, S. J.; Gai, M.; Garçon, M.; Gavalian, G.; Gilad, S.; Gilfoyle, G. P.; Giovanetti, K. L.; Girard, P.; Golovach, E.; Gordon, C. I.; Griffioen, K.; Grimes, S.; Guidal, M.; Guillo, M.; Guo, L.; Gyurjyan, V.; Hadjidakis, C.; Hakobyan, R. S.; Hardie, J.; Heddle, D.; Heimberg, P.; Hersman, F. W.; Hicks, K.; Hicks, R. S.; Holtrop, M.; Hu, J.; Hyde-Wright, C. E.; Ishkhanov, B.; Ito, M. M.; Jenkins, D.; Kelley, J. H.; Kellie, J. D.; Khandaker, M.; Kim, K. Y.; Kim, K.; Kim, W.; Klein, A.; Klein, F. J.; Klimenko, A. V.; Klusman, M.; Kossov, M.; Kramer, L. H.; Kuang, Y.; Kuhn, S. E.; Kuhn, J.; Lachniet, J.; Laget, J. M.; Lawrence, D.; Li, J.; Livingston, K.; Longhi, A.; Lukashin, K.; Manak, J. J.; Marchand, C.; Mart, T.; McAleer, S.; McCarthy, J.; McNabb, J. W.; Mecking, B. A.; Mehrabyan, S.; Melone, J. J.; Meyer, C. A.; Mikhailov, K.; Minehart, R.; Mirazita, M.; Miskimen, R.; Mokeev, V.; Morand, L.; Morrow, S. A.; Mozer, M. U.; Muccifora, V.; Mueller, J.; Murphy, L. Y.; Mutchler, G. S.; Napolitano, J.; Nasseripour, R.; Nelson, S. O.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Niczyporuk, B. B.; Niyazov, R. A.; Nozar, M.; O'Rielly, G. V.; Opper, A. K.; Osipenko, M.; Park, K.; Paschke, K.; Pasyuk, E.; Peterson, G.; Pivnyuk, N.; Pocanic, D.; Pogorelko, O.; Polli, E.; Pozdniakov, S.; Preedom, B. M.; Price, J. W.; Prok, Y.; Protopopescu, D.; Qin, L. M.; Riccardi, G.; Ricco, G.; Ripani, M.; Ritchie, B. G.; Ronchetti, F.; Rossi, P.; Rowntree, D.; Rubin, P.; Sabatié, F.; Sabourov, K.; Salgado, C.; Santoro, J.; Sapunenko, V.; Schumacher, R. A.; Serov, V. S.; Sharabian, Y. G.; Shaw, J.; Simionatto, S.; Skabelin, A. V.; Smith, E. S.; Smith, L. C.; Sober, D. I.; Spraker, M.; Stavinsky, A.; Stepanyan, S.; Stoler, P.; Taiuti, M.; Taylor, S.; Tedeschi, D. J.; Thoma, U.; Thompson, R.; Todor, L.; Tur, C.; Ungaro, M.; Vineyard, M. F.; Vlassov, A. V.; Wang, K.; Weinstein, L. B.; Weller, H.; Weygand, D. P.; Whisnant, C. S.; Wolin, E.; Wood, M. H.; Yegneswaran, A.; Yun, J.; Zhang, B.; Zhao, J.; Zhou, Z.

    2003-04-01

    The first measurements of the transferred polarization for the exclusive e→p→e'K+Λ→ reaction have been performed at Jefferson Laboratory using the CLAS spectrometer. A 2.567GeV beam was used to measure the hyperon polarization over Q2 from 0.3 to 1.5 (GeV/c)2, W from 1.6 to 2.15GeV, and over the full K+ center-of-mass angular range. Comparison with predictions of hadrodynamic models indicates strong sensitivity to the underlying resonance contributions. A nonrelativistic quark-model interpretation of our data suggests that the ss¯ quark pair is produced with spins predominantly antialigned. Implications for the validity of the most widely used quark-pair creation operator are discussed.

  12. Proton-transfer reaction dynamics and energetics in calcification and decalcification.

    Science.gov (United States)

    Suwa, Ryota; Hatta, Masayuki; Ichikawa, Kazuhiko

    2014-10-13

    CaCO3 -saturated saline waters at pH values below 8.5 are characterized by two stationary equilibrium states: reversible chemical calcification/decalcification associated with acid dissociation, Ca(2+) +HCO3 (-) ⇌CaCO3 +H(+) ; and reversible static physical precipitation/dissolution, Ca(2+) +CO3 (2-) ⇌CaCO3 . The former reversible reaction was determined using a strong base and acid titration. The saturation state described by the pH/PCO2 -independent solubility product, [Ca(2+) ][CO3 (2-) ], may not be observed at pH below 8.5 because [Ca(2+) ][CO3 (2-) ]/([Ca(2+) ][HCO3 (-) ]) ≪1. Since proton transfer dynamics controls all reversible acid dissociation reactions in saline waters, the concentrations of calcium ion and dissolved inorganic carbon (DIC) were expressed as a function of dual variables, pH and PCO2 . The negative impact of ocean acidification on marine calcifying organisms was confirmed by applying the experimental culture data of each PCO2 /pH-dependent coral polyp skeleton weight (Wskel) to the proton transfer idea. The skeleton formation of each coral polyp was performed in microspaces beneath its aboral ectoderm. This resulted in a decalcification of 14 weight %, a normalized CaCO3 saturation state Λ of 1.3 at PCO2 ≈400 ppm and pH ≈8.0, and serious decalcification of 45 % and Λ 2.5 at PCO2 ≈1000 ppm and pH ≈7.8.

  13. Two-particle momentum correlations in jets produced in + − annihilation at $\\sqrt{s} = 60$ GeV

    Indian Academy of Sciences (India)

    M E Zomorrodian; F Khorramabadi; A Sepehri; P Eslami

    2012-05-01

    The goal of this analysis is to measure the two-particle momentum correlation in jets, in the reaction + − → hadrons, to study its dependence on jet energy, and compare the results with analytical predictions of the next-to-leading log approximation (NLLA), using data collected by the AMY detector at a centre of mass energy of 60 GeV. Results are obtained for charged particles and for events with $E_{c.m.} = 60$ GeV.

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

    Science.gov (United States)

    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.

  15. Three-Body Model Calculation of Spin Distribution in Two-Nucleon Transfer Reaction

    CERN Document Server

    Ogata, Kazuyuki; Chiba, Satoshi

    2011-01-01

    The differential cross sections of two-nucleon transfer reactions 238U(18O,16O)240U around 10 MeV per nucleon are calculated by one-step Born-approximation with a 16O+2n+238U three-body model. The three-body wave function in the initial channel is obtained with the continuum-discretized coupled-channels method, and that in the final channel is evaluated with adiabatic approximation. The resulting cross sections have a peak around the grazing angle, and the spin distribution, i.e., the cross section at the peak as a function of the transferred spin, is investigated. The shape of the spin distribution is found not sensitive to the incident energies, optical potentials, and treatment of the breakup channels both in the initial and final states, while it depends on the excitation energy of the residual nucleus 240U. The peak of the spin distribution moves to the large-spin direction as the excitation energy increases. To fulfill the condition that the peak position should not exceeds 10 hbar, which is necessary f...

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

    Science.gov (United States)

    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.

  17. A Langevin equation approach to electron transfer reactions in the diabatic basis.

    Science.gov (United States)

    Song, XiaoGeng; Wang, Haobin; Van Voorhis, Troy

    2008-10-14

    A linear Langevin equation that governs the population dynamics of electron transfer reactions is derived. The noise in the Langevin equation is eliminated by treating the diabatic population fluctuations as the relevant variables, leaving only the memory kernel responsible for the population relaxation. Within the memory kernel, the diabatic coupling is treated perturbatively and a second order expansion is found to give a simple closed form expression for the kernel. The accuracy of the second order truncation is maximized by performing a fixed rotation of the diabatic electronic states that minimizes the first order free energy of the system and thus minimizes the effect of the perturbation on the thermodynamics. The resulting two-hop Langevin equation (THLE) is then validated by applying it to a simple spin-boson model, where exact results exist. Excellent agreement is found in a wide parameter range, even where the perturbation is moderately strong. Results obtained in the rotated electronic basis are found to be consistently more accurate than those from the unrotated basis. These benchmark calculations also allow us to demonstrate the advantage of treating the population fluctuations instead of the populations as the relevant variables, as only the former lead to reliable results at long time. Thus, the THLE appears to provide a viable alternative to established methods--such as Ehrenfest dynamics or surface hopping--for the treatment of nonadiabatic effects in electron transfer simulations.

  18. Influence of mass transfer and chemical reaction on ozonation of azo dyes

    Energy Technology Data Exchange (ETDEWEB)

    Choi, I.S.; Wiesmann, U. [Dept. of Environmental Engineering, Technical Univ. of Berlin, Berlin (Germany)

    2003-07-01

    Azo dyes can be only mineralised by chemical oxidation. In this paper the oxidation of reactive black 5 (RB 5) and reactive orange 96 (RO 96) with concentrations between 35 and 5700 mgL{sup -1} (RB 5) and between 20 and 2050 mgL{sup -1} (RO 96) is investigated. A lab scale bubble column was used, which was gassed by a mixture of O{sub 2} and O{sub 3}. The oxidation rate was influenced by mass transfer for all dye concentrations used. For lower dye concentrations mass transfer alone was decisive for reaction rate showing an enhancement factor of E {approx} 1. However, in the region of higher dye concentrations, the slope of the decreasing ozone concentration inside the liquid boundary layer increases more and more with increasing dye concentration as a result of a chemical oxidation. Therefore, the enhancement factor depends on the kind and concentration of the azo dyes. For RB 5 as an diazo dye an enhancement factor of E = 9 was observed for 3800 mgL{sup -1}, RO 96 as a mono azo dye with a remarkable higher chemical oxidation rate shows an E = 17 already for 2050 mgL{sup -1}. (orig.)

  19. The protein's role in triplet energy transfer in bacterial reaction centers.

    Energy Technology Data Exchange (ETDEWEB)

    Laible, P. D.

    1998-08-14

    When photosynthetic organisms are subjected to high-light conditions in nature, electron transfer becomes blocked as the rate of conversion of light into charge-separated states in the reaction center (RC) exceeds the capacity of the soluble carriers involved in cyclic electron transfer. In that event, a well-characterized T{sub 0}-polarized triplet state {sup T}P, is formed on the primary donor, P, from the P{sup +}H{sub A}{sup {minus}} state (reviewed in [1]). In an aerobic or semi-aerobic environment, the major role of the carotenoid (C), also bound by the RC, is to quench {sup T}P prior to its sensitization of the {sup 1}{Delta}{sub g} singlet state of oxygen--a potentially damaging biological oxidant. The carotenoid performs this function efficiently in most bacterial RCs by rapidly accepting the triplet state from P and dissipating this excited-state energy into heat through internal conversion. The lowest-lying triplet states of P and the carotenoid are sufficiently different that {sup T}P can promote oxygen to its excited singlet state whereas {sup T}C can quench the {sup T}P state (reviewed in [2]).

  20. Transfer reactions in inverse kinematics, an experimental approach for fission investigations

    CERN Document Server

    Rodríguez-Tajes, C; Derkx, X; Caamaño, M; Delaune, O; Schmidt, K -H; Clément, E; Dijon, A; Heinz, A; Roger, T; Audouin, L; Benlliure, J; Casarejos, E; Cortina, D; Doré, D; Fernández-Domínguez, B; Jacquot, B; Jurado, 1 B; Navin, A; Paradela, C; Ramos, D; Romain, P; Salsac, M D; Schmitt, C

    2013-01-01

    Inelastic and multi-nucleon transfer reactions between a $^{238}$U beam, accelerated at 6.14 MeV/u, and a $^{12}$C target were used for the production of neutron-rich, fissioning systems from U to Cm. A Si telescope, devoted to the detection of the target-like nuclei, provided a characterization of the fissioning systems in atomic and mass numbers, as well as in excitation energy. Cross-sections, angular and excitation-energy distributions were measured for the inelastic and transfer channels. Possible excitations of the target-like nuclei were experimentally investigated for the first time, by means of g -ray measurements. The decays from the first excited states of $^{12}$C, $^{11}$B and $^{10}$Be were observed with probabilities of 0.12 - 0.14, while no evidence for the population of higher-lying states was found. Moreover, the fission probabilities of $^{238}$U, $^{239}$Np and $^{240,241,242}$Pu and $^{244}$Cm were determined as a function of the excitation energy.

  1. The 2H(e, e' p)n reaction at large energy transfers

    Science.gov (United States)

    Willering, Hendrik Willem

    2003-04-01

    At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron breakup reaction 2H(e, e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the quasielastic region to just below the Delta(1232)-resonance, and for proton polar angles up to Thetanp = 145 o in the center-of-momentum system. This angular range represents missing momenta up to pm = 1000 MeV/c. By detecting the scattered protons in two segmented 3 3 m2 scintillator time-of-flight detectors, we have covered a considerable part of the out-of-plane region. The clearly visible variation of the cross section with the proton azimuthal angle fnp has enabled us to extract values for the longitudinal-transverse interference form factor fLT and for a combination of the non-interference form factors fL and fT for proton angles up to Thetanp = 40o in the center-of-momentum system. The experimental results have been compared to the full model calculations by Arenhövel et al. For the major part of our kinematical range the shape of the cross section and of the form factors is reproduced by the model, but some differences remain in the normalization, especially at higher energy transfers. Our results corroborate the conclusions from other recent experiments concerning the importance of subnuclear degrees-of-freedom beyond the quasielastic region, but the discrepancy indicates that the model can still be improved

  2. Soft symmetry improvement of two particle irreducible effective actions

    Science.gov (United States)

    Brown, Michael J.; Whittingham, Ian B.

    2017-01-01

    Two particle irreducible effective actions (2PIEAs) are valuable nonperturbative techniques in quantum field theory; however, finite truncations of them violate the Ward identities (WIs) of theories with spontaneously broken symmetries. The symmetry improvement (SI) method of Pilaftsis and Teresi attempts to overcome this by imposing the WIs as constraints on the solution; however, the method suffers from the nonexistence of solutions in linear response theory and in certain truncations in equilibrium. Motivated by this, we introduce a new method called soft-symmetry improvement (SSI) which relaxes the constraint. Violations of WIs are allowed but punished in a least-squares implementation of the symmetry improvement idea. A new parameter ξ controls the strength of the constraint. The method interpolates between the unimproved (ξ →∞ ) and SI (ξ →0 ) cases, and the hope is that practically useful solutions can be found for finite ξ . We study the SSI 2PIEA for a scalar O (N ) model in the Hartree-Fock approximation. We find that the method is IR sensitive; the system must be formulated in finite volume V and temperature T =β-1 , and the V β →∞ limit must be taken carefully. Three distinct limits exist. Two are equivalent to the unimproved 2PIEA and SI 2PIEA respectively, and the third is a new limit where the WI is satisfied but the phase transition is strongly first order and solutions can fail to exist depending on ξ . Further, these limits are disconnected from each other; there is no smooth way to interpolate from one to another. These results suggest that any potential advantages of SSI methods, and indeed any application of (S)SI methods out of equilibrium, must occur in finite volume.

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

    Science.gov (United States)

    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.

  4. Integration of Ultraviolet Photodissociation with Proton Transfer Reactions and Ion Parking for Analysis of Intact Proteins.

    Science.gov (United States)

    Holden, Dustin D; McGee, William M; Brodbelt, Jennifer S

    2016-01-05

    We report the implementation of proton transfer reactions (PTR) and ion parking on an Orbitrap mass spectrometer. PTR/ion parking allows charge states of proteins to be focused into a single lower charge state via sequential deprotonation reactions with a proton scavenging reagent, in this case, a nitrogen-containing adduct of fluoranthene. Using PTR and ion parking, we evaluate the charge state dependence of fragmentation of ubiquitin (8.6 kDa), myoglobin (17 kDa), and carbonic anhydrase (29 kDa) upon higher energy collisional dissociation (HCD) or ultraviolet photodissociation (UVPD). UVPD exhibited less charge state dependence, thus yielding more uniform distributions of cleavages along the protein backbone and consequently higher sequence coverage than HCD. HCD resulted in especially prominent cleavages C-terminal to amino acids containing acidic side-chains and N-terminal to proline residues; UVPD did not exhibit preferential cleavage adjacent to acidic residues but did show enhancement next to proline and phenylalanine.

  5. Pore to Core Scale Simulation of the Mass Transfer with Mineral Reaction in Porous Media

    Directory of Open Access Journals (Sweden)

    Bekri S.

    2015-04-01

    Full Text Available Pore Network Model (PNM is used to simulate mass transfer with mineral reaction in a single phase flow through porous medium which is here a sandstone sample from the reservoir formation of the Pakoslaw gas field. The void space of the porous medium is represented by an idealized geometry of pore-bodies joined by pore-throats. Parameters defining the pore-bodies and the pore-throats distribution are determined by an optimization process aiming to match the experimental Mercury Intrusion Capillary Pressure (MICP curve and petrophysical properties of the rock such as intrinsic permeability and formation factor. The generated network is used first to simulate the multiphase flow by solving Kirchhoff’s laws. The capillary pressure and relative permeability curves are derived. Then, reactive transport is addressed under asymptotic regime where the solute concentration undergoes an exponential evolution with time. The porosity/permeability relationship and the three phenomenological coefficients of transport, namely the solute velocity, the dispersion and the mean reaction rate are determined as functions of Peclet and Peclet-Damköhler dimensionless numbers. Finally, the role of the dimensionless numbers on the reactive flow properties is highlighted.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  8. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Science.gov (United States)

    Barmet, P.; Dommen, J.; DeCarlo, P. F.; Tritscher, T.; Praplan, A. P.; Platt, S. M.; Prévôt, A. S. H.; Donahue, N. M.; Baltensperger, U.

    2012-03-01

    The hydroxyl free radical (OH) is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS). 3-pentanol, 3-pentanone and pinonaldehyde (PA) were used as OH tracers in α-pinene (AP) secondary organic aerosol (SOA) aging studies. In addition we tested butanol-d9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88) × 10-12 cm3 molecule-1 s-1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time) dimension: the OH clock, which corresponds to the integrated OH concentration over time.

  9. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Directory of Open Access Journals (Sweden)

    P. Barmet

    2011-12-01

    Full Text Available The hydroxyl free radical (OH is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS. 3-pentanol, 3-pentanone and pinonaldehyde (PA were used as OH tracers in α-pinene (AP secondary organic aerosol (SOA aging studies. In addition we tested butanol-d9 as potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88 · 10−12 cm3molecule−1s−1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time dimension:~the OH clock, which corresponds to the integrated OH concentration over time.

  10. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Directory of Open Access Journals (Sweden)

    P. Barmet

    2012-03-01

    Full Text Available The hydroxyl free radical (OH is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS. 3-pentanol, 3-pentanone and pinonaldehyde (PA were used as OH tracers in α-pinene (AP secondary organic aerosol (SOA aging studies. In addition we tested butanol-d9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88 × 10−12 cm3 molecule−1 s−1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time dimension: the OH clock, which corresponds to the integrated OH concentration over time.

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

    Science.gov (United States)

    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.

  12. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    A. Guenther

    2009-04-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated. SQT calibration standards were prepared by a capillary diffusion method and the PTR-MS-estimated mixing ratios were derived from the counts of product ions and proton transfer reaction constants. These values were compared with mixing ratios determined by a calibrated Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions from soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+, out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+, are accounted for. Considerable fragmentation of bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, cause the accuracy to be reduced to 50% if only the parent ion (m/z 205+ is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1, and 0.0016 μg m−3 (0.10 mg m−2 h−1, respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly

  13. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    S. Kim

    2008-12-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated with SQT standards, prepared by a capillary diffusion method, and the estimated mixing ratios, derived from the counts of product ions and proton transfer reaction constants were intercompared with measured mixing ratios, measured by a complementary Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions due to soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+ out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+ are accounted for. Bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, showed considerable fragmentation causing the accuracy of their analysis to be reduced to 50% if only the parent ion (m/z 205 is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred Average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1 and 0.0016 μg m−3 (0.10 mgm−2 h−1 respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly underestimated OH

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. [Ruder Boskovic Institute, Zagreb (Croatia); INFN, Laboratori Nazionali di Legnaro, Legnaro (Italy); IPHC, CNRS-IN2P3, Universite de Strasbourg, Strasbourg (France); 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.

  16. Theoretical Study on Proton-Transfer Reaction of Intracellular Second-messenger 3',5'-Cyclic Nucleotide

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ai-Hua; YANG Bao-Hua; LI Zong-He

    2008-01-01

    The gas-phase proton-transfer reaction mechanism of intracellular second-messenger 3',5'-cyclic nucleotide (cAMPm) has been theoretically investigated at the B3LYP/6-31G** level. One or two H2O molecules have been used to simulate the catalyst. It is found that H shift reaction between conformation Bm and conformation Dm of cAMPm involves a cyclic transition state with one or two water molecules as a shuttle. Furthermore, H shift reac- tion proceeds easily with the participation of two water molecules. The results provide evidence in theory to study proton-transfer reaction mechanism of related phosphodiesters. Our present calculations have rationalized all the possible reaction channels.

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

    Science.gov (United States)

    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.

  18. Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Harun Al Rasid Gazi; Ranjit Biswas

    2010-07-01

    An intramolecular charge transfer (ICT) molecule with an extra hetero atom in its donor moiety has been synthesized in order to investigate how ICT reaction is affected by hetero atom replacement. Photo-physical and photo-dynamical properties of this molecule, 4-(morpholenyl)benzonitrile (M6C), have been studied in 20 different solvents. The correlation between the reaction driving force (- ) and activation barrier ( #) has been explored in order to understand the solvent effects (static and dynamic) on the photo-excited ICT reaction in this molecule. A Kramer’s model analysis of the experimentally observed reaction rate constants indicates a solvent-averaged activation barrier of ∼ 4 in the absence of solvent dynamical control. The reaction in M6C is therefore not a barrier-less reaction but close to the limit where conventional kinetics might break down.

