WorldWideScience

Sample records for proton transfer steps

  1. A spectral study of the elementary step of proton transfer in heterogeneous acid catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Kazanskii, V B

    1977-09-01

    A spectral study of the elementary step of proton transfer in heterogeneous acid catalysis involved a determination of the potential curves of the OH bond in surface hydroxyl groups (e.g., those on silica, NaHY zeolite, or glass) of differing acidity from IR stretching frequency data in the overtone region; a calculation of the activation energies for proton transfer during acid catalysis from the changes in the curve forms after adsorption of various molecules (e.g., water, ammonia, benzene, toluene, xylenes, acetone, and cyclohexane); and a comparison of the IR predictions with quantum-chemical calculations of the potential curves. The results appear to furnish a new criterion for the coordinate of reactions involving Broensted sites: if the activation energy measured during actual catalysis is close to that calculated from the IR stretching data, the reaction proceeds by the stepwise mechanism of acid catalysis; but if these values differ greatly, the reaction involves a concerted mechanism (i.e., activation of the adsorbed molecule without involvement of OH groups). Tables, graphs, and 15 references.

  2. Involvement of a cytosine side chain in proton transfer in the rate-determining step of ribozyme self-cleavage

    Science.gov (United States)

    Shih, I-hung; Been, Michael D.

    2001-01-01

    Ribozymes of hepatitis delta virus have been proposed to use an active-site cytosine as an acid-base catalyst in the self-cleavage reaction. In this study, we have examined the role of cytosine in more detail with the antigenomic ribozyme. Evidence that proton transfer in the rate-determining step involved cytosine 76 (C76) was obtained from examining cleavage activity of the wild-type and imidazole buffer-rescued C76-deleted (C76Δ) ribozymes in D2O and H2O. In both reactions, a similar kinetic isotope effect and shift in the apparent pKa indicate that the buffer is functionally substituting for the side chain in proton transfer. Proton inventory of the wild-type reaction supported a mechanism of a single proton transfer at the transition state. This proton transfer step was further characterized by exogenous base rescue of a C76Δ mutant with cytosine and imidazole analogues. For the imidazole analogues that rescued activity, the apparent pKa of the rescue reaction, measured under kcat/KM conditions, correlated with the pKa of the base. From these data a Brønsted coefficient (β) of 0.51 was determined for the base-rescued reaction of C76Δ. This value is consistent with that expected for proton transfer in the transition state. Together, these data provide strong support for a mechanism where an RNA side chain participates directly in general acid or general base catalysis of the wild-type ribozyme to facilitate RNA cleavage. PMID:11171978

  3. Analysis of the critical step in catalytic carbodiimide transformation: proton transfer from amines, phosphines, and alkynes to guanidinates, phosphaguanidinates, and propiolamidinates with Li and Al catalysts.

    Science.gov (United States)

    Rowley, Christopher N; Ong, Tiow-Gan; Priem, Jessica; Richeson, Darrin S; Woo, Tom K

    2008-12-15

    While lithium amides supported by tetramethylethylenediamine (TMEDA) are efficient catalysts in the synthesis of substituted guanidines via the guanylation of an amine with carbodiimide, as well as the guanylation of phosphines and conversion of alkynes into propiolamidines, aluminum amides are only efficient catalysts for the guanylation of amides. Density functional theory (DFT) calculations were used to explain this difference in activity. The origin of this behavior is apparent in the critical step where a proton is transferred from the substrate to a metal guanidinate. The activation energies of these steps are modest for amines, phosphines, and alkynes when a lithium catalyst was used, but are prohibitively high for the analogous reactions with phosphines and alkynes for aluminum amide catalysts. Energy decomposition analysis (EDA) indicates that these high activations energies are due to the high energetic cost of the detachment of a chelating guanidinate nitrogen from the aluminum in the proton transfer transition state. Amines are able to adopt an ideal geometry for facile proton transfer to the aluminum guanidinate and concomitant Al-N bond formation, while phosphines and alkynes are not.

  4. Proton transfer events in GFP

    NARCIS (Netherlands)

    Di Donato, M.; van Wilderen, L.J.G.W.; van Stokkum, I.H.M.; Cohen Stuart, T.A.; Kennis, J.T.M.; Hellingwerf, K.J.; van Grondelle, R.; Groot, M.L.

    2011-01-01

    Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton

  5. Proton solvation and proton transfer in chemical and electrochemical processes

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

    This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

  6. Proton transfer events in GFP.

    Science.gov (United States)

    Di Donato, Mariangela; van Wilderen, Luuk J G W; Van Stokkum, Ivo H M; Stuart, Thomas Cohen; Kennis, John T M; Hellingwerf, Klaas J; van Grondelle, Rienk; Groot, Marie Louise

    2011-09-28

    Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton transfer through a 'proton-wire', formed by the chromophore (the proton donor), water molecule W22, Ser205 and Glu222 (the acceptor), on a picosecond time scale. To obtain a more refined view of this process, we have used a combined approach of time resolved mid-infrared spectroscopy and visible pump-dump-probe spectroscopy to resolve with atomic resolution how and how fast protons move through this wire. Our results indicate that absorption of light by GFP induces in 3 ps (10 ps in D(2)O) a shift of the equilibrium positions of all protons in the H-bonded network, leading to a partial protonation of Glu222 and to a so-called low barrier hydrogen bond (LBHB) for the chromophore's proton, giving rise to dual emission at 475 and 508 nm. This state is followed by a repositioning of the protons on the wire in 10 ps (80 ps in D(2)O), ultimately forming the fully deprotonated chromophore and protonated Glu222.

  7. Origin of the Proton-transfer Step in the Cofactor-free (1H)-3-Hydroxy-4-oxoquinaldine 2,4-Dioxygenase

    Science.gov (United States)

    Hernandez-Ortega, Aitor; Quesne, Matthew G.; Bui, Soi; Heuts, Dominic P. H. M.; Steiner, Roberto A.; Heyes, Derren J.; de Visser, Sam P.; Scrutton, Nigel S.

    2014-01-01

    Dioxygenases catalyze a diverse range of chemical reactions that involve the incorporation of oxygen into a substrate and typically use a transition metal or organic cofactor for reaction. Bacterial (1H)-3-hydroxy-4-oxoquinaldine 2,4-dioxygenase (HOD) belongs to a class of oxygenases able to catalyze this energetically unfavorable reaction without any cofactor. In the quinaldine metabolic pathway, HOD breaks down its natural N-heteroaromatic substrate using a mechanism that is still incompletely understood. Experimental and computational approaches were combined to study the initial step of the catalytic cycle. We have investigated the role of the active site His-251/Asp-126 dyad, proposed to be involved in substrate hydroxyl group deprotonation, a critical requirement for subsequent oxygen reaction. The pH profiles obtained under steady-state conditions for the H251A and D126A variants show a strong pH effect on their kcat and kcat/Km constants, with a decrease in kcat/Km of 5500- and 9-fold at pH 10.5, respectively. Substrate deprotonation studies under transient-state conditions show that this step is not rate-limiting and yield a pKa value of ∼7.2 for WT HOD. A large solvent isotope effect was found, and the pKa value was shifted to ∼8.3 in D2O. Crystallographic and computational studies reveal that the mutations have a minor effect on substrate positioning. Computational work shows that both His-251 and Asp-126 are essential for the proton transfer driving force of the initial reaction. This multidisciplinary study offers unambiguous support to the view that substrate deprotonation, driven by the His/Asp dyad, is an essential requirement for its activation. PMID:24482238

  8. What's new in the proton transfer reaction from pyranine to water? A femtosecond study of the proton transfer dynamics

    International Nuclear Information System (INIS)

    Prayer, C.; Gustavsson, T.; Tran-Thi, T.-H.

    1996-01-01

    The proton transfer from excited pyranine to water is studied by the femtosecond fluorescence upconversion technique. It is shown for the first time that the proton transfer reaction in water proceeds by three successive steps: the solvent cage relaxation, the specific solute-solvent hydrogen-bond formation and finally the ion pair dissociation/diffusion

  9. Solvent control of intramolecular proton transfer

    DEFF Research Database (Denmark)

    Manolova, Y.; Marciniak, Heinz; Tschierlei, S.

    2017-01-01

    of molecules in the enol and zwitterionic proton transfer (PT) form exists in the ground state. However, the zwitterion is the energetically favored one in the electronically excited state. Optical excitation of the enol form results in intramolecular proton transfer and formation of the PT form within 1.4 ps...

  10. A NOVEL PROTON TRANSFER COMPOUND (A NEW ...

    African Journals Online (AJOL)

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    intermolecular proton transfer from (MoO4H2) to (OHRNH2) results in the formation of a new molybdate salt that ... KEY WORDS: Proton transfer, Molybdate salt, X-ray structure, MoO2(acac)2, 2-Amino-2-methyl-1-propanol ..... data can be obtained free of charge on application to The Director, CCDC, 12 Union Road,.

  11. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

    Møller, Søren; Andersen, Kristine B.; Spanget-Larsen, Jens

    1998-01-01

    Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results in an unus......Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results......, associated with an excited-state intramolecular proton transfer process....

  12. Proton polarimeters for spin transfer experiments

    International Nuclear Information System (INIS)

    McNaughton, M.W.

    1985-01-01

    The design and use of proton polarimeters for spin transfer (Wolfenstein parameter) measurements is discussed. Polarimeters are compared with polarized targets for spin dependent experiments. 32 refs., 4 figs

  13. Tunneling induced electron transfer between separated protons

    Science.gov (United States)

    Vindel-Zandbergen, Patricia; Meier, Christoph; Sola, Ignacio R.

    2018-04-01

    We study electron transfer between two separated protons using local control theory. In this symmetric system one can favour a slow transfer by biasing the algorithm, achieving high efficiencies for fixed nuclei. The solution can be parametrized using a sequence of a pump followed by a dump pulse that lead to tunneling-induced electron transfer. Finally, we study the effect of the nuclear kinetic energy on the efficiency. Even in the absence of relative motion between the protons, the spreading of the nuclear wave function is enough to reduce the yield of electronic transfer to less than one half.

  14. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  15. Hydrogen-bond dynamics and proton transfer in nanoconfinement

    NARCIS (Netherlands)

    van der Loop, T.H.

    2015-01-01

    Proton transfer is of fundamental importance to both biology and chemistry. Much is known about proton transfer in large water volumes but often proton transfer reactions take place in very small nanometer sized volumes for example between lipid layers and in proton channels in mitochondria and

  16. Pumped energy transfer stations (STEP)

    International Nuclear Information System (INIS)

    Tournery, Jean-Francois

    2015-12-01

    As objectives of development are high for renewable energies (they are supposed to cover 50 per cent of new energy needs by 2035), pumped energy transfer stations are to play an important role in this respect. The author first discusses the consequences of the development of renewable energies on the exploitation of electric grids: issue of intermittency for some of them, envisaged solutions. Then, he addresses one of the solutions: the storage of electric power. He notices that increasing the potential energy of a volume of water is presently the most mature solution to face massive needs of the power system. Dams and pumped energy transfer stations represent now almost the whole installed storage power in the world. The author then presents these pumped energy transfer stations: principle, brief history (the first appeared in Italy and Switzerland at the end of the 1890's). He indicates the various parameters of assessment of such stations: maximum stored energy, installed power in pumping mode and turbine mode, time constant, efficiency, level of flexibility. He discusses economic issues. He describes and comments the operation of turbine-pump groups: ternary groups, reversible binary groups. He discusses barriers to be overcome and technical advances to be made for varying speed groups and for marine stations. He finally gives an overview (table with number of stations belonging to different power ranges, remarkable installations) of existing stations in China, USA, Japan, Germany, Austria, Spain, Portugal, Italy, Switzerland, France and UK, and indicate predictions regarding storage needs at the world level. Some data are finally indicated for the six existing French installations

  17. Proton-transfer doping of polyacetylene

    Energy Technology Data Exchange (ETDEWEB)

    Tolbert, L.M.; Schomaker, J.A. (School of Chemistry and Biochemistry, Georgia Inst. of Tech., Atlanta (USA))

    1991-04-30

    Exhaustive deprotonation of films of poly(acetylene-co-1,3-butadiene) (PAB) fails to produce a conductive film. In contrast, deprotonation of segmented polyacetylene (SPA) produces a conductive material with similar characteristics to n-doped polyacetylene. Thus the feasibility of a proton-transfer approach to doping of polyacetylene has been demonstrated. (orig.).

  18. Proton-transfer reactions in ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.; Schmidt, R.; Schuster, R.

    1985-01-01

    Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

  19. Proton transfers in the Strecker reaction revealed by DFT calculations

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-08-01

    Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

  20. Proton Transfer in Nucleobases is Mediated by Water

    Energy Technology Data Exchange (ETDEWEB)

    Khistyaev, Kirill; Golan, Amir; Bravaya, Ksenia B.; Orms, Natalie; Krylov, Anna I.; Ahmed, Musahid

    2013-08-08

    Water plays a central role in chemistry and biology by mediating the interactions between molecules, altering energy levels of solvated species, modifying potential energy proles along reaction coordinates, and facilitating ecient proton transport through ion channels and interfaces. This study investigates proton transfer in a model system comprising dry and microhydrated clusters of nucleobases. With mass spectrometry and tunable vacuum ultraviolet synchrotron radiation, we show that water shuts down ionization-induced proton transfer between nucleobases, which is very ecient in dry clusters. Instead, a new pathway opens up in which protonated nucleo bases are generated by proton transfer from the ionized water molecule and elimination of a hydroxyl radical. Electronic structure calculations reveal that the shape of the potential energy prole along the proton transfer coordinate depends strongly on the character of the molecular orbital from which the electron is removed, i.e., the proton transfer from water to nucleobases is barrierless when an ionized state localized on water is accessed. The computed energetics of proton transfer is in excellent agreement with the experimental appearance energies. Possible adiabatic passage on the ground electronic state of the ionized system, while energetically accessible at lower energies, is not ecient. Thus, proton transfer is controlled electronically, by the character of the ionized state, rather than statistically, by simple energy considerations.

  1. 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

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

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

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

  3. Structure and Intramolecular Proton Transfer of Alanine Radical Cations

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2012-01-01

    The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

  4. Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer

    International Nuclear Information System (INIS)

    Auer, Benjamin; Fernandez, Laura; Hammes-Schiffer, Sharon

    2011-01-01

    The coupling of long-range electron transfer to proton transport over multiple sites plays a vital role in many biological and chemical processes. Recently a molecule with a hydrogen-bond relay inserted between the proton donor and acceptor sites in a proton-coupled electron transfer (PCET) system was studied electrochemically. The standard rate constants and kinetic isotope effects (KIEs) were measured experimentally for this system and a related single proton transfer system. In the present paper, these systems are studied theoretically using vibronically nonadiabatic rate constant expressions for electrochemical PCET. Application of this approach to proton relays requires the calculation of multidimensional proton vibrational wavefunctions and incorporation of multiple proton donor-acceptor motions. The calculated KIEs and relative standard rate constants for the single and double proton transfer systems are in agreement with the experimental data. The calculations indicate that the standard rate constant is lower for the double proton transfer system because of the smaller overlap integral between the ground state reduced and oxidized proton vibrational wavefunctions for this system, resulting in greater contributions from excited electron-proton vibronic states with higher free energy barriers. The decrease in proton donor-acceptor distances due to thermal fluctuations and the contributions from excited electron-proton vibronic states play important roles in proton relay systems. The theory suggests that the PCET rate constant may be increased by decreasing the equilibrium proton donor-acceptor distances or modifying the thermal motions of the molecule to facilitate the concurrent decrease of these distances. The submission of this journal article in ERIA is a requirement of the EFRC subcontract with Pennsylvania State University collaborators to get publications to OSTI.

  5. Spectroscopy and dynamics of double proton transfer in formic acid dimer

    DEFF Research Database (Denmark)

    Mackeprang, Kasper; Xu, Zhen-Hao; Maroun, Zeina

    2016-01-01

    , a combination of symmetric single and double minimum potential energy surfaces (PESs) provides a good description of the double proton transfer PES. In a next step, potential morphing together with electronic structure calculations at the B3LYP and MP2 level of theory was used to align the computed...

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  7. Proton position near QB and coupling of electron and proton transfer in photosynthesis

    International Nuclear Information System (INIS)

    Belousov, R V; Poltev, S V; Kukushkin, A K

    2003-01-01

    We have calculated the energy levels and wavefunctions of a proton in a histidine (His)-plastoquinone (PQ) system in the reaction centre (RC) of photosystem 2 of higher plants and the RC of purple bacteria for different redox states of PQ Q B . For oxidized Q B , the proton is located near His. For once-reduced PQ, it is positioned in the middle between the nitrogen of His and the oxygen of PQ. For twofold-reduced PQ, the proton is localized near the oxygen of PQ. Using the values of total energy of the system in these states, we have also estimated the frequency of proton oscillations. On the basis of these results we propose a hypothesis about the coupling of electron-proton transfer

  8. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

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

    2018-04-01

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

  9. Kinetics of water-mediated proton transfer in our atmosphere

    International Nuclear Information System (INIS)

    Loerting, T.

    2000-07-01

    Variational transition state theory and multidimensional tunneling methods on hybrid density functional theory generated hypersurfaces have been used to investigate the temperature dependence of the reaction rate constants of water-mediated proton transfer reactions relevant to the chemistry of our atmosphere, namely the hydration of sulfur dioxide and sulfur trioxide and the decomposition of chlorine nitrate. Highly accurate reaction barriers were calculated using ab initio methods taking into account most of the electron correlation, namely CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ and G2(MP2). On comparing the determined rate constants with laboratory and atmospheric data, the following points could be established: All of the investigated reactions are highly sensitive to changes in humidity, as water acts as efficient catalyst, i.e., the barrier to the reaction is reduced drastically. Present-day atmospheric chemistry can only be explained when a limited number of water molecules is available for the formation of molecular clusters. Both in the troposphere and in the stratosphere SO 3 is hydrated rather than SO 2 . SO 2 emissions have to be oxidized, therefore, before being subject to hydration. A mechanism involving two or three water molecules is relevant for the production of sulfate aerosols, which play a decisive role in the context of global climate change and acid rain. A third water molecule has the function of assisting double-proton transfer rather than acting as active participant in triple-proton transfer in the case of the hydration of sulfur oxides. The observed ozone depletion above Arctica and Antarctica can be explained either by decomposition of chlorine nitrate in the presence of three water molecules (triple proton transfer) or by decomposition of chlorine nitrate in the presence of one molecule of HCl and one molecule of water (double proton transfer). The preassociation reaction required for homogeneous gas-phase conversion of chlorine

  10. Effect of proton transfer on the electronic coupling in DNA

    International Nuclear Information System (INIS)

    Rak, Janusz; Makowska, Joanna; Voityuk, Alexander A.

    2006-01-01

    The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, V da , in DNA are studied on the bases of quantum chemical calculations. Four dimers [AT,AT], [GC,GC], [GC,AT] and [GC,TA)] are considered. Three techniques - the generalized Mulliken-Hush scheme, the fragment charge method and the diabatic states method - are employed to estimate V da for hole transfer between base pairs. We show that both single- and double proton transfer (PT) reactions may substantially affect the electronic coupling in DNA. The electronic coupling in [AT,AT] is predicted to be most sensitive to PT. Single PT within the first base pair in the dimer leads to increase in the hole transfer efficiency by a factor of 4, while proton transfer within the second pair should substantially, by 2.7 times, decrease the rate of charge transfer. Thus, directional asymmetry of the PT effects on the electronic coupling is predicted. The changes in the V da matrix elements correlate with the topological properties of orbitals of donor and acceptor and can be qualitatively rationalized in terms of resonance structures of donor and acceptor. Atomic pair contributions to the V da matrix elements are also analyzed

  11. Single proton transfer reactions on odd-even nuclei

    International Nuclear Information System (INIS)

    Blasi, N.

    1984-01-01

    This thesis is devoted to the study of one proton transfer reactions, performed with the use of the magnetic spectrograph QMG/2 of the KVI, in two regions of the mass table. Stripping and pickup reactions on the odd-A target nuclei 193 Ir and 197 Au are described in the first part. The experimental spectroscopic factors obtained are used to test several collective models that are based on coupling between bosons (phonons) and fermions. In the second part, the proton stripping reactions on 113 In and 115 In are studied. Shell model calculations are performed and applied to the experimental results. (Auth.)

  12. Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

    Science.gov (United States)

    Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

    2011-03-24

    The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

  13. Probing hydrogen bonding interactions and proton transfer in proteins

    Science.gov (United States)

    Nie, Beining

    Scope and method of study. Hydrogen bonding is a fundamental element in protein structure and function. Breaking a single hydrogen bond may impair the stability of a protein. It is therefore important to probe dynamic changes in hydrogen bonding interactions during protein folding and function. Time-resolved Fourier transform infrared spectroscopy is highly sensitive to hydrogen bonding interactions. However, it lacks quantitative correlation between the vibrational frequencies and the number, type, and strength of hydrogen bonding interactions of ionizable and polar residues. We employ quantum physics theory based ab initio calculations to study the effects of hydrogen bonding interactions on vibrational frequencies of Asp, Glu, and Tyr residues and to develop vibrational spectral markers for probing hydrogen bonding interactions using infrared spectroscopy. In addition, proton transfer process plays a crucial role in a wide range of energy transduction, signal transduction, and enzymatic reactions. We study the structural basis for proton transfer using photoactive yellow protein as an excellent model system. Molecular dynamics simulation is employed to investigate the structures of early intermediate states. Quantum theory based ab initio calculations are used to study the impact of hydrogen bond interactions on proton affinity and proton transfer. Findings and conclusions. Our extensive density function theory based calculations provide rich structural, spectral, and energetic information on hydrogen bonding properties of protonated side chain groups of Asp/Glu and Tyr. We developed vibrational spectral markers and 2D FTIR spectroscopy for structural characterization on the number and the type of hydrogen bonding interactions of the COOH group of Asp/Glu and neutral phenolic group of Tyr. These developments greatly enhance the power of time-resolved FTIR spectroscopy as a major experimental tool for structural characterization of functionally important

  14. Proton Transfer Time-of-Flight Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Watson, Thomas B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2016-03-01

    The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H3O+), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-charge ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.