  19. Quantum Chemical Study on a New Mechanism of One-carbon Unit Transfer Reaction:The Water-assisted Mechanism

    Institute of Scientific and Technical Information of China (English)

    QIAO,Qing-An(乔青安); CAI,Zheng-Ting(蔡政亭); FENG,Da-Cheng(冯大诚)

    2004-01-01

    It is a theoretical study on the water-assisted mechanism of one-carbon unit transfer reaction, in which the energy barrier for each transition state lowered by about 80-100 kJ/mol when compared with the one in no-water-involved mechanism. The water-assisted path 4 is the favorite reaction way. Our results well explained the presumption from experiments.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  2. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

    Directory of Open Access Journals (Sweden)

    Andri Cahyo Kumoro

    2015-03-01

    Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

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

    Directory of Open Access Journals (Sweden)

    M. H. Erickson

    2012-02-01

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

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

    Science.gov (United States)

    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

  5. Eddy covariance flux measurements of ammonia by electron transfer reaction-mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Sintermann

    2010-11-01

    Full Text Available A system for fast ammonia (NH3 measurements based on a commercial Proton Transfer Reaction-Mass Spectrometer is presented. It uses electron transfer reaction (eTR as ionisation pathway and features a drift tube of polyetheretherketone (PEEK and silica-coated steel. Heating the instrumental inlet and the drift tube to 180° C enabled an effective time resolution of ~1 s and made it possible to apply the eTR-MS for eddy covariance (EC measurements. EC fluxes of NH3 were measured over two agricultural fields in Oensingen, Switzerland, following fertilisations with cattle slurry. Air was aspirated close to a sonic anemometer at a flow of 100 STP L min−1 and was directed through a 23 m long 1/2" PFA tube heated to 150°C to an air-conditioned trailer where the eTR-MS sub-sampled from the large bypass stream. This setup minimised damping of fast NH3 concentration changes between the sampling point and the actual measurement. High-frequency attenuation loss of the NH3 fluxes of 20 to 40% was quantified and corrected for using an empirical ogive method. The instrumental NH3 background signal showed a minor interference with H2O which was characterised in the laboratory. The resulting correction of the NH3 flux after slurry spreading was less than 1‰. The flux detection limit of the EC system was about 5 ng m−2 s−1 while the accuracy of individual flux measurements was estimated 16% for the high-flux regime during these experiments. The NH3 emissions after broad spreading of the slurry showed an initial maximum of 150 μg m2 s−1 with a fast decline in the following hours.

  6. Fusion and neutron transfer reactions with weakly bound nuclei within time-dependent and coupled channel approaches

    Science.gov (United States)

    Samarin, V. V.

    2016-05-01

    The time-dependent Schrödinger equation and the coupled channel approach based on the method of perturbed stationary two-center states are used to describe nucleon transfers and fusion in low-energy nuclear reactions. Results of the cross sections calculation for the formation of the 198Au and fusion in the 6He+197Au reaction and for the formation of the 65Zn in 6He+64Zn reaction agree satisfactorily with the experimental data near the barrier. The Feynman's continual integrals calculations for a few-body systems were used for the proposal of the new form of the shell model mean field for helium isotopes.

  7. Detection of trace gases from fermentation processes using photoacoustic spectroscopy and proton-transfer-reaction mass spectrometry

    NARCIS (Netherlands)

    Boamfă-Ivan, Elena Iuliana

    2005-01-01

    This thesis presents novel interdisciplinary Physics - Biology research work that employed Photoacoustic Spectroscopy and Proton-Transfer-Reaction Mass Spectrometry. Both techniques were used in biological studies of trace gasses emitted by crop plants and fruit under stress situations. The findings

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

    Science.gov (United States)

    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)

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

    NARCIS (Netherlands)

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

    2012-01-01

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

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

    Science.gov (United States)

    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…

  11. Phase transfer reagent promoted tandem ring-opening and ring-closing reactions of unique 3-(1-alkynyl) chromones.

    Science.gov (United States)

    Liu, Yang; Jin, Shiyu; Huang, Liping; Hu, Youhong

    2015-05-01

    A phase transfer reagent promoted tandem ring-opening and ring-closing reaction of 3-(1-alkynyl) chromones has been developed. This process remarkably generates functionalized 3-acyl-2-substituted chromones. Interestingly, when 3-(hepta-1,6-diyn-1-yl)chromone derivatives are applied, a novel tetracyclic chromone scaffold can be obtained by a further intramolecular 4 + 2 cyclization.

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

    NARCIS (Netherlands)

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

    2012-01-01

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

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

    NARCIS (Netherlands)

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

    2015-01-01

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

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

    Science.gov (United States)

    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…

  15. A simple approach to the solvent reorganisation Gibbs free energy in electron transfer reactions of redox metalloproteins

    DEFF Research Database (Denmark)

    Ulstrup, Jens

    1999-01-01

    We discuss a simple model for the environmental reorganisation Gibbs free energy, E-r, in electron transfer between a metalloprotein and a small reaction partner. The protein is represented as a dielectric globule with low dielectric constant, the metal centres as conducting spheres, all embedded...

  16. 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.

    Science.gov (United States)

    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.

  17. The frozen nucleon approximation in two-particle two-hole response functions

    Directory of Open Access Journals (Sweden)

    I. Ruiz Simo

    2017-07-01

    Full Text Available We present a fast and efficient method to compute the inclusive two-particle two-hole (2p–2h electroweak responses in the neutrino and electron quasielastic inclusive cross sections. The method is based on two approximations. The first neglects the motion of the two initial nucleons below the Fermi momentum, which are considered to be at rest. This approximation, which is reasonable for high values of the momentum transfer, turns out also to be quite good for moderate values of the momentum transfer q≳kF. The second approximation involves using in the “frozen” meson-exchange currents (MEC an effective Δ-propagator averaged over the Fermi sea. Within the resulting “frozen nucleon approximation”, the inclusive 2p–2h responses are accurately calculated with only a one-dimensional integral over the emission angle of one of the final nucleons, thus drastically simplifying the calculation and reducing the computational time. The latter makes this method especially well-suited for implementation in Monte Carlo neutrino event generators.

  18. Searching for the minimum energy path in the sulfuryl transfer reaction catalyzed by human estrogen sulfotransferase: Role of enzyme dynamics

    Science.gov (United States)

    Lin, Ping; Yang, Weitao; Pedersen, Lars C.; Negishi, Masa; Pedersen, Lee G.

    The enzymatic transfer of a sulfuryl group from the ubiquitous biological source of sulfate 3?-phosphoadenosine 5?-phosphosulfate (PAPS) to estrogen is investigated by the pseudo-bond quantum mechanical/molecular mechanical method (QM/MM) method. Calculations of the reaction path are performed starting with models based on two crystal structures, which differ in information about the cofactor and substrates. In addition, a subsequent relaxation of the enzyme was performed with the found transition state frozen, followed by redetermination of the path. An activation barrier of 22 kcal/mol is estimated. The reaction mechanism features a proton transfer from the estrogen to a catalytic histidine followed by the rate determining SO3 transfer. The mechanism found is largely dissociative.

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

    Science.gov (United States)

    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.

  20. Experimental study of the $^{66}$Ni$(d,p)^{67}$Ni one-neutron transfer reaction

    CERN Document Server

    Diriken, J.; Andreyev, A.N.; Antalic, S.; Bildstein, V.; Blazhev, A.; Darby, I.G.; De Witte, H.; Eberth, J.; Elseviers, J.; Fedosseev, V.N.; Flavigny, F.; Fransen, Ch.; Georgiev, G.; Gernhauser, R.; Hess, H.; Huyse, M.; Jolie, J.; Kröll, Th.; Krücken, R.; Lutter, R.; Marsh, B.A.; Mertzimekis, T.; Muecher, D.; Orlandi, R.; Pakou, A.; Raabe, R.; Randisi, G.; Reiter, P.; Roger, T.; Seidlitz, M.; Seliverstov, M.; Sotty, C.; Tornqvist, H.; Van De Walle, J.; Van Duppen, P.; Voulot, D.; Warr, N.; Wenander, F.; Wimmer, K.

    2015-01-01

    The quasi-SU(3) sequence of the positive parity $νg_{9/2}, d_{5/2}, s_{1/2}$ orbitals above the N=40 shell gap are assumed to induce strong quadrupole collectivity in the neutron-rich Fe (Z=26) and Cr (Z=24) isotopes below the nickel region. In this paper the position and strength of these single-particle orbitals are characterized in the neighborhood of $^{68}$Ni (Z=28,N=40) through the $^{66}$Ni($d,p$)$^{67}$Ni one-neutron transfer reaction at 2.95 MeV/nucleon in inverse kinematics, performed at the REX-ISOLDE facility in CERN. A combination of the Miniball $\\gamma$-array and T-REX particle-detection setup was used and a delayed coincidence technique was employed to investigate the 13.3-$\\mu$s isomer at 1007 keV in $^{67}$Ni. Excited states up to an excitation energy of 5.8 MeV have been populated. Feeding of the $νg_{9/2}$ (1007 keV) and $νd_{5/2}$ (2207 keV and 3277 keV) positive-parity neutron states and negative parity ($νpf$) states have been observed at low excitation energy. The extracted relativ...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    CERN Document Server

    Raimondi, Francesco; Navrátil, Petr; Quaglioni, Sofia

    2016-01-01

    Background: 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. Ab initio approaches have been successfully applied to describe the $^3$H$(d,n)^4$He and $^3$He$(d,p)^4$He fusion processes. Purpose: 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 first application, we study the elastic scattering of deuterium on $^7$Li and the ${}^{7}$Li($d$,$p$)${}^{8}$Li transfer reaction based on a two-body Hamiltonian. Methods: 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-clu...

  4. Residual Water Modulates QA−-to-QB Electron Transfer in Bacterial Reaction Centers Embedded in Trehalose Amorphous Matrices

    Science.gov (United States)

    Francia, Francesco; Palazzo, Gerardo; Mallardi, Antonia; Cordone, Lorenzo; Venturoli, Giovanni

    2003-01-01

    The role of protein dynamics in the electron transfer from the reduced primary quinone, QA−, to the secondary quinone, QB, was studied at room temperature in isolated reaction centers (RC) from the photosynthetic bacterium Rhodobacter sphaeroides by incorporating the protein in trehalose water systems of different trehalose/water ratios. The effects of dehydration on the reaction kinetics were examined by analyzing charge recombination after different regimes of RC photoexcitation (single laser pulse, double flash, and continuous light) as well as by monitoring flash-induced electrochromic effects in the near infrared spectral region. Independent approaches show that dehydration of RC-containing matrices causes reversible, inhomogeneous inhibition of QA−-to-QB electron transfer, involving two subpopulations of RCs. In one of these populations (i.e., active), the electron transfer to QB is slowed but still successfully competing with P+QA− recombination, even in the driest samples; in the other (i.e., inactive), electron transfer to QB after a laser pulse is hindered, inasmuch as only recombination of the P+QA− state is observed. Small residual water variations (∼7 wt %) modulate fully the relative fraction of the two populations, with the active one decreasing to zero in the driest samples. Analysis of charge recombination after continuous illumination indicates that, in the inactive subpopulation, the conformational changes that rate-limit electron transfer can be slowed by >4 orders of magnitude. The reported effects are consistent with conformational gating of the reaction and demonstrate that the conformational dynamics controlling electron transfer to QB is strongly enslaved to the structure and dynamics of the surrounding medium. Comparing the effects of dehydration on P+QA−→PQA recombination and QA−QB→QAQB− electron transfer suggests that conformational changes gating the latter process are distinct from those stabilizing the primary

  5. Two-Particle Cluster Theory for Biaxial Nematic Phase Based on a Recently Proposed Interaction Potential

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhi-Dong; ZHANG Yan-Jun; SUN Zong-Li

    2006-01-01

    @@ Two-particle cluster theory is applied to study the biaxial nematic phase formed by biaxial molecules interacting with a simplified model proposed by Sonnet et al. [Phys. Rev. E 67 (2003) 061701]. For the temperature dependences of the internal energy per particle and of the order parameters, the two-particle theory yields an improved result compared with mean field theory. Concerning the phase diagram, the two-particle theory gives the numerical result in qualitative agreement with the mean field theory.

  6. Rummukainen-Gottlieb's formula on two-particle system with different mass

    CERN Document Server

    Fu, Ziwen

    2011-01-01

    A proposal by L\\"uscher enables us to extract elastic scattering phases from two-particle energy spectrum using lattice simulations. Rummukainen-Gottlieb further extend it to the moving frame (MF), which is devoted to the system of two identical particles. In this work, we generalize Rummukainen-Gottlieb's formula to the case where two particles are distinguishable, i.e., the masses of the two particles are different. Their relation with the elastic scattering phases of the two particles in the continuum are obtained for $C_{4v}$ symmetry. Our results will be very helpful for the study of some resonances, such as kappa, and so on.

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

    Science.gov (United States)

    Raimondi, Francesco; Hupin, Guillaume; Navrátil, Petr; Quaglioni, Sofia

    2016-05-01

    Background: 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. Ab initio approaches have been successfully applied to describe the 3H (d ,n )4He and 3He(d ,p )4He fusion processes. Purpose: 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 first application, we study the elastic scattering of deuterium on 7Li and the 7Li(d ,p )8Li transfer reaction based on a two-body Hamiltonian. Methods: 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. Results: 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. Conclusions: Deuteron stripping reactions with p -shell targets can now be computed ab initio, but calculations are very demanding. 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.

  8. The Electron Transfer Reaction between p-Nitrobenzoates and β-N, N-Dimethylaminonaphthalene

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A few of p-nitrobenzoates were synthesized, and the electron transfer of them with β-N, N-dimethylaminonaphthalene (DMAN) in methanol solution was studied. Steady-state fluore-scence results showed the cyclodextrin moiety in p-nitrobenzoyl-β-cyclodextrin would block the electron transfer pathway from DMAN compared with other electron acceptors, thus, reduced the electron transfer efficiency.

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

    Energy Technology Data Exchange (ETDEWEB)

    Matsunaga, Phillip Thomas [Univ. of California, Berkeley, CA (United States)

    1991-11-01

    The divalent lanthanide complex, (Me5C5)2Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me5C5)2YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me5C5)2YbCH(SiMe3)2, displays similar chemistry to (Me5C5)2YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me5C5)3YbCH(SiMe5)2. Copper and silver halide salts react with (Me5C5)2V to produce the trivalent halide derivatives, (Me5C5)2VX (X + F, Cl, Br, I). The chloride complex, (Me5C5)2VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me5C5)2V producing the vanadium-oxo complex, (Me5Ce5)2VO. The trivalent titanium species, (Me5C5)2TiX (X = Cl, Br, Me, BH4), form bimetallic coordination complexes with (Me5C5)2Yb. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. 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.

    Science.gov (United States)

    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.

  12. Imaging Three Dimensional Two-Particle Correlations for Heavy-Ion Reaction Studies

    Energy Technology Data Exchange (ETDEWEB)

    Brown, D; Enokizono, A; Heffner, M; Soltz, R; Danielewicz, P; Pratt, S

    2005-06-27

    The authors report an extension of the source imaging method for analyzing three-dimensional sources from three-dimensional correlations. The technique consists of expanding the correlation data and the underlying source function in spherical harmonics and inverting the resulting system of one-dimensional integral equations. With this strategy, they can image the source function quickly, even with the extremely large data sets common in three-dimensional analyses.

  13. Elastic scattering and cluster-transfer reactions of 98Rb on 7Li at REX-ISOLDE

    CERN Document Server

    Bouma, Jake

    Exotic nuclei are nuclei with unusual proton to neutron ratios that exist far away from stability. Due to their instability, these nuclei are only available for nuclear reactions as radioactive ion beams. Experiments must therefore be performed in inverse kinematics at advanced radioactive isotope separation and acceleration facilities. REX-ISOLDE at CERN is one such facility, capable of producing post-accelerated radioactive ion beams with energies up to 2.85 MeV/u. Cluster-transfer reactions in inverse kinematics with a $^{7}$Li target are proposed as a tool for the study of exotic nuclei at REX-ISOLDE. In these reactions, either the $\\alpha$ or triton clusters that make up the weakly bound $^{7}$Li nucleus can be transfered to the beam nucleus. The remaining cluster that is not transferred can be detected, and identifies the particular transfer channel. Through this mechanism it is possible to populate states of very high spin, which is useful for $\\gamma$-spectroscopy in poorly known exotic regions. Speci...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    K. B. Haase

    2012-07-01

    Full Text Available 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.

  17. MHD oscillatory channel flow, heat and mass transfer in a physiological fluid in presence of chemical reaction

    Directory of Open Access Journals (Sweden)

    J.C. Misra

    2016-03-01

    Full Text Available In the present paper, the problem of oscillatory MHD flow of blood in a porous arteriole in presence of chemical reaction and an external magnetic field has been investigated. Heat and mass transfer during arterial blood flow are also studied. A mathematical model is developed and analyzed by using appropriate mathematical techniques. Expressions for the velocity profile, volumetric flow rate, wall shear stress and rates of heat and mass transfer have been obtained. Variations of the said quantities with different parameters are computed by using MATHEMATICA software. The quantitative estimates are presented through graphs and table.

  18. Mass transfer and chemical reaction in gas-liquid-liquid systems

    NARCIS (Netherlands)

    Brilman, Derk Willem Frederik

    1998-01-01

    Gas-liquid-liquid reaction systems may be encountered in several important fields of application as e.g. hydroformylation, alkylation, carboxylation, polymerisation, hydrometallurgy, biochemical processes and fine chemicals manufacturing. However, the reaction engineering aspects of these systems ha

  19. Measurements of Sub-Barrier Transfer Yields in SULFUR-32 + NIOBIUM-93, MOLYBDENUM(98,100) Reactions at 180 Degrees

    Science.gov (United States)

    Roberts, Roland Blaine

    1994-01-01

    The Rochester RMS was used to measure excitation functions for 180^circ sub -barrier one- and two-neutron pickup reactions for E _{rm lab} final states were not identified. The RMS technique was chosen for its self-normalizing property which makes obtaining absolute cross sections straightforward. The distorted-wave Born-approximation (DWBA) computer code scPTOLEMY was used to obtain quantal predictions of the one-neutron pickup yields. The calculations were performed for several final states and summed (using the appropriate spectroscopic factors) to estimate the total quasi-elastic transfer yield. P scTOLEMY over-predicted the yield in each system by a factor of 2-3. Since DWBA calculations for heavy-ion reactions are known to have difficulty reproducing experimentally measured yields within a factor of two, this discrepancy is not surprising. Although the absolute yields were not reproduced by the calculations, the shape of the excitation function is well reproduced. No calculations were performed for two-neutron transfer due to the lack of reliable spectroscopic factors. The transfer probabilities are obtained directly from these measurements. Distances of closest approach were calculated using a proximity potential. The slopes of transfer probability vs distance of closest approach are in good agreement with the predictions obtained from semi-classical theory using binding energies, indicating the absence of a "slope anomaly." This is consistent with the prediction that diffractive effects, which may distort the measured slope, are minimized at backward angles and sub-barrier energies--the precise conditions under which these measurements were performed. Angle-integrated transfer cross sections were derived from the measured transfer probabilities by assuming the ions follow Rutherford trajectories. These derived yields are consistent with the hypothesis that fusion enhancements in previously measured fusion yields for the ^ {32}S + ^{98,100} Mo systems are

  20. One-and Two-Neutron Transfer Reactions in 11Be+208Pb and Mechanism of Lowering Fusion Barrier

    Institute of Scientific and Technical Information of China (English)

    WANG Ning; LI Zhu-Xia; WU Xi-Zhen; WANG Nan; SUN Xiu-Quan

    2000-01-01

    We study one-and two-neutron transfer reactions in 11Be+208Pb by using the quantum molecular dynamics model. We find that lowering about 1-2 MeV of the potential barrier of 208Pb for fusion is gained when two neutrons separated from 11Be enter into 208Pb. Whereas no significant change of potential barrier is found when only the halo neutron separated from 11Be enters into 208Pb. The dynamical interplay between suppression and enhancement effects on the fusion probability in reaction 11Be+208Pb stemming from the easy separation of halo neutron and the long extending of neutron distribution is discussed.

  1. Heteropolymolybdate as a New Reaction-controlled Phase-transfer Catalyst for Efficient Alcohol Oxidation with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    Zhi Huan WENG; Jin Yan WANG; Xi Gao JIAN

    2006-01-01

    A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H2O2 with high selectivity was studied. In this system, heteropolymolybdate [C7H7N(CH3)3]3{PO4[MoO(O2)2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.

  2. Neutron Transfer Reactions on Neutron-Rich N=50 and N=82 Nuclei Near the r-Process Path

    Energy Technology Data Exchange (ETDEWEB)

    Cizewski, J. A. [Rutgers University; Jones, K. L. [University of Tennessee, Knoxville (UTK); Kozub, R. L. [Tennessee Technological University; Pain, S. D. [Rutgers University; Thomas, J. S. [Rutgers University; Arbanas, Goran [ORNL; Adekola, Aderemi S [ORNL; Bardayan, Daniel W [ORNL; Blackmon, Jeff C [ORNL; Chae, K. Y. [University of Tennessee, Knoxville (UTK); Chipps, K. [Colorado School of Mines, Golden; Dean, David Jarvis [ORNL; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; Johnson, Micah [ORNL; Kapler, R. [University of Tennessee, Knoxville (UTK); Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Livesay, Jake [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Moazen, Brian [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Paulauskas, Stanley V [ORNL; Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Wilson, Gemma L [ORNL

    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.

  3. Mixing of photons with massive spin-two particles in a magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Biggio, Carla [Universidad Autonoma de Madrid (Spain). Dept. de Fisica Teorica]|[Max-Planck-Institut fuer Physik, Muenchen (Germany)]|[Genova Univ. (Italy). Dipt. di Fisica; Masso, Eduard [Universitat Autonoma de Barcelona (Spain). Inst. di Fisica D' Altes Energies; Redondo, Javier [Universitat Autonoma de Barcelona (Spain). Inst. di Fisica D' Altes Energies]|[Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

    2008-12-15

    We study the mixing of photons with hypothetical massive spin-two particles in the presence of a magnetic field. Mixing phenomena have been studied in the case of axion-like particles and strictly massless spin-two particles (gravitons) but not in this case. We find several interesting differences between them. (orig.)

  4. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才

    2004-01-01

    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  5. Proton-coupled electron transfer in tyrosine and a β-hairpin maquette: reaction dynamics on the picosecond time scale.

    Science.gov (United States)

    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.

  6. Formation, Isolation and Characterization of a New Ruthenium Complex in Reaction of Acetone Masked Terminal Alkynone with Transfer Hydrogenation Catalyst

    Institute of Scientific and Technical Information of China (English)

    郭敏捷; 李到; 孙延辉; 成江; 张兆国

    2004-01-01

    Reaction of [1S,2S-(Ts-diphen)Ru(Ⅱ)(p-cymene)] (1S,2S-Ts-diphen= 1S,2S-N-tosyl-1,2-diphenylethylenediamine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex bearing a 2,5-dihydrofuran moiety. The complex was characterized and a possible mechanism for the formation of the complex was proposed.

  7. Rapid Detection of Meat Spoilage by Measuring Volatile Organic Compounds by Using Proton Transfer Reaction Mass Spectrometry

    OpenAIRE

    Mayr, D; Margesin, R.; Klingsbichel, E.; E. Hartungen; Jenewein, D.; Schinner, F.; Märk, T.D.

    2003-01-01

    The evolution of the microbial spoilage population for air- and vacuum-packaged meat (beef and pork) stored at 4°C was investigated over 11 days. We monitored the viable counts (mesophilic total aerobic bacteria, Pseudomonas spp., Enterobacteriaceae, lactic acid bacteria, and Enterococcus spp.) by the microbiological standard technique and by measuring the emission of volatile organic compounds (VOCs) with the recently developed proton transfer reaction mass spectrometry system. Storage time,...

  8. Excited state charge transfer reaction in (mixed solvent + electrolyte) systems: Role of reactant-solvent and reactant-ion interactions

    Indian Academy of Sciences (India)

    Harun Al Rasid Gazi; Ranjit Biswas

    2011-05-01

    Fluorescence spectroscopic techniques have been used to study the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in two sets of mixed solvents, (1-propanol + ethyl acetate) and (propylene carbonate + acetonitrile), in the absence and presence of a strong electrolyte, lithium perchlorate. These two sets of mixed solvent systems represent binary solvent mixtures of low and high polarities, respectively. Density, sound velocity and viscosity measurements indicate that these two mixed solvent systems are structurally different. Stronger ion-reactant interaction is evidenced in the mole fraction independence of emission frequencies in electrolyte solutions of low polar binary solvent mixtures. For both these mixtures, the reaction driving force (- ) decreases with increase in mole fraction of the relatively less polar solvent component of the mixture. Interestingly, - increases significantly on addition of electrolyte in low polar mixtures and exhibits mixture composition dependence but, in contrast, - in high polar mixtures does not sense variation in mixture composition in presence of electrolyte. This insensitivity to mixture composition for high polar mixtures is also observed for the measured reaction time constant. In addition, the reaction time constant does not sense the presence of electrolyte in the high polar solvent mixtures. The reaction time constant in low polar mixtures, which becomes faster on addition of electrolyte, lengthens on increasing the mole fraction of the relatively less polar solvent component of the mixture. These observations have been qualitatively explained in terms of the measured solvent reorganization energy and reaction driving force by using expressions from the classical theory of electron transfer reaction.

  9. A novel salt of antidiabetic drug metformin resulting from a proton transfer reaction: Synthesis, characterization, crystal structure and solution studies

    Science.gov (United States)

    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.

  10. Excited states in electron-transfer reaction products: ultrafast relaxation dynamics of an isolated acceptor radical anion.

    Science.gov (United States)

    Horke, Daniel A; Roberts, Gareth M; Verlet, Jan R R

    2011-08-04

    The spectroscopy and ultrafast relaxation dynamics of excited states of the radical anion of a representative charge-transfer acceptor molecule, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, have been studied in the gas phase using time-resolved photoelectron spectroscopy. The photoelectron spectra reveal that at least two anion excited states are bound. Time-resolved studies show that both excited states are very short-lived and internally convert to the anion ground state, with the lower energy state relaxing within 200 fs and a near-threshold valence-excited state relaxing on a 60 fs time scale. These excited states, and in particular the valence-excited state, present efficient pathways for electron-transfer reactions in the highly exergonic inverted region which commonly displays rates exceeding predictions from electron-transfer theory.

  11. Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O + 232Th reaction

    Science.gov (United States)

    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.

  12. Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O+232Th reaction

    Directory of Open Access Journals (Sweden)

    R. Léguillon

    2016-10-01

    Full Text Available 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.

  13. Using intramolecular energy transfer to transform non-photoactive, visible-light-absorbing chromophores into sensitizers for photoredox reactions.

    Science.gov (United States)

    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.

  14. Dielectric image effects in environmental reorganization free energies and inter-reactant work terms of metalloprotein electron transfer reactions

    Science.gov (United States)

    Kharkats, Yurij I.; Ulstrup, Jens

    1990-02-01

    Kinetics of electron transfer between redox metalloproteins and small inorganic reaction partners has become a powerful tool for investigations of protein electron transport. We introduce here a model for metalloprotein electron transfer which incorporates essential features omitted in previous approaches to metalloprotein electron transfer data analysis. The protein is represented by a spherical region of low dielectric constant, with a conducting sphere excentrically located inside the protein simulating the metal centre. A conducting sphere outside the protein represents the small reaction partners, and the whole system is embedded in a dielectric solvent. The inter-reactant work terms and overall protein and solvent reorganization free energy for this model have been calculated. It appears that dielectric image interactions for multiply charged small reactants are important and comparable to interactions with both the protein surface charges and the solvent. The character of work terms and reorganization free energies for proteins is thus different from those of small ionic reactants. Cross relations and other frames where these features are disregarded should therefore be used with care for protein electron transfer.

  15. SYNTHESIS AND APPLICATIONS OF CROSS-LINKED POLY(DIALLYLDIMETHYL AMMONIUM CHLORIDE) AND ITS DERIVATIVE COPOLYMERS AS EFFICIENT PHASE TRANSFER CATALYST FOR NUCLEOPHILIC SUBSTITUTION REACTIONS

    Institute of Scientific and Technical Information of China (English)

    Hossein Mahdavi; Mahdi Mahmoudian

    2011-01-01

    Cross-linked poly(diallyldimethylammonium chloride) and its derivative eopolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions. In addition, the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.

  16. Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

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

  18. TDDFT study of the polarity controlled ion-pair separation in an excited-state proton transfer reaction.

    Science.gov (United States)

    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.

  19. Separation of electron-transfer and coupled chemical reaction components of biocatalytic processes using Fourier transform ac voltammetry.

    Science.gov (United States)

    Fleming, Barry D; Zhang, Jie; Bond, Alan M; Bell, Stephen G; Wong, Luet-Lok

    2005-06-01

    The underlying electron-transfer and coupled chemical processes associated with biologically important catalytic reactions can be resolved using a combination of Fourier transform ac voltammetry with an analysis of the separated dc and ac components. This outcome can be achieved because the response associated with generation of the catalytic current is essentially confined to the steady-state dc component, whereas the electron-transfer step is dominant in the fundamental and higher harmonics. For the mediated oxidation of glucose with glucose oxidase, it was found that the underlying reversible redox chemistry of the mediator, ferrocenemonocarboxylic acid, as detected in the third and higher harmonics, was totally unaffected by introduction of the catalytic process. In contrast, for the catalytic reduction of molecular oxygen by cytochrome P450, slight changes in the P450 redox process were detected when the catalytic reaction was present. Simulations of a simple catalytic reaction scheme support the fidelity of this novel FT ac voltammetric approach for examining mechanistic nuances of catalytic forms of electrochemical reaction schemes.

  20. Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors.

    Science.gov (United States)

    Uchida, Tatsuya; Katsuki, Tsutomu

    2014-02-01

    Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Time-dependent Hartree-Fock calculations for multinucleon transfer and quasifission processes in $^{64}$Ni+$^{238}$U reaction

    CERN Document Server

    Sekizawa, Kazuyuki

    2016-01-01

    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 TDHF calculations and measurements for $^{64}$Ni+$^{238}$U 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 $^{64}$Ni+$^{238}$U reaction. They show reasonable agreements with measurements. At small impact parameters, collision dynamics depends sensitively on th...

  2. A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with [COW12O40]5-

    Institute of Scientific and Technical Information of China (English)

    Fatemeh F. Bamoharram; Mohammad M. Heravi; Touran Ardalan; Pouran Ardalan

    2009-01-01

    A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with potassium 12-tungsto cobalt (Ⅲ) ate ion, K5[CoW12O40], abbreviated as Co(Ⅲ)W, has been performed in different solvents. The studies were carried out in methanol, ethanol, acetonitrile and acetic acid/water. The rate constants, reaction rates and activation parameters were calculated. Our findings show that the rate of disappearance of the Co(Ⅲ) is pseudo-first order. The kinetic data is strongly affected by used solvents. The maximum and minimum rate constants were achieved in the ethanol and acetic acid/water (70/30) as a solvent, respectively. In all of the used solvents, negative value of activation entropies was observed, but negative activation enthalpies are observed in methanol, ethanol and acetonitrile. The reaction rate is increased with increase of Co(Ⅲ) concentration.

  3. Kinetic analysis of the effect of HIV nucleocapsid protein (NCp) on internal strand transfer reactions.

    Science.gov (United States)

    Raja, A; DeStefano, J J

    1999-04-20

    The mechanism of HIV reverse transcriptase (RT) catalyzed strand transfer synthesis (i.e., switching of the primer to a new template) from internal regions on RNA templates in the presence and absence of HIV nucleocapsid protein (NCp) was investigated. Two different systems each consisting of DNA-primed RNA donor (on which primer extension initiated) and acceptor (to which DNAs initiated on the donor could transfer) templates were used to determine kinetic parameters of strand transfer. The donor and acceptor shared an internal region of homology where homologous strand transfer could occur. The rate of strand transfer at various acceptor concentrations was determined by monitoring the production of transfer products over time. These rates were used to construct Lineweaver-Burk plots. In each system, NCp increased the Vmax about 3-fold while the Km for acceptor template was decreased severalfold. NCp's effects on RT extension ranged from no effect to inhibition depending on the primer-template used. The lowered Km shows that NCp increases the affinity of the acceptor template for the transferring DNA. Vmax increases despite the inhibition of RT extension. The increased Vmax implies a stimulatory mechanism that cannot be mimicked by high acceptor concentrations. Therefore, NCp does not act by merely increasing the effective concentration of nucleic acids.

  4. Energy, Electron Transfer and Photocatalytic Reactions of Visible Light Absorbing Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Schmehl, Russell H. [Tulane Univ., New Orleans, LA (United States)

    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.

  5. Probabilistic Teleportation of an Arbitrary Three-Level Two-Particle State and Classical Communication Cost

    Institute of Scientific and Technical Information of China (English)

    DAIHong-Yi; KUANGLe-Man; LICheng-Zu

    2005-01-01

    We propose a scheme to probabilistically teleport an unknown arbitrary three-level two-particle state by using two partial entangled two-particle states of three-level as the quantum channel. The classical communication cost required in the ideal probabilistic teleportation process is also calculated. This scheme can be directly generalized to teleport an unknown and arbitrary three-level K-particle state by using K partial entangled two-particle states of three-level as the quantum channel.

  6. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2017-04-01

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

  8. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path.

    Science.gov (United States)

    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 (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(+).

  9. Cyclic Square Wave Voltammetry of Surface-Confined Quasireversible Electron Transfer Reactions.

    Science.gov (United States)

    Mann, Megan A; Bottomley, Lawrence A

    2015-09-01

    The theory for cyclic square wave voltammetry of surface-confined quasireversible electrode reactions is presented and experimentally verified. 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. These criteria were experimentally confirmed using two well-established surface-confined analytes. When properly applied, these criteria will enable non-experts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

  10. Elastic scattering and transfer reactions for the system 7Be + 58Ni at Coulomb barrier energies

    Science.gov (United States)

    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.

  11. Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2017-08-08

    Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh2Ln and Ru2Ln complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Nonlocality Proof for Two-Particle Systems in 3 3 Hilbert Space

    Institute of Scientific and Technical Information of China (English)

    WU Xiao-Hua; ZONG Hong-Shi; PANG Hou-Rong; WANG Fan

    2001-01-01

    For a two-particle system in 3 3 Hilbert space, we derive a new type of inequality for local hidden variable model. Using an entangled state, we give a realizable experiment whose joint probabilities violate the inequality.``

  14. On the reaction mechanism of the complete intermolecular O2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands.

    Science.gov (United States)

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J; Liakos, Dimitrios G; Neese, Frank

    2014-10-01

    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.

  15. Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

    Science.gov (United States)

    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.

  16. Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

    Science.gov (United States)

    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.

  17. A novel high-throughput format assay for HIV-1 integrase strand transfer reaction using magnetic beads

    Institute of Scientific and Technical Information of China (English)

    Hong-qiu HE; Xiao-hui MA; Bin LIU; Wei-zu CHEN; Cun-xin WANG; Shao-hui CHENG

    2008-01-01

    Aim:To develop a novel high-throughput format assay to monitor the integrase (IN) strand transfer (ST) reaction in vitro and apply it to a reaction character study and the identification of antiviral drugs.Methods:The donor DNA duplex,with a sequence identical to the U5 end of HIV-1 long terminal repeats,is labeled at its 5' end with biotin (BIO).The target DNA duplex is labeled at its 3' end with digoxin (DIG).IN mediates the integration of donor DNA into target DNA and results in a 5' BIO and 3' DIG-labeled duplex DNA product.Streptavidin-coated magnetic beads were used to capture the product,and the amount of DIG was measured as the ST reaction product.The assay was optimized in 96-well microplate format for high-throughput screening purpose.Moreover,the assay was applied in a ST reaction character study,and the efficiency of the assay in the identification of antiviral compounds was tested.Results:The end-point values,measured as absorbance at 405 nm was approximately 1.5 for the IN-mediated ST reaction as compared with no more than 0.05 of background readings.The ST reaction char-acter and the half maximal inhibitory concentration (IC50) values of 2 known IN inhibitors obtained in our assay were similar to previously reported results using other assays.The evaluation parameter Z' factor for this assay ranged from 0.6 to 0.9.Conclusion:The assay presented here has been proven to be rapid,sensitive,and specific for the detection of IN ST activity,the reaction character study,as well as for the identification of antiviral drugs targeting IN.

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

    Science.gov (United States)

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

    1994-08-01

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

  19. Exploring chemoselective S-to-N acyl transfer reactions in synthesis and chemical biology

    Science.gov (United States)

    Burke, Helen M.; McSweeney, Lauren; Scanlan, Eoin M.

    2017-05-01

    S-to-N acyl transfer is a high-yielding chemoselective process for amide bond formation. It is widely utilized by chemists for synthetic applications, including peptide and protein synthesis, chemical modification of proteins, protein-protein ligation and the development of probes and molecular machines. Recent advances in our understanding of S-to-N acyl transfer processes in biology and innovations in methodology for thioester formation and desulfurization, together with an extension of the size of cyclic transition states, have expanded the boundaries of this process well beyond peptide ligation. As the field develops, this chemistry will play a central role in our molecular understanding of Biology.

  20. 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.

    Science.gov (United States)

    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.

  1. Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.

    Science.gov (United States)

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jahn, Ullrich

    2014-09-01

    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.

  2. Hydrogen transfer reactions in viscous media — Potential and free energy surfaces in solvent–solute coordinates and their kinetic implications

    National Research Council Canada - National Science Library

    Wiebe, Heather; Prachnau, Melissa; Weinberg, Noham

    2013-01-01

    Two-dimensional potential energy and free energy surfaces are obtained using quantum mechanical and molecular dynamics calculations for four hydrogen transfer reactions in n-hexane solvent: the methyl–methane, n-propyl–n-propane, n-pentyl...

  3. Drift mechanism of mass transfer on heterogeneous reaction in crystalline silicon substrate

    Energy Technology Data Exchange (ETDEWEB)

    Kukushkin, S.A. [Institute of Problems of Mechanical Engineering, Russian Academy of Science, St Petersburg, 199178 (Russian Federation); St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 (Russian Federation); Osipov, A.V., E-mail: Andrey.V.Osipov@gmail.com [Institute of Problems of Mechanical Engineering, Russian Academy of Science, St Petersburg, 199178 (Russian Federation); St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 (Russian Federation)

    2017-05-01

    This work aims to study the pressure dependence of the thickness of the epitaxial silicon carbide film growing from crystalline silicon due to the heterogeneous reaction with gaseous carbon monoxide. It turned out that this dependence exhibits the clear maximum. On further pressure increasing the film thickness decreases. The theoretical model has been developed which explains such a character of the dependence by the fact that the gaseous silicon monoxide reaction product inhibits the drift of the gaseous reagent through the channels of a crystal lattice, thus decreasing their hydraulic diameter. In the proposed hydraulic model, the dependences of the film thickness both on the gas pressure and time have been calculated. It was shown that not only the qualitative but also quantitative correspondence between theoretical and experimental results takes place. As one would expect, due to the Einstein relation, at short growth times the drift model coincides with the diffusion one. Consequences of this drift mechanism of epitaxial film growing are discussed. - Graphical abstract: This work aims to study the pressure dependence of the thickness of the epitaxial silicon carbide film growing from crystalline silicon due to the heterogeneous reaction with gaseous carbon monoxide. It turned out that this dependence exhibits the clear maximum. On further pressure increasing the film thickness decreases. The theoretical model has been developed which explains such a character of the dependence by the fact that the gaseous silicon monoxide reaction product inhibits the drift of the gaseous reagent through the channels of a crystal lattice, thus decreasing their hydraulic diameter. - Highlights: • It is established that the greater pressure, the smaller is the reaction rate. • The reaction product prevents penetration of the reagent into a reaction zone. • For description the hydraulic model of crystal lattice channels is developed. • Theoretical results for polytropic

  4. Proton transfer reaction-mass spectrometry: online and rapid determination of volatile organic compounds of microbial origin.

    Science.gov (United States)

    Romano, Andrea; Capozzi, Vittorio; Spano, Giuseppe; Biasioli, Franco

    2015-05-01

    Analytical tools for the identification and quantification of volatile organic compounds (VOCs) produced by microbial cultures have countless applications in an industrial and research context which are still not fully exploited. The various techniques for VOC analysis generally arise from the application of different scientific and technological philosophies, favoring either sample throughput or chemical information. Proton transfer reaction-mass spectrometry (PTR-MS) represents a valid compromise between the two aforementioned approaches, providing rapid and direct measurements along with highly informative analytical output. The present paper reviews the main applications of PTR-MS in the microbiological field, comprising food, environmental, and medical applications.

  5. Ultrafast twisting motions and intramolecular charge-transfer reaction in a cyanine dye trapped in molecular nanocavities

    Science.gov (United States)

    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.

  6. Mixed convection effects on heat and mass transfer in a non Newtonian fluid with chemical reaction over a vertical plate

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    This paper studies mixed convection,double dispersion and chemical reaction effects on heat and mass transfer in a non-Darcy non-Newtonian fluid over a vertical surface in a porous medium under the constant temperature and concentration.The governing boundary layer equations,namely,momentum,energy and concentration,are converted to ordinary differential equations by introducing similarity variables and then are solved numerically by means of fourth-order Runge-Kutta method coupled with double-shooting techn...

  7. A simple approach to the solvent reorganization Gibbs free energy in electron transfer reactions of redox metalloproteins

    Science.gov (United States)

    Kharkats, Yurij I.; Ulstrup, Jens

    1999-04-01

    We discuss a simple model for the environmental reorganisation Gibbs free energy, Er, in electron transfer between a metalloprotein and a small reaction partner. The protein is represented as a dielectric globule with low dielectric constant, the metal centres as conducting spheres, all embedded in a continuous solvent with high dielectric constant. This model has previously reproduced thermodynamic metalloprotein properties. Er takes an analytic form expressed by a continuous image charge distribution, and depends weakly on the globular radius, indicating that repolarisation at the globule/solvent interface contributes less to these effects than to the work terms and driving force.

  8. Light-induced ruthenium-catalyzed nitrene transfer reactions: a photochemical approach towards N-acyl sulfimides and sulfoximines.

    Science.gov (United States)

    Bizet, Vincent; Buglioni, Laura; Bolm, Carsten

    2014-05-26

    1,4,2-Dioxazol-5-ones are five-membered heterocycles known to decarboxylate under thermal or photochemical conditions, thus yielding N-acyl nitrenes. Described herein is a light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2-dioxazol-5-ones at room temperature, thus providing direct access to N-acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one-pot sulfur imidation/oxidation sequence catalyzed by a single ruthenium complex is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Relevance of single-particle and collective excitations in zirconium isotopes populated by neutron transfer reactions in the {sup 90}Zr+{sup 208}Pb system

    Energy Technology Data Exchange (ETDEWEB)

    Pajtler, M. Varga, E-mail: maja.varga@fizika.unios.hr [Department of Physics, University of Osijek, Trg Ljudevita Gaja 6, 31000 Osijek (Croatia); Szilner, S.; Malenica, D. Jelavić; Mijatović, T.; Soić, N. [Ruer Bošković Institute, HR-10001, Zagreb (Croatia); Corradi, L.; Angelis, G. de; Fioretto, E.; Montanari, D.; Stefanini, A. M.; Valiente-Dobón, J. J. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, I-35020 Legnaro (Italy); Gadea, A. [IFIC, CSIC-Universidad de Valencia, E-46071 Valencia (Spain); Haas, F. [Institut Pluridisciplinaire Hubert Curien, CNRS-IN2P3 and Université de Strasbourg, F-67037 Strasbourg (France); Lunardi, S.; Mengoni, D.; Montagnoli, G.; Recchia, F.; Scarlassara, F. [Dipartimento di Fisica, Universitá di Padova, and Istituto Nazionale di Fisica Nucleare, I-35131 Padova (Italy); Märginean, N. [Horia Hulubei National Institute of Physics and Nuclear Engineering, RO-077125 Bucharest-Magurele (Romania); Pollarolo, G. [Dipartimento di Fisica Teorica, Universitá di Torino,and Istituto Nazionale di Fisica Nucleare, I-10125 Torino (Italy); 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.