  15. Recovery of forward stepping in spinal cord injured patients does not transfer to untrained backward stepping.

    Science.gov (United States)

    Grasso, Renato; Ivanenko, Yuri P; Zago, Myrka; Molinari, Marco; Scivoletto, Giorgio; Lacquaniti, Francesco

    2004-08-01

    Six spinal cord injured (SCI) patients were trained to step on a treadmill with body-weight support for 1.5-3 months. At the end of training, foot motion recovered the shape and the step-by-step reproducibility that characterize normal gait. They were then asked to step backward on the treadmill belt that moved in the opposite direction relative to standard forward training. In contrast to healthy subjects, who can immediately reverse the direction of walking by time-reversing the kinematic waveforms, patients were unable to step backward. Similarly patients were unable to perform another untrained locomotor task, namely stepping in place on the idle treadmill. Two patients who were trained to step backward for 2-3 weeks were able to develop control of foot motion appropriate for this task. The results show that locomotor improvement does not transfer to untrained tasks, thus supporting the idea of task-dependent plasticity in human locomotor networks.

  16. 4-Hydroxy-1-naphthaldehydes: proton transfer or deprotonation

    DEFF Research Database (Denmark)

    Manolova, Y; Kurteva, V; Antonov, L

    2015-01-01

    A series of naphthaldehydes, including a Mannich base, have been investigated by UV-Vis spectroscopy, NMR and theoretical methods to explore their potential tautomerism. In the case of 4-hydroxy-1-naphthaldehyde concentration dependent deprotonation has been detected in methanol and acetonitrile....... For 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (a Mannich base) an intramolecular proton transfer involving the OH group and the piperidine nitrogen occurs. In acetonitrile the equilibrium is predominantly at the OH-form, whereas in methanol the proton transferred tautomer is the preferred form....... In chloroform and toluene, the OH form is completely dominant. Both 4-hydroxy-1-naphthaldehyde and 4-methoxy-1-naphthaldehyde (fixed enol form) show dimerization in the investigated solvents and the crystallographic data, obtained for the latter, confirm the existence of a cyclic dimer...

  17. Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation.

    Science.gov (United States)

    Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho, Jr-Wei; Chen, Yi-Wei; Cheng, Po-Yuan

    2017-10-28

    In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH 3 ) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH 3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S 1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH 3 ] + cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ∼70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

  18. Proton Linear Energy Transfer measurement using Emulsion Cloud Chamber

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Jae-ik [Proton Therapy Center, National Cancer Center (Korea, Republic of); Division of Heavy Ion Clinical Research, Korea Institute of Radiological & Medical Sciences (KIRAMS), Seoul (Korea, Republic of); Park, Seyjoon [Department of Radiation Oncology, Samsung Medical Center, Sungkyunkwan University, School of Medicine, Seoul (Korea, Republic of); Kim, Haksoo; Kim, Meyoung [Proton Therapy Center, National Cancer Center (Korea, Republic of); Jeong, Chiyoung [Department of Radiation Oncology, Asan Medical Center, University of Ulsan College of Medicine, Seoul (Korea, Republic of); Cho, Sungkoo [Department of Radiation Oncology, Samsung Medical Center, Sungkyunkwan University, School of Medicine, Seoul (Korea, Republic of); Lim, Young Kyung; Shin, Dongho [Proton Therapy Center, National Cancer Center (Korea, Republic of); Lee, Se Byeong, E-mail: sblee@ncc.re.kr [Proton Therapy Center, National Cancer Center (Korea, Republic of); Morishima, Kunihiro; Naganawa, Naotaka; Sato, Osamu [Department of Physics, Nagoya University, Nagoya (Japan); Kwak, Jungwon [Department of Radiation Oncology, Asan Medical Center, University of Ulsan College of Medicine, Seoul (Korea, Republic of); Kim, Sung Hyun [Center for Underground Physics, Institute for Basic Science (IBS), Daejeon (Korea, Republic of); Cho, Jung Sook [Department of refinement education, Dongseo University, Busan (Korea, Republic of); Ahn, Jung Keun [Department of Physics, Korea University, Seoul (Korea, Republic of); Kim, Ji Hyun; Yoon, Chun Sil [Gyeongsang National University, Jinju (Korea, Republic of); Incerti, Sebastien [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Université Bordeaux 1, CENBG, UMR 5797, F-33170 Gradignan (France)

    2015-04-15

    This study proposes to determine the correlation between the Volume Pulse Height (VPH) measured by nuclear emulsion and Linear Energy Transfer (LET) calculated by Monte Carlo simulation based on Geant4. The nuclear emulsion was irradiated at the National Cancer Center (NCC) with a therapeutic proton beam and was installed at 5.2 m distance from the beam nozzle structure with various thicknesses of water-equivalent material (PMMA) blocks to position with specific positions along the Bragg curve. After the beam exposure and development of the emulsion films, the films were scanned by S-UTS developed in Nagoya University. The proton tracks in the scanned films were reconstructed using the ‘NETSCAN’ method. Through this procedure, the VPH can be derived from each reconstructed proton track at each position along the Bragg curve. The VPH value indicates the magnitude of energy loss in proton track. By comparison with the simulation results obtained using Geant4, we found the correlation between the LET calculated by Monte Carlo simulation and the VPH measured by the nuclear emulsion.

  19. Proton Linear Energy Transfer measurement using Emulsion Cloud Chamber

    International Nuclear Information System (INIS)

    Shin, Jae-ik; Park, Seyjoon; Kim, Haksoo; Kim, Meyoung; Jeong, Chiyoung; Cho, Sungkoo; Lim, Young Kyung; Shin, Dongho; Lee, Se Byeong; Morishima, Kunihiro; Naganawa, Naotaka; Sato, Osamu; Kwak, Jungwon; Kim, Sung Hyun; Cho, Jung Sook; Ahn, Jung Keun; Kim, Ji Hyun; Yoon, Chun Sil; Incerti, Sebastien

    2015-01-01

    This study proposes to determine the correlation between the Volume Pulse Height (VPH) measured by nuclear emulsion and Linear Energy Transfer (LET) calculated by Monte Carlo simulation based on Geant4. The nuclear emulsion was irradiated at the National Cancer Center (NCC) with a therapeutic proton beam and was installed at 5.2 m distance from the beam nozzle structure with various thicknesses of water-equivalent material (PMMA) blocks to position with specific positions along the Bragg curve. After the beam exposure and development of the emulsion films, the films were scanned by S-UTS developed in Nagoya University. The proton tracks in the scanned films were reconstructed using the ‘NETSCAN’ method. Through this procedure, the VPH can be derived from each reconstructed proton track at each position along the Bragg curve. The VPH value indicates the magnitude of energy loss in proton track. By comparison with the simulation results obtained using Geant4, we found the correlation between the LET calculated by Monte Carlo simulation and the VPH measured by the nuclear emulsion

  20. Proton Linear Energy Transfer measurement using Emulsion Cloud Chamber

    Science.gov (United States)

    Shin, Jae-ik; Park, Seyjoon; Kim, Haksoo; Kim, Meyoung; Jeong, Chiyoung; Cho, Sungkoo; Lim, Young Kyung; Shin, Dongho; Lee, Se Byeong; Morishima, Kunihiro; Naganawa, Naotaka; Sato, Osamu; Kwak, Jungwon; Kim, Sung Hyun; Cho, Jung Sook; Ahn, Jung Keun; Kim, Ji Hyun; Yoon, Chun Sil; Incerti, Sebastien

    2015-04-01

    This study proposes to determine the correlation between the Volume Pulse Height (VPH) measured by nuclear emulsion and Linear Energy Transfer (LET) calculated by Monte Carlo simulation based on Geant4. The nuclear emulsion was irradiated at the National Cancer Center (NCC) with a therapeutic proton beam and was installed at 5.2 m distance from the beam nozzle structure with various thicknesses of water-equivalent material (PMMA) blocks to position with specific positions along the Bragg curve. After the beam exposure and development of the emulsion films, the films were scanned by S-UTS developed in Nagoya University. The proton tracks in the scanned films were reconstructed using the 'NETSCAN' method. Through this procedure, the VPH can be derived from each reconstructed proton track at each position along the Bragg curve. The VPH value indicates the magnitude of energy loss in proton track. By comparison with the simulation results obtained using Geant4, we found the correlation between the LET calculated by Monte Carlo simulation and the VPH measured by the nuclear emulsion.

  1. Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

    Science.gov (United States)

    Rhile, Ian J.

    2011-01-01

    To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O⋯N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG°(2 + 3a+) = +0.078 V vs. ΔG°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δln(k)/Δln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly

  2. Kinetics of proton transfer in a green fluorescent protein: A laser ...

    Indian Academy of Sciences (India)

    Unknown

    therefore implicates bulk solvent-controlled protein dynamics in the protonation process. ... recently to protein–protein interactions in the bacterial response regulator SpoOF. NMR ..... molecular mechanism for redox-driven proton transfer to a buried iron–sulphur cluster ... Dynamic simulations of proton transfer from bulk.

  3. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

    Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

  4. Umbrella sampling of proton transfer in a creatine-water system

    Science.gov (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra

    2014-04-01

    Proton transfer reactions are among the most common processes in chemistry and biology. Proton transfer between creatine and surrounding solvent water is underlying the chemical exchange saturation transfer used as a contrast in magnetic resonance imaging. The free energy barrier, determined by first-principles umbrella sampling simulations (EaDFT 3 kcal/mol) is in the same order of magnitude as the experimentally obtained activation energy. The underlying mechanism is a first proton transfer from the guanidinium group to the water pool, followed by a second transition where a proton is "transferred back" from the nearest water molecule to the deprotonated nitrogen atom of creatine.

  5. The Membrane Modulates Internal Proton Transfer in Cytochrome c Oxidase

    DEFF Research Database (Denmark)

    Öjemyr, Linda Nasvik; Ballmoos, Christoph von; Faxén, Kristina

    2012-01-01

    The functionality of membrane proteins is often modulated by the surrounding membrane. Here, we investigated the effect of membrane reconstitution of purified cytochrome c oxidase (CytcO) on the kinetics and thermodynamics of internal electron and proton-transfer reactions during O-2 reduction...... DOPC lipids. In conclusion, the data show that the membrane significantly modulates internal charge-transfer reactions and thereby the function of the membrane-bound enzyme.......-glycerol) (DOPG). In addition, a small Change in the internal Cu-A-heme a electron equilibrium constant was observed. This effect was lipid-dependent and explained in terms of a lower electrostatic potential within the membrane-spanning part of the protein with the anionic DOPG lipids than with the zwitterionic...

  6. New memory devices based on the proton transfer process

    International Nuclear Information System (INIS)

    Wierzbowska, Małgorzata

    2016-01-01

    Memory devices operating due to the fast proton transfer (PT) process are proposed by the means of first-principles calculations. Writing  information is performed using the electrostatic potential of scanning tunneling microscopy (STM). Reading information is based on the effect of the local magnetization induced at the zigzag graphene nanoribbon (Z-GNR) edge—saturated with oxygen or the hydroxy group—and can be realized with the use of giant magnetoresistance (GMR), a magnetic tunnel junction or spin-transfer torque devices. The energetic barriers for the hop forward and backward processes can be tuned by the distance and potential of the STM tip; this thus enables us to tailor the non-volatile logic states. The proposed system enables very dense packing of the logic cells and could be used in random access and flash memory devices. (paper)

  7. New memory devices based on the proton transfer process

    Science.gov (United States)

    Wierzbowska, Małgorzata

    2016-01-01

    Memory devices operating due to the fast proton transfer (PT) process are proposed by the means of first-principles calculations. Writing information is performed using the electrostatic potential of scanning tunneling microscopy (STM). Reading information is based on the effect of the local magnetization induced at the zigzag graphene nanoribbon (Z-GNR) edge—saturated with oxygen or the hydroxy group—and can be realized with the use of giant magnetoresistance (GMR), a magnetic tunnel junction or spin-transfer torque devices. The energetic barriers for the hop forward and backward processes can be tuned by the distance and potential of the STM tip; this thus enables us to tailor the non-volatile logic states. The proposed system enables very dense packing of the logic cells and could be used in random access and flash memory devices.

  8. Infrared spectra of proton transfer complexes of the cycleanine alkaloid in solid state

    Science.gov (United States)

    Kasende, Okuma E.; de Waal, D.

    2003-01-01

    Proton transfer complexes obtained between the cycleanine alkaloid and hydrogen chloride, hydrogen bromide and nitric acids have been investigated by infrared spectroscopic technique between 4000 and 400 cm -1 in KBr. The vibrational perturbations brought about by proton transfer complex formation, discussed in terms of preferred site of interaction, show that the proton of the inorganic acids is transferred to cycleanine through one of its N sites.

  9. Theory of two-step two-proton decays of nuclei

    International Nuclear Information System (INIS)

    Kadmensky, S. G.; Ivankov, Yu. V.

    2014-01-01

    A general theory of many-body diagonal and nondiagonal one-proton decays of spherical and deformed nuclei is developed on the basis of an approach not employing R-matrix theory in describing deep-subbarrier alpha and one-proton decays of nuclei but relying on integral formulas for the widths with respect to these decays. With the aid of this theory and by means of a diagram technique, a formalism is developed for describing two-step two-proton decays of a (Z, A) parent nucleus, which proceed as two successive time-separated one-proton decays of the parent and intermediate [(Z − 1, A − 1)] nuclei, these decays being related by the Green’s function for the intermediate nucleus, G(Z − 1, A − 1). It is shown that, upon taking into account, in this Green’s function, intermediate-nucleus states that are on- and off-shell states for the decaying system, there arise, respectively, sequential and virtual two-proton decays of parent nuclei. Expressions for the widths with respect to sequential and virtual two-proton decays from the ground and excited states of spherical and deformed nuclei and for the angular and energy distributions of emitted protons are obtained

  10. Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

    Science.gov (United States)

    Li, Ailin; Yan, Tianying; Shen, Panwen

    Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer.

  11. Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ailin; Yan, Tianying; Shen, Panwen [Department of Material Chemistry, Institute of New Energy Material Chemistry, Nankai University, Tianjin, 300071 (China)

    2011-02-01

    Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer. (author)

  12. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

    Science.gov (United States)

    Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

    2016-11-10

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

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

    Science.gov (United States)

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

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

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

    International Nuclear Information System (INIS)

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

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

  15. Intermolecular proton transfer in anionic complexes of uracil with alcohols

    International Nuclear Information System (INIS)

    Haranczyk, Maciej; Rak, Janusz; Gutowski, Maciej S.; Radisic, Dunja; Stokes, Sarah T.; Bowen, Kit H.

    2005-01-01

    A series of eighteen alcohols (ROH) has been designed with an enthalpy of deprotonation (H DP ) in a range of 13.8-16.3 eV. The effects of excess electron attachment to the binary alcohol-uracil (ROH...U) complexes have been studied at the density functional level with a B3LYP exchange-correlation functional and at the second order Moeller-Plesset perturbation theory level. The photoelectron spectra of anionic complexes of uracil with three alcohols (ethanol, 2,2,3,3,3-pentafluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol) have been measured with 2.54 eV photons. For ROHs with deprotonation enthalpies larger than 14.8 eV only the ROH...U - minimum exists on the potential energy surface of the anionic complex. For alcohols with deprotonation enthalpies in a range of 14.3-14.8 eV two minima might exist on the anionic potential energy surface, which correspond to the RO - ...HU . and ROH...U - structures. For ROHs with deprotonation enthalpies smaller than 14.3 eV, the excess electron attachment to the ROH...U complex always induces a barrier-free proton transfer from the hydroxyl group of ROH to the O8 atom of U, with the product being RO - ...HU . . A driving force for the intermolecular proton transfer is to stabilize the excess negative charge localized on a orbital of uracil. Therefore, these complexes with proton transferred to the anionic uracil are characterized by larger values of electron vertical detachment energy (VDE). The values of VDE for anionic complexes span a range from 1.0 to 2.3 eV and roughly correlate with the acidity of alcohols. However, there is a gap of ∼0.5 eV in the values of VDE, which separates the two families, ROH...U - and RO - ...HU . , of anionic complexes. The energy of stabilization for the anionic complexes spans a range from 0.6 to 1.7 eV and roughly correlates with the acidity of alcohols. The measured photoelectron spectra are in good agreement with the theoretical predictions

  16. Theoretical Insights Into the Excited State Double Proton Transfer Mechanism of Deep Red Pigment Alkannin.

    Science.gov (United States)

    Zhao, Jinfeng; Dong, Hao; Zheng, Yujun

    2018-02-08

    As the most important component of deep red pigments, alkannin is investigated theoretically in detail based on time-dependent density functional theory (TDDFT) method. Exploring the dual intramolecular hydrogen bonds (O1-H2···O3 and O4-H5···O6) of alkannin, we confirm the O1-H2···O3 may play a more important role in the first excited state than the O4-H5···O6 one. Infrared (IR) vibrational analyses and subsequent charge redistribution also support this viewpoint. Via constructing the S 1 -state potential energy surface (PES) and searching transition state (TS) structures, we illuminate the excited state double proton transfer (ESDPT) mechanism of alkannin is the stepwise process that can be first launched by the O1-H2···O3 hydrogen bond wire in gas state, acetonitrile (CH 3 CN) and cyclohexane (CYH) solvents. We present a novel mechanism that polar aprotic solvents can contribute to the first-step proton transfer (PT) process in the S 1 state, and nonpolar solvents play important roles in lowering the potential energy barrier of the second-step PT reaction.

  17. Proton Transfers at the Air-Water Interface

    Science.gov (United States)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the

  18. Proton Transfer in Perfluorosulfonic Acid Fuel Cell Membranes with Differing Pendant Chains and Equivalent Weights.

    Science.gov (United States)

    Thomaz, Joseph E; Lawler, Christian M; Fayer, Michael D

    2017-05-04

    Proton transfer in the nanoscopic water channels of polyelectrolyte fuel cell membranes was studied using a photoacid, 8-hydroxypyrene-1,3,6-trisulfonic acid sodium salt (HPTS), in the channels. The local environment of the probe was determined using 8-methoxypyrene-1,3,6-trisulfonic acid sodium salt (MPTS), which is not a photoacid. Three fully hydrated membranes, Nafion (DuPont) and two 3M membranes, were studied to determine the impact of different pendant chains and equivalent weights on proton transfer. Fluorescence anisotropy and excited state population decay data that characterize the local environment of the fluorescent probes and proton transfer dynamics were measured. The MPTS lifetime and anisotropy results show that most of the fluorescent probes have a bulk-like water environment with a relatively small fraction interacting with the channel wall. Measurements of the HPTS protonated and deprotonated fluorescent bands' population decays provided information on the proton transport dynamics. The decay of the protonated band from ∼0.5 ns to tens of nanoseconds is in part determined by dissociation and recombination with the HPTS, providing information on the ability of protons to move in the channels. The dissociation and recombination is manifested as a power law component in the protonated band fluorescence decay. The results show that equivalent weight differences between two 3M membranes resulted in a small difference in proton transfer. However, differences in pendant chain structure did significantly influence the proton transfer ability, with the 3M membranes displaying more facile transfer than Nafion.

  19. Charge transfer in proton-hydrogen collisions under Debye plasma

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharya, Arka [Department of Mathematics, Burdwan University, Golapbag, Burdwan 713 104, West Bengal (India); Kamali, M. Z. M. [Centre for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Ghoshal, Arijit, E-mail: arijit98@yahoo.com [Department of Mathematics, Burdwan University, Golapbag, Burdwan 713 104, West Bengal (India); Department of Mathematics, Kazi Nazrul University, B.C.W. Campus, Asansol 713 304, West Bengal (India); Institute of Mathematical Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Ratnavelu, K. [Department of Mathematics, Kazi Nazrul University, B.C.W. Campus, Asansol 713 304, West Bengal (India)

    2015-02-15

    The effect of plasma environment on the 1s → nlm charge transfer, for arbitrary n, l, and m, in proton-hydrogen collisions has been investigated within the framework of a distorted wave approximation. The effect of external plasma has been incorporated using Debye screening model of the interacting charge particles. Making use of a simple variationally determined hydrogenic wave function, it has been possible to obtain the scattering amplitude in closed form. A detailed study has been made to investigate the effect of external plasma environment on the differential and total cross sections for electron capture into different angular momentum states for the incident energy in the range of 20–1000 keV. For the unscreened case, our results are in close agreement with some of the most accurate results available in the literature.

  20. Membrane introduction proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  1. Excited state proton transfer in strongly enhanced GFP (sGFP2)

    NARCIS (Netherlands)

    van Oort, B.F.; ter Veer, M.J.T.; Groot, M.L.; van Stokkum, I.H.M.

    2012-01-01

    Proton transfer is an elementary process in biology. Green fluorescent protein (GFP) has served as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. We have used pump-dump-probe spectroscopy to study

  2. 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...

  3. Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

    Science.gov (United States)

    Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

    2010-05-05

    A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

  4. Excited state proton transfer in strongly enhanced GFP (sGFP2).

    Science.gov (United States)

    van Oort, Bart; ter Veer, Mirelle J T; Groot, Marie Louise; van Stokkum, Ivo H M

    2012-07-07

    Proton transfer is an elementary process in biology. Green fluorescent protein (GFP) has served as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. We have used pump-dump-probe spectroscopy to study how proton transfer through the 'proton-wire' around the chromophore is affected by a combination of mutations in a modern GFP variety (sGFP2). The results indicate that in H(2)O, after absorption of a photon, a proton is transferred (A* → I*) in 5 ps, and back-transferred from a ground state intermediate (I → A) in 0.3 ns, similar to time constants found with GFPuv, although sGFP2 shows less heterogeneous proton transfer. This suggests that the mutations left the proton-transfer largely unchanged, indicating the robustness of the proton-wire. We used pump-dump-probe spectroscopy in combination with target analysis to probe suitability of the sGFP2 fluorophore for super-resolution microscopy.

  5. Field theoretical approach to proton-nucleus reactions: II-Multiple-step excitation process

    International Nuclear Information System (INIS)

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

    1989-01-01

    A field theoretical formulation to multiple step excitation process in proton-nucleus collision within the context of a relativistic eikonal approach is presented. A closed form expression for the double differential cross section can be obtained whose structure is very simple and makes the physics transparent. Glauber's formulation of the same process is obtained as a limit of ours and the necessary approximations are studied and discussed. (author) [pt

  6. Linear energy transfer incorporated intensity modulated proton therapy optimization

    Science.gov (United States)

    Cao, Wenhua; Khabazian, Azin; Yepes, Pablo P.; Lim, Gino; Poenisch, Falk; Grosshans, David R.; Mohan, Radhe

    2018-01-01

    The purpose of this study was to investigate the feasibility of incorporating linear energy transfer (LET) into the optimization of intensity modulated proton therapy (IMPT) plans. Because increased LET correlates with increased biological effectiveness of protons, high LETs in target volumes and low LETs in critical structures and normal tissues are preferred in an IMPT plan. However, if not explicitly incorporated into the optimization criteria, different IMPT plans may yield similar physical dose distributions but greatly different LET, specifically dose-averaged LET, distributions. Conventionally, the IMPT optimization criteria (or cost function) only includes dose-based objectives in which the relative biological effectiveness (RBE) is assumed to have a constant value of 1.1. In this study, we added LET-based objectives for maximizing LET in target volumes and minimizing LET in critical structures and normal tissues. Due to the fractional programming nature of the resulting model, we used a variable reformulation approach so that the optimization process is computationally equivalent to conventional IMPT optimization. In this study, five brain tumor patients who had been treated with proton therapy at our institution were selected. Two plans were created for each patient based on the proposed LET-incorporated optimization (LETOpt) and the conventional dose-based optimization (DoseOpt). The optimized plans were compared in terms of both dose (assuming a constant RBE of 1.1 as adopted in clinical practice) and LET. Both optimization approaches were able to generate comparable dose distributions. The LET-incorporated optimization achieved not only pronounced reduction of LET values in critical organs, such as brainstem and optic chiasm, but also increased LET in target volumes, compared to the conventional dose-based optimization. However, on occasion, there was a need to tradeoff the acceptability of dose and LET distributions. Our conclusion is that the

  7. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

    electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

  8. A short comparison of electron and proton transfer processes in biological systems

    International Nuclear Information System (INIS)

    Bertrand, Patrick

    2005-01-01

    The main differences between electron and proton transfers that take place in biological systems are examined. The relation between the distance dependence of the rate constant and the mass of the transferred particle is analyzed in detail. Differences between the two processes have important consequences at the experimental level, which are discussed. The various mechanisms that ensure the coupling between electron and proton transfers are briefly described

  9. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    Science.gov (United States)

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-01-01

    The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

  10. Virtual Compton scattering off protons at moderately large momentum transfer

    International Nuclear Information System (INIS)

    Kroll, P.

    1996-01-01

    The amplitudes for virtual Compton scattering off protons are calculated within the framework of the diquark model in which protons are viewed as being built up by quarks and diquarks. The latter objects are treated as quasi-elementary constituents of the proton. Virtual Compton scattering, electroproduction off protons and the Bethe-Heitler contamination are photon discussed for various kinematical situations. We particularly emphasize the role of the electron asymmetry for measuring the relative phases between the virtual Compton and the Bethe-Heitler amplitudes. It is also shown that the model is able to describe very well the experimental data for real Compton scattering off protons. (orig.)

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

    Science.gov (United States)

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

    2018-03-22

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

  12. Two-step sintering of ultrafine-grained barium cerate proton conducting ceramics

    International Nuclear Information System (INIS)

    Wang, Siwei; Zhang, Lei; Zhang, Lingling; Brinkman, Kyle; Chen, Fanglin

    2013-01-01

    Ultra-fine grained dense BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3−δ (BZCYYb) ceramics have been successfully prepared via a two-step sintering method. Co-precipitation method has been adopted to prepare nano-sized BZCYYb precursors with an average particle size of 30 nm. By controlling the sintering profile, an average grain size of 184 nm was obtained for dense BZCYYb ceramics via the two-step sintering method, compared to 445 nm for the conventional sintered samples. The two-step sintered BZCYYb samples showed less impurity and an enhanced electrical conductivity compared with the conventional sintered ones. Further, the two-step sintering method was applied to fabricate anode supported solid oxide fuel cells (SOFCs) using BZCYYb as the electrolyte, resulting in dense ultrafine-grained electrolyte membranes and porous anode substrates with fine particles. Due to the reduced ohmic as well as polarization resistances, the maximum power output of the cells fabricated from the two-step sintering method reached 349 mW m −2 at 700 °C, significantly improved from 172 mW cm −2 for the conventional sintered cells, suggesting that two-step sintering method is very promising for optimizing the microstructure and thus enhancing the electrochemical performances for barium cerate based proton-conducting SOFCs.

  13. Stripping of two protons and one alpha particle transfer reactions for 16 O + A Sm and their influence on the fusion cross section

    International Nuclear Information System (INIS)

    Maciel, A.M.M.; Gomes, P.R.S.

    1995-01-01

    Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the 16 O + A Sm systems (A=144, 148, 150, 152 and 154), at near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author)

  14. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

    Science.gov (United States)

    Chen, Mohan; Zheng, Lixin; Santra, Biswajit; Ko, Hsin-Yu; DiStasio, Robert A., Jr.; Klein, Michael L.; Car, Roberto; Wu, Xifan

    2018-03-01

    Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid-base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

  15. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

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

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  17. Imaging of endogenous exchangeable proton signals in the human brain using frequency labeled exchange transfer imaging.

    Science.gov (United States)

    Yadav, Nirbhay N; Jones, Craig K; Hua, Jun; Xu, Jiadi; van Zijl, Peter C M

    2013-04-01

    To image endogenous exchangeable proton signals in the human brain using a recently reported method called frequency labeled exchange transfer (FLEX) MRI. As opposed to labeling exchangeable protons using saturation (i.e., chemical exchange saturation transfer, or CEST), FLEX labels exchangeable protons with their chemical shift evolution. The use of short high-power frequency pulses allows more efficient labeling of rapidly exchanging protons, while time domain acquisition allows removal of contamination from semi-solid magnetization transfer effects. FLEX-based exchangeable proton signals were detected in human brain over the 1-5 ppm frequency range from water. Conventional magnetization transfer contrast and the bulk water signal did not interfere in the FLEX spectrum. The information content of these signals differed from in vivo CEST data in that the average exchange rate of these signals was 350-400 s(-1) , much faster than the amide signal usually detected using direct saturation (∼30 s(-1) ). Similarly, fast exchanging protons could be detected in egg white in the same frequency range where amide and amine protons of mobile proteins and peptides are known to resonate. FLEX MRI in the human brain preferentially detects more rapidly exchanging amide/amine protons compared to traditional CEST experiments, thereby changing the information content of the exchangeable proton spectrum. This has the potential to open up different types of endogenous applications as well as more easy detection of rapidly exchanging protons in diaCEST agents or fast exchanging units such as water molecules in paracest agents without interference of conventional magnetization transfer contrast. Copyright © 2013 Wiley Periodicals, Inc.

  18. Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

    International Nuclear Information System (INIS)

    Nonose, Shinji; Yamashita, Kazuki; Sudo, Ayako; Kawashima, Minami

    2013-01-01

    Highlights: • Proton transfer from angiotensin I ions (z = 2, 3) to gaseous molecules was studied. • Temperature dependence of absolute reaction rate constants was measured. • Remarkable changes were obtained for distribution of product ions and reaction rate constants. • Proton transfer reaction was enhanced and reduced by complex formation. • Conformation changes are induced by complex formation and or by thermal collision with He. - Abstract: Proton transfer reactions of angiotensin I ions for +2 charge state, [M + 2H] 2+ , to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M + 2H] 2+ with gaseous molecules. The results relate to conformation changes of [M + 2H] 2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M + 3H] 3+ , were also studied. The reaction rates did not depend on temperature so definitely

  19. An S-N2-model for proton transfer in hydrogen-bonded systems

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

  20. Virtual compton scattering off protons at moderately large momentum transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kroll, P; Schuermann, M [Wuppertal Univ. (Gesamthochschule) (Germany); Guichon, P A.M. [CEA Centre d` Etudes de Saclay, 91 - Gif-sur-Yvette (France). Dept. d` Astrophysique, de la Physique des Particules, de la Physique Nucleaire et de l` Instrumentation Associee

    1995-06-28

    The amplitudes for virtual Compton scattering off protons are calculated within the framework of the diquark model in which protons are viewed as being built up by quarks and diquarks. The latter objects are treated as quasi-elementary constituents of the proton. Virtual Compton scattering, electroproduction of photons and the Bethe-Heitler contamination are discussed for various kinematical situations. We particularly emphasize the role of the electron asymmetry for measuring the relative phases between the virtual Compton and the Bethe-Heitler amplitudes. It is also shown that the model is able to describe very well the experimental data for real Compton scattering off protons. (authors). 35 refs., 8 figs., 1 tab.

  1. Virtual compton scattering off protons at moderately large momentum transfer

    International Nuclear Information System (INIS)

    Kroll, P.; Schuermann, M.; Guichon, P.A.M.

    1995-01-01

    The amplitudes for virtual Compton scattering off protons are calculated within the framework of the diquark model in which protons are viewed as being built up by quarks and diquarks. The latter objects are treated as quasi-elementary constituents of the proton. Virtual Compton scattering, electroproduction of photons and the Bethe-Heitler contamination are discussed for various kinematical situations. We particularly emphasize the role of the electron asymmetry for measuring the relative phases between the virtual Compton and the Bethe-Heitler amplitudes. It is also shown that the model is able to describe very well the experimental data for real Compton scattering off protons. (authors). 35 refs., 8 figs., 1 tab

  2. Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, Stephen C. [Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States; Bettis Homan, Stephanie [Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States; Weiss, Emily A. [Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States

    2016-01-28

    This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecond time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.

  3. Isotope effects for base-promoted, gas-phase proton transfer reactions

    International Nuclear Information System (INIS)

    Grabowski, J.J.; Cheng, Xueheng

    1991-01-01

    Proton transfer reactions are among the most basic, the most common and the most important of chemical transformations; despite their apparent simplicity, much is unknown about this most fundamental of all chemical processes. Active interest in understanding the underlying principles of organic proton transfer reactions continues because of efforts being made to develop the theory of elementary chemical processes, because of the resurgence of interest in mechanistic organic chemistry and because of the resurgence of interest in mechanistic organic chemistry processes, because of the resurgence of interest in mechanistic organic chemistry and because of the dynamic role played by proton transfers in biochemical transformations. As organic chemists, the authors have used the flowing afterglow technique to gain an appreciation of the fundamental issues involved in reaction mechanisms by examining such processes in a solvent-free environment under thermally-equilibrated (300 K) conditions. Recent characterization of the facile production of both acetate and the monoenolate anion from the interaction of hydroxide or fluoride with acetic acid reinforces the idea that much yet must be learned about proton transfers/proton abstractions in general. Earlier work by Riveros and co-workers on competitive H vs D abstraction from α-d 1 -toluenes and by Noest and Nibbering on competitive H vs D abstraction from α,α,α-d 3 -acetone, in combination with the acetic acid results, challenged the author's to assemble a comprehensive picture of the competitive nature of proton transfer reactions for anionic base-promoted processes

  4. Proton pump inhibitor step-down therapy for GERD: A multi-center study in Japan

    Science.gov (United States)

    Tsuzuki, Takao; Okada, Hiroyuki; Kawahara, Yoshiro; Takenaka, Ryuta; Nasu, Junichiro; Ishioka, Hidehiko; Fujiwara, Akiko; Yoshinaga, Fumiya; Yamamoto, Kazuhide

    2011-01-01

    AIM: To investigate the predictors of success in step-down of proton pump inhibitor and to assess the quality of life (QOL). METHODS: Patients who had heartburn twice a week or more were treated with 20 mg omeprazole (OPZ) once daily for 8 wk as an initial therapy (study 1). Patients whose heartburn decreased to once a week or less at the end of the initial therapy were enrolled in study 2 and treated with 10 mg OPZ as maintenance therapy for an additional 6 mo (study 2). QOL was investigated using the gastrointestinal symptom rating scale (GSRS) before initial therapy, after both 4 and 8 wk of initial therapy, and at 1, 2, 3, and 6 mo after starting maintenance therapy. RESULTS: In study 1, 108 patients were analyzed. Their characteristics were as follows; median age: 63 (range: 20-88) years, sex: 46 women and 62 men. The success rate of the initial therapy was 76%. In the patients with successful initial therapy, abdominal pain, indigestion and reflux GSRS scores were improved. In study 2, 83 patients were analyzed. Seventy of 83 patients completed the study 2 protocol. In the per-protocol analysis, 80% of 70 patients were successful for step-down. On multivariate analysis of baseline demographic data and clinical information, no previous treatment for gastroesophageal reflux disease (GERD) [odds ratio (OR) 0.255, 95% CI: 0.06-0.98] and a lower indigestion score in GSRS at the beginning of step-down therapy (OR 0.214, 95% CI: 0.06-0.73) were found to be the predictors of successful step-down therapy. The improved GSRS scores by initial therapy were maintained through the step-down therapy. CONCLUSION: OPZ was effective for most GERD patients. However, those who have had previous treatment for GERD and experience dyspepsia before step-down require particular monitoring for relapse. PMID:21472108

  5. Amide Proton Transfer (APT) MR imaging and Magnetization Transfer (MT) MR imaging of pediatric brain development

    International Nuclear Information System (INIS)

    Zhang, Hong; Kang, Huiying; Peng, Yun; Zhao, Xuna; Jiang, Shanshan; Zhang, Yi; Zhou, Jinyuan

    2016-01-01

    To quantify the brain maturation process during childhood using combined amide proton transfer (APT) and conventional magnetization transfer (MT) imaging at 3 Tesla. Eighty-two neurodevelopmentally normal children (44 males and 38 females; age range, 2-190 months) were imaged using an APT/MT imaging protocol with multiple saturation frequency offsets. The APT-weighted (APTW) and MT ratio (MTR) signals were quantitatively analyzed in multiple brain areas. Age-related changes in MTR and APTW were evaluated with a non-linear regression analysis. The APTW signals followed a decreasing exponential curve with age in all brain regions measured (R"2 = 0.7-0.8 for the corpus callosum, frontal and occipital white matter, and centrum semiovale). The most significant changes appeared within the first year. At maturation, larger decreases in APTW and lower APTW values were found in the white matter. On the contrary, the MTR signals followed an increasing exponential curve with age in the same brain regions measured, with the most significant changes appearing within the initial 2 years. There was an inverse correlation between the MTR and APTW signal intensities during brain maturation. Together with MT imaging, protein-based APT imaging can provide additional information in assessing brain myelination in the paediatric population. (orig.)

  6. Amide Proton Transfer (APT) MR imaging and Magnetization Transfer (MT) MR imaging of pediatric brain development

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hong; Kang, Huiying; Peng, Yun [Beijing Children' s Hospital, Capital Medical University, Imaging Center, Department of Radiology, Beijing (China); Zhao, Xuna [Philips Healthcare, Beijing (China); Jiang, Shanshan; Zhang, Yi; Zhou, Jinyuan [Johns Hopkins University, Division of MR Research, Department of Radiology, Baltimore, MD (United States)

    2016-10-15

    To quantify the brain maturation process during childhood using combined amide proton transfer (APT) and conventional magnetization transfer (MT) imaging at 3 Tesla. Eighty-two neurodevelopmentally normal children (44 males and 38 females; age range, 2-190 months) were imaged using an APT/MT imaging protocol with multiple saturation frequency offsets. The APT-weighted (APTW) and MT ratio (MTR) signals were quantitatively analyzed in multiple brain areas. Age-related changes in MTR and APTW were evaluated with a non-linear regression analysis. The APTW signals followed a decreasing exponential curve with age in all brain regions measured (R{sup 2} = 0.7-0.8 for the corpus callosum, frontal and occipital white matter, and centrum semiovale). The most significant changes appeared within the first year. At maturation, larger decreases in APTW and lower APTW values were found in the white matter. On the contrary, the MTR signals followed an increasing exponential curve with age in the same brain regions measured, with the most significant changes appearing within the initial 2 years. There was an inverse correlation between the MTR and APTW signal intensities during brain maturation. Together with MT imaging, protein-based APT imaging can provide additional information in assessing brain myelination in the paediatric population. (orig.)

  7. Optimization of 7-T Chemical Exchange Saturation Transfer Parameters for Validation of Glycosaminoglycan and Amide Proton Transfer of Fibroglandular Breast Tissue

    NARCIS (Netherlands)

    Dula, Adrienne N.; Dewey, Blake E.; Arlinghaus, Lori R.; Williams, Jason M.; Klomp, DWJ; Yankeelov, Thomas E.; Smith, Seth

    Purpose: To (a) implement simulation-optimized chemical exchange saturation transfer (CEST) measurements sensitive to amide proton transfer (APT) and glycosaminoglycan (GAG) hydroxyl proton transfer effects in the human breast at 7 T and (b) determine the reliability of these techniques for

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

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  9. Momentum Transfer and Viscosity from Proton-Hydrogen Collisions Relevant to Shocks and Other Astrophysical Environments

    International Nuclear Information System (INIS)

    Schultz, David Robert; Krstic, Predrag S.; Lee, Teck G.; Raymond, J.C.

    2008-01-01

    The momentum transfer and viscosity cross sections for proton-hydrogen collisions are computed in the velocity range of ∼200-20,000 km s -1 relevant to a wide range of astrophysical environments such as SNR shocks, the solar wind, winds within young stellar objects or accretion disks, and the interstellar protons interacting with the heliosphere. A variety of theoretical approaches are used to arrive at a best estimate of these cross sections in this velocity range that smoothly connect with very accurate results previously computed for lower velocities. Contributions to the momentum transfer and viscosity cross sections from both elastic scattering and charge transfer are included

  10. Measurement of polarization-transfer to bound protons in carbon and its virtuality dependence

    Science.gov (United States)

    Izraeli, D.; Brecelj, T.; Achenbach, P.; Ashkenazi, A.; Böhm, R.; Cohen, E. O.; Distler, M. O.; Esser, A.; Gilman, R.; Kolar, T.; Korover, I.; Lichtenstadt, J.; Mardor, I.; Merkel, H.; Mihovilovič, M.; Müller, U.; Olivenboim, M.; Piasetzky, E.; Ron, G.; Schlimme, B. S.; Schoth, M.; Sfienti, C.; Širca, S.; Štajner, S.; Strauch, S.; Thiel, M.; Weber, A.; Yaron, I.; A1 Collaboration

    2018-06-01

    We measured the ratio Px /Pz of the transverse to longitudinal components of polarization transferred from electrons to bound protons in 12C by the 12C (e → ,e‧ p →) process at the Mainz Microtron (MAMI). We observed consistent deviations from unity of this ratio normalized to the free-proton ratio, (Px /Pz) 12C /(Px /Pz) 1H, for both s- and p-shell knocked out protons, even though they are embedded in averaged local densities that differ by about a factor of two. The dependence of the double ratio on proton virtuality is similar to the one for knocked out protons from 2H and 4He, suggesting a universal behavior. It further implies no dependence on average local nuclear density.

  11. Proton transfer in malonaldehyde: From reaction path to Schrödinger's Cat

    Science.gov (United States)

    Fillaux, François; Nicolaï, Béatrice

    2005-11-01

    Proton transfer in the chelated form of malonaldehyde is commonly supposed to occur between two tautomers, across a transition state involving changes of the chemical bonding. We show that this view is in conflict with rotational spectra. The molecule is better thought of as a superposition of indistinguishable and non-separable C s tautomers and proton tunneling is totally decoupled from the other degrees of freedom. Double minimum potential functions are determined from experiments and ab initio calculations.