  10. Characteristics of Homogeneous-Heterogeneous Reactions and Melting Heat Transfer in the Stagnation Point flow of Jeffrey Fluid

    Directory of Open Access Journals (Sweden)

    T. Hayat

    2016-01-01

    Full Text Available This work focuses on melting heat transfer in the stagnation point flow of Jeffrey fluid past an impermeable stretching cylinder with homogeneous-heterogeneous reactions. Characteristics of magnetohydrodynamic flow are explored in presence of heat generation/absorption. Diffusion coefficients of species A and B are taken of the same size. Heat released during chemical reaction is negligible. A system of ordinary differential equations is obtained by using suitable transformations. Convergent series solutions are derived. Impacts of various pertinent parameters on the velocity, temperature and concentration distributions are discussed. Numerical values of skin friction coefficient and Nusselt number are computed and analyzed. Present results are compared with the previous published data.

  11. Isotopic Yield Distributions of Transfer- and Fusion-Induced Fission from 238U+12C Reactions in Inverse Kinematics

    CERN Document Server

    Caamaño, M; Farget, F; Derkx, X; Schmidt, K -H; Audouin, L; Bacri, C -O; Barreau, G; Benlliure, J; Casarejos, E; Chbihi, A; Fernandez-Dominguez, B; Gaudefroy, L; Golabek, C; Jurado, B; Lemasson, A; Navin, A; Rejmund, M; Roger, T; Shrivastava, A; Schmitt, C

    2013-01-01

    A novel method to access the complete identification in atomic number Z and mass A of fragments produced in low-energy fission of actinides is presented. This method, based on the use of multi- nucleon transfer and fusion reactions in inverse kinematics, is applied in this work to reactions between a 238U beam and a 12C target to produce and induce fission of moderately excited actinides. The fission fragments are detected and fully identified with the VAMOS spectrometer of GANIL, allowing the measurement of fragment yields of several hundreds of isotopes in a range between A ~ 80 and ~ 160, and from Z ~ 30 to ~ 64. For the first time, complete isotopic yield distributions of fragments from well-defined fissioning systems are available. Together with the precise measurement of the fragment emission angles and velocities, this technique gives further insight into the nuclear-fission process.

  12. The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions

    DEFF Research Database (Denmark)

    Ulstrup, Jens; Jortner, Joshua

    1975-01-01

    -frequency intramolecular degrees of feedom on the free energy relationship for series of closely related reactions was investigated for various model systems involving displacement of potential energy surfaces, frequency shift, and anharmonicity effects. The free energy plots are generally found to pass through a maximum...... and to be asymmetric with a slower decrease in the transition probability with increasing energy of reaction. For high-frequency intramolecular modes this provides a rationalization of the experimental observation of ''activationless'' regions. Isotope effects are discussed as also are the oscillatory free energy...

  13. Charged particle sub-barrier transfer reactions for {sup 16}O + {sup A}Sm and their influence on the fusion cross section

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, P.R.S.; Maciel, A.M.M.; Cabezas, R. [and others

    1995-10-01

    Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the {sup 16}O + {sup A}Sm systems (A = 144, 148, 150, 152 and 154), at energies slightly lower than the Coulomb barriers and angles up to 0 = 170{degrees}. From a semiclassical formalism, transfer and elastic scattering data, the transfer form factors is derived. For only one of the ten channels studied there are signatures for the interpretation that the transfer reaction mechanism at backward angles, corresponding to small distances, may behave as a multi-step process leading to fusion. Coupled channel calculations including transfer channels are performed for the study of the sub-barrier fusion of these systems. The influence of short distance transfer reactions on the fusion is discussed. For these and other systems, the conclusions from this approach are found t to long range fusion absorptive potentials.

  14. Direct observation of charge-transfer-to-solvent (CTTS) reactions: Ultrafast dynamics of the photoexcited alkali metal anion sodide (Na-)

    Science.gov (United States)

    Barthel, Erik R.; Martini, Ignacio B.; Schwartz, Benjamin J.

    2000-06-01

    Charge-transfer-to-solvent (CTTS) transitions have been the subject of a great deal of interest recently because they represent the simplest possible charge transfer reaction: The CTTS electron transfer from an atomic ion to a cavity in the surrounding solvent involves only electronic degrees of freedom. Most of the work in this area, both experimental and theoretical, has focused on aqueous halides. Experimentally, however, halides make a challenging choice for studying the CTTS phenomenon because the relevant spectroscopic transitions are deep in the UV and because the charge-transfer dynamics can be monitored only indirectly through the appearance of the solvated electron. In this paper, we show that these difficulties can be overcome by taking advantage of the CTTS transitions in solutions of alkali metal anions, in particular, the near-IR CTTS band of sodide (Na-) in tetrahydrofuran (THF). Using femtosecond pump-probe techniques, we have been able to spectroscopically separate and identify transient absorption contributions not only from the solvated electron, but also from the bleaching dynamics of the Na- ground state and from the absorption of the neutral sodium atom. Perhaps most importantly, we also have been able to directly observe the decay of the Na-* excited CTTS state, providing the first direct measure of the electron transfer rate for any CTTS system. Taken together, the data at a variety of pump and probe wavelengths provide a direct test for several kinetic models of the CTTS process. The model which best fits the data assumes a delayed ejection of the electron from the CTTS excited state in ˜700 fs. Once ejected, a fraction of the electrons, which remain localized in the vicinity of the neutral sodium parent atom, recombine on a ˜1.5-ps time scale. The fraction of electrons that recombine depends sensitively on the choice of excitation wavelength, suggesting multiple pathways for charge transfer. The spectrum of the neutral sodium atom, which

  15. Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction.

    Science.gov (United States)

    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.

    Science.gov (United States)

    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.

    Science.gov (United States)

    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. Light induced EPR spectra of reaction centers from Rhodobacter sphaeroides at 80K: Evidence for reduction of QB by B-branch electron transfer in native reaction centers.

    Science.gov (United States)

    Paddock, M. L; Isaacson, R. A.; Abresch, E. C.; Okamura, M. Y.

    2006-01-01

    Photosynthetic reaction centers (RCs) from Rhodobacter sphaeroides capture solar energy by electron transfer from primary donor, D, to quinone acceptor, QB, through the active A-branch of electron acceptors, but not the inactive B-branch. The light induced EPR spectrum from native RCs that had Fe2+ replaced by Zn2+ was investigated at cryogenic temperature (80K, 35 GHz). In addition to the light induced signal due to formation of D+•QA−• observed previously, a small fraction (~5%) of the signal displayed very different characteristics: (1) The signal was absent in RCs in which the QB was displaced by the inhibitor stigmatellin. (2) Its decay time (τ=6 s) was the same as observed for D+•QB−• in mutant RCs lacking QA, which is significantly slower than for D+•QA−• (τ=30 ms). (3) Its EPR spectrum was identical to that of D+•QB−•. (4) The quantum efficiency for forming the major component of the signal was the same as that found for mutant RCs lacking QA (Φ =0.2%) and was temperature independent. These results are explained by direct photochemical reduction of QB via B-branch electron transfer in a small fraction of native RCs. PMID:18163156

  19. Charge transfer reactions at interfaces between neutral gas and plasma: Dynamical effects and X-ray emission

    Science.gov (United States)

    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.

  20. Mass transfer controlled reactions in packed beds at low Reynolds numbers

    Energy Technology Data Exchange (ETDEWEB)

    Fedkiw, P.S.

    1978-12-01

    The a priori prediction and correlation of mass-transfer rates in transport limited, packed-bed reactors at low Reynolds numbers is examined. The solutions to the governing equations for a flow-through porous electrode reactor indicate that these devices must operate at a low space velocity to suppress a large ohmic potential drop. Packed-bed data for the mass-transfer rate at such low Reynolds numbers were examined and found to be sparse, especially in liquid systems. Prior models to simulate the solid-void structure in a bed are reviewed. Here the bed was envisioned as an array of sinusoidal periodically constricted tubes (PCT). Use of this model has not appeared in the literature. The velocity field in such a tube should be a good approximation to the converging-diverging character of the velocity field in an actual bed. The creeping flow velocity profiles were calculated. These results were used in the convective-diffusion equation to find mass transfer rates at high Peclet number for both deep and shallow beds, for low Peclet numbers in a deep bed. All calculations assumed that the reactant concentration at the tube surface is zero. Mass-transfer data were experimentally taken in a transport controlled, flow-through porous electrode to test the theoretical calculations and to provide data resently unavailable for deeper beds. It was found that the sinusoidal PCT model could not fit the data of this work or that available in the literature. However, all data could be adequately described by a model which incorporates a channelingeffect. The bed was successfully modeled as an array of dual sized straight tubes.

  1. TRANSFER

    African Journals Online (AJOL)

    “Chemistry Department, Kenyatta University, P. 0. Box 43844 ... harvester (X) [L 2] in a manner consistent with the following Forster equation for long range energy transfer [3-7]. .... sensitive foods, chemical reactors and essences. Recently we ...

  2. Study of shell evolution around the doubly magic $^{208}$Pb via a multinucleon transfer reaction with an unstable beam

    CERN Multimedia

    This proposal aims at the study of the neutron-rich region around the doubly-magic nucleus $^{208}$Pb populated via a multinucleon transfer reaction. An unstable $^{94}$Rb beam will be delivered by HIE-ISOLDE at 5.5 MeV$\\cdot$u onto a $^{208}$Pb 13.0 mg/cm$^{2}$ target. The $\\gamma$- rays will be recorded by the MINIBALL $\\gamma$-ray spectrometer. The aim of the experiment is twofold: \\\\ \\\\ i) firstly it will represent the proof of principle that multinucleon transfer reactions with neutron-rich unstable beams is efficient to populate neutron-rich heavy binary partners and represents a competitive method to cold fragmentation \\\\ ii) secondly we aim at populating medium- to high-spin states in $^{212;214}$Pb and $^{208;210}$Hg to elucidate the existence of the 16$^{+}$ isomer in the lead isotopes and at the same time to disentangle the puzzling case of a very low energy 3$^{-}$ state in $^{210}$Hg not described by any nuclear model. \\\\ \\\\ The experimental results will be compared with large-scale shell-model ...

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

    Science.gov (United States)

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

    2014-06-23

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

  4. The citric acid-Mn III,IVO 2(birnessite) reaction. Electron transfer, complex formation, and autocatalytic feedback

    Science.gov (United States)

    Wang, Yun; Stone, Alan T.

    2006-09-01

    Citrate released by plants, bacteria, and fungi into soils is subject to abiotic oxidation by MnO 2(birnessite), yielding 3-ketoglutarate, acetoacetate, and Mn II. Citrate loss and generation of products as a function of time all yield S-shaped curves, indicating autocatalysis. Increasing the citrate concentration decreases the induction period. The maximum rate ( rmax) along the reaction coordinate follows a Langmuir-Hinshelwood dependence on citrate concentration. Increases in pH decrease rmax and increase the induction time. Adding Mn II, Zn II, orthophosphate, or pyrophosphate at the onset of reaction decreases rmax. Mn II addition eliminates the induction period, while orthophosphate and pyrophosphate addition increase the induction period. These findings indicate that two parallel processes are responsible. The first, relatively slow process involves the oxidation of free citrate by surface-bound Mn III,IV, yielding Mn II and citrate oxidation products. The second process, which is subject to strong positive feedback, involves electron transfer from Mn II-citrate complexes to surface-bound Mn III,IV, generating Mn III-citrate and Mn II. Subsequent intramolecular electron transfer converts Mn III-citrate into Mn II and citrate oxidation products.

  5. Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

    Science.gov (United States)

    Laszlo, Kenneth J.; Bush, Matthew F.

    2015-12-01

    Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

  6. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Science.gov (United States)

    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.

  7. Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

    Directory of Open Access Journals (Sweden)

    Yannick Borguet

    2010-12-01

    Full Text Available The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymeneRu(μ-Cl3RuCl(3-phenyl-1-indenylidene(PCy3] (1 to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II–Ru(III mixed-valence compound [(p-cymeneRu(μ-Cl3RuCl2(PCy3], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

  8. Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.

    Science.gov (United States)

    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

  9. MASS TRANSFER EFFECTS ON ACCELERATED VERTICAL PLATE IN A ROTATING FLUID WITH FIRST ORDER CHEMICAL REACTION

    Directory of Open Access Journals (Sweden)

    R. Muthucumaraswamy

    2012-12-01

    Full Text Available The precise analysis of the rotation effects on the unsteady flow of an incompressible fluid past a uniformly accelerated infinite vertical plate with variable temperature and mass diffusion has been undertaken, in the presence of a homogeneous first order chemical reaction. The dimensionless governing equations are solved using the Laplace-transform technique. The plate temperature as well as the concentration near the plate increase linearly with time. The velocity profiles, temperature and concentration are studied for different physical parameters, like the chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number, Prandtl number and time. It is observed that the velocity increases with increasing values of thermal Grashof number or mass Grashof number. It is also observed that the velocity increases with decreasing rotation parameter Ω.

  10. Reaction of benzeneselenol with tri- and tetrachloroethylenes under conditions of phase-transfer catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Martynov, A.V.; Mirskova, A.N.; Kalikhman, I.D.; Voronkov, M.G.

    1988-08-10

    The reaction of benzeneselenol with trichloroethylene in concentrated sodium hydroxide solution, catalyzed by ammonium salts, leads to Z-phenyl /alpha/,/beta/-dichlorovinyl selenide with an equimolar ratio of the catalyst and the selenol or to a mixture of the Z and E isomers with a ratio of 1:10. In addition to the expected trichlorovinyl selenide PhSeCCl=CCl/sub 2/, the analogous reaction with tetrachloroethylene also gives a mixture of the Z and E isomers of /alpha/-/beta/-dichlorovinyl selenides, and in addition, 1,2-bis(phenylseleno)-1,2-dichloroethylene PhSeCCl = CClSePh. If trialkylbenzylammonium chlorides R/sub 3/PhCH/sub 2/N/sup +/Cl/sup /minus// are used as catalyst, phenyl benzyl selenide PhSeCH/sub 2/Ph is formed as a side product. The results of the reaction in the case of trichloroethylene are explained by the addition of the selenolate ion to the CCl/identical to/CCl, generated from the trichloroethylene in situ, and isomerization of the initially formed Z-phenyl /alpha/,/beta/-dichlorovinyl selenide to the thermodynamically more stable E isomer. In the case of tetrachloroethylene they are explained by the usual addition-elimination mechanism with the formation of trichlorovinyl selenide, accompanied by reductive dechlorination of the CCl/sub 2/-CCl/sub 2/ to CHCl=CCl/sub 2/ by the selenolate and subsequent reaction of the selenolate with CHCl=CCl/sub 2/.

  11. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in tr

  12. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in

  13. Examining the effect of nonlocality in $(d,n)$ transfer reactions

    CERN Document Server

    Ross, A; Nunes, F M

    2016-01-01

    Background: In the last year we have been exploring the effect of the explicit inclusion of nonlocality in (d,p) reactions. Purpose: 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. Method: We apply our methods (both the distorted wave Born approximation and the adiabatic wave approximation) to $(d,n)$ reactions on $^{16}$O, $^{40}$Ca, $^{48}$Ca, $^{126}$Sn, $^{132}$Sn, and $^{208}$Pb at $20$ and $50$ MeV. Results: We look separately at the modifications introduced by nonlocality in the final bound and scattering states, as well as the consequences reflected 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). Conclusions: Our results...

  14. Spectrophotometric determination of quetiapine fumarate in pharmaceuticals and human urine by two charge-transfer complexation reactions

    Directory of Open Access Journals (Sweden)

    Vinay K.B.

    2012-01-01

    Full Text Available Two simple, rapid and accurate spectrophotometric procedures are proposed for the determination of quetiapine fumarate (QTF in pharmaceuticals and in spiked human urine. The methods are based on charge transfer complexation reactions of free base form of the drug (quetiapine, QTP, as n-electron donor (D, with either p-chloranilic acid (p-CAA (method A or 2,3-dichloro-5,6-dicyanoquinone (DDQ (method B as π-acceptors (A. The coloured charge transfer complexes produced exhibit absorption maxima at 520 and 540 nm, in method A and method B, respectively. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the maximum sensitivity. Beer’s law is obeyed over the concentration ranges of 8.0 - 160 and 4.0 - 80.0 μg ml-1, for method A and method B, respectively. The calculated molar absorptivity values are 1.77 × 103 and 4.59 × 103 l mol-1cm-1, respectively, for method A and method B. The Sandell sensitivity values, limits of detection (LOD and quantification (LOQ have also been reported. The stoichiometry of the reaction in both cases was accomplished adopting the limiting logarithmic method and was found to be 1: 2 (D: A. The accuracy and precision of the methods were evaluated on intra-day and inter-day basis. The proposed methods were successfully applied for the determination of QTF in pharmaceutical formulations and spiked human urine.

  15. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

    Science.gov (United States)

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-05-01

    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.

  16. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS).

    Science.gov (United States)

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-05-01

    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. Graphical Abstract ᅟ.

  17. Effect of Chemical Reaction on Convective Heat Transfer of Boundary Layer Flow in Nanofluid over a Wedge with Heat Generation/Absorption and Suction

    Directory of Open Access Journals (Sweden)

    R. M. Kasmani

    2016-01-01

    Full Text Available The aim of the present study is to examine the convective heat transfer of nanofluid past a wedge subject to first-order chemical reaction, heat generation/absorption and suction effects. The influence of wedge angle parameter, thermophoresis, Dufour and Soret type diffusivity are included. The local similarity transformation is applied to convert the governing nonlinear partial differential equations into ordinary differential equations. Shooting method integrated with fourth-order Runge-Kutta method is used to solve the ordinary differential equations. The skin friction, heat and mass transfer rates as well as the effects of various parameters on velocity, temperature and solutal concentration profiles are analyzed. The results indicate that when the chemical reaction parameter increases, the heat transfer coefficient increases while the mass transfer coefficient decreases. The effect of chemical reaction parameter is very important in solutal concentration field compared to velocity and temperature profiles since it decreases the solutal concentration of the nanoparticle.

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

    Science.gov (United States)

    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 to

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

    Energy Technology Data Exchange (ETDEWEB)

    Geibel, Kerstin

    2012-06-15

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

  20. Donor-acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions.

    Science.gov (United States)

    Stergiou, Anastasios; Pagona, Georgia; Tagmatarchis, Nikos

    2014-01-01

    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.

  1. Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

    KAUST Repository

    Alsam, Amani Abdu

    2016-09-21

    Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

  2. Efficient oxidation of benzyl alcohol with heteropolytungstate as reaction-controlled phase-transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.

  3. Studies of One-Nucleon Transfer Reactions on Boron -11 and CARBON-12.

    Science.gov (United States)

    Foot, Penelope Bernadette

    This thesis describes a study of the ^{11}B(d,n)^{12 }C and ^{12}C(t, alpha)^{11} B reactions. The Indiana University Cyclotron Facility produced the 79 MeV deuterons for the ^{11} B(d,n)^{12}C experiment. Time of flight measurements were performed to obtain neutron energy spectra. The energy resolution was typically 300 keV (~{1over 2} nsec). Cross sections were extracted for five well-resolved bound states in ^{12}C at 0.00, 4.44, 9.64, 12.71 and 15.11 MeV. The experimental cross sections were compared with the results of theoretical predictions. The effect of including, in these calculations, the breakup of the deuteron into low energy relative S states during the course of the reaction was investigated. Spectroscopic factors were then determined for the above five states in ^{12}C and compared with theoretical values. A subsequent experiment was performed at the same energy with vector polarized deuterons in order to study the effects of deuteron breakup on the corresponding analysing powers. This was the first time that analysing powers had been measured for this reaction. The effects on the cross section and analysing power calculations of exact finite range and the D state of the deuteron were investigated using the Reid soft-core potential for the proton-neutron interaction. The possible role of a two step process in the population of the 2 ^{+} state at 4.44 MeV in ^{12}C was examined. The effects on the analysing power for this state, of contributions from the 2p-1f shell in the 4.44 MeV wavefunction, were also discussed. Differential cross sections for the ^ {12}C(t,alpha) ^{11}B reaction, using 33 MeV tritons from the Daresbury Nuclear Structure Facility, were extracted for transitions to the 0.00, 2.125, 4.445, 5.021, 6.743, 7.286, 7.978 and 8.559 MeV states in ^{11 }B. The results of CRC calculations were compared with DWBA and CCBA calculation for the single step and two step transitions respectively. The spin of the 8.559 MeV state in ^{11}B, which

  4. Structure of 26Al studied by one - nucleon transfer reaction 27Al(d,t

    Directory of Open Access Journals (Sweden)

    Srivastava Vishal

    2015-01-01

    Full Text Available The excited states of 26Al have been produced and studied using 27Al(d,t reaction with 25 MeV deuteron as projectile. Optical model potential parameters were extracted from the measured elastic scattering angular distribution. Zero range distorted wave Born approximation analysis for the ground and 0.223 MeV states of 26Al have been done. The spectroscopic factors calculated for these states are found to be in good agreement with the previously reported values.

  5. Probabilistic teleportation of a two-particle entangled state via a partially entangled pair

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiu-bo; LIU Xin-yuan; WEN Qiao-yan; ZHU Fu-chen

    2006-01-01

    A scheme for teleporting an unknown two-particle entangled state is proposed. In comparison with the recent protocol (Cola et al., Phys. Lett. A 337 (2005)), the entangled state as quantum channel required by this scheme is a single,partially entangled pair, which is much easier to prepare and maintain. Furthermore, a positive operator valued measure (POVM) is adopted and all kinds of transformations performed by sender and receiver are given in detail. It is shown that the probability of successful teleportation is twice the modulus square of the smaller Schmidt coefficient of the two-particle entangled state, and the fidelity can reach one.

  6. Teleportation of an unknown bipartite state via non-maximally entangled two-particle state

    Institute of Scientific and Technical Information of China (English)

    Cao Hai-Jing; Guo Yan-Qing; Song He-Shan

    2006-01-01

    In this paper a new scheme for teleporting an unknown entangled state of two particles is proposed. To weaken the requirement for the quantum channel, without loss of generality, two communicators only share a non-maximally entangled two-particle state. Teleportation can be probabilistically realized if sender performs Bell-state measurements and Hadamard transformation and receiver introduces two auxiliary particles, operates G-not operation, single-qubit measurements and appropriate unitary transformations. The probability of successful teleportation is determined by the smaller one among the coefficients' absolute values of the quantum channel.