  12. The control system for the CERN proton synchrotron continuous transfer ejection

    International Nuclear Information System (INIS)

    Bloess, D.; Boucheron, J.; Flander, D.; Grier, D.; Krusche, A.; Ollenhauer, F.; Pearce, P.; Riege, H.; Schneider, G.C.

    1978-01-01

    This report describes the hardware and the software structure of a stand-alone control system for the continuous transfer ejection from the CERN Proton Synchrotron to the Super Proton Synchrotron. The process control system is built around a PDP 11/40 mini-computer interfaced to the ejection elements via CAMAC. It features automatic failure recovery and real-time process optimization. Performance, flexibility, and reliability of the system is evaluated. (Auth.)

  13. Challenges in reduction of dinitrogen by proton and electron transfer.

    Science.gov (United States)

    van der Ham, Cornelis J M; Koper, Marc T M; Hetterscheid, Dennis G H

    2014-08-07

    Ammonia is an important nutrient for the growth of plants. In industry, ammonia is produced by the energy expensive Haber-Bosch process where dihydrogen and dinitrogen form ammonia at a very high pressure and temperature. In principle one could also reduce dinitrogen upon addition of protons and electrons similar to the mechanism of ammonia production by nitrogenases. Recently, major breakthroughs have taken place in our understanding of biological fixation of dinitrogen, of molecular model systems that can reduce dinitrogen, and in the electrochemical reduction of dinitrogen at heterogeneous surfaces. Yet for efficient reduction of dinitrogen with protons and electrons major hurdles still have to be overcome. In this tutorial review we give an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen.

  14. Anion Photoelectron Spectroscopy of the Homogenous 2-Hydroxypyridine Dimer Electron Induced Proton Transfer System

    Science.gov (United States)

    Vlk, Alexandra; Stokes, Sarah; Wang, Yi; Hicks, Zachary; Zhang, Xinxing; Blando, Nicolas; Frock, Andrew; Marquez, Sara; Bowen, Kit; Bowen Lab JHU Team

    Anion photoelectron spectroscopic (PES) and density functional theory (DFT) studies on the dimer anion of (2-hydroxypyridine)2-are reported. The experimentally measured vertical detachment energy (VDE) of 1.21eV compares well with the theoretically predicted values. The 2-hydroxypyridine anionic dimer system was investigated because of its resemblance to the nitrogenous heterocyclic pyrimidine nucleobases. Experimental and theoretical results show electron induced proton transfer (EIPT) in both the lactim and lactam homogeneous dimers. Upon electron attachment, the anion can serve as the intermediate between the two neutral dimers. A possible double proton transfer process can occur from the neutral (2-hydroxypyridine)2 to (2-pyridone)2 through the dimer anion. This potentially suggests an electron catalyzed double proton transfer mechanism of tautomerization. Research supported by the NSF Grant No. CHE-1360692.

  15. Mechanism for the Excited-State Multiple Proton Transfer Process of Dihydroxyanthraquinone Chromophores.

    Science.gov (United States)

    Zhou, Qiao; Du, Can; Yang, Li; Zhao, Meiyu; Dai, Yumei; Song, Peng

    2017-06-22

    The single and dual cooperated proton transfer dynamic process in the excited state of 1,5-dihydroxyanthraquinone (1,5-DHAQ) was theoretically investigated, taking solvent effects (ethanol) into account. The absorption and fluorescence spectra were simulated, and dual fluorescence exhibited, which is consistent with previous experiments. Analysis of the calculated IR and Raman vibration spectra reveals that the intramolecular hydrogen bonding interactions (O 20 -H 21 ···O 24 and O 22 -H 23 ···O 25 ) are strengthened following the excited proton transfer process. Finally, by constructing the potential energy surfaces of the ground state, first excited singlet state, and triplet state, the mechanism of the intramolecular proton transfer of 1,5-DHAQ can be revealed.

  16. Proton transfer reaction time-of-flight mass spectrometry advancement in detection of hazardous substances

    International Nuclear Information System (INIS)

    Agarwal, B.

    2012-01-01

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a mass spectrometric technique based on chemical ionization, which provides very rapid measurements (within seconds) of volatile organic compounds in air, usually without special sample preparation, and with a very low detection limit. The detection and study of product ion patterns of threat agents such as explosives and drugs and some major environmental pollutants (isocyanates and polychlorinated biphenyls (PCBs)) is explored in detail here using PTR-MS, specifically Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). The proton transfer reaction (PTR) principle works on the detection of the compound in the vapor phase. For some compounds, which have extremely low vapor pressures, both sample and inlet line heating were needed. Generally, the protonated parent molecule (MH+) is found to be the dominant product ion, which therefore provides us with a higher level of confidence in the assignment of a trace compound. However, for several compounds, dissociative proton transfer can occur at various degrees resulting in other product ions. Analysis of other compounds, such as the presence of taggants and impurities were carried out, and in certain compounds unusual E/N anomalies were discovered (E/N is an instrumental set of parameters, where E is the electric field strength and N is the number density). Head space measurements above four different drinks (plain water, tea, red wine and white wine) spiked with four different 'date rape' drugs were also conducted. (author)

  17. Reoptimization of Intensity Modulated Proton Therapy Plans Based on Linear Energy Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Unkelbach, Jan, E-mail: junkelbach@mgh.harvard.edu [Department of Radiation Oncology, Massachusetts General Hospital, Boston, Massachusetts (United States); Botas, Pablo [Department of Radiation Oncology, Massachusetts General Hospital, Boston, Massachusetts (United States); Faculty of Physics, Ruprecht-Karls-Universität Heidelberg, Heidelberg (Germany); Giantsoudi, Drosoula; Gorissen, Bram L.; Paganetti, Harald [Department of Radiation Oncology, Massachusetts General Hospital, Boston, Massachusetts (United States)

    2016-12-01

    Purpose: We describe a treatment plan optimization method for intensity modulated proton therapy (IMPT) that avoids high values of linear energy transfer (LET) in critical structures located within or near the target volume while limiting degradation of the best possible physical dose distribution. Methods and Materials: To allow fast optimization based on dose and LET, a GPU-based Monte Carlo code was extended to provide dose-averaged LET in addition to dose for all pencil beams. After optimizing an initial IMPT plan based on physical dose, a prioritized optimization scheme is used to modify the LET distribution while constraining the physical dose objectives to values close to the initial plan. The LET optimization step is performed based on objective functions evaluated for the product of LET and physical dose (LET×D). To first approximation, LET×D represents a measure of the additional biological dose that is caused by high LET. Results: The method is effective for treatments where serial critical structures with maximum dose constraints are located within or near the target. We report on 5 patients with intracranial tumors (high-grade meningiomas, base-of-skull chordomas, ependymomas) in whom the target volume overlaps with the brainstem and optic structures. In all cases, high LET×D in critical structures could be avoided while minimally compromising physical dose planning objectives. Conclusion: LET-based reoptimization of IMPT plans represents a pragmatic approach to bridge the gap between purely physical dose-based and relative biological effectiveness (RBE)-based planning. The method makes IMPT treatments safer by mitigating a potentially increased risk of side effects resulting from elevated RBE of proton beams near the end of range.

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

    International Nuclear Information System (INIS)

    Lindinger, W.; Hansel, A.

    1996-01-01

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

  20. An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

    Science.gov (United States)

    Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

    2015-07-07

    We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

  1. Electrostatic models of electron-driven proton transfer across a lipid membrane

    International Nuclear Information System (INIS)

    Smirnov, Anatoly Yu; Nori, Franco; Mourokh, Lev G

    2011-01-01

    We present two models for electron-driven uphill proton transport across lipid membranes, with the electron energy converted to the proton gradient via the electrostatic interaction. In the first model, associated with the cytochrome c oxidase complex in the inner mitochondria membranes, the electrostatic coupling to the site occupied by an electron lowers the energy level of the proton-binding site, making proton transfer possible. In the second model, roughly describing the redox loop in a nitrate respiration of E. coli bacteria, an electron displaces a proton from the negative side of the membrane to a shuttle, which subsequently diffuses across the membrane and unloads the proton to its positive side. We show that both models can be described by the same approach, which can be significantly simplified if the system is separated into several clusters, with strong Coulomb interaction inside each cluster and weak transfer couplings between them. We derive and solve the equations of motion for the electron and proton creation/annihilation operators, taking into account the appropriate Coulomb terms, tunnel couplings, and the interaction with the environment. For the second model, these equations of motion are solved jointly with a Langevin-type equation for the shuttle position. We obtain expressions for the electron and proton currents and determine their dependence on the electron and proton voltage build-ups, on-site charging energies, reorganization energies, temperature, and other system parameters. We show that the quantum yield in our models can be up to 100% and the power-conversion efficiency can reach 35%.

  2. Electrostatic models of electron-driven proton transfer across a lipid membrane

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, Anatoly Yu; Nori, Franco [Advanced Science Institute, RIKEN, Wako-shi, Saitama, 351-0198 (Japan); Mourokh, Lev G [Department of Physics, Queens College, The City University of New York, Flushing, NY 11367 (United States)

    2011-06-15

    We present two models for electron-driven uphill proton transport across lipid membranes, with the electron energy converted to the proton gradient via the electrostatic interaction. In the first model, associated with the cytochrome c oxidase complex in the inner mitochondria membranes, the electrostatic coupling to the site occupied by an electron lowers the energy level of the proton-binding site, making proton transfer possible. In the second model, roughly describing the redox loop in a nitrate respiration of E. coli bacteria, an electron displaces a proton from the negative side of the membrane to a shuttle, which subsequently diffuses across the membrane and unloads the proton to its positive side. We show that both models can be described by the same approach, which can be significantly simplified if the system is separated into several clusters, with strong Coulomb interaction inside each cluster and weak transfer couplings between them. We derive and solve the equations of motion for the electron and proton creation/annihilation operators, taking into account the appropriate Coulomb terms, tunnel couplings, and the interaction with the environment. For the second model, these equations of motion are solved jointly with a Langevin-type equation for the shuttle position. We obtain expressions for the electron and proton currents and determine their dependence on the electron and proton voltage build-ups, on-site charging energies, reorganization energies, temperature, and other system parameters. We show that the quantum yield in our models can be up to 100% and the power-conversion efficiency can reach 35%.

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

    Science.gov (United States)

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

    2015-02-01

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

  4. Kinetic isotope effects and tunnelling in the proton-transfer reaction between 4-nitrophenylnitromethane and tetramethylguanidine in various aprotic solvents

    International Nuclear Information System (INIS)

    Caldin, E.F.; Mateo, S.

    1975-01-01

    Rates and equilibrium constants have been determined for the proton-transfer reaction of 4-nitrophenylnitromethane, NO 2 C 6 H 4 CH 2 NO 2 , and its αα-deuterated analogue NO 2 C 6 H 4 CD 2 NO 2 , with the strong base tetramethylguanidine [HN=C(NMe 2 ) 2 ), at temperatures between -60 0 C and +65 0 in a range of aprotic solvents. Spectrophotometry and the stopped-flow technique were used. The reaction is a simple proton-transfer process leading to an ion-pair. The kinetic isotope effects are correlated with the polarity of the solvents, as measured by the dielectric constant or by the empirical parameter Esub(T). In the less polar solvents they are exceptionally large. In toluene, for example, at 25 0 C the rate ratio ksup(H)/ksup(D) = 45 +- 2, the activation energy difference Esub(a)sup(D) - Esub(a)sup(H) =4.3 +- 0.3 kcal molsup(-1) (16 kJ molsup(-1), and the ratio of the pre-exponential factors logsub(10) (Asup(D)/Asup(H)) = 1.5 +- 0.2+ and even larger values of logsub(10)(Asup(D)/Asup(H)) are found for mesitylene (1.94 +- 0.06) and cyclohexane (2.4 +- 0.2). Positive deviations from linear Arrhenius plots are found for these solvents. Tunnelling is the only interpretation that cannot account for these results. For the more polar solvents (dielectric constant 7 to 37), the isotope effects are closer to the range predicted by semi-classical theory. The isotope effects in all solvents have been fitted to Bell's equation for a parabolic barrier, and the barrier dimensions calculated for each solvent. The suggested interpretation of the results is that the solvent-solute interactions affect the height of the barrier and that motions of solvent molecules are coupled with the motion of the proton in the more polar solvents but not in the less polar ones; reorganization of solvent molecules accompanies the proton-transfer in the more polar solvents, but only electron-polarization in the less polar. Tunnelling has large effects in the less polar solvents, where the

  5. Status of the proton and electron transfer lines for the AWAKE Experiment at CERN

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, J.S., E-mail: janet.schmidt@cern.ch [CERN, Geneva (Switzerland); Bauche, J. [CERN, Geneva (Switzerland); Biskup, B. [CERN, Geneva (Switzerland); Czech Technical University, Prague (Czech Republic); Bracco, C.; Doebert, S.; Goddard, B.; Gschwendtner, E.; Jensen, L.K.; Jones, O.R.; Mazzoni, S.; Meddahi, M.; Pepitone, K.; Petrenko, A.; Velotti, F.M.; Vorozhtsov, A. [CERN, Geneva (Switzerland)

    2016-09-01

    The AWAKE project at CERN is planned to study proton driven plasma wakefield acceleration with an externally injected electron beam. Therefore two transfer lines are being designed in order to provide the proton beam from the SPS and the electron beam from an RF gun to the plasma cell. The commissioning of the proton line will take place in 2016 for the first phase of the experiment, which is focused on the self-modulation of a 12 cm long proton bunch in the plasma. The electron line will be added for the second phase of AWAKE in 2017, when the wakefield will be probed with an electron beam of 10–20 MeV/c. The challenge for these transfer lines lies in the parallel operation of the proton, electron and laser beam used to ionize the plasma and seed the self-modulation. These beams, of different characteristics, need to be synchronized and positioned for optimized injection conditions into the wakefield. This task requires great flexibility in the transfer line optics. The status of these designs will be presented in this paper.

  6. Proton-proton elastic scattering at 50 GeV/c incident momentum in the momentum transfer range 0.82

    International Nuclear Information System (INIS)

    Baglin, C.; Guillaud, J.P.; Poulet, M.; Myrheim, J.; Asa'd, Z.; Coupland, M.; Davis, D.G.; Duff, B.G.; Fearnley, T.; Heymann, F.F.; Imrie, D.C.; Lush, G.J.; Phillips, M.; Brom, J.M.; Kenyon Gjerpe, I.; Buran, T.; Buzzo, A.; Ferroni, S.; Gracco, V.; Kirsebom, K.; Macri, M.; Santroni, A.; Skjevling, G.; Soerensen, S.O.

    1983-01-01

    A measurement of the proton-proton elastic differential cross section at 50 GeV/c incident momentum in the momentum transfer range 0.8 2 is presented. The data are compared to pp data at lower and higher energies, and to some model predictions. (orig.)

  7. Theoretical study of the mechanism of proton transfer in tautomeric ...

    Indian Academy of Sciences (India)

    Unknown

    transferred is forced to come close to the positively charged carbon atom at ..... geometry of the transition state, and the charge densities on the atoms involved in the ..... One of the authors (VK) thanks the Council of Scientific and Industrial ...

  8. Proton transfers in a channelrhodopsin-1 studied by Fourier transform infrared (FTIR) difference spectroscopy and site-directed mutagenesis.

    Science.gov (United States)

    Ogren, John I; Yi, Adrian; Mamaev, Sergey; Li, Hai; Spudich, John L; Rothschild, Kenneth J

    2015-05-15

    Channelrhodopsin-1 from the alga Chlamydomonas augustae (CaChR1) is a low-efficiency light-activated cation channel that exhibits properties useful for optogenetic applications such as a slow light inactivation and a red-shifted visible absorption maximum as compared with the more extensively studied channelrhodopsin-2 from Chlamydomonas reinhardtii (CrChR2). Previously, both resonance Raman and low-temperature FTIR difference spectroscopy revealed that unlike CrChR2, CaChR1 under our conditions exhibits an almost pure all-trans retinal composition in the unphotolyzed ground state and undergoes an all-trans to 13-cis isomerization during the primary phototransition typical of other microbial rhodopsins such as bacteriorhodopsin (BR). Here, we apply static and rapid-scan FTIR difference spectroscopy along with site-directed mutagenesis to characterize the proton transfer events occurring upon the formation of the long-lived conducting P2 (380) state of CaChR1. Assignment of carboxylic C=O stretch bands indicates that Asp-299 (homolog to Asp-212 in BR) becomes protonated and Asp-169 (homolog to Asp-85 in BR) undergoes a net change in hydrogen bonding relative to the unphotolyzed ground state of CaChR1. These data along with earlier FTIR measurements on the CaChR1 → P1 transition are consistent with a two-step proton relay mechanism that transfers a proton from Glu-169 to Asp-299 during the primary phototransition and from the Schiff base to Glu-169 during P2 (380) formation. The unusual charge neutrality of both Schiff base counterions in the P2 (380) conducting state suggests that these residues may function as part of a cation selective filter in the open channel state of CaChR1 as well as other low-efficiency ChRs. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  9. Dynamics of Excited State Proton Transfer in Nitro Substituted 10-Hydroxybenzo[h]quinolines

    DEFF Research Database (Denmark)

    Marciak, H; Hristova, S.; Deneva, V

    2017-01-01

    The ground state tautomerism and excited state intramolecular proton transfer (ESIPT) of 10-hydroxybenzo[h]quinoline (HBQ) and its nitro derivatives, 7-nitrobenzo[h]quinolin-10-ol (2) and 7,9-dinitrobenzo[h]quinolin-10-ol (3), have been studied in acetonitrile using steady state as well as time d...

  10. Amide proton transfer imaging of high intensity focused ultrasound-treated tumor tissue

    NARCIS (Netherlands)

    Hectors, S.J.C.G.; Jacobs, I.; Strijkers, G.J.; Nicolay, K.

    2014-01-01

    Purpose: In this study, the suitability of amide proton transfer (APT) imaging as a biomarker for the characterization of high intensity focused ultrasound (HIFU)-treated tumor tissue was assessed. Methods: APT imaging was performed on tumor-bearing mice before (n=15), directly after (n=15) and at 3

  11. Amide Proton Transfer Imaging of High Intensity Focused Ultrasound-Treated Tumor Tissue

    NARCIS (Netherlands)

    Hectors, Stefanie J. C. G.; Jacobs, Igor; Strijkers, Gustav J.; Nicolay, Klaas

    2014-01-01

    PurposeIn this study, the suitability of amide proton transfer (APT) imaging as a biomarker for the characterization of high intensity focused ultrasound (HIFU)-treated tumor tissue was assessed. MethodsAPT imaging was performed on tumor-bearing mice before (n=15), directly after (n=15) and at 3

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

    International Nuclear Information System (INIS)

    Palusiak, Marcin; Simon, Silvia; Sola, Miquel

    2007-01-01

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

  13. Long-Range Electrostatics-Induced Two-Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site.

    Science.gov (United States)

    Gerlits, Oksana; Wymore, Troy; Das, Amit; Shen, Chen-Hsiang; Parks, Jerry M; Smith, Jeremy C; Weiss, Kevin L; Keen, David A; Blakeley, Matthew P; Louis, John M; Langan, Paul; Weber, Irene T; Kovalevsky, Andrey

    2016-04-11

    Neutron crystallography was used to directly locate two protons before and after a pH-induced two-proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV-1 protease. The two-proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low-pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Angular distribution in proton-hydrogen charge-transfer collisions

    International Nuclear Information System (INIS)

    Glembocki, O.; Halpern, A.M.

    1977-01-01

    Theoretical angular distributions for p-H charge transfer to the 1s state for energies of 1 keV and above have been examined and compared for three approximation schemes: the plane-wave Born approximation of Jackson and Schiff (JS), the Coulomb projected Born approximation of Geltman (G), and the distorted-wave eikonal approximation of one of the authors (D). The sharp dip in the forward distribution characteristic of JS is found to exist in G and D as well. As expected, G and D give identical results for all but the lowest energies. In the cases of G and D the dip, which is located close to that of JS, disappears and then reappears as the energy rises. Analytic high-energy limits for the angular dependence in both the JS and G cases have been found and are discussed

  15. Infrared laser driven double proton transfer. An optimal control theory study

    Science.gov (United States)

    Abdel-Latif, Mahmoud K.; Kühn, Oliver

    2010-02-01

    Laser control of ultrafast double proton transfer is investigated for a two-dimensional model system describing stepwise and concerted transfer pathways. The pulse design has been done by employing optimal control theory in combination with the multiconfiguration time-dependent Hartree wave packet propagation. The obtained laser fields correspond to multiple pump-dump pulse sequences. Special emphasis is paid to the relative importance of stepwise and concerted transfer pathways for the driven wave packet and its dependence on the parameters of the model Hamiltonian as well as on the propagation time. While stepwise transfer is dominating in all cases considered, for high barrier systems concerted transfer proceeding via tunneling can make a contribution.

  16. Facilitated ion transfer of protonated primary organic amines studied by square wave voltammetry and chronoamperometry

    Energy Technology Data Exchange (ETDEWEB)

    Torralba, E. [Departamento de Química Física, Facultad de Química, Universidad de Murcia, Murcia 30100 (Spain); Ortuño, J.A. [Departamento de Química Analítica, Facultad de Química, Universidad de Murcia, Murcia 30100 (Spain); Molina, A., E-mail: amolina@um.es [Departamento de Química Física, Facultad de Química, Universidad de Murcia, Murcia 30100 (Spain); Serna, C. [Departamento de Química Física, Facultad de Química, Universidad de Murcia, Murcia 30100 (Spain); Karimian, F. [Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad (Iran, Islamic Republic of)

    2014-05-01

    Highlights: • Facilitated ion transfer of organic protonated amines is studied. • Cyclic square wave voltammetry is used as main technique. • Complexation constants and standard ion transfer potentials are determined. • Diffusion coefficients in the organic and aqueous phases are determined. • The goodness of square wave voltammetry as analytical tool is shown. - Abstract: The transfer of the protonated forms of heptylamine, octylamine, decylamine, procaine and procainamide facilitated by dibenzo-18-crown-6 from water to a solvent polymeric membrane has been investigated by using cyclic square wave voltammetry. The experimental voltammograms obtained are in good agreement with theoretical predictions. The values of the standard ion transfer potential, complexation constant and diffusion coefficient in water have been obtained from these experiments, and have been used to draw some conclusions about the lipophilicity of these species and the relative stability of the organic ammonium complexes with dibenzo-18-crown-6. The results have been compared with those provided by linear sweep voltammetry. Calibration graphs were obtained with both techniques. An interesting chronoamperometric method for the determination of the diffusion coefficient of the target ion in the membrane has been developed and applied to all these protonated amines.

  17. Stripping of two protons and one alpha particle transfer reactions for {sup 16} O + {sup A} Sm and their influence on the fusion cross section

    Energy Technology Data Exchange (ETDEWEB)

    Maciel, A.M.M.; Gomes, P.R.S

    1995-12-31

    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 near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author) 16 refs., 5 figs., 5 tabs.

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

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

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

  19. Pattern recognition and data mining software based on artificial neural networks applied to proton transfer in aqueous environments

    International Nuclear Information System (INIS)

    Tahat Amani; Marti Jordi; Khwaldeh Ali; Tahat Kaher

    2014-01-01

    In computational physics proton transfer phenomena could be viewed as pattern classification problems based on a set of input features allowing classification of the proton motion into two categories: transfer ‘occurred’ and transfer ‘not occurred’. The goal of this paper is to evaluate the use of artificial neural networks in the classification of proton transfer events, based on the feed-forward back propagation neural network, used as a classifier to distinguish between the two transfer cases. In this paper, we use a new developed data mining and pattern recognition tool for automating, controlling, and drawing charts of the output data of an Empirical Valence Bond existing code. The study analyzes the need for pattern recognition in aqueous proton transfer processes and how the learning approach in error back propagation (multilayer perceptron algorithms) could be satisfactorily employed in the present case. We present a tool for pattern recognition and validate the code including a real physical case study. The results of applying the artificial neural networks methodology to crowd patterns based upon selected physical properties (e.g., temperature, density) show the abilities of the network to learn proton transfer patterns corresponding to properties of the aqueous environments, which is in turn proved to be fully compatible with previous proton transfer studies. (condensed matter: structural, mechanical, and thermal properties)

  20. The nuclear spin response to intermediate energy protons and deuterons at low momentum transfer

    International Nuclear Information System (INIS)

    Baker, F.T.; Djalali, C.; Glashausser, C.; Lenske, H.; Love, W.G.; Tomasi-Gustafsson, E.; Wambach, J.

    1997-01-01

    Measurements of polarization transfer in the inelastic scattering of intermediate energy protons and deuterons have yielded a wealth of data on the spin response of nuclei. This work complements the well-known studies of Gamow-Teller strength in charge-exchange reactions. The emphasis here is on a consistent determination of the S=1, T=0 response, practical only with deuterons, and on the proper separation of S=0 and S=1 strength in proton spectra for appropriate comparison with sum rules. We concentrate on two nuclei, 40 Ca and 12 C, at momentum transfers below about 1 fm -1 and on excitations up to about 50 MeV. The continuum second random phase approximation provides the primary theoretical tool for calculating and interpreting the response in terms of properties of the nucleon-nucleon force inside the nuclear medium. The reaction mechanism is described by the DWIA, applied here to continuum proton scattering almost as rigorously as it is usually applied to low energy excitations. A new DWIA formalism for the description of spin observables in deuteron scattering is used. Comparison of the proton and deuteron data with each other and with RPA/DWIA calculations yields interesting insights into the current state of understanding of collectivity and the nuclear spin response. (orig.)

  1. A role of proton transfer in peroxidase-catalyzed process elucidated by substrates docking calculations

    Directory of Open Access Journals (Sweden)

    Ziemys Arturas

    2001-08-01

    Full Text Available Abstract Background Previous kinetic investigations of fungal-peroxidase catalyzed oxidation of N-aryl hydroxamic acids (AHAs and N-aryl-N-hydroxy urethanes (AHUs revealed that the rate of reaction was independent of the formal redox potential of substrates. Moreover, the oxidation rate was 3–5 orders of magnitude less than for oxidation of physiological phenol substrates, though the redox potential was similar. Results To explain the unexpectedly low reactivity of AHAs and AHUs we made ab initio calculations of the molecular structure of the substrates following in silico docking in the active center of the enzyme. Conclusions AHAs and AHUs were docked at the distal side of heme in the sites formed by hydrophobic amino acid residues that retarded a proton transfer and finally the oxidation rate. The analogous phenol substrates were docked at different sites permitting fast proton transfer in the relay of distal His and water that helped fast substrate oxidation.

  2. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    Energy Technology Data Exchange (ETDEWEB)

    Soniat, Marielle; Rick, Steven W., E-mail: srick@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148 (United States); Kumar, Revati [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70808 (United States)

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  3. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    International Nuclear Information System (INIS)

    Soniat, Marielle; Rick, Steven W.; Kumar, Revati

    2015-01-01

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface

  4. Enhancement of proton transfer in ion channels by membrane phosphate headgroups.

    Science.gov (United States)

    Wyatt, Debra L; de Godoy, Carlos Marcelo G; Cukierman, Samuel

    2009-05-14

    The transfer of protons (H+) in gramicidin (gA) channels is markedly distinct in monoglyceride and phospholipid membranes. In this study, the molecular groups that account for those differences were investigated using a new methodology. The rates of H+ transfer were measured in single gA channels reconstituted in membranes made of plain ceramides or sphingomyelins and compared to those in monoglyceride and phospholipid bilayers. Single-channel conductances to protons (gH) were significantly larger in sphingomyelin than in ceramide membranes. A novel and unsuspected finding was that H+ transfer was heavily attenuated or completely blocked in ceramide (but not in sphingomyelin) membranes in low-ionic-strength solutions. It is reasoned that H-bond dynamics at low ionic strengths between membrane ceramides and gA makes channels dysfunctional. The rate of H+ transfer in gA channels in ceramide membranes is significantly higher than that in monoglyceride bilayers. This suggests that solvation of the hydrophobic surface of gA channels by two acyl chains in ceramides stabilizes the gA channels and the water wire inside the pore, leading to an enhancement of H+ transfer in relation to that occurring in monoglyceride membranes. gH values in gA channels are similar in ceramide and monoglyceride bilayers and in sphingomyelin and phospholipid membranes. It is concluded that phospho headgroups in membranes have significant effects on the rate of H+ transfer at the membrane gA channel/solution interfaces, enhancing the entry and exit rates of protons in channels.

  5. Tunneling dynamics of double proton transfer in formic acid and benzoic acid dimers

    Science.gov (United States)

    Smedarchina, Zorka; Fernández-Ramos, Antonio; Siebrand, Willem

    2005-04-01

    Direct dynamics calculations based on instanton techniques are reported of tunneling splittings due to double proton transfer in formic and benzoic acid dimers. The results are used to assign the observed splittings to levels for which the authors of the high-resolution spectra could not provide a definitive assignment. In both cases the splitting is shown to be due mainly to the zero-point level rather than to the vibrationally or electronically excited level whose spectrum was investigated. This leads to zero-point splittings of 375MHz for (DCOOH)2 and 1107MHz for the benzoic acid dimer. Thus, contrary to earlier calculations, it is found that the splitting is considerably larger in the benzoic than in the formic acid dimer. The calculations are extended to solid benzoic acid where the asymmetry of the proton-transfer potential induced by the crystal can be overcome by suitable doping. This has allowed direct measurement of the interactions responsible for double proton transfer, which were found to be much larger than those in the isolated dimer. To account for this observation both static and dynamic effects of the crystal forces on the intradimer hydrogen bonds are included in the calculations. The same methodology, extended to higher temperatures, is used to calculate rate constants for HH, HD, and DD transfers in neat benzoic acid crystals. The results are in good agreement with reported experimental rate constants measured by NMR relaxometry and, if allowance is made for small structural changes induced by doping, with the transfer matrix elements observed in doped crystals. Hence the method used allows a unified description of tunneling splittings in the gas phase and in doped crystals as well as of transfer rates in neat crystals.

  6. A Molecular Dynamic Simulation of Hydrated Proton Transfer in Perfluorosulfonate Ionomer Membranes (Nafion 117

    Directory of Open Access Journals (Sweden)

    Hong Sun

    2015-01-01

    Full Text Available A molecular dynamic model based on Lennard-Jones Potential, the interaction force between two particles, molecular diffusion, and radial distribution function (RDF is presented. The diffusion of the hydrated ion, triggered by both Grotthuss and vehicle mechanisms, is used to study the proton transfer in Nafion 117. The hydrated ion transfer mechanisms and the effects of the temperature, the water content in the membrane, and the electric field on the diffusion of the hydrated ion are analyzed. The molecular dynamic simulation results are in good agreement with those reported in the literature. The modeling results show that when the water content in Nafion 117 is low, H3O+ is the main transfer ion among the different hydrated ions. However, at higher water content, the hydrated ion in the form of H+(H2O2 is the main transfer ion. It is also found that the negatively charged sulfonic acid group as the fortified point facilitates the proton transfer in Nafion 117 better than the free water molecule. The diffusion of the hydrated ion can be improved by increasing the cell temperature, the water content in Nafion, and the electric field intensity.

  7. Optimal Design and Analysis of the Stepped Core for Wireless Power Transfer Systems

    Directory of Open Access Journals (Sweden)

    Xiu Zhang

    2016-01-01

    Full Text Available The key of wireless power transfer technology rests on finding the most suitable means to improve the efficiency of the system. The wireless power transfer system applied in implantable medical devices can reduce the patients’ physical and economic burden because it will achieve charging in vitro. For a deep brain stimulator, in this paper, the transmitter coil is designed and optimized. According to the previous research results, the coils with ferrite core can improve the performance of the wireless power transfer system. Compared with the normal ferrite core, the stepped core can produce more uniform magnetic flux density. In this paper, the finite element method (FEM is used to analyze the system. The simulation results indicate that the core loss generated in the optimal stepped ferrite core can reduce about 10% compared with the normal ferrite core, and the efficiency of the wireless power transfer system can be increased significantly.

  8. A Mechanistic Study of the Influence of Proton Transfer Processes on the Behavior of Thiol/Disulfide Redox Couples

    National Research Council Canada - National Science Library

    Shouji, Eiichi

    1998-01-01

    .... In order to elucidate the influence of proton transfers on these redox processes, special attention has been paid to the influence of various bases, including triethylamine, pyridine, 3-chloro...

  9. Polymer-inorganic hybrid proton conductive membranes: Effect of the interfacial transfer pathways

    International Nuclear Information System (INIS)

    Chen, Pingping; Hao, Lie; Wu, Wenjia; Li, Yifan; Wang, Jingtao

    2016-01-01

    Highlights: • A series of hybrid membranes are prepared using fillers with different structures. • The fillers (0-D, 1-D, and 2-D) are sulfonated to ensure close surface component. • The effect of filler’s structure on microstructure of hydrid membrane is explored. • For single-kind filler series, 2-D filler has the strongest conduction promotion. • The synergy effect of different kinds of fillers is systematacially investigated. - Abstract: For hybrid membrane, the polymer-inorganic interface along filler surface can be facilely created to be distinctive and controllable pathway for mass transfer. Herein, three kinds of fillers are used as inorganic additives including zero-dimensional silica (0-D, SiO_2), one-dimensional halloysite nanotube (1-D, HNT), and two-dimensional graphene oxide (2-D, GO), which are functionalized by sulfonated polymer layer to ensure close surface component. Then the fillers are incorporated into two types of polymer matrixes (phase-separated sulfonated poly(ether ether ketone) and non-phase-separated chitosan) to prepare three series of hybrid membranes with single-kind filler, double-kinds fillers, or triple-kinds fillers, respectively. The microstructures, physicochemical properties, and proton conduction properties (under hydrated and anhydrous conditions) of the membranes are extensively investigated. It is found that (i) for the single-kind filler-filled membranes, 2-D filler has the strongest promotion ability for proton conductivity of membrane due to the constructed wide and long-range pathways for proton transfer; (ii) while for the hybrid membranes with double-kinds fillers, instead of synergistic promotion effect, the fillers cause more tortuous transfer pathways within membranes and then decrease proton conductivity; (iii) the hybrid membranes with triple-kinds fillers exhibit similar behavior but a little higher conductivity than the membranes with double-kinds fillers.

  10. Study of neutron-proton pairing in N=Z unstable nuclei through transfer reactions

    International Nuclear Information System (INIS)

    Le Crom, B.

    2016-01-01

    A nucleus is described as a set of independent neutrons and protons linked by a mean-field potential. However, in order to have a better description one needs to take into account some residual interactions such as pairing. Neutron-neutron and proton-proton pairings are well-studied but neutron-proton pairing is not well-known. np pairing can be isovector pairing such as nn and pp pairing or isoscalar which is yet unknown. Over-binding of N=Z nuclei could be a manifestation of np pairing. We have studied np pairing through transfer reactions. In this case, the cross-section of np pair transfer is expected to be enhanced in the presence of important np pairing. np pairing is expected to be important in N=Z nuclei with high J orbitals. Since the development of radioactive beam facilities, such beams are only available. The experiment was performed at GANIL with an efficient set-up so as to detect products from the (p, 3 He) transfer reaction. This reaction is affected by isovector and isoscalar np pairing. We used 56 Ni and 52 Fe beams so as to see the effect of the occupancy of 0f 7/2 shell on the np pairing. First, we analysed the data from the 56 Ni(p,d) 55 Ni reaction and we compared the results with the literature to validate analysis procedure. After analysing data from the 56 Ni(p, 3 He) 54 Co reaction and extracting the population of the various states of 54 Co, we obtained information about the relative intensity between isoscalar and isovector np pairing in 56 Ni showing the predominance of isovector np pairing in this nucleus. Moreover, in the framework of developing a new charged particle detector, research on the discrimination of light nuclei using pulse shape analysis was performed and is also presented. (author)

  11. [Proton pump inhibitors in gastro-oesophageal reflux disease: what is the further step?].

    Science.gov (United States)

    Simon, Mireille; Zerbib, Frank

    2013-01-01

    Optimisation of proton pump inhibitors use may improve reflux symptoms in 20-25% of the patients. Pathological gastro-oesophageal reflux should be documented in a patient with refractory reflux symptoms using upper endoscopy and/or pH testing. While on proton pump inhibitors twice daily, persistent symptoms are not related to gastro-oesophageal refluxdisease(GERD) in 50% of the patients. The new anti-reflux compounds have yet a limited efficacy and side effects that currently limit their development. Copyright © 2012. Published by Elsevier Masson SAS.

  12. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

    KAUST Repository

    Gil, Michał; Kijak, Michał; Piwonski, Hubert Marek; Herbich, Jerzy; Waluk, Jacek

    2017-01-01

    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters.We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donoracceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  13. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

    KAUST Repository

    Gil, Michał

    2017-02-03

    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters.We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donoracceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  14. Excited-state intramolecular proton transfer and photoswitching in hydroxyphenyl-imidazopyridine derivatives: A theoretical study

    Science.gov (United States)

    Omidyan, Reza; Iravani, Maryam

    2016-11-01

    The MP2/CC2 and CASSCF theoretical approaches have been employed to determine the excited state proton transfer and photophysical nature of the four organic compounds, having the main frame of hydroxyphenyl-imidzaopyridine (HPIP). The nitrogen insertion effect, in addition to amine (-NH2) substitution has been investigated extensively by following the transition energies and deactivation pathways of resulted HPIP derivatives. It has been predicted that the excited state intramolecular proton transfer with or without small barrier is the most important feature of these compounds. Also, for all of the considered HPIP derivatives, a conical intersection (CI) between ground and the S1 excited state has been predicted. The strong non-adiabatic coupling in the CI (S1/S0), drives the system back to the ground state in which the proton may either return to the phenoxy unit and thus close the photocycle, or the system can continue the twisting motion that results in formation of a γ-photochromic species. This latter species can be responsible for photochromism of HPIP derivative systems.

  15. Proton-coupled electron transfer promotes the reduction of ferrylmyoglobin by uric acid under physiological conditions

    DEFF Research Database (Denmark)

    de Zawadzki, Andressa; Cardoso, Daniel R.; Skibsted, Leif Horsfelt

    2017-01-01

    The hypervalent muscle pigment ferrylmyoglobin, MbFe(IV)]O, is not reduced by urate monoanions at physiological conditions despite a strong driving force of around 30 kJ mol1 while for low pH, uric acid was found to reduce protonated ferrylmyoglobin, MbFe(IV)]O,H+, efficiently in a bimolecular...... reaction with k1 ¼ 1.1 0.1 103 L mol1 s1, DH‡ ¼ 66.1 0.1 kJ mol1 and DS‡ ¼ 35.2 0.2 J mol1 K1. For intermediate pH, like for anaerobic muscles and for meat, proton-oupled electron transfer occurs in a transition state, {MbFe(IV)]O/H+/urate}‡, which is concluded to be formed from uric acid and Mb...... in uric acid concentration may serve as an inherent protection against radical formation by ferrylmyoglobin...

  16. A proton medical accelerator by the SBIR route — an example of technology transfer

    Science.gov (United States)

    Martin, R. L.

    1989-04-01

    Medical facilities for radiation treatment of cancer with protons have been established in many laboratories throughout the world. Essentially all of these have been designed as physics facilities, however, because of the requirement for protons up to 250 MeV. Most of the experience in this branch of accelerator technology lies in the national laboratories and a few large universities. A major issue is the transfer of this technology to the commercial sector to provide hospitals with simple, reliable and relatively inexpensive accelerators for this application. The author has chosen the SBIR route to accomplish this goal. ACCTEK Associates has received grants from the National Cancer Institute for development of the medical accelerator and beam delivery systems. Considerable encouragement and help has been received from Argonne National Laboratory and the Department of Energy. The experiences to date and the pros and cons on this approach to commercializing medical accelerators are described.

  17. A proton medical accelerator by the SBIR route - an example of technology transfer

    International Nuclear Information System (INIS)

    Martin, R.L.

    1989-01-01

    Medical facilities for radiation treatment of cancer with protons have been established in many laboratories throughout the world. Essentially all of these have been designed as physics facilities, however, because of the requirement for protons up to 250 MeV. Most of the experience on this branch of accelerator technology lies in the national laboratories and a few large universities. A major issue is the transfer of this technology to the commercial sector to provide hospitals with simple, reliable, and relatively inexpensive accelerators for this application. The author has chosen the SBIR route to accomplish this goal. ACCTEK Associates has received grants from the National Cancer Institute for development of the medical accelerator and beam delivery systems. Considerable encouragement and help has been received from Argonne National Laboratory and the Department of Energy. The experiences to date and the pros and cons on this approach to commercializing medical accelerators are described. (orig.)

  18. A proton medical accelerator by the SBIR route: An example of technology transfer

    International Nuclear Information System (INIS)

    Martin, R.L.

    1988-01-01

    Medical facilities for radiation treatment of cancer with protons have been established in many laboratories throughout the world. Essentially all of these have been designed as physics facilities, however, because of the requirement for protons up to 250 MeV. Most of the experience in this branch of accelerator technology lies in the national laboratories and a few large universities. A major issue is the transfer of this technology to the commercial sector to provide hospitals with simple, reliable, and relatively inexpensive accelerators for this application. The author has chosen the SBIR route to accomplish this goal. ACCTEK Associates have received grants from the National Cancer Institute for development of the medical accelerator and beam delivery systems. Considerable encouragement and help has been received from Argonne National Laboratory and the Department of Energy. The experiences to date and the pros and cons on this approach to commercializing medical accelerators are described. 4 refs., 1 fig

  19. A quantum chemical study of the mechanism for proton-coupled electron transfer leading to proton pumping in cytochrome c oxidase

    Science.gov (United States)

    Blomberg, Margareta R. A.; Siegbahn, Per E. M.

    2010-10-01

    The proton pumping mechanism in cytochrome c oxidase, the terminal enzyme in the respiratory chain, has been investigated using hybrid DFT with large chemical models. In previous studies, a gating mechanism was suggested based on electrostatic interpretations of kinetic experiments. The predictions from that analysis are tested here. The main result is that the suggestion of a positively charged transition state for proton transfer is confirmed, while some other suggestions for the gating are not supported. It is shown that a few critical relative energy values from the earlier studies are reproduced with quite high accuracy using the present model calculations. Examples are the forward barrier for proton transfer from the N-side of the membrane to the pump-loading site when the heme a cofactor is reduced, and the corresponding back leakage barrier when heme a is oxidised. An interesting new finding is an unexpected double-well potential for proton transfer from the N-side to the pump-loading site. In the intermediate between the two transition states found, the proton is bound to PropD on heme a. A possible purpose of this type of potential surface is suggested here. The accuracy of the present values are discussed in terms of their sensitivity to the choice of dielectric constant. Only one energy value, which is not critical for the present mechanism, varies significantly with this choice and is therefore less certain.