  7. Study of 11Be on 9Be one neutron transfer reactions at TRIUMF ISAC-II

    Science.gov (United States)

    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).

  8. Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

    Science.gov (United States)

    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.

  9. Radioactive beam EXperiments at ISOLDE : Coulomb excitation and neutron transfer reactions of exotic nuclei.

    CERN Multimedia

    Kugler, E; Ratzinger, U; Wenander, F J C

    2002-01-01

    % IS347 \\\\ \\\\We propose to perform a pilot experiment to study very neutron rich (A<32) Na-Mg and (A<52) K-Ca isotopes in the region around the neutron shell closures of N=20 and N=28 after Coulomb excitation and neutron transfer, and to demonstrate highly efficient and cost-effective ways to bunch, charge-state breed and accelerate already existing mass-separated singly-charged radioactive ion beams. \\\\ \\\\To do this we plan to accelerate the ISOLDE beams up to 2~MeV/u by means of a novel acceleration scheme and to install an efficient $\\gamma$-ray array for low-multiplicity events around the target position.

  10. Donor–acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions

    Directory of Open Access Journals (Sweden)

    Anastasios Stergiou

    2014-09-01

    Full Text Available 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.

  11. Thermodynamic changes in the photoinduced proton-transfer reaction of the triplet state of safranine-T.

    Science.gov (United States)

    Borsarelli, Claudio D; Bertolotti, Sonia G; Previtali, Carlos M

    2002-08-01

    The enthalpy and volume changes occurring in the triplet excited state proton-transfer reactions of safranine-T (SH+) in aqueous solutions at pH 4.8, 8.3, and 10.4 were investigated using time-resolved photoacoustics (TRP). The transient triplet state species were also studied using laser-flash photolysis (LFP). The LFP experiments showed the prompt formation of 3SH+ with a triplet quantum yield phiT = 0.28 between pH 4.8 and 10.4. At pH 8.3 3SH+ decays directly to the ground state. However, at pH 4.8 and 10.4, 3SH+ reacts with protons or hydroxy ions to form the dication 3SH2(2+) or the neutral 3S species, with diffusion-controlled rate constants of kH+ = 1.6 x 10(10) M(-1) s(-1), and kHO- = 2.6 x 10(10) M(-1) s(-1), respectively. Under the same experimental conditions, the TRP measurements allowed the accurate determination of the energy content of the rapidly formed triplet state 3SH+ i.e. E(T) = 175 kJ mol(-1). The slow component (0.1-3 micros) of the TRP signal at pH 4.8 and 10.4 was attributed to the formation of the species 3SH2(2+) and 3S, respectively. The enthalpy changes associated with the proton-transfer reactions of 3SH+, calculated from the values of the heat released as obtained by TRP, were in remarkable agreement with the values estimated from the thermodynamic data of the acid-base equilibria of the triplet states of the dye. The formation of 3SH+ was accompanied by a volume expansion of 1.8 cm3 mol(-1), which was explained by changes in the hydrogen-bonding interaction of the dye with its solvation sphere. Instead, the volume changes observed upon the formation of 3SH2(2-) and 3S accounted for the electrostrictive effect produced by the change in the charge distribution on the dye after the proton-transfer reaction.

  12. Excited state intramolecular charge transfer reaction in non-aqueous reverse micelles: Effects of solvent confinement and electrolyte concentration

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Harun Al Rasid Gazi; Biswajit Guchhait; Ranjit Biswas

    2012-03-01

    Steady state and time resolved fluorescence emission spectroscopy have been employed to investigate the effects of solvent confinement and electrolyte concentration on excited state intramolecular charge transfer (ICT) reaction in 4-(1-pyrrolidinyl) benzonitrile (P5C), 4-(1-piperidinyl) benzonitrile (P6C), and 4-(1-morpholenyl) benzonitrile (M6C) in AOT/n-heptane/acetonitrile and AOT/n-heptane/methanol reverse micelles. Dramatic confinement effects have been revealed via a huge reduction (factor ranging between 100 and 20) over bulk values of both equilibrium and reaction rate constants. A strong dependence on the size of the confinement () of these quantities has also been observed. dependent average static dielectric constant, viscosity and solvation time-scale have been determined. Estimated dielectric constants for confined methanol and acetonitrile show a decrease from the respective bulk values by a factor of 3-5 and viscosities increased by a factor of 2 at the highest considered. Addition of electrolyte at = 5 for acetonitrile is found to produce a linear increase of confined solvent viscosity but leads to a non-monotonic electrolyte concentration dependence of average solvation time. Reaction rate constant is found to decrease linearly with electrolyte concentration for P5C and P6C but non-monotonically for M6C, the highest decrease for all the molecules being ∼ 20% over the value in the absence of added electrolyte in the solvent pool. The observed huge reduction in reaction rate constant is attributed to the effects of decreased solution polarity, enhanced viscosity and slowed-down solvent reorganization of the solvent under confinement in these non-aqueous reverse micelles.

  13. Vibrational population distributions of the product of the chemiluminescent charge transfer reaction: O + (2D)+HCl --> O+HCl + (A 2Sigma + )

    Science.gov (United States)

    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).

  14. Testing two-nucleon transfer reaction mechanism with elementary modes of excitation in exotic nuclei

    CERN Document Server

    Broglia, R A; Idini, A; Barranco, F; Vigezzi, E

    2015-01-01

    Nuclear Field Theory of structure and reactions is confronted with observations made on neutron halo dripline nuclei, resulting in the prediction of a novel (symbiotic) mode of nuclear excitation, and on the observation of the virtual effect of the halo phenomenon in the apparently non-halo nucleus $^7$Li. This effect is forced to become real by intervening the virtual process with an external (t,p) field which, combined with accurate predictive abilities concerning the absolute differential cross section, reveals an increase of a factor 2 in the cross section due to the presence of halo ground state correlations, and is essential to reproduce the value of the observed $d \\sigma(^7$Li(t,p)$^9$Li)/d$\\Omega$.

  15. Impact of Chemical Reaction on MHD Mixed Convection Heat and Mass Transfer Flow with Thermophoresis

    Directory of Open Access Journals (Sweden)

    Prabir Kumar KUNDU

    2014-02-01

    Full Text Available A mathematical model is analyzed in order to study the effects of chemical reaction and thermophoresis on MHD mixed convection boundary layer flow of an incompressible, electrically conducting fluid past a heated vertical permeable flat plate embedded in a uniform porous medium, by taking into account the radiative heat flux and variable suction. The governing partial differential equations are transformed into a set of coupled ordinary differential equations which are solved analytically using the regular perturbation technique. Numerical results for dimensionless velocity, temperature, concentration as well as the skin friction coefficient, Nusselt number and Sherwood number are presented through graphs and a table for pertinent parameters to show interesting aspects of the solution.doi:10.14456/WJST.2014.35

  16. Charge-transfer processes and redox reactions in planar lipid monolayers and bilayers.

    Science.gov (United States)

    Krysiñki, P; Tien, H T; Ottova, A

    1999-01-01

    Supported bilayer lipid membranes (BLMs) and lipid monolayers have been known for quite sometime and are attracting sustained interest since they open new research vista and offer practical approaches in biosensor development and molecular device applications. Central to these areas of interest are electric processes and redox reactions where the movement of ions and electrons plays a pivotal role. In this paper an overview of the major findings in this field is presented. Further, we summarize the work on planar lipid bilayers and monolayers that have been done in the past few years in a number of laboratories. Supported planar BLMs and their closely related systems provide the foundation for a variety of lipid bilayer-based molecular sensors that are sensitive, versatile, as well as potentially inexpensive (i.e., disposable), and open to all sorts of experimentation.

  17. Conformational changes of active site of copper zinc superoxide dismutase can be detected sensitively by electron-transfer reaction

    Institute of Scientific and Technical Information of China (English)

    舒占永

    1996-01-01

    The electron-transfer (ET) reaction between Fe(CN)64- and copper zinc superoxide dismutase (CuZn-SOD) occurs at the active site of the enzyme. The ET parameters which are sensitive to the denaturation have been used to determine the conformational changes of the active site induced by guanidine hydrochloride and thermal denaturation. The decreases of ET rates for all the denatured enzyme samples reflect the collapse of the active cavity of enzyme in the unfolding processes. The interesting changes of ET amplitude for the enzyme denatured at different pH values suggest that electrostatic interaction plays an important role in the conformational changes of active site. From the results of the kinetic analyses, it is concluded that the conformational changes of the active site are parallel with the inactivation.

  18. Membrane inlet proton transfer reaction mass spectrometry (MI-PTRMS) for direct measurements of VOCs in water

    Science.gov (United States)

    Boscaini, Elena; Alexander, Michael L.; Prazeller, Peter; Märk, Tilmann D.

    2004-12-01

    The use of a membrane inlet proton transfer reaction mass spectrometry (MI-PTRMS) system was investigated for the quantitative analysis of VOCs directly from water. Compounds playing an important role in environmental, biological and health issues such as methanol, acetonitrile, acetone, dimethylsulfide (DMS), isoprene, benzene, and toluene have been analyzed both in fresh and salty water. The system shows very good sensitivity, reproducibility, and a linear response of up to five orders of magnitude. The detection limit for DMS is about 100 ppt and for methanol is about 10 ppb both in fresh and salty water. The response time of the various compounds across the membrane is on the order of a few minutes. This fast response and the fact that the PTRMS can perform absolute measurements without the necessity of calibration make the system suitable for on-line and -site measurements of VOCs directly from water.

  19. Analysis of heat and mass transfer with MHD and chemical reaction effects on viscoelastic fluid over a stretching sheet

    Science.gov (United States)

    Mishra, S. R.; Pattnaik, P. K.; Bhatti, M. M.; Abbas, T.

    2017-10-01

    This article addresses the mass and heat transfer analysis over an electrically conducting viscoelastic (Walters B') fluid over a stretching surface in presence of transverse magnetic field. The impact of chemical reaction, as well as non-uniform heat source, are also taken into account. Similarity transformations are employed to model the equations. The governing equations comprises of momentum, energy, and concentration which are modified to a set of non-linear differential equations and then solved by applying confluent hypergeometric function known as " Kummer's function". The exact solution for heat equation is obtained for two cases i.e. (1) Prescribed surface temperature, (2) Prescribed wall heat flux. Physical behavior of all the sundry parameters are against concentration, temperature, and velocity profile are presented through graphs. The inclusion of magnetic field is counterproductive in diminishing the velocity distribution whereas reverse effect is encountered for concentration and temperature profiles.

  20. Versatile In Situ Generated N-Boc-Imines: Application to Phase-Transfer-Catalyzed Asymmetric Mannich-Type Reactions.

    Science.gov (United States)

    Kano, Taichi; Kobayashi, Ryohei; Maruoka, Keiji

    2015-07-13

    The efficient construction of nitrogen-containing organic compounds is a major challenge in chemical synthesis. Imines are one of the most important classes of electrophiles for this transformation. However, both the available imines and applicable nucleophiles for them are quite limited given the existing preparative methods. Described herein are imine precursors which generate reactive imines with a wide variety of substituents under mild basic conditions. This approach enables the construction of various nitrogen-containing molecules which cannot be accessed by the traditional approach. The utility of the novel imine precursor was demonstrated in the asymmetric Mannich-type reaction under phase-transfer conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Experimental study of bound states in $^{12}$Be through low-energy $^{11}$Be($d,p$)-transfer reactions

    CERN Document Server

    Johansen, J G; Borge, M J G; Cubero, M; Diriken, J; Elsevier, J; Fraile, L M; Fynbo, H O U; Gaffney, L P; Gernhäuser, R; Jonson, B; Koldste, G T; Konki, J; Kröll, T; Krücken, R; Mücher, D; Nilsson, T; Nowak, K; Pakarinen, J; Pesudo, V; Raabe, R; Riisager, K; Seidlitz, M; Tengblad, O; Törnqvist, H; Voulot, D; Warr, N; Wenander, F; Wimmer, K; De Witte, H

    2013-01-01

    The bound states of $^{12}$Be have been studied through a $^{11}$Be$(d,p)^{12}$Be transfer reaction experiment in inverse kinematics. A 2.8 MeV/u beam of $^{11}$Be was produced using the REX-ISOLDE facility at CERN. The outgoing protons were detected with the T-REX silicon detector array. The MINIBALL germanium array was used to detect $\\gamma$-rays from the excited states in $^{12}$Be. The $\\gamma$-ray detection enabled a clear identification of the four known bound states in $^{12}$Be, and each of the states has been studied individually. Differential cross sections over a large angular range have been extracted. Spectroscopic factors for each of the states have been determined from DWBA calculations and have been compared to previous experimental and theoretical results.

  2. Monte Carlo simulation of transfer reactions using extended R-matrix theory picturing surrogate-type WFCF features

    Science.gov (United States)

    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. Effects of magnetic, radiation and chemical reaction on unsteady heat and mass transfer flow of an oscillating cylinder

    Science.gov (United States)

    Ahmed, Rubel; Rana, B. M. Jewel; Ahmmed, S. F.

    2017-06-01

    The effects of magnetic, radiation and chemical reaction parameters on the unsteady heat and mass transfer boundary layer flow past an oscillating cylinder is considered. The dimensionless momentum, energy and concentration equations are solved numerically by using explicit finite difference method with the help of a computer programming language Compaq visual FORTRAN 6.6a. The obtained results of this study have been discussed for different values of well-known parameters with different time steps. The effect of these parameters on the velocity field, temperature field and concentration field, skin-friction, Nusselt number, streamlines and isotherms has been studied and results are presented by graphically represented by the tabular form quantitatively. The stability and convergence analysis of the solution parameters that have been used in the mathematical model have been tested.

  4. Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3P ruthenium pincer complex under base-free Conditions

    KAUST Repository

    He, Lipeng

    2012-03-01

    A dearomatized complex [RuH(PN 3P)(CO)] (PN 3PN, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN 3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. © 2011 Elsevier B.V. All rights reserved.

  5. ELECTRON-TRANSFER REACTIONS OF CROSSLINKED POLY(1-PYRIDINIOMETHYL)STYRENE CHLORIDE 2. REDUCTION OF NITRO-COMPOUNDS

    Institute of Scientific and Technical Information of China (English)

    NI Yushan; SHAO Yunglin; XU Jiping

    1984-01-01

    Continuing the study of electron transfer reactions of polypyridiniomethylstyrene chloride (PSPyCl), the reduction of nitro-compounds by the PSPyCl-Zn system was investigated. In general azoxy compounds were obtained as chief intermediate product of reduction. Reduction of nitrobenzo-15-crown-5 and its homologues give a new class of bis-crown ether compounds--azoxy-bisbenzocrown ethers. Azoxybisbenzocrown ethers undergo photoinduced trans-cis isomerization,which is reversible on irradiation with UV and on storage in darkness, similar to the case of azobiscrown ethers. Investigation of solvent extraction of various cations by azobiscrown ether isomers shows that cis-azoxybisbenzo-15-crown-5 exhibit good selectivity toward Nd3+ from other rare earth cations.

  6. Rapid detection of meat spoilage by measuring volatile organic compounds by using proton transfer reaction mass spectrometry.

    Science.gov (United States)

    Mayr, D; Margesin, R; Klingsbichel, E; Hartungen, E; Jenewein, D; Schinner, F; Märk, T D

    2003-08-01

    The evolution of the microbial spoilage population for air- and vacuum-packaged meat (beef and pork) stored at 4 degrees C was investigated over 11 days. We monitored the viable counts (mesophilic total aerobic bacteria, Pseudomonas spp., Enterobacteriaceae, lactic acid bacteria, and Enterococcus spp.) by the microbiological standard technique and by measuring the emission of volatile organic compounds (VOCs) with the recently developed proton transfer reaction mass spectrometry system. Storage time, packaging type, and meat type had statistically significant (P meat. We found statistically significant strong correlations (up to 99%) between some of the VOCs and the bacterial contamination. The concentrations of these VOCs increased linearly with the bacterial numbers. This study is a first step toward replacing the time-consuming plate counting by fast headspace air measurements, where the bacterial spoilage can be determined within minutes instead of days.

  7. 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.

    Science.gov (United States)

    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.

  8. Side chain effects in reactions of the potassium-tyrosine charge transfer complex

    Science.gov (United States)

    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.

  9. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: 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 (-NH{sub 2}) 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

  10. Teleportation of a two-particle four-component squeezed vacuum state by linear optical elements

    Institute of Scientific and Technical Information of China (English)

    Huina Chen; Jinming Liu

    2009-01-01

    We present a linear optical scheme for achieving a unity fidelity teleportation of a two-particle four component squeezed vacuum state using two entangled squeezed vacuum states as quantum channel.The devices used are beam splitters and ideal photon detectors capable of distinguishing between odd and even photon numbers.Moreover,we also obtain the success probability of the teleportation scheme.

  11. Suppression and Two-Particle Correlations of Heavy Mesons in Heavy-Ion Collisions

    Science.gov (United States)

    Cao, Shanshan; Qin, Guang-You; Bass, Steffen A.

    2016-12-01

    We study the medium modification of heavy quarks produced in heavy-ion collisions. The evolution of heavy quarks inside the QGP is described using a modified Langevin framework that simultaneously incorporates their collisional and radiative energy loss. Within this framework, we provide good descriptions of the heavy meson suppression and predictions for the two-particle correlation functions of heavy meson pairs.

  12. Inertialess Velocity Change and a Two Particle Model of the Photon

    OpenAIRE

    David L. Spencer

    2017-01-01

    Building on the idea presented earlier that the gravitational fields outside of basic particles are those particles’ inertia and that acceleration results only from inertial field imbalances, inertialess velocity changes may result when motivation for motion arises from within basic particles. A two particle model of the photon shows how this might work

  13. Computer simulation of the collision frequency of two particles in optical tweezers

    Institute of Scientific and Technical Information of China (English)

    Xu Sheng-Hua; Li Yin-Mei; Lou Li-Ren; Sun Zhi-Wei

    2005-01-01

    Optical tweezers have been successfully used in the study of colloid science. In most applications people are concerned with the behaviour of a single particle held in the optical tweezers. Recently, the ability of the optical tweezers to simultaneously hold two particles has been used to determine the stability ratio of colloidal dispersion. This new development stimulates the efforts to explore the characteristics of a two-particle system in the optical tweezers.An infinite spherical potential well has been used to estimate the collision frequency for two particles in the optical trap based on a Monte Carlo simulation. In this article, a more reasonable harmonic potential, commonly accepted for the optical tweezers, is adopted in a Monte Carlo simulation of the collision frequency. The effect of hydrodynamic interaction of particles in the trap is also considered. The simulation results based on this improved model show quantitatively that the collision frequency drops down sharply at first and then decreases slowly as the distance between the two particles increases. The simulation also shows how the collision frequency is related to the stiffness of the optical tweezers.

  14. An Exact Solution to the Two-Particle Boltzmann Equation System for Maxwell Gases

    Institute of Scientific and Technical Information of China (English)

    布仁满都拉; 赵迎春

    2012-01-01

    An exact solution to the two-particle Boltzmann equation system for Maxwell gases is obtained with use of Bobylev approach.The relationship between the exact solution and the self-similar solution of the boltzmann equation is also given.

  15. Conservation in two-particle self-consistent extensions of dynamical mean-field theory

    Science.gov (United States)

    Krien, Friedrich; van Loon, Erik G. C. P.; Hafermann, Hartmut; Otsuki, Junya; Katsnelson, Mikhail I.; Lichtenstein, Alexander I.

    2017-08-01

    Extensions of dynamical mean-field theory (DMFT) make use of quantum impurity models as nonperturbative and exactly solvable reference systems which are essential to treat the strong electronic correlations. Through the introduction of retarded interactions on the impurity, these approximations can be made two-particle self-consistent. This is of interest for the Hubbard model because it allows to suppress the antiferromagnetic phase transition in two dimensions in accordance with the Mermin-Wagner theorem, and to include the effects of bosonic fluctuations. For a physically sound description of the latter, the approximation should be conserving. In this paper, we show that the mutual requirements of two-particle self-consistency and conservation lead to fundamental problems. For an approximation that is two-particle self-consistent in the charge and longitudinal spin channels, the double occupancy of the lattice and the impurity is no longer consistent when computed from single-particle properties. For the case of self-consistency in the charge and longitudinal as well as transversal spin channels, these requirements are even mutually exclusive so that no conserving approximation can exist. We illustrate these findings for a two-particle self-consistent and conserving DMFT approximation.

  16. "Abnormal" salt and solvent effects on anion/cation electron-transfer reactions: an interpretation based on Marcus-Hush treatment.

    Science.gov (United States)

    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.

  17. Cyclic voltammetry and scanning electrochemical microscopy studies of the heterogeneous electron transfer reaction of some nitrosoaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bollo, S.; Finger, S.; Sturm, J.C.; Nunez-Vergara, L.J.; Squella, J.A. [Bioelectrochemistry Laboratory, Chemical and Pharmaceutical Sciences Faculty, University of Chile, P.O. Box 233, Santiago 1 (Chile)

    2007-04-20

    The heterogeneous electron transfer reaction for the reduction of some nitroso aromatic derivatives in aqueous-alcoholic medium was studied on both mercury and glassy carbon electrodes (GCE) by using cyclic voltammetry (CV) and scanning electrochemical microscopy techniques (SECM). The nitrosoaromatic derivatives followed a two-electron two-proton mechanism producing a quasi-reversible overall process. This strongly pH dependent mechanism varied from ECCE mechanism at pH < 8.5 to ECEC mechanism at pH > 8.5. The apparent heterogeneous rate constant for the reduction of the nitroso derivatives was calculated using CV or SECM. The rate constant for the electron transfer process depends on the nature of the electrode material. The heterogeneous rate constant on the GCE is almost two orders of magnitude smaller than that on mercury electrode i.e. (3.4 {+-} 0.3) x 10{sup -3} cm s{sup -1} on Hg and (7.0 {+-} 1.0) x 10{sup -5} cm s{sup -1} on GCE, for the same nitroso compound and pH. The heterogeneous rate constant values were checked by comparison between experimental and simulated cyclic voltammograms. (author)

  18. Transfer reaction measurements and the stellar nucleosynthesis of 26Al and 44Ti

    CERN Document Server

    AUTHOR|(CDS)2086831

    Progress in the description of stellar evolution is driven by the collaborative effort of nuclear physics, astrophysics and astronomy. Using those developments, the theory of the origin of elements in the Universe is challenged. This thesis addresses the problem behind the abundance of 44Ti and the origin of 26Al. The mismatch between the predicted abundance of 44Ti as produced by the only sites known to be able to create 44Ti, core collapse supernovae (CCSNe), and the observations, highlight the current uncertainty that exists in the physics of these stars. Several satellite based gamma-ray observations of the isotope 44Ti have been reported in recent times and conrm the disagreement. As the amount of this isotope in stellar ejecta is thought to critically depend on the explosion mechanism, the ability to accurately model the observed abundance would be a pivotal step towards validating that theory. The most in influential reaction to the amount of 44Ti in supernovae is 44Ti(alpha, p)47V. Here we report on a...