  20. CALCULATION OF THE PROTON-TRANSFER RATE USING DENSITY-MATRIX EVOLUTION AND MOLECULAR-DYNAMICS SIMULATIONS - INCLUSION OF THE PROTON EXCITED-STATES

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC

    1995-01-01

    The methodology for treatment of proton transfer processes by density matrix evolution (DME) with inclusion of many excited states is presented. The DME method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. 1993, 97, 13464) that simulates the dynamics of quantum systems embedded in a classical

  1. Amide proton transfer (APT) imaging of brain tumors at 7 T : The role of tissue water T1 -Relaxation properties

    NARCIS (Netherlands)

    Khlebnikov, V; Polders, Daniel; Hendrikse, J; Robe, Pierre A.; Voormolen, Eduard H; Luijten, Peter R; Klomp, DWJ; Hoogduin, Hans

    PURPOSE: To provide insight into the effect of water T1 relaxation (T1wat ) on amide proton transfer (APT) contrast in tumors. Three different metrics of APT contrast-magnetization transfer ratio (MTRRex ), relaxation-compensated MTRRex (AREX), and traditional asymmetry (MTRasym )-were compared in

  2. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...... of control by ATRP and click chemistry enables a wide selection of polymer structures with the handles: degree of substitution (DS), polymerization and sulfonation, and blending....

  3. Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

    International Nuclear Information System (INIS)

    Hirakawa, Kazutaka; Segawa, Hiroshi

    2016-01-01

    Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

  4. Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

    Energy Technology Data Exchange (ETDEWEB)

    Hirakawa, Kazutaka, E-mail: hirakawa.kazutaka@shizuoka.ac.jp [Applied Chemistry and Biochemical Engineering Course, Department of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Department of Optoelectronics and Nanostructure Science, Graduate School of Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Segawa, Hiroshi [Department of Multi-Disciplinary Science - General Systems Studies, Graduate School of Arts and Sciences, The University of Tokyo, Komaba 3-8-1, Meguro-ku, Tokyo 153-8904 (Japan); Research Center for Advanced Science and Technology, The University of Tokyo, Komaba 4-6-1, Meguro-ku, Tokyo 153-8904 (Japan)

    2016-11-15

    Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

  5. The Effect of Isotopic Substitution on Quantum Proton Transfer Across Short Water Bridges in Biological Systems

    Science.gov (United States)

    Blazejewski, Jacob; Schultz, Chase; Mazzuca, James

    2015-03-01

    Many biological systems utilize water chains to transfer charge over long distances by means of an excess proton. This study examines how quantum effects impact these reactions in a small model system. The model consists of a water molecule situated between an imidazole donor and acceptor group, which simulate a fixed amino acid backbone. A one dimensional energy profile is evaluated using density functional theory at the 6-31G*/B3LYP level, which generates a barrier with a width of 0.6 Å and a height of 20.7 kcal/mol. Quantum transmission probability is evaluated by solving the time dependent Schrödinger equation on a grid. Isotopic effects are examined by performing calculations with both hydrogen and deuterium. The ratio of hydrogen over the deuterium shows a 130-fold increase in transmission probability at low temperatures. This indicates a substantial quantum tunneling effect. The study of higher dimensional systems as well as increasing the number of water molecules in the chain will be necessary to fully describe the proton transfer process. Alma College Provost's Office.

  6. Can membrane-bound carotenoid pigment zeaxanthin carry out a transmembrane proton transfer?

    Science.gov (United States)

    Kupisz, Kamila; Sujak, Agnieszka; Patyra, Magdalena; Trebacz, Kazimierz; Gruszecki, Wiesław I

    2008-10-01

    Polar carotenoid pigment zeaxanthin (beta,beta-carotene-3,3'-diol) incorporated into planar lipid membranes formed with diphytanoyl phosphatidylcholine increases the specific electric resistance of the membrane from ca. 4 to 13 x 10(7) Omega cm2 (at 5 mol% zeaxanthin with respect to lipid). Such an observation is consistent with the well known effect of polar carotenoids in decreasing fluidity and structural stabilization of lipid bilayers. Zeaxanthin incorporated into the lipid membrane at 1 mol% has very small effect on the overall membrane resistance but facilitates equilibration of the transmembrane proton gradient, as demonstrated with the application of the H+-sensitive antimony electrodes. Relatively low changes in the electrical potential suggest that the equilibration process may be associated with a symport/antiport activity or with a transmembrane transfer of the molecules of acid. UV-Vis linear dichroism analysis of multibilayer formed with the same lipid-carotenoid system shows that the transition dipole moment of the pigment molecules forms a mean angle of 21 degrees with respect to the axis normal to the plane of the membrane. This means that zeaxanthin spans the membrane and tends to have its two hydroxyl groups anchored in the opposite polar zones of the membrane. Detailed FTIR analysis of beta-carotene and zeaxanthin indicates that the polyene chain of carotenoids is able to form weak hydrogen bonds with water molecules. Possible molecular mechanisms responsible for proton transport by polyenes are discussed, including direct involvement of the polyene chain in proton transfer and indirect effect of the pigment on physical properties of the membrane.

  7. Mixed convection flow and heat transfer over different geometries of backward-facing step

    Directory of Open Access Journals (Sweden)

    BADER SHABEEB ALSHURAIAAN

    2013-12-01

    Full Text Available Mixed convective flow and heat transfer characteristics for two-dimensional laminar flow in a channel with different geometries of a backward-facing step are presented for various Grashof numbers. The wall downstream of the step was maintained at a constant temperature; TH, while the upper wall was considered isothermal at TC. The wall upstream of the step and the backward-facing step were considered as adiabatic surfaces. Navier-Stokes equations were employed to represent the transport phenomena in the channel. Further, the governing equations were solved using a finite element formulation based on the Galerkin method of weighted residuals. The numerical results of the reattachement lengths for recirculation region in a vertical channel with a backward-facing step (Re = 100 were validated by comparing them against documented studies in the literature. The results of this investigation show that the local skin friction coefficient increases with an increase in Grashof numbers. The results of this investigation show that configuration II of the backward-facing step (inclined exhibited an absence of vortices for all values of Grashof numbers and consequently the minimum skin friction coefficient. However, configuration I is found to have the largest local skin friction coefficient.

  8. CFD Simulation of Heat Transfer and Turbulent Fluid Flow over a Double Forward-Facing Step

    Directory of Open Access Journals (Sweden)

    Hussein Togun

    2013-01-01

    Full Text Available Heat transfer and turbulent water flow over a double forward-facing step were investigated numerically. The finite volume method was used to solve the corresponding continuity, momentum, and energy equations using the K-ε model. Three cases, corresponding to three different step heights, were investigated for Reynolds numbers ranging from 30,000 to 100,000 and temperatures ranging from 313 to 343 K. The bottom of the wall was heated, whereas the top was insulated. The results show that the Nusselt number increased with the Reynolds number and step height. The maximum Nusselt number was observed for case 3, with a Reynolds number of 100,000 and temperature of 343 K, occurring at the second step. The behavior of the Nusselt number was similar for all cases at a given Reynolds number and temperature. A recirculation zone was observed before and after the first and second steps in the contour maps of the velocity field. In addition, the results indicate that the coefficient pressure increased with increasing Reynolds number and step height. ANSYS FLUENT 14 (CFD software was employed to run the simulations.

  9. Photoinduced proton transfer coupled with energy transfer: Mechanism of sensitized luminescence of terbium ion by salicylic acid doped in polymer.

    Science.gov (United States)

    Misra, Vinita; Mishra, Hirdyesh

    2008-06-28

    In the present work, excited state intramolecular proton transfer (ESIPT) in salicylic acid (SA) monoanion and subsequent sensitization of Tb(3+) ion in polyvinyl alcohol (PVA) have been studied. The study has been carried out both by steady state and time domain fluorescence measurement techniques at room temperature. It is found that the SA completely ionizes and exists as monoanion in PVA. It exhibits a large Stokes shifted blue emission (10 000 cm(-1)) due to ESIPT and shows a decay time of 6.85 ns. On the other hand, Tb(3+) ion shows a very weak green emission and a decay time of approximately 641 mus in PVA film. Upon incorporating Tb(3+) ion in SA doped PVA film, both intensity and decay time of SA decrease and sensitized emission from Tb(+3) ion along with 3.8 mus rise time is observed. Energy transfer is found to take place both from excited singlet as well as triplet states. A brief description of the properties of the present system from the viewpoint of luminescent solar collector material is addressed.

  10. Theoretical studies of π-electron delocalization and localization on intramolecular proton transfer in the ground state

    Science.gov (United States)

    Peng, Hongliang; Huang, Pengru; Yi, Pinggui; Xu, Fen; Sun, Lixian

    2018-02-01

    Proton transfer processes of 15 benzimidazole compounds are studied by density functional theory methods, and natural orbital energy index (NOEI) is introduced. Here, NOEI and nucleus independent chemical shift (NICS) are applied to estimate the π-electron localization and delocalization, respectively. Proton transfer potential energy surfaces are calculated to explore these processes, and the results show that the changes of the π-electron delocalization of the phenyl (pyridyl) is the main factors for the stability of keto form. There is high correlation between the π-electron delocalization and the proton transfer barrier. When the π-electron localization is considered, the regression increases the correlation coefficient, increasing from 0.9663 to 0.9864. NOEI index is sensitive to π-electron localization; it is a beneficial and useful complement to NICS.

  11. Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

    Science.gov (United States)

    Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

    2018-02-14

    Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

  12. Measurement and investigation of proton irradiation-induced charge transfer inefficiency in PPD CIS at different integration times

    Science.gov (United States)

    Xue, Yuanyuan; Wang, Zujun; Zhang, Fengqi; Bian, Jingying; Yao, Zhibin; He, Baoping; Liu, Minbo; Sheng, Jiangkun; Ma, Wuying; Dong, Guantao; Jin, Junshan

    2018-04-01

    Charge transfer inefficiency (CTI) is an important parameter for photodiode (PPD) CMOS image sensors (CISs). A test system was built and used to measure the CTI of PPD CIS devices at different integration times. The radiation effects of 3 MeV and 10 MeV protons on the CTI were investigated. The experiments were carried out at the EN Tandem Van de Graaff accelerator at proton fluences in the range 1010 to 1011 p/cm2. The CTI was measured within the 2 h following proton radiations. The dependence of CTI on integration time, proton energy and fluence were investigated. The CTI was observed to increase after proton irradiation: with the effect of irradiation with 3 MeV proton being more severe than that with 10 MeV protons. The CTI was also observed to decrease with increasing integration time, which is thought to be related to the charge density in the space charge region (SCR) of the CIS devices. This work has provided a simple method to measure the CTI and helped us to understand proton radiation effects on the CTI of PPD CISs.

  13. Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

    Science.gov (United States)

    Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

    1998-06-01

    We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

  14. Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

    Science.gov (United States)

    Zhang, Jiaxu; Xie, Jing; Hase, William L

    2015-12-17

    Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

  15. Proton induced nuclide production cross section by HETC-3STEP/FRG-R

    Energy Technology Data Exchange (ETDEWEB)

    Shigyo, Nobuhiro; Ishibashi, Kenji [Kyushu Univ., Fukuoka (Japan); Yoshizawa, Nobuaki; Takada, Hiroshi

    1998-03-01

    High Energy Transport Code (HETC) based on the intranuclear-cascade-evaporation model is modified to calculate the fragmentation cross section. The exciton model is adopted for improvement of backward nucleon-emission cross section for low-energy nucleon-incident events. The level density parameter depending on the excitation energy is taken in the evaporation process. The fragmentation reaction is incorporated into HETC as a subroutine set by the use of the systematics of the reaction. The modified HETC (HETC-3STEP/FRG-R) reproduces experimental fragment yields to a reasonable degree. (author)

  16. Tunneling splitting in double-proton transfer: direct diagonalization results for porphycene.

    Science.gov (United States)

    Smedarchina, Zorka; Siebrand, Willem; Fernández-Ramos, Antonio

    2014-11-07

    Zero-point and excited level splittings due to double-proton tunneling are calculated for porphycene and the results are compared with experiment. The calculation makes use of a multidimensional imaginary-mode Hamiltonian, diagonalized directly by an effective reduction of its dimensionality. Porphycene has a complex potential energy surface with nine stationary configurations that allow a variety of tunneling paths, many of which include classically accessible regions. A symmetry-based approach is used to show that the zero-point level, although located above the cis minimum, corresponds to concerted tunneling along a direct trans - trans path; a corresponding cis - cis path is predicted at higher energy. This supports the conclusion of a previous paper [Z. Smedarchina, W. Siebrand, and A. Fernández-Ramos, J. Chem. Phys. 127, 174513 (2007)] based on the instanton approach to a model Hamiltonian of correlated double-proton transfer. A multidimensional tunneling Hamiltonian is then generated, based on a double-minimum potential along the coordinate of concerted proton motion, which is newly evaluated at the RI-CC2/cc-pVTZ level of theory. To make it suitable for diagonalization, its dimensionality is reduced by treating fast weakly coupled modes in the adiabatic approximation. This results in a coordinate-dependent mass of tunneling, which is included in a unique Hermitian form into the kinetic energy operator. The reduced Hamiltonian contains three symmetric and one antisymmetric mode coupled to the tunneling mode and is diagonalized by a modified Jacobi-Davidson algorithm implemented in the Jadamilu software for sparse matrices. The results are in satisfactory agreement with the observed splitting of the zero-point level and several vibrational fundamentals after a partial reassignment, imposed by recently derived selection rules. They also agree well with instanton calculations based on the same Hamiltonian.

  17. Measurements of the deuteron and proton magnetic form factors at large momentum transfers

    International Nuclear Information System (INIS)

    Bosted, P.E.; Katramatou, A.T.; Arnold, R.G.; Benton, D.; Clogher, L.; DeChambrier, G.; Lambert, J.; Lung, A.; Petratos, G.G.; Rahbar, A.; Rock, S.E.; Szalata, Z.M.; Debebe, B.; Frodyma, M.; Hicks, R.S.; Hotta, A.; Peterson, G.A.; Gearhart, R.A.; Alster, J.; Lichtenstadt, J.; Dietrich, F.; van Bibber, K.

    1990-01-01

    Measurements of the deuteron elastic magnetic structure function B(Q 2 ) are reported at squared four-momentum transfer values 1.20≤Q 2 ≤2.77 (GeV/c) 2 . Also reported are values for the proton magnetic form factor G Mp (Q 2 ) at 11 Q 2 values between 0.49 and 1.75 (GeV/c) 2 . The data were obtained using an electron beam of 0.5 to 1.3 GeV. Electrons backscattered near 180 degree were detected in coincidence with deuterons or protons recoiling near 0 degree in a large solid-angle double-arm spectrometer system. The data for B(Q 2 ) are found to decrease rapidly from Q 2 =1.2 to 2 (GeV/c) 2 , and then rise to a secondary maximum around Q 2 =2.5 (GeV/c) 2 . Reasonable agreement is found with several different models, including those in the relativistic impulse approximation, nonrelativistic calculations that include meson-exchange currents, isobar configurations, and six-quark configurations, and one calculation based on the Skyrme model. All calculations are very sensitive to the choice of deuteron wave function and nucleon form factor parametrization. The data for G Mp (Q 2 ) are in good agreement with the empirical dipole fit

  18. Roles of multi-step transfer in fusion process induced by heavy-ion reactions

    International Nuclear Information System (INIS)

    Imanishi, B.; Oertzen, W. von.

    1993-06-01

    In nucleus-nucleus collisions of the systems, 12 C+ 13 C and 13 C+ 16 O- 12 C+ 17 O, the effects of the multi-step transfers and inelastic excitations on the fusion cross sections are investigated in the framework of the coupled-reaction-channel (CRC) method. Strong CRC effects of the multi-step processes are observed. Namely, the valence neutron in 13 C or 17 O plays an important role in the enhancement of the fusion. The potential barrier is effectively lowered with the formation of the covalent molecule of the configuration, 12 C+n+ 12 C or 12 C+n+ 16 O. In the analyses of the system 12 C+ 13 C, however, it is still required to introduce core-core optical potential of lower barrier height in the state of the positive total parity. This could be due to the neck formation with the nucleons contained in two core nuclei. (author)

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

    Directory of Open Access Journals (Sweden)

    A. Vlasenko

    2010-08-01

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

  20. Hybrid mesh finite volume CFD code for studying heat transfer in a forward-facing step

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, J S; Kumar, Inder [Bhabha Atomic Research Center, Mumbai (India); Eswaran, V, E-mail: jsjayan@gmail.com, E-mail: inderk@barc.gov.in, E-mail: eswar@iitk.ac.in [Indian Institute of Technology, Kanpur (India)

    2010-12-15

    Computational fluid dynamics (CFD) methods employ two types of grid: structured and unstructured. Developing the solver and data structures for a finite-volume solver is easier than for unstructured grids. But real-life problems are too complicated to be fitted flexibly by structured grids. Therefore, unstructured grids are widely used for solving real-life problems. However, using only one type of unstructured element consumes a lot of computational time because the number of elements cannot be controlled. Hence, a hybrid grid that contains mixed elements, such as the use of hexahedral elements along with tetrahedral and pyramidal elements, gives the user control over the number of elements in the domain, and thus only the domain that requires a finer grid is meshed finer and not the entire domain. This work aims to develop such a finite-volume hybrid grid solver capable of handling turbulence flows and conjugate heat transfer. It has been extended to solving flow involving separation and subsequent reattachment occurring due to sudden expansion or contraction. A significant effect of mixing high- and low-enthalpy fluid occurs in the reattached regions of these devices. This makes the study of the backward-facing and forward-facing step with heat transfer an important field of research. The problem of the forward-facing step with conjugate heat transfer was taken up and solved for turbulence flow using a two-equation model of k-{omega}. The variation in the flow profile and heat transfer behavior has been studied with the variation in Re and solid to fluid thermal conductivity ratios. The results for the variation in local Nusselt number, interface temperature and skin friction factor are presented.

  1. Hybrid mesh finite volume CFD code for studying heat transfer in a forward-facing step

    Science.gov (United States)

    Jayakumar, J. S.; Kumar, Inder; Eswaran, V.

    2010-12-01

    Computational fluid dynamics (CFD) methods employ two types of grid: structured and unstructured. Developing the solver and data structures for a finite-volume solver is easier than for unstructured grids. But real-life problems are too complicated to be fitted flexibly by structured grids. Therefore, unstructured grids are widely used for solving real-life problems. However, using only one type of unstructured element consumes a lot of computational time because the number of elements cannot be controlled. Hence, a hybrid grid that contains mixed elements, such as the use of hexahedral elements along with tetrahedral and pyramidal elements, gives the user control over the number of elements in the domain, and thus only the domain that requires a finer grid is meshed finer and not the entire domain. This work aims to develop such a finite-volume hybrid grid solver capable of handling turbulence flows and conjugate heat transfer. It has been extended to solving flow involving separation and subsequent reattachment occurring due to sudden expansion or contraction. A significant effect of mixing high- and low-enthalpy fluid occurs in the reattached regions of these devices. This makes the study of the backward-facing and forward-facing step with heat transfer an important field of research. The problem of the forward-facing step with conjugate heat transfer was taken up and solved for turbulence flow using a two-equation model of k-ω. The variation in the flow profile and heat transfer behavior has been studied with the variation in Re and solid to fluid thermal conductivity ratios. The results for the variation in local Nusselt number, interface temperature and skin friction factor are presented.

  2. Hybrid mesh finite volume CFD code for studying heat transfer in a forward-facing step

    International Nuclear Information System (INIS)

    Jayakumar, J S; Kumar, Inder; Eswaran, V

    2010-01-01

    Computational fluid dynamics (CFD) methods employ two types of grid: structured and unstructured. Developing the solver and data structures for a finite-volume solver is easier than for unstructured grids. But real-life problems are too complicated to be fitted flexibly by structured grids. Therefore, unstructured grids are widely used for solving real-life problems. However, using only one type of unstructured element consumes a lot of computational time because the number of elements cannot be controlled. Hence, a hybrid grid that contains mixed elements, such as the use of hexahedral elements along with tetrahedral and pyramidal elements, gives the user control over the number of elements in the domain, and thus only the domain that requires a finer grid is meshed finer and not the entire domain. This work aims to develop such a finite-volume hybrid grid solver capable of handling turbulence flows and conjugate heat transfer. It has been extended to solving flow involving separation and subsequent reattachment occurring due to sudden expansion or contraction. A significant effect of mixing high- and low-enthalpy fluid occurs in the reattached regions of these devices. This makes the study of the backward-facing and forward-facing step with heat transfer an important field of research. The problem of the forward-facing step with conjugate heat transfer was taken up and solved for turbulence flow using a two-equation model of k-ω. The variation in the flow profile and heat transfer behavior has been studied with the variation in Re and solid to fluid thermal conductivity ratios. The results for the variation in local Nusselt number, interface temperature and skin friction factor are presented.