  19. Study of the 66Ni(t,d)67Ni Transfer Reaction in Inverse Kinematics

    CERN Document Server

    Callens, Maarten

    The nickel isotopes with 28 protons are an interesting series in the study of nuclear structure. In the framework of the shell model nickel has a closed proton shell and the number of neutrons ranges from the magic numbers 20 to 50. The neutron-rich isotope $^{78}$Ni, is a waiting point in the nucleosynthesis r-process. In this process an intense neutron flux such as in supernovae results in the rapid capture of neutrons. The reaction sequence halts at $^{78}$Ni and waits for this nucleus to decay [Hea05]. For several decades the nickel isotopes have been studied extensively, particularly how the nuclear structure evolves when moving to the exotic boundaries of the nuclear chart. A remarkable feature was observed in $^{68}$Ni. This nucleus with 40 neutrons exhibits properties that are characteristic for doubly magic nuclei. Such as the energy of the first 2$^+$ state lies significantly higher than in neighbouring even-A isotopes, and is also higher than the energy of the second 0$^+$ state. Moreover also the ...

  20. Electron transfer kinetics in purified reaction centers from the green sulfur bacterium Chlorobium tepidum studied by multiple-flash excitation.

    Science.gov (United States)

    Kusumoto, N; Sétif, P; Brettel, K; Seo, D; Sakurai, H

    1999-09-14

    Reaction center preparations from the green sulfur bacterium Chlorobium tepidum, which contain monoheme cytochrome c, were studied by flash-absorption spectroscopy in the near-UV, visible, and near-infrared regions. The decay kinetics of the photooxidized primary donor P840(+), together with the amount of photooxidized cytochrome c, were analyzed along a series of four flashes spaced by 1 ms: 95% of the P840(+) was reduced by cytochrome c with a t(1/2) of approximately 65 micros after the first flash, 80% with a t(1/2) of approximately 100 micros after the second flash, and 23% with a t(1/2) of approximately 100 micros after the third flash; after the fourth flash, almost no cytochrome c oxidation occurred. The observed rates, the establishment of redox equilibrium after each flash, and the total amount of photooxidizable cytochrome c are consistent with the presence of two equivalent cytochrome c molecules per photooxidizable P840. The data are well fitted assuming a standard free energy change DeltaG degrees of -53 meV for electron transfer from one cytochrome c to P840(+), DeltaG degrees being independent of the oxidation state of the other cytochrome c. These observations support a model with two monoheme cytochromes c which are symmetrically arranged around the reaction center core. From the ratio of menaquinone-7 to the bacteriochlorophyll pigment absorbing at 663 nm, it was estimated that our preparations contain 0.6-1.2 menaquinone-7 molecules per reaction center. However, no transient signal due to menaquinone could be observed between 360 and 450 nm in the time window from 10 ns to 4 micros. No recombination reaction between the primary partners P840(+) and A(0)(-) could be detected under normal conditions. Such a recombination was observed (t(1/2) approximately 19 ns) under highly reducing conditions or after accumulation of three electrons on the acceptor side during a series of flashes, showing that the secondary acceptors can stabilize three electrons

  1. Spectrophotometric Determination of Some Fluoroquinolone Antibacterials through Charge-transfer and Ion-pair Complexation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    El-Brashy, Amina Mohamed; El-Sayed Metwally Mohamed; El-Sepai, Fawzi Abdallah [University of Mansoura, Mansoura (Egypt)

    2004-03-15

    Two simple, rapid and sensitive spectrophotometric methods for the determination of three fluoroquinolones, namely levofloxacin, norfloxacin and ciprofloxacin have been performed either in pure form or in their tablets. In the first method, levofloxacin and norfloxacin are directly treated with bromocresol green (BCG) in dichloromethane while ciprofloxacin is allowed to react with the same dye in aqueous acidic buffer. Highly yellow colored complex species were formed instantaneously in case of levofloxacin and norfloxacin or after extraction into dichloromethane for ciprofloxacin. The formed complexes are quantified spectrophotometrically at their absorption maxima at 411 nm for levofloxacin and 412 nm for norfloxacin and ciprofloxacin. The second method involves the reaction of levofloxacin with {rho}-chloranilic acid ({rho}-CA) and norfloxacin with tetracyanoethylene (TCNE) in acetonitrile to give complexes with maximum absorbance at 521 and 333 nm for the two drugs, respectively. Adopting the first procedure, calibration graphs were linear over the range 1- 20 {mu}g mL{sup .1} with mean percentage recoveries of 100.41 {+-} 0.72, 99.99 {+-} 0.54 and 100.23 {+-} 0.91 for the three drugs, respectively. For the second procedure, the concentration ranges were 15-250 {mu}g mL{sup .1} for levofloxacin using {rho}-CA and 0.8-16 {mu}g mL{sup .1} for norfloxacin using TCNE with mean percentage recoveries of 99.88 {+-} 0.45 and 100.26 {+-} 0.68 for the two drugs, respectively. The proposed methods were successfully applied to determine these drugs in their tablet formulations and the results compared favorably to that of reference methods. The proposed methods are recommended for quality control and routine analysis

  2. Reproducibility of creatine kinase reaction kinetics in human heart: a (31) P time-dependent saturation transfer spectroscopy study.

    Science.gov (United States)

    Bashir, Adil; Gropler, Robert

    2014-06-01

    Creatine kinase (CK) is essential for the buffering and rapid regeneration of adenosine triphosphate (ATP) in heart tissue. Herein, we demonstrate a (31) P MRS protocol to quantify CK reaction kinetics in human myocardium at 3 T. Furthermore, we sought to quantify the test-retest reliability of the measured metabolic parameters. The method localizes the (31) P signal from the heart using modified one-dimensional image-selected in vivo spectroscopy (ISIS), and a time-dependent saturation transfer (TDST) approach was used to measure CK reaction parameters. Fifteen healthy volunteers (22 measurements in total) were tested. The CK reaction rate constant (kf ) was 0.32 ± 0.05 s(-1) and the coefficient of variation (CV) was 15.62%. The intrinsic T1 for phosphocreatine (PCr) was 7.36 ± 1.79 s with CV = 24.32%. These values are consistent with those reported previously. The PCr/ATP ratio was equal to 1.94 ± 0.15 with CV = 7.73%, which is within the range of healthy subjects. The reproducibility of the technique was tested in seven subjects and inferred parameters, such as kf and T1 , exhibited good reliability [intraclass correlation coefficient (ICC) of 0.90 and 0.79 for kf and T1 , respectively). The reproducibility data provided in this study will enable the calculation of the power and sample sizes required for clinical and research studies. The technique will allow for the examination of cardiac energy metabolism in clinical and research studies, providing insight into the relationship between energy deficit and functional deficiency in the heart.

  3. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach.

    Science.gov (United States)

    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.

  4. Rhodium-catalyzed acyl-transfer reaction between benzyl ketones and thioesters: synthesis of unsymmetric ketones by ketone CO-C bond cleavage and intermolecular rearrangement.

    Science.gov (United States)

    Arisawa, Mieko; Kuwajima, Manabu; Toriyama, Fumihiko; Li, Guangzhe; Yamaguchi, Masahiko

    2012-07-20

    In the presence of catalytic amounts of RhH(CO)(PPh3)3 and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of ketone CO-C bonds and intermolecular rearrangement giving unsymmetric ketones. The acyl-transfer reaction also occurred with 1-(p-chlorophenyl)-3-(p-cyanophenyl)propane-2-one giving unsymmetric ketones.

  5. 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

    Science.gov (United States)

    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.

  6. Why does neutron transfer play different roles in sub-barrier fusion reactions $^{32}$S+$^{94,96}$Zr and $^{40}$Ca+$^{94,96}$Zr?

    CERN Document Server

    Sargsyan, V V; Antonenko, N V; Scheid, W; Zhang, H Q

    2014-01-01

    The sub-barrier capture (fusion) reactions $^{32}$S+$^{90,94,96}$Zr, $^{36}$S+$^{90,96}$Zr, $^{40}$Ca+$^{90,94,96}$Zr, and $^{48}$Ca+$^{90,96}$Zr with positive and negative $Q$-values for neutron transfer are studied within the quantum diffusion approach and the universal fusion function representation. For these systems, the s-wave capture probabilities are extracted from the experimental excitation functions and are also analyzed. Different effects of the positive $Q_{xn}$-value neutron transfer in the fusion enhancement are revealed in the relatively close reactions $^{32}$S+$^{94,96}$Zr and $^{40}$Ca+$^{94,96}$Zr.

  7. Spectroscopic investigation on kinetics, thermodynamics and mechanism for electron transfer reaction of iron(III) complex with sulphur centered radical in stimulated biological system.

    Science.gov (United States)

    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.

  8. Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers.

    Science.gov (United States)

    Waidmann, Christopher R; Zhou, Xin; Tsai, Erin A; Kaminsky, Werner; Hrovat, David A; Borden, Weston Thatcher; Mayer, James M

    2009-04-08

    Reactions are described that interconvert vanadium(IV) oxo-hydroxo complexes [V(IV)O(OH)(R(2)bpy)(2)]BF(4) (1a-c) and vanadium(V) dioxo complexes [V(V)O(2)(R(2)bpy)(2)]BF(4) (2a-c) [R(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy), a; 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), b; 2,2'-bipyridine (bpy), c]. These are rare examples of pairs of isolated, sterically unencumbered, first-row metal-oxo/hydroxo complexes that differ by a hydrogen atom (H(+) + e(-)). The V(IV)-(t)Bu(2)bpy derivative 1a has a useful (1)H NMR spectrum, despite being paramagnetic. Complex 2a abstracts H(*) from organic substrates with weak O-H and C-H bonds, converting 2,6-(t)Bu(2)-4-MeO-C(6)H(2)OH (ArOH) and 2,2,6,6-tetramethyl-N-hydroxypiperidine (TEMPOH) to their corresponding radicals ArO(*) and TEMPO, hydroquinone to benzoquinone, and dihydroanthracene to anthracene. The equilibrium constant for 2a + ArOH 1a + ArO(*) is (4 +/- 2) x 10(-3), implying that the VO-H bond dissociation free energy (BDFE) is 70.6 +/- 1.2 kcal mol(-1). Consistent with this value, 1a is oxidized by 2,4,6-(t)Bu(3)C(6)H(2)O(*). All of these reactions are surprisingly slow, typically occurring over hours at ambient temperatures. The net hydrogen-atom pseudo-self-exchange 1a + 2b 2a + 1b, using the (t)Bu- and Me-bpy substituents as labels, also occurs slowly, with k(se) = 1.3 x 10(-2) M(-1) s(-1) at 298 K, DeltaH(double dagger) = 15 +/- 2 kcal mol(-1), and DeltaS(double dagger) = 16 +/- 5 cal mol(-1) K. Using this k(se) and the BDFE, the vanadium reactions are shown to follow the Marcus cross relation moderately well, with calculated rate constants within 10(2) of the observed values. The vanadium self-exchange reaction is ca. 10(6) slower than that for the related Ru(IV)O(py)(bpy)(2)(2+)/Ru(III)OH(py)(bpy)(2)(2+) self-exchange. The origin of this dramatic difference has been probed with DFT calculations on the self-exchange reactions of 1c + 2c and on monocationic ruthenium complexes with pyrrolate or

  9. Synthesis of 2'(3')-O-DL-alanyl hexainosinic acid using T4 RNA ligase: suppression of the enzymic reverse transfer reaction by alkaline phosphatase.

    Science.gov (United States)

    Profy, A T; Lo, K M; Usher, D A

    1983-03-11

    2'(3')-O-DL-Alanyl (Ip)5I was synthesized by a new method. An alanine ortho ester of inosine 5'-phosphate was added to (Ip)4I using the ATP-independent reaction of T4 RNA ligase, and the product was converted smoothly to the desired ester. The enzymic reverse transfer reaction was conveniently suppressed by the dephosphorylation of the adenosine 5'-phosphate coproduct, catalyzed in situ by alkaline phosphatase.

  10. Photochemistry with fast sample renewal using cluster beams: formation of rare-gas halides in charge-transfer reactions in NF 3-doped rare-gas clusters

    Science.gov (United States)

    Moussavizadeh, L.; von Haeften, K.; Museur, L.; Kanaev, A. V.; Castex, M. C.; von Pietrowski, R.; Möller, T.

    1999-05-01

    Charge transfer reactions in free clusters are observed in a photoluminescence study on doped rare-gas clusters (Rg clusters, Rg=Ar, Kr and Xe). Following photoexcitation into the first absorption bands of Rg clusters, fluorescence from free RgF* excimers ejected from the clusters and from Rg 2F* excimers localized in the interior of the clusters is observed. The results show that the reaction dynamics in clusters differs considerably from that in the gas and solid phase.

  11. A Lattice Gas Automata Model for the Coupled Heat Transfer and Chemical Reaction of Gas Flow Around and Through a Porous Circular Cylinder

    Directory of Open Access Journals (Sweden)

    Hongsheng Chen

    2015-12-01

    Full Text Available Coupled heat transfer and chemical reaction of fluid flow in complex boundaries are explored by introducing two additional properties, i.e. particle type and energy state into the Lattice gas automata (LGA Frisch–Hasslacher–Pomeau (FHP-II model. A mix-redistribute of energy and type of particles is also applied on top of collision rules to ensure randomness while maintaining the conservation of mass, momentum and energy. Simulations of heat transfer and heterogeneous reaction of gas flow passing a circular porous cylinder in a channel are presented. The effects of porosity of cylinder, gas inlet velocity, and reaction probability on the reaction process are further analyzed with respect to the characteristics of solid morphology, product concentration, and temperature profile. Numerical results indicate that the reaction rate increases with increasing reaction probability as well as gas inlet velocity. Cylinders with a higher value of porosity and more homogeneous structure also react with gas particles faster. These results agree well with the basic theories of gas–solid reactions, indicating the present model provides a method for describing gas–solid reactions in complex boundaries at mesoscopic level.

  12. Measuring acetic and formic acid by proton transfer reaction-mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    Science.gov (United States)

    Baasandorj, M.; Millet, D. B.; Hu, L.; Mitroo, D.; Williams, B. J.

    2014-10-01

    We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA) and their relevant mass analogues by proton transfer reaction-mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. On the other hand, for E/N = 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5-20× lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is product ions of AA, glycoaldehyde, and propanols occur at m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (<∼100 Td). Addition of water vapor affects the PTR-MS response to a given compound by (i) changing the yield for fragmentation reactions, and (ii) increasing the importance of ligand switching reactions. In the case of AA, sensitivity to the molecular ion increases with humidity at low E/N, but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycoaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N) and reduced fragmentation in the presence of water (at high E/N). Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the humidity effect depends strongly on the collisional energy in the drift tube, simple humidity correction factors (XR) will only be

  13. Measuring acetic and formic acid by proton-transfer-reaction mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    Science.gov (United States)

    Baasandorj, M.; Millet, D. B.; Hu, L.; Mitroo, D.; Williams, B. J.

    2015-03-01

    We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA), and their relevant mass analogues by proton-transfer-reaction mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate, and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. For a reduced electric field (E/N) of 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5-20 times lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is product ions of AA, glycolaldehyde, and propanols occur at m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (≲100 Td). Addition of water vapor affects the PTR-MS response to a given compound by (i) changing the yield for fragmentation reactions and (ii) increasing the importance of ligand switching reactions. In the case of AA, sensitivity to the molecular ion increases with humidity at low E/N but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycolaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N) and reduced fragmentation in the presence of water (at high E/N). Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the humidity effect depends strongly on the collisional energy in the drift tube, simple humidity correction factors (XR

  14. Two-particle scattering on the lattice: Phase shifts, spin-orbit coupling, and mixing angles

    CERN Document Server

    Borasoy, Bugra; Krebs, Hermann; Lee, Dean; Meißner, Ulf-G

    2007-01-01

    We determine two-particle scattering phase shifts and mixing angles for quantum theories defined with lattice regularization. The method is suitable for any nonrelativistic effective theory of point particles on the lattice. In the center-of-mass frame of the two-particle system we impose a hard spherical wall at some fixed large radius. For channels without partial-wave mixing the partial-wave phase shifts are determined from the energies of the nearly-spherical standing waves. For channels with partial-wave mixing further information is extracted by decomposing the standing wave at the wall boundary into spherical harmonics, and we solve coupled-channels equations to extract the phase shifts and mixing angles. The method is illustrated and tested by computing phase shifts and mixing angles on the lattice for spin-1/2 particles with an attractive Gaussian potential containing both central and tensor force parts.

  15. Two-particle anomalous diffusion: probability density functions and self-similar stochastic processes.

    Science.gov (United States)

    Pagnini, Gianni; Mura, Antonio; Mainardi, Francesco

    2013-05-13

    Two-particle dispersion is investigated in the context of anomalous diffusion. Two different modelling approaches related to time subordination are considered and unified in the framework of self-similar stochastic processes. By assuming a single-particle fractional Brownian motion and that the two-particle correlation function decreases in time with a power law, the particle relative separation density is computed for the cases with time sub-ordination directed by a unilateral M-Wright density and by an extremal Lévy stable density. Looking for advisable mathematical properties (for instance, the stationarity of the increments), the corresponding self-similar stochastic processes are represented in terms of fractional Brownian motions with stochastic variance, whose profile is modelled by using the M-Wright density or the Lévy stable density.

  16. Remote preparation of a Greenberger-Home-Zeilinger state via a two-particle entangled state

    Institute of Scientific and Technical Information of China (English)

    Li Hong-Cai; Lin Xiu-Min; Li Xing-Min Hua; Yang Rang-Can

    2007-01-01

    We present two schemes for realizing the remote preparation of a Greenberger- Home- Zeilinger (GHZ) state. The first scheme is to remotely prepare a general N-particle GHZ state with two steps. One is to prepare a qubit state by using finite classical bits from sender to receiver via a two-particle entangled state, and the other is that the receiver introduces N - 1 additional particles and performs N - 1 controlled-not (C-Not) operations. The second scheme is to remotely prepare an JV-atom GHZ state via a two-atom entangled state in cavity quantum electrodynamics (QED). The two schemes require only a two-particle entangled state used as a quantum channel, so we reduce the requirement for entanglement.

  17. A random walk solution for modeling solute transport with network reactions and multi-rate mass transfer in heterogeneous systems: Impact of biofilms

    Science.gov (United States)

    Henri, Christopher V.; Fernàndez-Garcia, Daniel

    2015-12-01

    The interplay between the spatial variability of the aquifer hydraulic properties, mass transfer due to sub-grid heterogeneity and chemical reactions often complicates reactive transport simulations. It is well documented that hydro-biochemical properties are ubiquitously heterogeneous and that diffusion and slow advection at the sub-grid scale typically leads to the conceptualization of an aquifer as a multi-porosity system. Within this context, chemical reactions taking place in mobile/immobile water regions can be substantially different between each other. This paper presents a particle-based method that can efficiently simulate heterogeneity, network reactions and multi-rate mass transfer. The approach is based on the development of transition probabilities that describe the likelihood that particles belonging to a given species and mobile/immobile domain at a given time will be transformed into another species and mobile/immobile domain afterwards. The joint effect of mass transfer and sequential degradation is shown to be non-trivial. A characteristic rebound of degradation products can be observed. This late rebound of concentrations is not driven by any change in the flow regime (e.g., pumping ceases in the pump-and-treat remediation strategy) but due to the natural interplay between mass transfer and chemical reactions. To illustrate that the method can simultaneously represent mass transfer, spatially varying properties and network reactions without numerical problems, we have simulated the degradation of tetrachloroethylene (PCE) in a three-dimensional fully heterogeneous aquifer subjected to rate-limited mass transfer. Two types of degradation modes were considered to compare the effect of an active biofilm with that of clay pods present in the aquifer. Results of the two scenarios display significantly differences. Biofilms that promote the degradation of compounds in an immobile region are shown to significantly enhance degradation, rapidly producing

  18. Scattering resonances and two-particle bound states of the extended Hubbard model

    Energy Technology Data Exchange (ETDEWEB)

    Valiente, M; Petrosyan, D [Institute of Electronic Structure and Laser, FORTH, 71110 Heraklion, Crete (Greece)

    2009-06-28

    We present a complete derivation of two-particle states of the one-dimensional extended Bose-Hubbard model involving attractive or repulsive on-site and nearest-neighbour interactions. We find that this system possesses scattering resonances and two families of energy-dependent interaction-bound states which are not present in the Hubbard model with the on-site interaction alone. (fast track communication)

  19. Probabilistic Teleportation of an Arbitrary Two-Particle State and Its Quantum Circuits

    Institute of Scientific and Technical Information of China (English)

    GUO Zhan-Ying; FANG Jian-Xing; ZHU Shi-Qun; QIAN Xue-Min

    2006-01-01

    Two simple schemes for probabilistic teleportation of an arbitrary unknown two-particle state using a non-maximally entangled EPR pair and a non-maximally entangled GHZ state as quantum channels are proposed.After receiving Alice's Bell state measurement results, Bob performs a collective unitary transformation on his inherent particles without introducing the auxiliary qubit. The original state can be probabilistically teleported. Meanwhile,quantum circuits for realization of successful teleportation are also presented.