  3. SIMULATION OF TURBULENT FLOW AND HEAT TRANSFER OVER A BACKWARD -FACING STEP WITH RIBS TURBULATORS

    Directory of Open Access Journals (Sweden)

    Khudheyer S Mushatet

    2011-01-01

    Full Text Available Simulation is presented for a backward facing step flow and heat transfer inside a channel with ribs turbulators. The problem was investigated for Reynolds numbers up to 32000. The effect of a step height, the number of ribs and the rib thickness on the flow and thermal field were investigated. The computed results are presented as streamlines counters, velocity vectors and graphs of Nusselt number and turbulent kinetic energy variation. A control volume method employing a staggered grid techniques was imposed to discretize the governing continuity, full Navier Stockes and energy equations. A computer program using a SIMPLE algorithm was developed to handle the considered problem. The effect of turbulence was modeled by using a k-є model with its wall function formulas. The obtained results show that the strength and size of the re-circulation zones behind the step are increased with the increase of contraction ratio(i.e. with the increase of a step height. The size of recirculation regions and the reattachment length after the ribs are decreased with increasing of the contraction ratio. Also the results show that the Reynolds number and contraction ratio have a significant effect on the variation of turbulent kinetic energy and Nusselt number

  4. 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.

  5. Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

    Science.gov (United States)

    Chang, Xue-Ping; Fang, Qiu; Cui, Ganglong

    2014-10-01

    Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S0, T1, and S1 states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S1 system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S1/S0 conical intersection funnels the S1 to S0 state. Then, some trajectories continue completing the decarboxylation reaction in the S0 state; the remaining trajectories via a reverse hydrogen transfer return to the S0 minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S1 -T1 energy gap and a large S1/T1 spin-orbit coupling, an efficient S1 → T1 intersystem crossing process happens again near this S1/S0 conical intersection. When decaying to T1 state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S1 system first decays to the T1 state via an S1 → T1 intersystem crossing; then, the T1 system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T1 decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T1 ESIPT process, there also exists a comparable Norrish type I reaction in the T1 state, which forms the ground-state products of CH3CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S1-T1 and S1-S0 energy gaps, effecting an S1/T1/S0 three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

  6. Amide proton transfer imaging in clinics: Basic concepts and current and future use in brain tumors and stoke

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ji Eun [Dept. of Radiology and Research Institute of Radiology, University of Ulsan College of Medicine, Asan Medical Center, Seoul (Korea, Republic of); Jahng, Geon Ho [Dept. of Radiology, Kyung Hee University Hospital at Gangdong, College of Medicine, Kyung Hee University, Seoul (Korea, Republic of); Jeong, Ha Kyu [Philips Korea, Seoul (Korea, Republic of)

    2016-12-15

    Amide proton transfer (APT) imaging is gaining attention as a relatively new in vivo molecular imaging technique that has higher sensitivity and spatial resolution than magnetic resonance spectroscopy imaging. APT imaging is a subset of the chemical exchange saturation transfer mechanism, which can offer unique image contrast by selectively saturating protons in target molecules that get exchanged with protons in bulk water. In this review, we describe the basic concepts of APT imaging, particularly with regard to the benefit in clinics from the current literature. Clinical applications of APT imaging are described from two perspectives: in the diagnosis and monitoring of the treatment response in brain glioma by reflecting endogenous mobile proteins and peptides, and in the potential for stroke imaging with respect to tissue acidity.

  7. In vitro and in vivo volatile flavour analysis of red kidney beans by proton transfer reaction-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Dings, L.; Buhr, K.; Posthumus, M.A.

    2004-01-01

    The volatile flavour released from red kidney beans was evaluated in vitro (in a model mouth system) and in vivo (in-nose). The dynamic release of the volatile flavour compounds was analysed by proton transfer reaction¿mass spectrometry. The flavour compounds were identified by gas

  8. Environment-sensitive quinolone demonstrating long-lived fluorescence and unusually slow excited-state intramolecular proton transfer kinetics

    Czech Academy of Sciences Publication Activity Database

    Zamotaiev, O. M.; Shvadchak, Volodymyr; Sych, T. P.; Melnychuk, N. A.; Yushchenko, Dmytro A.; Mely, Y.; Pivovarenko, V. G.

    2016-01-01

    Roč. 4, č. 3 (2016), č. článku 034004. ISSN 2050-6120 Institutional support: RVO:61388963 Keywords : quinolone * fluorescent probes * local polarity * hydration * excited-state intramolecular proton transfer * kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.656, year: 2016

  9. Comparison between proton transfer reaction mass spectrometry and near infrared spectroscopy for the authentication of Brazilian coffee

    NARCIS (Netherlands)

    Monteiro, Pablo Inocêncio; Santos, Jânio Sousa; Alvarenga Brizola, Vitor Rafael; Pasini Deolindo, Carolina Turnes; Koot, Alex; Boerrigter-Eenling, Rita; Ruth, van Saskia; Georgouli, Konstantia; Koidis, Anastasios; Granato, Daniel

    2018-01-01

    In this study, proton-transfer reaction mass spectrometry (PTR-MS) and near-infrared spectroscopy (NIRS) were compared for the authentication of geographical and farming system origins of Brazilian coffees. For this purpose, n = 19 organic (ORG) and n = 26 conventional (CONV) coffees from

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

    NARCIS (Netherlands)

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

    2017-01-01

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

  11. Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    NARCIS (Netherlands)

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

    2017-01-01

    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. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds

  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

  13. Femtosecond double proton transfer dynamics in [2,2'-bipyridyl]-3,3'-diol in sol-gel glasses

    NARCIS (Netherlands)

    Prosposito, P.; Marks, D.R.A.; Zhang, H.; Glasbeek, M.

    1998-01-01

    Abstract: Intramolecular excited state double proton-transfer dynamics has been studied for [2,2'-bipyridyl]-3,3'-diol (BP(OH)2) in sol-gel glass. By means of the femtosecond fluorescence up-conversion technique, the spectral dependence of the fluorescence transients obtained for BP(OH)2 in a few

  14. 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

  15. Sequential Proton Loss Electron Transfer in Deactivation of Iron(IV) Binding Protein by Tyrosine Based Food Components

    DEFF Research Database (Denmark)

    Tang, Ning; Skibsted, Leif Horsfelt

    2017-01-01

    The iron(IV) binding protein ferrylmyoglobin, MbFe(IV)=O, was found to be reduced by tyrosine based food components in aqueous solution through a sequential proton loss electron transfer reaction mechanism without binding to the protein as confirmed by isothermal titration calorimetry. Dopamine a...

  16. Fundamental Insights into Proton-Coupled Electron Transfer in Soybean Lipoxygenase from Quantum Mechanical/Molecular Mechanical Free Energy Simulations.

    Science.gov (United States)

    Li, Pengfei; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2018-02-28

    The proton-coupled electron transfer (PCET) reaction catalyzed by soybean lipoxygenase has served as a prototype for understanding hydrogen tunneling in enzymes. Herein this PCET reaction is studied with mixed quantum mechanical/molecular mechanical (QM/MM) free energy simulations. The free energy surfaces are computed as functions of the proton donor-acceptor (C-O) distance and the proton coordinate, and the potential of mean force is computed as a function of the C-O distance, inherently including anharmonicity. The simulation results are used to calculate the kinetic isotope effects for the wild-type enzyme (WT) and the L546A/L754A double mutant (DM), which have been measured experimentally to be ∼80 and ∼700, respectively. The PCET reaction is found to be exoergic for WT and slightly endoergic for the DM, and the equilibrium C-O distance for the reactant is found to be ∼0.2 Å greater for the DM than for WT. The larger equilibrium distance for the DM, which is due mainly to less optimal substrate binding in the expanded binding cavity, is primarily responsible for its higher kinetic isotope effect. The calculated potentials of mean force are anharmonic and relatively soft at shorter C-O distances, allowing efficient thermal sampling of the shorter distances required for effective hydrogen tunneling. The primarily local electrostatic field at the transferring hydrogen is ∼100 MV/cm in the direction to facilitate proton transfer and increases dramatically as the C-O distance decreases. These simulations suggest that the overall protein environment is important for conformational sampling of active substrate configurations aligned for proton transfer, but the PCET reaction is influenced primarily by local electrostatic effects that facilitate conformational sampling of shorter proton donor-acceptor distances required for effective hydrogen tunneling.

  17. Spin transfer matrix formulation and snake resonances for polarized proton beams

    International Nuclear Information System (INIS)

    Tepikian, S.

    1986-01-01

    The polarization of a spin polarized proton beam in a circular accelerator is described by a spin transfer matrix. Using this method, they investigate three problems: (1) the crossing of multiple spin resonances, (2) resonance jumping and (3) an accelerator with Siberian snakes. When crossing two (or more) spin resonances, there are no analytic solutions available. However, they can obtain analytic expressions if the two spin resonances are well separated (nonoverlapping) or very close together (overlapping). Between these two extremes they resort to numerical solution of the spin equations. Resonance jumping can be studied using the tools developed for analyzing the cross of multiple spin resonances. These theoretical results compare favorably with experimental results obtained from the AGS at Brookhaven. For large accelerators, resonance jumping becomes impractical and other methods such as Siberian snakes must be used to keep the beam spin polarized. An accelerator with Siberian snakes and isolated spin resonances can be described with a spin transfer matrix. From this, they find a new type of spin depolarizing resonance, called snake resonances

  18. Characterizing amide proton transfer imaging in haemorrhage brain lesions using 3T MRI

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Ha-Kyu [Philips Korea, Seoul (Korea, Republic of); Korea Basic Science Institute, Chungcheongbuk-do (Korea, Republic of); Han, Kyunghwa [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, Seodaemun-gu, Seoul (Korea, Republic of); Yonsei University College of Medicine, Yonsei Biomedical Research Institute, Seoul (Korea, Republic of); Zhou, Jinyuan [Johns Hopkins University School of Medicine, Division of MRI Research, Department of Radiology, Baltimore, MD (United States); Zhao, Yansong [Philips Healthcare, MR Clinical Science, Cleveland, OH (United States); Choi, Yoon Seong; Lee, Seung-Koo; Ahn, Sung Soo [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, Seodaemun-gu, Seoul (Korea, Republic of)

    2017-04-15

    The aim of this study was to characterize amide proton transfer (APT)-weighted signals in acute and subacute haemorrhage brain lesions of various underlying aetiologies. Twenty-three patients with symptomatic haemorrhage brain lesions including tumorous (n = 16) and non-tumorous lesions (n = 7) were evaluated. APT imaging was performed and analyzed with magnetization transfer ratio asymmetry (MTR{sub asym}). Regions of interest were defined as the enhancing portion (when present), acute or subacute haemorrhage, and normal-appearing white matter based on anatomical MRI. MTR{sub asym} values were compared among groups and components using a linear mixed model. MTR{sub asym} values were 3.68 % in acute haemorrhage, 1.6 % in subacute haemorrhage, 2.65 % in the enhancing portion, and 0.38 % in normal white matter. According to the linear mixed model, the distribution of MTR{sub asym} values among components was not significantly different between tumour and non-tumour groups. MTR{sub asym} in acute haemorrhage was significantly higher than those in the other regions regardless of underlying pathology. Acute haemorrhages showed high MTR{sub asym} regardless of the underlying pathology, whereas subacute haemorrhages showed lower MTR{sub asym} than acute haemorrhages. These results can aid in the interpretation of APT imaging in haemorrhage brain lesions. (orig.)

  19. Amide proton transfer imaging for differentiation of benign and atypical meningiomas

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Bio [The Armed Forces Capital Hospital, Department of Radiology, Seongnam, Gyeonggi-do (Korea, Republic of); Han, Kyunghwa; Choi, Yoon Seong; Lee, Seung-Koo [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, College of Medicine, Seoul (Korea, Republic of); Ahn, Sung Soo [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, College of Medicine, Seoul (Korea, Republic of); Yonsei University, Department of Radiology, College of Medicine, Seoul (Korea, Republic of); Chang, Jong Hee; Kang, Seok-Gu [Yonsei University College of Medicine, Department of Neurosurgery, Seoul (Korea, Republic of); Kim, Se Hoon [Yonsei University College of Medicine, Department of Pathology, Seoul (Korea, Republic of); Zhou, Jinyuan [Johns Hopkins University School of Medicine, Division of MRI Research, Department of Radiology, Baltimore, MD (United States)

    2018-01-15

    To investigate the difference in amide proton transfer (APT)-weighted signals between benign and atypical meningiomas and determine the value of APT imaging for differentiating the two. Fifty-seven patients with pathologically diagnosed meningiomas (benign, 44; atypical, 13), who underwent preoperative MRI with APT imaging between December 2014 and August 2016 were included. We compared normalised magnetisation transfer ratio asymmetry (nMTR{sub asym}) values between benign and atypical meningiomas on APT-weighted images. Conventional MRI features were qualitatively assessed. Both imaging features were evaluated by multivariable logistic regression analysis. The discriminative value of MRI with and without nMTR{sub asym} was evaluated. The nMTR{sub asym} of atypical meningiomas was significantly greater than that of benign meningiomas (2.46% vs. 1.67%; P < 0.001). In conventional MR images, benign and atypical meningiomas exhibited significant differences in maximum tumour diameter, non-skull base location, and heterogeneous enhancement. On multivariable logistic regression analysis, high nMTR{sub asym} was an independent predictor of atypical meningiomas (adjusted OR, 11.227; P = 0.014). The diagnostic performance of MRI improved with nMTR{sub asym} for predicting atypical meningiomas. Atypical meningiomas exhibited significantly higher APT-weighted signal intensities than benign meningiomas. The discriminative value of conventional MRI improved significantly when combined with APT imaging for diagnosis of atypical meningioma. (orig.)

  20. Tyrosine oxidation in heme oxygenase: examination of long-range proton-coupled electron transfer.

    Science.gov (United States)

    Smirnov, Valeriy V; Roth, Justine P

    2014-10-01

    Heme oxygenase is responsible for the degradation of a histidine-ligated ferric protoporphyrin IX (Por) to biliverdin, CO, and the free ferrous ion. Described here are studies of tyrosyl radical formation reactions that occur after oxidizing Fe(III)(Por) to Fe(IV)=O(Por(·+)) in human heme oxygenase isoform-1 (hHO-1) and the structurally homologous protein from Corynebacterium diphtheriae (cdHO). Site-directed mutagenesis on hHO-1 probes the reduction of Fe(IV)=O(Por(·+)) by tyrosine residues within 11 Å of the prosthetic group. In hHO-1, Y58· is implicated as the most likely site of oxidation, based on the pH and pD dependent kinetics. The absence of solvent deuterium isotope effects in basic solutions of hHO-1 and cdHO contrasts with the behavior of these proteins in the acidic solution, suggesting that long-range proton-coupled electron transfer predominates over electron transfer.

  1. Proton transfer along water bridges in biological systems with density-functional tight-binding

    Science.gov (United States)

    Reiss, Krystle; Wise, Abigail; Mazzuca, James

    2015-03-01

    When examining the dynamics of charge transfer in high dimensional enzymatic systems, the cost of quantum mechanical treatment of electrons increases exponentially with the size of the system. As a semi-empirical method, density-functional tight-binding aids in shortening these calculation times, but can be inaccurate in the regime where bonds are being formed and broken. To address these inaccuracies with respect to proton transfer in an enzymatic system, DFTB is being used to calculate small model systems containing only a single amino acid residue donor, represented by an imidazole molecule, and a water acceptor. When DFTB calculations are compared to B3LYP geometry calculations of the donor molecule, we observe a bond angle error on the order of 1.2 degrees and a bond length error on the order of 0.011 Å. As we move forward with small donor-acceptor systems, comparisons between DFTB and B3LYP energy profiles will provide a better clue as to what extent improvements need to be made. To improve the accuracy of the DFTB calculations, the internuclear repulsion term may be altered. This would result in energy profiles that closely resemble those produced by higher-level theory. Alma College Provost's Office.

  2. Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

    Science.gov (United States)

    Gupta, Ashutosh; Jaeger, Heather M; Compaan, Katherine R; Schaefer, Henry F

    2012-05-17

    The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine. The Watson-Crick monohydrated GC anion is compared to neutral GC·H2O, as well as to the proton-transferred analogue on the basis of structural and energetic properties. In all three systems, local minima are identified that correspond to water positioned in the major and minor grooves of macromolecular DNA. On the anionic surface, two novel structures have water positioned above or below the GC plane. On the neutral and anionic surfaces, the global minimum can be described as water interacting with the minor groove. These structures are predicted to have hydration energies of 9.7 and 11.8 kcal mol(-1), respectively. Upon interbase proton-transfer (PT), the anionic global minimum has water positioned in the major groove, and the hydration energy increases to 13.4 kcal mol(-1). PT GC·H2O(•-) has distonic character; the radical character resides on cytosine, while the negative charge is localized on guanine. The effects of proton transfer are further investigated through the computed adiabatic electron affinities (AEA) of GC and monohydrated GC, and the vertical detachment energies (VDE) of the corresponding anions. Monohydration increases the AEAs and VDEs by only 0.1 eV, while proton-transfer increases the VDEs substantially (0.8 eV). The molecular charge distribution of monohydrated guanine-cytosine radical anion depends heavily on interbase proton transfer.

  3. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    International Nuclear Information System (INIS)

    Casadesus, Ricard; Vendrell, Oriol; Moreno, Miquel; Lluch, Jose M.; Morokuma, Keiji

    2006-01-01

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S 0 ) and first singlet excited (S 1 ) electronic states. In S 0 the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S 1 . The ab initio configuration interaction singles (CIS) method overestimates the energy of S 1 and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S 1 and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media

  4. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Casadesus, Ricard [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States); Vendrell, Oriol [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Moreno, Miquel [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)], E-mail: mmf@klingon.uab.es; Lluch, Jose M. [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Morokuma, Keiji [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States)

    2006-06-20

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S{sub 0}) and first singlet excited (S{sub 1}) electronic states. In S{sub 0} the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S{sub 1}. The ab initio configuration interaction singles (CIS) method overestimates the energy of S{sub 1} and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S{sub 1} and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media.

  5. Spin-locking vs. chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2010-01-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of non-equivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolites with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: i) On-resonance SL is most sensitive to chemical exchanges in the intermediate exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. ii) Offset frequency-dependent SL and CEST spectra are very similar, and can be explained well with an SL model recently developed by Trott and Palmer. iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. iv) The asymmetry of the magnetization transfer ratio (MTRasym) is highly dependent on the choice of saturation pulse power. In the intermediate exchange regime, MTRasym becomes complicated and should be interpreted with care. PMID:21500270

  6. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2011-05-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care. Copyright © 2010 Wiley-Liss, Inc.

  7. Ab initio study of the excited-state coupled electron-proton-transfer process in the 2-aminopyridine dimer

    International Nuclear Information System (INIS)

    Sobolewski, Andrzej L.; Domcke, Wolfgang

    2003-01-01

    The low-lying 1 ππ* excited states of the 2-aminopyridine dimer have been investigated with multi-reference ab initio methods (CASSCF and MRMP2). The 2-aminopyridine dimer can be considered as a mimetic model of Watson-Crick DNA base pairs. The reaction path and the energy profile for single proton transfer in the lowest 1 ππ* inter-monomer charge-transfer state have been obtained. A weakly avoided crossing of the 1 ππ* surface with the electronic ground-state surface has been found near the single-proton-transfer minimum of the 1 ππ* surface. From the splitting of the adiabatic surfaces at the avoided crossing, an internal-conversion lifetime of the excited state of <100 ps has been estimated. The potential relevance of these results for the rationalization of radiation-induced mutations and the photostability of the genetic code is briefly discussed

  8. Linear Energy Transfer-Guided Optimization in Intensity Modulated Proton Therapy: Feasibility Study and Clinical Potential

    Energy Technology Data Exchange (ETDEWEB)

    Giantsoudi, Drosoula, E-mail: dgiantsoudi@partners.org [Department of Radiation Oncology, Massachusetts General Hospital and Harvard Medical School, Boston, Massachusetts (United States); Grassberger, Clemens; Craft, David; Niemierko, Andrzej; Trofimov, Alexei; Paganetti, Harald [Department of Radiation Oncology, Massachusetts General Hospital and Harvard Medical School, Boston, Massachusetts (United States)

    2013-09-01

    Purpose: To investigate the feasibility and potential clinical benefit of linear energy transfer (LET) guided plan optimization in intensity modulated proton therapy (IMPT). Methods and Materials: A multicriteria optimization (MCO) module was used to generate a series of Pareto-optimal IMPT base plans (BPs), corresponding to defined objectives, for 5 patients with head-and-neck cancer and 2 with pancreatic cancer. A Monte Carlo platform was used to calculate dose and LET distributions for each BP. A custom-designed MCO navigation module allowed the user to interpolate between BPs to produce deliverable Pareto-optimal solutions. Differences among the BPs were evaluated for each patient, based on dose–volume and LET–volume histograms and 3-dimensional distributions. An LET-based relative biological effectiveness (RBE) model was used to evaluate the potential clinical benefit when navigating the space of Pareto-optimal BPs. Results: The mean LET values for the target varied up to 30% among the BPs for the head-and-neck patients and up to 14% for the pancreatic cancer patients. Variations were more prominent in organs at risk (OARs), where mean LET values differed by a factor of up to 2 among the BPs for the same patient. An inverse relation between dose and LET distributions for the OARs was typically observed. Accounting for LET-dependent variable RBE values, a potential improvement on RBE-weighted dose of up to 40%, averaged over several structures under study, was noticed during MCO navigation. Conclusions: We present a novel strategy for optimizing proton therapy to maximize dose-averaged LET in tumor targets while simultaneously minimizing dose-averaged LET in normal tissue structures. MCO BPs show substantial LET variations, leading to potentially significant differences in RBE-weighted doses. Pareto-surface navigation, using both dose and LET distributions for guidance, provides the means for evaluating a large variety of deliverable plans and aids in

  9. Chemical Rescue of Enzymes: Proton Transfer in Mutants of Human Carbonic Anhydrase II

    Science.gov (United States)

    Maupin, C. Mark; Castillo, Norberto; Taraphder, Srabani; Tu, Chingkuang; McKenna, Robert; Silverman, David N.; Voth, Gregory A.