  20. Mechanisms and kinetics of noncatalytic ether reaction in supercritical water. 2. Proton-transferred fragmentation of dimethyl ether to formaldehyde in competition with hydrolysis.

    Science.gov (United States)

    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.

  1. Teaching the fundamentals of electron transfer reactions in mitochondria and the production and detection of reactive oxygen species.

    Science.gov (United States)

    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

  2. Teaching the fundamentals of electron transfer reactions in mitochondria and the production and detection of reactive oxygen species

    Directory of Open Access Journals (Sweden)

    Ryan J. Mailloux

    2015-04-01

    Full Text Available 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

  3. A homogeneous quenching resonance energy transfer assay for the kinetic analysis of the GTPase nucleotide exchange reaction.

    Science.gov (United States)

    Kopra, Kari; Ligabue, Alessio; Wang, Qi; Syrjänpää, Markku; Blaževitš, Olga; Veltel, Stefan; van Adrichem, Arjan J; Hänninen, Pekka; Abankwa, Daniel; Härmä, Harri

    2014-07-01

    A quenching resonance energy transfer (QRET) assay for small GTPase nucleotide exchange kinetic monitoring is demonstrated using nanomolar protein concentrations. Small GTPases are central signaling proteins in all eukaryotic cells acting as a "molecular switches" that are active in the GTP-state and inactive in the GDP-state. GTP-loading is highly regulated by guanine nucleotide exchange factors (GEFs). In several diseases, most prominently cancer, this process in misregulated. The kinetics of the nucleotide exchange reaction reports on the enzymatic activity of the GEF reaction system and is, therefore, of special interest. We determined the nucleotide exchange kinetics using europium-labeled GTP (Eu-GTP) in the QRET assay for small GTPases. After GEF catalyzed GTP-loading of a GTPase, a high time-resolved luminescence signal was found to be associated with GTPase bound Eu-GTP, whereas the non-bound Eu-GTP fraction was quenched by soluble quencher. The association kinetics of the Eu-GTP was measured after GEF addition, whereas the dissociation kinetics could be determined after addition of unlabeled GTP. The resulting association and dissociation rates were in agreement with previously published values for H-Ras(Wt), H-Ras(Q61G), and K-Ras(Wt), respectively. The broader applicability of the QRET assay for small GTPases was demonstrated by determining the kinetics of the Ect2 catalyzed RhoA(Wt) GTP-loading. The QRET assay allows the use of nanomolar protein concentrations, as more than 3-fold signal-to-background ratio was achieved with 50 nM GTPase and GEF proteins. Thus, small GTPase exchange kinetics can be efficiently determined in a HTS compatible 384-well plate format.

  4. Kinetic studies on the single electron transfer reaction between 2,2,6,6-tetramethylpiperidine oxoammonium ions and phenothiazines: the application of Marcus theory

    Institute of Scientific and Technical Information of China (English)

    吴隆民; 郭霞; 王隽; 郭庆祥; 刘中立; 刘有成

    1999-01-01

    Electron transfer reactions take place readily between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions (1a, 1b) and phenothiazines (2a—2g), giving corresponding nitroxides (3a, 3b) and phenothiazine radical cations (4a—4g). The rate constants for the electron self-exchange reactions between 1 and 3, as well as between 2 and 4, are determined by EPR and ~1H NMR line-broadening effect in acetonitrile. By application of the Marcus theory, the kinetics of the cross-exchange reactions between 1 and 2 is studied.

  5. Electron Transfer Reaction between M-C6H6 and M+-C6H6 Complexes in the Gas Phase: Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    DFT/BLYP method is used to theoretically investigate the electron transfer (ET) reactions between M (Li, Na, Mg)-C6H6 and M+-C6H6 complexes in the gas phase. The geometry optimization of the precursor complexes and the transition state in the process of ET reaction was performed at 6-31G basis set level. The activation energy, the coupling matrix element and the rate constant of the ET reaction are calculated at semi-quantitative level.

  6. Experimental study of bound states in 12Be through low-energy 11Be(d,p)-transfer reactions

    DEFF Research Database (Denmark)

    Johansen, Jacob S.; Bildstein, V.; Borge, M. J. G.

    2013-01-01

    The bound states of 12Be have been studied through a 11Be(d,p)12Be transfer reaction experiment in inverse kinematics. A 2.8 MeV/u beam of 11Be was produced using the REX-ISOLDE facility at CERN. The outgoing protons were detected with the T-REX silicon detector array. The MINIBALL germanium arra...

  7. Probing the semi-magicity of $^{68}$Ni via the $^{3}$H($^{66}$Ni,$^{68}$Ni)p two-neutron transfer reaction in inverse kinematics

    CERN Multimedia

    Reiter, P; Blazhev, A A; Kruecken, R; Franchoo, S; Mertzimekis, T; Darby, I G; Van de walle, J; Raabe, R; Elseviers, J; Gernhaeuser, R A; Sorlin, O H; Georgiev, G P; Bree, N C F; Habs, D; Chapman, R; Gaudefroy, L; Diriken, J V J; Jenkins, D G; Kroell, T; Axiotis, M; Huyse, M L; Patronis, N

    We propose to perform the two-neutron transfer reaction $^{3}$H($^{66}$Ni, $^{68}$Ni)$p$ using the ISOLDE radioactive ion beam at 2.7 $A$ MeV and the MINIBALL + T-REX setup to characterize the 0$^{+}$ and 2$^{+}$ states in $^{68}$Ni.

  8. Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Floris, V.; Fayoux, S.

    2006-01-01

    The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form (powder/

  9. Proton Transfer Reaction Mass Spectrometry detects rapid changes in volatile metabolite emission by Mycobacterium smegmatis after the addition of specific antimicrobial agents

    NARCIS (Netherlands)

    Crespo, E.; Cristescu, S. M.; de Ronde, H.; Kuijper, S.; Kolk, A.H.J.; Anthony, R.M.; Harren, F. J. M.

    2011-01-01

    The metabolic activity of plants, animals or microbes can be monitored by gas headspace analysis. This can be achieved using Proton Transfer Reaction Mass Spectrometry (PTR-MS), a highly sensitive detection method for trace gas analysis. PTR-MS is rapid and can detect metabolic responses on-line as

  10. Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory—I. Model development and isothermal study

    NARCIS (Netherlands)

    Frank, M.J.W.; Kuipers, J.A.M.; Versteeg, G.F.; Swaaij, W.P.M. van

    1995-01-01

    A general applicable model has been developed which can predict mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to describe th

  11. Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory II. Non-isothermal study

    NARCIS (Netherlands)

    Frank, M.J.W.; Frank, M.J.W.; Kuipers, J.A.M.; Krishna, R.; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    In Part I a general applicable model has been developed which calculates mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to

  12. SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

    Science.gov (United States)

    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...

  13. Influence of the solvent on the ground- and excited-state buffer-mediated proton-transfer reactions of a xanthenic dye.

    Science.gov (United States)

    Paredes, Jose M; Crovetto, Luis; Orte, Angel; Alvarez-Pez, Jose M; Talavera, Eva M

    2011-01-28

    The buffer-mediated proton-transfer reactions of the fluorescent xanthenic derivative 9-[1-(2-Methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II) have been studied in different aqueous media. We have employed various buffers to investigate the influence of donor/acceptor systems with different anion and/or cation chemical constituents on the kinetic parameters of proton-transfer. The kinetic parameters were recovered both in the ground-state by means of Fluorescence Lifetime Correlation Spectroscopy (FLCS) and in the excited-state by means of Time Correlated Single Photon Counting (TCSPC) and Global Compartmental Analysis (GCA). Both ground- and excited- deprotonation and protonation recovered rate constants in the presence of either phosphate or acetate buffer as donor/acceptor systems were similar. The presence of Tris-HCl buffer does not promote the excited-state proton-transfer (ESPT) reaction. The results indicate the influence of the ions on the ground-state proton-transfer (GSPT) rates and concomitantly on the ESPT reaction. The proton-transfer rate constants recovered here show a trend correlated with the Hofmeister series or the Marcus classification of ions.

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

    Science.gov (United States)

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

    2016-10-24

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

  15. Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Aircraft Turbine Engines.

    Science.gov (United States)

    Kilic, Dogushan; Brem, Benjamin T; Klein, Felix; El-Haddad, Imad; Durdina, Lukas; Rindlisbacher, Theo; Setyan, Ari; Huang, Rujin; Wang, Jing; Slowik, Jay G; Baltensperger, Urs; Prevot, Andre S H

    2017-03-17

    Nonmethane organic gas emissions (NMOGs) from in-service aircraft turbine engines were investigated using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an engine test facility at Zurich Airport, Switzerland. Experiments consisted of 60 exhaust samples for seven engine types (used in commercial aviation) from two manufacturers at thrust levels ranging from idle to takeoff. Emission indices (EIs) for more than 200 NMOGs were quantified, and the functional group fractions (including acids, carbonyls, aromatics, and aliphatics) were calculated to characterize the exhaust chemical composition at different engine operation modes. Total NMOG emissions were highest at idling with an average EI of 7.8 g/kg fuel and were a factor of ∼40 lower at takeoff thrust. The relative contribution of pure hydrocarbons (particularly aromatics and aliphatics) of the engine exhaust decreased with increasing thrust while the fraction of oxidized compounds, for example, acids and carbonyls increased. Exhaust chemical composition at idle was also affected by engine technology. Older engines emitted a higher fraction of nonoxidized NMOGs compared to newer ones. Idling conditions dominated ground level organic gas emissions. Based on the EI determined here, we estimate that reducing idle emissions could substantially improve air quality near airports.

  16. Development and characterization of a High-Temperature Proton-Transfer-Reaction Mass Spectrometer (HT-PTR-MS

    Directory of Open Access Journals (Sweden)

    T. Mikoviny

    2010-01-01

    Full Text Available We have developed a High-Temperature Proton-Transfer-Reaction Mass Spectrometer (HT-PTR-MS in which both the ion source and the ion drift tube can be continuously operated at temperatures up to 250 °C. The instrument was characterized in a high E/N-mode (130 Td and in a low E/N-mode (87 Td at an operating temperature of 200 °C. Instrumental sensitivities and 2σ-detection limits were on the order of 50–110 cps/ppb and 100 ppt (1 s signal integration time, respectively. The HT-PTR-MS is primarily intended for measuring "sticky" or semi-volatile trace gases. Alternatively, it may be coupled to a particle collection/thermal desorption apparatus to measure particle-bound organics in near real-time. In view of these applications, we have measured instrumental response times for a series of reference compounds. 1/e2-response times for dimethyl sulfoxide, ammonia and monoethanolamine were in the sub-second to second regime. 1/e2-response times for levoglucosan, oxalic acid and cis-pinonic acid ranged from 8 to 370 s.

  17. Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Cooking Emissions.

    Science.gov (United States)

    Klein, Felix; Platt, Stephen M; Farren, Naomi J; Detournay, Anais; Bruns, Emily A; Bozzetti, Carlo; Daellenbach, Kaspar R; Kilic, Dogushan; Kumar, Nivedita K; Pieber, Simone M; Slowik, Jay G; Temime-Roussel, Brice; Marchand, Nicolas; Hamilton, Jacqueline F; Baltensperger, Urs; Prévôt, André S H; El Haddad, Imad

    2016-02-02

    Cooking processes produce gaseous and particle emissions that are potentially deleterious to human health. Using a highly controlled experimental setup involving a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), we investigate the emission factors and the detailed chemical composition of gas phase emissions from a broad variety of cooking styles and techniques. A total of 95 experiments were conducted to characterize nonmethane organic gas (NMOG) emissions from boiling, charbroiling, shallow frying, and deep frying of various vegetables and meats, as well as emissions from vegetable oils heated to different temperatures. Emissions from boiling vegetables are dominated by methanol. Significant amounts of dimethyl sulfide are emitted from cruciferous vegetables. Emissions from shallow frying, deep frying and charbroiling are dominated by aldehydes of differing relative composition depending on the oil used. We show that the emission factors of some aldehydes are particularly large which may result in considerable negative impacts on human health in indoor environments. The suitability of some of the aldehydes as tracers for the identification of cooking emissions in ambient air is discussed.

  18. Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

    Science.gov (United States)

    Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

    2016-07-01

    For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

  19. Monte Carlo simulation of transfer reactions using extended R-matrix theory picturing surrogate-type WFCF features

    Directory of Open Access Journals (Sweden)

    Bouland Olivier H.

    2016-01-01

    Full Text Available 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.

  20. Transition Metal Donor-Peptide-Acceptor Complexes: From Intramolecular Electron Transfer Reactions to the Study of Reactive Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Isied, Stephan S.

    2003-03-11

    The trans-polyproline (PII) oligomers (Figure 1) are unusually rigid peptide structures which have been extensively studied by our group for peptide mediated intramolecular electron transfer (ET) at long distances. We have previously studied ET across a series of metal ion donor (D) acceptor (A) oligoproline peptides with different distances, driving forces and reorganizational energies. The majority of these experiments involve generating the ET intermediate using pulse radiolysis methods, although more recently photochemical methods are also used. Results of these studies showed that ET across peptides can vary by more than twelve orders of magnitude. Using ruthenium bipyridine donors, ET reaction rate constants across several proline residues (n = 4 - 9) occurred in the millisecond (ms) to {micro}s timescale, thus limiting the proline peptide conformational motions to only minor changes (far smaller than the large changes that occur on the ms to sec timescale, such as trans to cis proline isomerization). The present report describes our large data base of experimental results for D-peptide-A complexes in terms of a model where the involvement of both superexchange and hopping (hole and electron) mechanisms account for the long range ET rate constants observed. Our data shows that the change from superexchange to hopping mechanisms occurs at different distances depending on the type of D and A and their interactions with the peptides. Our model is also consistent with generalized models for superexchange and hopping which have been put forward by a number of theoretical groups to account for long range ET phenomena.

  1. Entanglement of the Common Eigenvector of Two Particles' Center-of-Mass Coordinate and Mass-Weighted Relative Momentum

    Institute of Scientific and Technical Information of China (English)

    FAN Hong-Yi; SUN Ming-Zhai

    2002-01-01

    We reveal that the common eigenvector of two particles' center-of-mass coordinate and mass-weightedrelative momentum is an entangled state. Its Schmidt decomposition exhibits that the entanglement involves squeezingwhich depends on the ratio of two particles' masses. The corresponding entangling operators are derived.

  2. Intramolecular charge transfer with crystal violet lactone in acetonitrile as a function of temperature: reaction is not solvent-controlled.

    Science.gov (United States)

    Druzhinin, Sergey I; Demeter, Attila; Zachariasse, Klaas A

    2013-08-22

    Intramolecular charge transfer (ICT) with crystal violet lactone (CVL) in the excited singlet state takes place in solvents more polar than n-hexane, such as ethyl acetate, tetrahydrofuran, and acetonitrile (MeCN). In these solvents, the fluorescence spectrum of CVL consists of two emission bands, from a locally excited (LE) and an ICT state. The dominant deactivation channel of the lowest excited singlet state is internal conversion, as the quantum yields of fluorescence (0.007) and intersystem crossing (0.015) in MeCN at 25 °C are very small. CVL is a weakly coupled electron donor/acceptor (D/A) molecule, similar to an exciplex (1)(A(-)D(+)). A solvatochromic treatment of the LE and ICT emission maxima results in the dipole moments μe(LE) = 17 D and μe(ICT) = 33 D, much larger than those previously reported. This discrepancy is attributed to different Onsager radii and spectral fluorimeter calibration. The LE and ICT fluorescence decays of CVL in MeCN are double exponential. As determined by global analysis, the LE and ICT decays at 25 °C have the times τ2 = 9.2 ps and τ1 = 1180 ps, with an amplitude ratio of 35.3 for LE. From these parameters, the rate constants ka = 106 × 10(9) s(-1) and kd = 3.0 × 10(9) s(-1) of the forward and backward reaction in the LE ⇄ ICT equilibrium are calculated, resulting in a free enthalpy difference ΔG of -8.9 kJ/mol. The amplitude ratio of the ICT fluorescence decay equals -1.0, which signifies that the ICT state is not prepared by light absorption in the S0 ground state, but originates exclusively from the directly excited LE precursor. From the temperature dependence of the fluorescence decays of CVL in MeCN (-45 to 75 °C), activation energies E(a) = 3.9 kJ/mol (LE → ICT) and E(d) = 23.6 kJ/mol (ICT → LE) are obtained, giving an enthalpy difference ΔH (= E(a) - E(d)) of -19.7 kJ/mol, and an entropy difference ΔS = -35.5 J mol(-1) K(-1). These data show that the ICT reaction of CVL in MeCN is not barrierless

  3. Repelling, binding, and oscillating of two-particle discrete-time quantum walks

    Science.gov (United States)

    Wang, Qinghao; Li, Zhi-Jian

    2016-10-01

    In this paper, we investigate the effects of particle-particle interaction and static force on the propagation of probability distribution in two-particle discrete-time quantum walk, where the interaction and static force are expressed as a collision phase and a linear position-dependent phase, respectively. It is found that the interaction can lead to boson repelling and fermion binding. The static force also induces Bloch oscillation and results in a continuous transition from boson bunching to fermion anti-bunching. The interplays of particle-particle interaction, quantum interference, and Bloch oscillation provide a versatile framework to study and simulate many-particle physics via quantum walks.

  4. Two-particle angular correlations in $e^+ e^-$ interactions compared with QCD predictions

    CERN Document Server

    Abreu, P; Adye, T; Adzic, P; Ajinenko, I; Alekseev, G D; Alemany, R; Allport, P P; Almehed, S; Amaldi, Ugo; Amato, S; Anassontzis, E G; Andersson, P; Andreazza, A; Andringa, S; Antilogus, P; Apel, W D; Arnoud, Y; Åsman, B; Augustin, J E; Augustinus, A; Baillon, Paul; Bambade, P; Barão, F; Barbiellini, Guido; Barbier, R; Bardin, Dimitri Yuri; Barker, G; Baroncelli, A; Battaglia, Marco; Baubillier, M; Becks, K H; Begalli, M; Beillière, P; Belokopytov, Yu A; Belous, K S; Benvenuti, Alberto C; Bérat, C; Berggren, M; Bertini, D; Bertrand, D; Besançon, M; Bianchi, F; Bigi, M; Bilenky, S M; Bizouard, M A; Bloch, D; Blom, H M; Bonesini, M; Bonivento, W; Boonekamp, M; Booth, P S L; Borgland, A W; Borisov, G; Bosio, C; Botner, O; Boudinov, E; Bouquet, B; Bourdarios, C; Bowcock, T J V; Boyko, I; Bozovic, I; Bozzo, M; Branchini, P; Brenke, T; Brenner, R A; Brückman, P; Brunet, J M; Bugge, L; Buran, T; Burgsmüller, T; Buschbeck, Brigitte; Buschmann, P; Cabrera, S; Caccia, M; Calvi, M; Camacho-Rozas, A J; Camporesi, T; Canale, V; Carena, F; Carroll, L; Caso, Carlo; Castillo-Gimenez, M V; Cattai, A; Cavallo, F R; Cerruti, C; Chabaud, V; Charpentier, P; Chaussard, L; Checchia, P; Chelkov, G A; Chierici, R; Chliapnikov, P V; Chochula, P; Chorowicz, V; Chudoba, J; Collins, P; Colomer, M; Contri, R; Cortina, E; Cosme, G; Cossutti, F; Cowell, J H; Crawley, H B; Crennell, D J; Crosetti, G; Cuevas-Maestro, J; Czellar, S; Damgaard, G; Davenport, Martyn; Da Silva, W; Deghorain, A; Della Ricca, G; Delpierre, P A; Demaria, N; De Angelis, A; de Boer, Wim; De Brabandere, S; De Clercq, C; De Lotto, B; De Min, A; De Paula, L S; Dijkstra, H; Di Ciaccio, Lucia; Di Diodato, A; Dolbeau, J; Doroba, K; Dracos, M; Drees, J; Dris, M; Duperrin, A; Durand, J D; Ehret, R; Eigen, G; Ekelöf, T J C; Ekspong, Gösta; Ellert, M; Elsing, M; Engel, J P; Erzen, B; Espirito-Santo, M C; Falk, E; Fanourakis, G K; Fassouliotis, D; Fayot, J; Feindt, Michael; Ferrari, P; Ferrer, A; Ferrer-Ribas, E; Fichet, S; Firestone, A; Fischer, P A; Flagmeyer, U; Föth, H; Fokitis, E; Fontanelli, F; Franek, B J; Frodesen, A G; Frühwirth, R; Fulda-Quenzer, F; Fuster, J A; Galloni, A; Gamba, D; Gamblin, S; Gandelman, M; García, C; García, J; Gaspar, C; Gaspar, M; Gasparini, U; Gavillet, P; Gazis, E N; Gelé, D; Gerber, J P; Gerdyukov, L N; Ghodbane, N; Gil, I; Glege, F; Gokieli, R; Golob, B; Gonçalves, P; González-Caballero, I; Gopal, Gian P; Gorn, L; Górski, M; Guz, Yu; Gracco, Valerio; Grahl, J; Graziani, E; Green, C; Gris, P; Grzelak, K; Günther, M; Guy, J; Hahn, F; Hahn, S; Haider, S; Hallgren, A; Hamacher, K; Harris, F J; Hedberg, V; Heising, S; Hernández, J J; Herquet, P; Herr, H; Hessing, T L; Heuser, J M; Higón, E; Holmgren, S O; Holt, P J; Holthuizen, D J; Hoorelbeke, S; Houlden, M A; Hrubec, Josef; Huet, K; Hultqvist, K; Jackson, J N; Jacobsson, R; Jalocha, P; Janik, R; Jarlskog, C; Jarlskog, G; Jarry, P; Jean-Marie, B; Johansson, E K; Jönsson, P E; Joram, C; Juillot, P; Kapusta, F; Karafasoulis, K; Katsanevas, S; Katsoufis, E C; Keränen, R; Khomenko, B A; Khovanskii, N N; Kiiskinen, A P; King, B J; Kjaer, N J; Klapp, O; Klein, H; Kluit, P M; Knoblauch, D; Kokkinias, P; Koratzinos, M; Kostyukhin, V; Kourkoumelis, C; Kuznetsov, O; Krammer, Manfred; Kreuter, C; Krstic, J; Krumshtein, Z; Kubinec, P; Kucewicz, W; Kurvinen, K L; Lamsa, J; Lane, D W; Langefeld, P; Lapin, V; Laugier, J P; Lauhakangas, R; Leder, Gerhard; Ledroit, F; Lefébure, V; Leinonen, L; Leisos, A; Leitner, R; Lenzen, Georg; Lepeltier, V; Lesiak, T; Lethuillier, M; Libby, J; Liko, D; Lipniacka, A; Lippi, I; Lörstad, B; Loken, J G; Lopes, J H; López, J M; López-Fernandez, R; Loukas, D; Lutz, P; Lyons, L; MacNaughton, J N; Mahon, J R; Maio, A; Malek, A; Malmgren, T G M; Malychev, V; Mandl, F; Marco, J; Marco, R P; Maréchal, B; Margoni, M; Marin, J C; Mariotti, C; Markou, A; Martínez-Rivero, C; Martínez-Vidal, F; Martí i García, S; Mastroyiannopoulos, N; Matorras, F; Matteuzzi, C; Matthiae, Giorgio; Masik, J; Mazzucato, F; Mazzucato, M; McCubbin, M L; McKay, R; McNulty, R; McPherson, G; Meroni, C; Meyer, W T; Myagkov, A; Migliore, E; Mirabito, L; Mitaroff, Winfried A; Mjörnmark, U; Moa, T; Møller, R; Mönig, K; Monge, M R; Moreau, X; Morettini, P; Morton, G A; Müller, U; Münich, K; Mulders, M; Mulet-Marquis, C; Muresan, R; Murray, W J; Muryn, B; Myatt, Gerald; Myklebust, T; Naraghi, F; Navarria, Francesco Luigi; Navas, S; Nawrocki, K; Negri, P; Neufeld, N; Neumeister, N; Nicolaidou, R; Nielsen, B S; Nikolaenko, V; Nikolenko, M; Nomokonov, V P; Normand, Ainsley; Nygren, A; Obraztsov, V F; Olshevskii, A G; Onofre, A; Orava, Risto; Orazi, G; Österberg, K; Ouraou, A; Paganoni, M; Paiano, S; Pain, R; Paiva, R; Palacios, J; Palka, H; Papadopoulou, T D; Papageorgiou, K; Pape, L; Parkes, C; Parodi, F; Parzefall, U; Passeri, A; Passon, O; Pegoraro, M; Peralta, L; Pernicka, Manfred; Perrotta, A; Petridou, C; Petrolini, A; Phillips, H T; Piana, G; Pierre, F; Pimenta, M; Piotto, E; Podobnik, T; Pol, M E; Polok, G; Poropat, P; Pozdnyakov, V; Privitera, P; Pukhaeva, N; Pullia, Antonio; Radojicic, D; Ragazzi, S; Rahmani, H; Rakoczy, D; Rames, J; Ratoff, P N; Read, A L; Rebecchi, P; Redaelli, N G; Reid, D; Reinhardt, R; Renton, P B; Resvanis, L K; Richard, F; Rídky, J; Rinaudo, G; Røhne, O M; Romero, A; Ronchese, P; Rosenberg, E I; Rosinsky, P; Roudeau, Patrick; Rovelli, T; Ruhlmann-Kleider, V; Ruiz, A; Saarikko, H; Sacquin, Yu; Sadovskii, A; Sajot, G; Salt, J; Sampsonidis, D; Sannino, M; Schneider, H; Schwemling, P; Schwickerath, U; Schyns, M A E; Scuri, F; Seager, P; Sedykh, Yu; Segar, A M; Sekulin, R L; Shellard, R C; Sheridan, A; Siebel, M; Silvestre, R; Simard, L C; Simonetto, F; Sissakian, A N; Skaali, T B; Smadja, G; Smirnova, O G; Smith, G R; Sopczak, André; Sosnowski, R; Spassoff, Tz; Spiriti, E; Sponholz, P; Squarcia, S; Stampfer, D; Stanescu, C; Stanic, S; Stapnes, Steinar; Stevenson, K; Stocchi, A; Strauss, J; Strub, R; Stugu, B; Szczekowski, M; Szeptycka, M; Tabarelli de Fatis, T; Chikilev, O G; Tegenfeldt, F; Terranova, F; Thomas, J; Tilquin, A; Timmermans, J; Tkatchev, L G; Todorov, T; Todorova, S; Toet, D Z; Tomaradze, A G; Tomé, B; Tonazzo, A; Tortora, L; Tranströmer, G; Treille, D; Tristram, G; Troncon, C; Tsirou, A L; Turluer, M L; Tyapkin, I A; Tzamarias, S; Überschär, B; Ullaland, O; Uvarov, V; Valenti, G; Vallazza, E; van Apeldoorn, G W; van Dam, P; Van Eldik, J; Van Lysebetten, A; Van Vulpen, I B; Vassilopoulos, N; Vegni, G; Ventura, L; Venus, W A; Verbeure, F; Verlato, M; Vertogradov, L S; Verzi, V; Vilanova, D; Vitale, L; Vlasov, E; Vodopyanov, A S; Voulgaris, G; Vrba, V; Wahlen, H; Walck, C; Weiser, C; Wicke, D; Wickens, J H; Wilkinson, G R; Winter, M; Witek, M; Wolf, G; Yi, J; Yushchenko, O P; Zalewska-Bak, A; Zalewski, Piotr; Zavrtanik, D; Zevgolatakos, E; Zimin, N I; Zucchelli, G C; Zumerle, G

    1998-01-01

    Two--particle angular correlations in jet cones have been measured in $e^+e^-$ annihilation into hadrons at LEP energies ($\\sqrt{s}=$ 91 and 183~GeV) and are compared with QCD predictions using the LPHD hypothesis. Two different functions have been tested. While the differentially normalized correlation function shows substantial deviations from the predictions, a globally normalized correlation function agrees well. The size of $\\alpha_S^{\\rm eff}$ (and other QCD parameters) and its running with the relevant angular scale, the validity of LPHD, and problems due to non--perturbative effects are discussed critically.

  5. Measuring two-particle Bose-Einstein correlations with PHOBOS@RHIC

    Energy Technology Data Exchange (ETDEWEB)

    Betts, R.; Barton, D.; Carroll, A. [and others

    1995-07-15

    The authors present results of a simulation of the measurement of two-particle Bose-Einstein correlations in central Au-Au collisions with the PHOBOS detector at RHIC. This measurement is expected to yield information on the relevant time and distance scales in these collisions. As the space-time scale is directly connected with the equation of state governing the evolution of the particle source, this information will be essential in understanding the physics of nucleus-nucleus collisions at RHIC energies. The authors demonstrate that the PHOBOS detector has sufficient resolution and acceptance to distinguish a variety of physics scenarios.

  6. Optimal conclusive teleportation of a d-dimensional two-particle unknown quantum state

    Institute of Scientific and Technical Information of China (English)

    Yang Yu-Guang; Wen Qiao-Yan; Zhu Fu-Chen

    2006-01-01

    A conclusive teleportation protocol of a d-dimensional two-particle unknown quantum state using three ddimensional particles in an arbitrary pure state is proposed. A sender teleports the unknown state conclusively to a receiver by using the positive operator valued measure(POVM) and introducing an ancillary qudit to perform the generalized Bell basis measurement. We calculate the optimal teleportation fidelity. We also discuss and analyse the reason why the information on the teleported state is lost in the course of the protocol.

  7. Measuring acetic and formic acid by proton transfer reaction-mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    Directory of Open Access Journals (Sweden)

    M. Baasandorj

    2014-10-01

    Full Text Available We present a detailed investigation of the factors governing the quantification of formic acid (FA, acetic acid (AA and their relevant mass analogues by proton transfer reaction-mass spectrometry (PTR-MS, assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. On the other hand, for E/N = 125 Townsend (Td, the PTR-MS sensitivity towards ethanol at m/z 47 is 5–20× lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (E/N, but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycoaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N and reduced fragmentation in the presence of water (at high E/N. Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the humidity effect depends strongly on the collisional energy in the drift tube, simple humidity correction factors (XR will only be relevant for a specific instrumental configuration. We recommend E/N∼125 Td as an effective condition for AA and FA measurements by PTR-MS, as it optimizes between the competing E/N-dependent mechanisms controlling their sensitivities and those of the interfering species. Finally, we present the design and evaluation of an online acid

  8. Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

    Science.gov (United States)

    D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

    2013-02-01

    The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

  9. Outer-sphere 2 e{sup -}/2 H{sup +} transfer reactions of ruthenium(II)-amine and ruthenium(IV)-amido complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cattaneo, Mauricio [Department of Chemistry, University of Washington (United States); INQUINOA-CONICET, Universidad Nacional de Tucuman, San Miguel de Tucuman (Argentina); Ryken, Scott A. [Department of Chemistry, University of Washington (United States); Mayer, James M. [Department of Chemistry, University of Washington (United States); Department of Chemistry, Yale University, New Haven, CT, 06520 (United States)

    2017-03-20

    A diverse set of 2 e{sup -}/2 H{sup +} reactions are described that interconvert [Ru{sup II}(bpy)(en*){sub 2}]{sup 2+} and [Ru{sup IV}(bpy)(en-H*){sub 2}]{sup 2+} (bpy=2,2'-bipyridine, en*=H{sub 2}NCMe{sub 2}CMe{sub 2}NH{sub 2}, en*-H=H{sub 2}NCMe{sub 2}CMe{sub 2}NH{sup -}), forming or cleaving different O-H, N-H, S-H, and C-H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3-cyclohexadiene. These proton-coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90 kcal mol{sup -1}, but the rates are more dependent on the type of X-H bond involved than the associated ΔG . There is a kinetic preference for substrates that have the transferring hydrogen atoms in close proximity, such as ortho-tetrachlorobenzoquinone over its para-isomer and 1,3-cyclohexadiene over its 1,4-isomer, perhaps hinting at the potential for concerted 2 e{sup -}/2 H{sup +} transfers. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. High throughput microwell spectrophotometric assay for olmesartan medoxomil in tablets based on its charge-transfer reaction with DDQ

    Directory of Open Access Journals (Sweden)

    Darwish Ibrahim A.

    2014-03-01

    Full Text Available The study describes the development and validation of a new microwell-based spectrophotometric assay for determination of olmesartan medoxomil (OLM in tablets. The formation of a colored charge-transfer (CT complex between OLM as an n-electron donor and 2,3-dichloro- -5,6-dicyano-1,4-benzoquinone (DDQ as a p-electron acceptor was investigated, and employed as the basis for the development of the new assay. The proposed assay was conducted in 96-microwell plates. The absorbance of the colored-CT complex was measured at 460 nm with a microplate reader. Optimum conditions of the reaction and the analytical procedures of the assay were established. Under the optimum conditions, a linear relationship with a good correlation coefficient was found between the absorbance and the concentration of OLM in the range of 2-200 μg per well. The limits of detection and quantitation were 0.53 and 1.61 μg per well, respectively. No interference was observed from the excipients present in OLM tablets or from hydrochlorothiazide and amlodipine besylate that were co-formulated with OLM in some of its formulations. The assay was successfully applied to the analysis of OLM in tablets with good accuracy and precision. The assay described herein has a great practical value in the routine analysis of OLM in quality control laboratories, since it has a high throughput property and consumes low volumes of organic solvent. It thus offers a reduction in the exposure of analysts to the toxic effects of organic solvents, as well as a reduction in the cost of analysis.

  11. Density Functional Studies of the Reaction of Ytterbium Monocation with Fluoromethane: C-F Bond Activation and Electron-Transfer Reactivity

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane,which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations,have been investigated for the first time by using density functional theory.A direct fluorine abstraction mechanism was revealed,and the related thermochemistry data were determined.The electron-transfer reactivity of the reaction was analyzed using the two-state model,and a strongly avoided crossing behavior on the transition state region was shown.The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.

  12. Selective properties of neutron transfer reactions in the {sup 90}Zr + {sup 208}Pb system for the population of excited states in zirconium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Varga Pajtler, M., E-mail: mvarga@fizika.unios.hr [Department of Physics, University of Osijek, HR-31000 Osijek (Croatia); Szilner, S. [Rudjer Bošković Institute, HR-10001 Zagreb (Croatia); Corradi, L.; Angelis, G. de; Fioretto, E. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, I-35020 Legnaro (Italy); Gadea, A. [IFIC, CSIC-Universidad de Valencia, E-46071 Valencia (Spain); Haas, F. [Institut Pluridisciplinaire Hubert Curien, CNRS-IN2P3 and Université de Strasbourg, F-67037 Strasbourg (France); Lunardi, S. [Dipartimento di Fisica, Universitá di Padova, and Istituto Nazionale di Fisica Nucleare, I-35131 Padova (Italy); Jelavić Malenica, D. [Rudjer Bošković Institute, HR-10001 Zagreb (Croatia); Mărginean, N. [Horia Hulubei National Institute of Physics and Nuclear Engineering, RO-077125 Bucharest-Magurele (Romania); Mengoni, D. [Dipartimento di Fisica, Universitá di Padova, and Istituto Nazionale di Fisica Nucleare, I-35131 Padova (Italy); Mijatović, T. [Rudjer Bošković Institute, HR-10001 Zagreb (Croatia); Montagnoli, G. [Dipartimento di Fisica, Universitá di Padova, and Istituto Nazionale di Fisica Nucleare, I-35131 Padova (Italy); Montanari, D. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, I-35020 Legnaro (Italy); Pollarolo, G. [Dipartimento di Fisica Teorica, Universitá di Torino, and Istituto Nazionale di Fisica Nucleare, I-10125 Torino (Italy); and others

    2015-09-15

    Nuclei produced via multineutron transfer channels have been studied in {sup 90}Zr + {sup 208}Pb close to the Coulomb barrier energy in a fragment-γ coincident measurement employing the PRISMA magnetic spectrometer coupled to the CLARA γ-array. The selective properties of the reaction mechanism have been discussed in terms of states and their strength excited in the neutron transfer channels leading to {sup 89–94}Zr isotopes. A strong population of yrast states, with energies up to ∼7.5 MeV has been observed.

  13. Selective properties of neutron transfer reactions in the 90Zr + 208Pb system for the population of excited states in zirconium isotopes

    Science.gov (United States)

    Varga Pajtler, M.; Szilner, S.; Corradi, L.; de Angelis, G.; Fioretto, E.; Gadea, A.; Haas, F.; Lunardi, S.; Jelavić Malenica, D.; Mărginean, N.; Mengoni, D.; Mijatović, T.; Montagnoli, G.; Montanari, D.; Pollarolo, G.; Recchia, F.; Salsac, M.-D.; Scarlassara, F.; Soić, N.; Stefanini, A. M.; Ur, C. A.; Valiente-Dobón, J. J.

    2015-09-01

    Nuclei produced via multineutron transfer channels have been studied in 90Zr + 208Pb close to the Coulomb barrier energy in a fragment-γ coincident measurement employing the PRISMA magnetic spectrometer coupled to the CLARA γ-array. The selective properties of the reaction mechanism have been discussed in terms of states and their strength excited in the neutron transfer channels leading to 89-94Zr isotopes. A strong population of yrast states, with energies up to ∼7.5 MeV has been observed.

  14. Non-linear heat and mass transfer in a MHD Homann nanofluid flow through a porous medium with chemical reaction, heat generation and uniform inflow

    Science.gov (United States)

    EL-Dabe, N. T.; Attia, H. A.; Essawy, M. A. I.; Ramadan, A. A.; Abdel-Hamid, A. H.

    2016-11-01

    The steady MHD axisymmetric flow of an incompressible viscous electrically conducting nanofluid impinging on a permeable plate is investigated with heat and mass transfer. An external uniform magnetic field as well as a uniform inflow, in the presence of either suction or injection, are applied normal to the plate. The effects of heat (generation/absorption) and chemical reaction have been accentuated. This study indicates the incorporated influence of both the thermophoresis phenomenon and the Brownian behavior. Numerical solutions for the governing non-linear momentum, energy and nanoparticle equations have been obtained. The rates of heat and mass transfer are presented and discussed.

  15. Simultaneous Comparison of Two Roller Compaction Techniques and Two Particle Size Analysis Methods.

    Science.gov (United States)

    Saarinen, Tuomas; Antikainen, Osmo; Yliruusi, Jouko

    2017-05-24

    A new dry granulation technique, gas-assisted roller compaction (GARC), was compared with conventional roller compaction (CRC) by manufacturing 34 granulation batches. The process variables studied were roll pressure, roll speed, and sieve size of the conical mill. The main quality attributes measured were granule size and flow characteristics. Within granulations also the real applicability of two particle size analysis techniques, sieve analysis (SA) and fast imaging technique (Flashsizer, FS), was tested. All granules obtained were acceptable. In general, the particle size of GARC granules was slightly larger than that of CRC granules. In addition, the GARC granules had better flowability. For example, the tablet weight variation of GARC granules was close to 2%, indicating good flowing and packing characteristics. The comparison of the two particle size analysis techniques showed that SA was more accurate in determining wide and bimodal size distributions while FS showed narrower and mono-modal distributions. However, both techniques gave good estimates for mean granule sizes. Overall, SA was a time-consuming but accurate technique that provided reliable information for the entire granule size distribution. By contrast, FS oversimplified the shape of the size distribution, but nevertheless yielded acceptable estimates for mean particle size. In general, FS was two to three orders of magnitude faster than SA.

  16. Two-particle correlations in p+p and Pb+Pb collisions at SPS energies

    CERN Document Server

    AUTHOR|(CDS)2081214

    In this thesis two-particle correlations in pseudorapidity and azimuthal angle in p+p collisions at beam momenta: 20, 31, 40, 80, and 158 GeV/c are presented. Data were recorded in the NA61/SHINE experiment at the CERN Super Proton Synchrotron (SPS). The results are compared to the EPOS and the UrQMD models as well as to the results from various experiments at the Relativistic Heavy-Ion Collider (RHIC) and the Large Hadron Collider (LHC). Dedicated comparison analysis was done also on NA49 data of Pb+Pb collisions. The inclusive results in p+p show correlation structures connected with resonance decays, Bose-Einstein statistics, momentum conservation, and strings fragmentation. No structures connected with hard processes were observed even at 158 GeV/c beam momentum. The EPOS model reproduces data fine except of Bose-Einstein enhancement; the UrQMD model shows many disagreements with data. The results provide an insight into forgotten realm of soft physics where jet peaks do not cast shadows onto two-particle...

  17. Two-Particle Elastic Scattering in a Finite Volume Including QED

    CERN Document Server

    Beane, Silas R

    2014-01-01

    The presence of long-range interactions violates a condition necessary to relate the energy of two particles in a finite volume to their S-matrix elements in the manner of Luscher. While in infinite volume, QED contributions to low-energy charged particle scattering must be resummed to all orders in perturbation theory (the Coulomb ladder diagrams), in a finite volume the momentum operator is gapped, allowing for a perturbative treatment. The leading QED corrections to the two-particle finite-volume energy quantization condition below the inelastic threshold, as well as approximate formulas for energy eigenvalues, are obtained. In particular, we focus on two spinless hadrons in the A1+ irreducible representation of the cubic group, and truncate the strong interactions to the s-wave. These results are necessary for the analysis of Lattice QCD+QED calculations of charged-hadron interactions, and can be straightforwardly generalized to other representations of the cubic group, to hadrons with spin, and to includ...

  18. A computer program for two-particle intrinsic coefficients of fractional parentage

    Science.gov (United States)

    Deveikis, A.

    2012-06-01

    A Fortran 90 program CESOS for the calculation of the two-particle intrinsic coefficients of fractional parentage for several j-shells with isospin and an arbitrary number of oscillator quanta (CESOs) is presented. The implemented procedure for CESOs calculation consistently follows the principles of antisymmetry and translational invariance. The approach is based on a simple enumeration scheme for antisymmetric many-particle states, efficient algorithms for calculation of the coefficients of fractional parentage for j-shells with isospin, and construction of the subspace of the center-of-mass Hamiltonian eigenvectors corresponding to the minimal eigenvalue equal to 3/2 (in ℏω). The program provides fast calculation of CESOs for a given particle number and produces results possessing small numerical uncertainties. The introduced CESOs may be used for calculation of expectation values of two-particle nuclear shell-model operators within the isospin formalism. Program summaryProgram title: CESOS Catalogue identifier: AELT_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AELT_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 10 932 No. of bytes in distributed program, including test data, etc.: 61 023 Distribution format: tar.gz Programming language: Fortran 90 Computer: Any computer with a Fortran 90 compiler Operating system: Windows XP, Linux RAM: The memory demand depends on the number of particles A and the excitation energy of the system E. Computation of the A=6 particle system with the total angular momentum J=0 and the total isospin T=1 requires around 4 kB of RAM at E=0,˜3 MB at E=3, and ˜172 MB at E=5. Classification: 17.18 Nature of problem: The code CESOS generates a list of two-particle intrinsic coefficients of fractional parentage for several

  19. Evidence for a Precursor Complex in C-H Hydrogen Atom Transfer Reactions Mediated by a Manganese(IV) Oxo Complex

    OpenAIRE

    Garcia Bosch, Isaac; Company Casadevall, Anna; Cady, Clyde W.; Styring, Stenbjörn; Browne, Wesley R; Ribas Salamaña, Xavi; Costas Salgueiro, Miquel

    2011-01-01

    HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2011, ...

  20. MHD boundary layer flow and heat transfer due to an exponentially shrinking sheet in a nanofluid with thermal radiation and chemical reaction

    Science.gov (United States)

    Hamid, Rohana Abdul; Nazar, Roslinda

    2017-08-01

    In this paper, the problem of magnetohydrodynamic (MHD) boundary layer flow and heat transfer of a nanofluid with the influences of the chemical reaction and thermal radiation over an exponentially shrinking sheet is studied numerically. The model used for the nanofluid is called the Buongiorno model which incorporates the effects of the Brownian motion and thermophoresis. The governing dimensionless ordinary differential equations are solved using the bvp4c method. The effects of the magnetic field parameter, thermal radiation parameter and chemical reaction parameter on the velocity, temperature and concentration profiles of the nanofluid over an exponentially permeable shrinking sheet are discussed and presented through graphs and tables.