    2011-01-01

    In human carbonic anhydrase II (HCA II) the mutation of position 64 from histidine to alanine (H64A) disrupts the rate limiting proton transfer (PT) event, resulting in a reduction of the catalytic activity of the enzyme as compared to the wild-type. Potential of mean force (PMF) calculations utilizing the multistate empirical valence bond (MS-EVB) methodology for H64A HCA II give a PT free energy barrier significantly higher than that found in the wild-type enzyme. This high barrier, determined in the absence of exogenous buffer and assuming no additional ionizable residues in the PT pathway, indicates the likelihood of alternate enzyme pathways that utilize either ionizable enzyme residues (self-rescue) and/or exogenous buffers (chemical rescue). It has been shown experimentally that the catalytic activity of H64A HCA II can be chemically rescued to near wild type levels by the addition of the exogenous buffer 4-methylimidazole (4MI). Crystallographic studies have identified two 4MI binding sites, yet site specific mutations intended to disrupt 4MI binding have demonstrated these sites to be non-productive. In the present work MS-EVB simulations show that binding of 4MI near Thr199 in the H64A HCA II mutant, a binding site determined by NMR spectroscopy, results in a viable chemical rescue pathway. Additional viable rescue pathways are also identified where 4MI acts as a proton transport intermediary from the active site to ionizable residues on the rim of the active site, revealing a probable mode of action for the chemical rescue pathway PMID:21452838

  10. Linear Energy Transfer-Guided Optimization in Intensity Modulated Proton Therapy: Feasibility Study and Clinical Potential

    International Nuclear Information System (INIS)

    Giantsoudi, Drosoula; Grassberger, Clemens; Craft, David; Niemierko, Andrzej; Trofimov, Alexei; Paganetti, Harald

    2013-01-01

    Purpose: To investigate the feasibility and potential clinical benefit of linear energy transfer (LET) guided plan optimization in intensity modulated proton therapy (IMPT). Methods and Materials: A multicriteria optimization (MCO) module was used to generate a series of Pareto-optimal IMPT base plans (BPs), corresponding to defined objectives, for 5 patients with head-and-neck cancer and 2 with pancreatic cancer. A Monte Carlo platform was used to calculate dose and LET distributions for each BP. A custom-designed MCO navigation module allowed the user to interpolate between BPs to produce deliverable Pareto-optimal solutions. Differences among the BPs were evaluated for each patient, based on dose–volume and LET–volume histograms and 3-dimensional distributions. An LET-based relative biological effectiveness (RBE) model was used to evaluate the potential clinical benefit when navigating the space of Pareto-optimal BPs. Results: The mean LET values for the target varied up to 30% among the BPs for the head-and-neck patients and up to 14% for the pancreatic cancer patients. Variations were more prominent in organs at risk (OARs), where mean LET values differed by a factor of up to 2 among the BPs for the same patient. An inverse relation between dose and LET distributions for the OARs was typically observed. Accounting for LET-dependent variable RBE values, a potential improvement on RBE-weighted dose of up to 40%, averaged over several structures under study, was noticed during MCO navigation. Conclusions: We present a novel strategy for optimizing proton therapy to maximize dose-averaged LET in tumor targets while simultaneously minimizing dose-averaged LET in normal tissue structures. MCO BPs show substantial LET variations, leading to potentially significant differences in RBE-weighted doses. Pareto-surface navigation, using both dose and LET distributions for guidance, provides the means for evaluating a large variety of deliverable plans and aids in

  11. Transfer characteristics of optical profilers with respect to rectangular edge and step height measurement

    Science.gov (United States)

    Xie, Weichang; Hagemeier, Sebastian; Bischoff, Jörg; Mastylo, Rostyslav; Manske, Eberhard; Lehmann, Peter

    2017-06-01

    Optical profilers are mature instruments used in research and industry to study surface topography features. Although the corresponding standards are based on simple step height measurements, in practical applications these instruments are often used to study the fidelity of surface topography. In this context it is well-known that in certain situations a surface profile obtained by an optical profiler will differ from the real profile. With respect to practical applications such deviations often occur in the vicinity of steep walls and in cases of high aspect ratio. In this contribution we compare the transfer characteristics of different 3D optical profiler principles, namely white-light interferometry, focus sensing, and confocal microscopy. Experimental results demonstrate that the transfer characteristics do not only depend on the parameters of the optical measurement system (e. g. wavelength and coherence of light, numerical aperture, evaluated signal feature, polarization) but also on the properties of the measuring object such as step height, aspect ratio, material properties and homogeneity, rounding and steepness of the edges, surface roughness. As a result, typical artefacts such as batwings occur for certain parameter combinations, particularly at certain height-to-wavelength ratio (HWR) values. Understanding of the mechanisms behind these phenomena enables to reduce them by an appropriate parameter adaption. However, it is not only the edge artefacts, but also the position of an edge that may be changed due to the properties of the measuring object. In order to investigate the relevant effects theoretically, several models are introduced. These are based on either an extension of Richards-Wolf modeling or rigorous coupled wave analysis (RCWA). Although these models explain the experimental effects quite well they suffer from different limitations, so that a quantitative correspondence of theoretical modeling and experimental results is hard to achieve

  12. Proton transfer processes in selenourea: UV-induced selenone → selenol photoreaction and ground state selenol → selenone proton tunneling

    International Nuclear Information System (INIS)

    Rostkowska, Hanna; Lapinski, Leszek; Khvorostov, Artem; Nowak, Maciej J.

    2004-01-01

    Infrared spectrum of selenourea isolated in low temperature Ar matrix indicates that monomers of this compound adopt exclusively the selenone tautomeric form. UV irradiation (λ>345 nm) of matrix-isolated selenourea leads to generation of the selenol tautomer (isoselenourea). Two conformers of the selenol tautomer with imino N-H bond oriented anti or syn with respect to the Se-H group were photoproduced. For the matrix kept at 10 K and in darkness, a proton tunneling transforming the photoproduced selenol anti form back into the initial selenone tautomer was observed. The time constant of this process was 16 h. The asymmetric barrier for the selenol → selenone proton tunneling was estimated at MP2/6-311++G(2d,p) level to be as high as 95 kJ mol -1 (7940 cm -1 ). The relation between the height of the barrier and the time constant of proton tunneling was discussed by comparing the current case with that previously studied for thiourea [J. Phys. Chem. A 107 (2003) 6373

  13. Smart Wireless Power Transfer Operated by Time-Modulated Arrays via a Two-Step Procedure

    Directory of Open Access Journals (Sweden)

    Diego Masotti

    2015-01-01

    Full Text Available The paper introduces a novel method for agile and precise wireless power transmission operated by a time-modulated array. The unique, almost real-time reconfiguration capability of these arrays is fully exploited by a two-step procedure: first, a two-element time-modulated subarray is used for localization of tagged sensors to be energized; the entire 16-element TMA then provides the power to the detected tags, by exploiting the fundamental and first-sideband harmonic radiation. An investigation on the best array architecture is carried out, showing the importance of the adopted nonlinear/full-wave computer-aided-design platform. Very promising simulated energy transfer performance of the entire nonlinear radiating system is demonstrated.

  14. Electrochemical model of polyaniline-based memristor with mass transfer step

    International Nuclear Information System (INIS)

    Demin, V.A.; Erokhin, V.V.; Kashkarov, P.K.; Kovalchuk, M.V.

    2015-01-01

    The electrochemical organic memristor with polyaniline active layer is a stand-alone device designed and realized for reproduction of some synapse properties in the innovative electronic circuits, such as the new field-programmable gate arrays or the neuromorphic networks capable for learning. In this work a new theoretical model of the polyaniline memristor is presented. The developed model of organic memristor functioning was based on the detailed consideration of possible electrochemical processes occuring in the active zone of this device including the mass transfer step of ionic reactants. Results of the calculation have demonstrated not only the qualitative explanation of the characteristics observed in the experiment, but also quantitative similarities of the resultant current values. This model can establish a basis for the design and prediction of properties of more complicated circuits and systems (including stochastic ones) based on the organic memristive devices

  15. Conjugate Heat Transfer Characteristics of Laminar Flows Through a Backward Facing Step Duct

    Directory of Open Access Journals (Sweden)

    Bayram CELİK

    2017-10-01

    Full Text Available Present study investigates the effects of solid to fluid conductivity ratio, Prandtl and Reynolds numbers, and solid wall thickness on conjugate heat transfer for a backward facing step duct with a conductive solid bottom wall. Although Kanna and Das performed a case study in 2006 for the same problem, the benchmark studies conducted later including the present one revealed that their results are arguable. Ramsak states in a study “Professor Kanna has confirmed in personal communication that their results are probably wrong”. The temperature and Nusselt number variations along the solid-fluid interface presented here are in excellent agreement with those obtained by Ramsak. The analyses presented here reveal that even though the decrease in Pr and the increase in solid to fluid conductivity ratio have similar global influence with the thinning wall on the interface temperature, the influence of the former parameters are limited in recirculation zone.

  16. Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Xue-Ping; Fang, Qiu, E-mail: fangqiu917@bnu.edu.cn; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)

    2014-10-21

    Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S{sub 0}, T{sub 1}, and S{sub 1} states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S{sub 1} system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S{sub 1}/S{sub 0} conical intersection funnels the S{sub 1} to S{sub 0} state. Then, some trajectories continue completing the decarboxylation reaction in the S{sub 0} state; the remaining trajectories via a reverse hydrogen transfer return to the S{sub 0} minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S{sub 1} −T{sub 1} energy gap and a large S{sub 1}/T{sub 1} spin-orbit coupling, an efficient S{sub 1} → T{sub 1} intersystem crossing process happens again near this S{sub 1}/S{sub 0} conical intersection. When decaying to T{sub 1} state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S{sub 1} system first decays to the T{sub 1} state via an S{sub 1} → T{sub 1} intersystem crossing; then, the T{sub 1} system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T{sub 1} decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T{sub 1} ESIPT process, there also exists a comparable Norrish type I reaction in the T{sub 1} state, which forms the ground-state products of CH{sub 3}CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S{sub 1}-T{sub 1} and S{sub 1}-S{sub 0} energy gaps, effecting an S{sub 1}/T{sub 1}/S{sub 0} three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

  17. TDDFT study on excited state intramolecular proton transfer mechanism in 2-amino-3-(2‧-benzazolyl)-quinolines

    Science.gov (United States)

    Jia, Xueli; Li, Chaozheng; Li, Donglin; Liu, Yufang

    2018-03-01

    The intramolecular proton transfer reaction of the 2-amino-3-(2‧-benzoxazolyl)-quinoline (ABO) and 2-amino-3-(2‧-benzothiazolyl)-quinoline (ABT) molecules in both S0 and S1 states at B3LYP/6-311 ++G(d,p) level in ethanol solvent have been studied to reveal the deactivation mechanism of the tautomers of the two molecules from the S1 state to the S0 state. The results show that the tautomers of ABO and ABT molecules may return to the S0 state by emitting fluorescence. In addition, the bond lengths, angles and infrared spectra are analyzed to confirm the hydrogen bonds strengthened upon photoexcitation, which can facilitate the proton transfer process. The frontier molecular orbitals (MOs) and natural bond orbital (NBO) are also calculated to indicate the intramolecular charge transfer which can be used to explore the tendency of ESIPT reaction. The potential energy surfaces of the ABO and ABT molecules in the S0 and S1 states have been constructed. According to the energy potential barrier of 9.12 kcal/mol for ABO molecule and 5.96 kcal/mol for ABT molecule, it can be indicated that the proton transfer may occur in the S1 state.

  18. Measurement of the proton form factor ratio at low momentum transfer

    Energy Technology Data Exchange (ETDEWEB)

    Friedman, Moshe [Hebrew Univ. of Jerusalem (Israel)

    2016-08-01

    Experiment E08-007-II measured the proton elastic form factor ratio μGE=GM in the momentum transfer range of Q2 ~ 0.02 - 0.08 GeV2, the lowest ever measured by polarization transfer techniques. The experiment was performed at the Thomas Jefferson National Accelerator Facility in Newport News, Virginia, USA during 2012. A polarized electron beam with energies of 1.1, 1.7, and 2.2 GeV was elastically scattered off a polarized solid NH3 target. The asymmetries between the cross section of positive and negative helicity states of the beam were determined. These asymmetries can be used to determine the form factor ratio. In this thesis, we present the asymmetry analysis of the experiment, discuss the main challenges and show preliminary results for part of the data. Preliminary asymmetries indicate an increase in the form factor ratio above unity. However, a complete analysis is required before any conclusion can be made. Further analysis is ongoing, and final asymmetry results and form factor extraction is expected during 2017. We also present first results for 14N asymmetries for elastic and quasi-elastic scattering. The measured asymmetries are in agreement with the shell model approximation, within the low accuracy of the measurement. A change in the asymmetry sign between the elastic and the quasi-elastic processes is seen, and should motivate further theoretical studies. These experimental asymmetries will also be useful for systematic studies of other experiments using polarized NH3 targets.

  19. Spin Transfer in Inclusive Λ0 Production by Transversely Polarized Protons at 200GeV/c

    International Nuclear Information System (INIS)

    Grosnick, D.P.; Hill, D.A.; Laghai, M.; Lopiano, D.; Ohashi, Y.; Spinka, H.; Stanek, R.W.; Underwood, D.G.; Yokosawa, A.; Bystricky, J.; Lehar, F.; Lesquen, A. de; Rossum, L. van; Cossairt, J.D.; Read, A.L.; Iwatani, K.; Belikov, N.I.; Derevschikov, A.A.; Grachov, O.A.; Matulenko, Y.A.; Meschanin, A.P.; Nurushev, S.B.; Patalakha, D.I.; Rykov, V.L.; Solovyanov, V.L.; Vasiliev, A.N.; Akchurin, N.; Onel, Y.; Maki, T.; Enyo, H.; Funahashi, H.; Goto, Y.; Iijima, T.; Imai, K.; Itow, Y.; Makino, S.; Masaike, A.; Miyake, K.; Nagamine, T.; Saito, N.; Yamashita, S.; Takashima, R.; Takeutchi, F.; Kuroda, K.; Michalowicz, A.; Rappazzo, G.F.; Salvato, G.; Luehring, F.C.; Miller, D.H.; Tamura, N.; Yoshida, T.; Adams, D.L.; Bonner, B.E.; Corcoran, M.D.; Cranshaw, J.; Nessi-Tedaldi, F.; Nessi, M.; Nguyen, C.; Roberts, J.B.; Skeens, J.; White, J.L.; Bravar, A.

    1997-01-01

    Surprisingly large polarizations in hyperon production by unpolarized protons have been known for a long time. The spin dynamics of the production process can be further investigated with polarized beams. Recently, a negative asymmetry A N was found in inclusive Λ 0 production with a 200GeV/c transversely polarized proton beam. The depolarization D NN in p↑+p→Λ 0 +X has been measured with the same beam over a wide x F range and at moderate p T . D NN reaches positive values of about 30% at high x F and p T ∼1.0GeV/c . This result shows a sizable spin transfer from the incident polarized proton to the outgoing Λ 0 . copyright 1997 The American Physical Society

  20. Applying protein-based amide proton transfer MR imaging to distinguish solitary brain metastases from glioblastoma

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Hao; Zou, Tianyu; Wang, Xianlong; Du, Yongxing; Jiang, Chunxiu; Ma, Ling; Zhu, Jianbin; He, Wen; Rui, Qihong; Wen, Zhibo [Zhujiang Hospital, Southern Medical University, Department of Radiology, Guangzhou, Guangdong (China); Lou, Huiling [The First People' Hospital of Guangzhou, Department of Geriatrics, Guangzhou, Guangdong (China); Jiang, Shanshan [Zhujiang Hospital, Southern Medical University, Department of Radiology, Guangzhou, Guangdong (China); Johns Hopkins University School of Medicine, Division of MR Research, Department of Radiology, Baltimore, MD (United States); Huang, Zhongqing [Shantou University Medical College, Department of Medical Image Center, Yuebei People' s Hospital, Shantou, Guangdong (China); Zhou, Jianyuan [Johns Hopkins University School of Medicine, Division of MR Research, Department of Radiology, Baltimore, MD (United States)

    2017-11-15

    To determine the utility of amide proton transfer-weighted (APTw) MR imaging in distinguishing solitary brain metastases (SBMs) from glioblastomas (GBMs). Forty-five patients with SBMs and 43 patients with GBMs underwent conventional and APT-weighted sequences before clinical intervention. The APTw parameters and relative APTw (rAPTw) parameters in the tumour core and the peritumoral brain zone (PBZ) were obtained and compared between SBMs and GBMs. The receiver-operating characteristic (ROC) curve was used to assess the best parameter for distinguishing between the two groups. The APTw{sub max}, APTw{sub min}, APTw{sub mean}, rAPTw{sub max}, rAPTw{sub min} or rAPTw{sub mean} values in the tumour core were not significantly different between the SBM and GBM groups (P = 0.141, 0.361, 0.221, 0.305, 0.578 and 0.448, respectively). However, the APTw{sub max}, APTw{sub min}, APTw{sub mean}, rAPTw{sub max}, rAPTw{sub min} or rAPTw{sub mean} values in the PBZ were significantly lower in the SBM group than in the GBM group (P < 0.001). The APTw{sub min} values had the highest area under the ROC curve 0.905 and accuracy 85.2% in discriminating between the two neoplasms. As a noninvasive imaging method, APT-weighted MR imaging can be used to distinguish SBMs from GBMs. (orig.)

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

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

    Science.gov (United States)

    Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Park, Sanghyuk

    2018-02-01

    Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480 nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.

  3. Excited state proton transfer in 9-aminoacridine carboxamides in water and in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Charles A. [Iowa State Univ., Ames, IA (United States)

    1995-09-26

    The 9-aminoacridine molecule is important in several different fields of chemistry. The absorption and fluorescence spectra of this compound are pH sensitive and it is this property that allowed it to be used as a pH probe in different chemical environments. The compound exhibits proton transfer reactions which are among the most fundamental of chemical reactions. The planarity of 9-aminoacridine allows it to intercalate into DNA. Intercalation is a process in which the aromatic flat surface of the intercalator inserts between adjacent base pairs of DNA. The large surface area of 9-aminoacridine`s fused tricyclic ring system allows strong intercalative binding through van der Waals attractions. 9-aminoacridine and many of its derivatives have been tried as possible antitumor drugs. The cytotoxicity of an antitumor agent can be dramatically increased through the addition of one or two cationic side chains. This increase in cytotoxicity using the 9-aminoacridine compound as a parent molecule has been investigated through various derivatives with cationic side chains consisting of different number of carbon atoms between the proximal and distal N atoms. Similar derivatives varied the position of the carboxamide side chain on the aromatic ring system. The objective of this work is to first create a baseline study of the excited state kinetics of the 9-aminoacridine carboxamides in the absence of DNA. The baseline study will allow the excited state kinetics of these antitumor drugs when placed in DNA to be more fully understood.

  4. Experimental and computational studies on creatininium 4-nitrobenzoate - An organic proton transfer complex

    Science.gov (United States)

    Thirumurugan, R.; Anitha, K.

    2017-10-01

    A new organic proton transfer complex of creatininium 4-nitrobenzoate (C4NB) has been synthesized and its single crystals were grown successfully by slow evaporation technique. The grown single crystal was subjected to various characterization techniques like single crystal X-ray diffraction (SCXRD), FTIR, FT-Raman and Kurtz-Perry powder second harmonic generation (SHG). The SCXRD analysis revealed that C4NB was crystallized into orthorhombic crystal system, with noncentrosymmetric (NCS), P212121 space group. The creatininium cation and 4-nitrobenzoate anion were connected through a pair of N__H⋯O hydrogen bonds (N(3)__H(6) ⋯ O(3) (x+1, y, z) and N(2)__H(5) &ctdot O(2) (x-1/2, -y-1/2, -z+2)) and fashioned a R22(8) ring motif. The crystal structure was stabilized by strong N__H⋯O and weak C__H⋯O intermolecular interactions and it was quantitatively analysed by Hirshfeld surface and fingerprint (FP) analysis. FTIR and FT-Raman studies confirmed the vibrational modes of functional groups present in C4NB compound indubitably. SHG efficiency of grown crystal was 4.6 times greater than that of standard potassium dihydrogen phosphate (KDP) material. Moreover, density functional theory (DFT) studies such as Mulliken charge distribution, frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) map, natural bond orbital analysis (NBO) and first order hyperpolarizability (β0) were calculated to explore the structure-property relationship.

  5. Influence of different environments on the excited-state proton transfer and dual fluorescence of fisetin

    Science.gov (United States)

    Guharay, Jayanti; Dennison, S. Moses; Sengupta, Pradeep K.

    1999-05-01

    The influence of different protic and aprotic solvent environments on the excited-state intramolecular proton transfer (ESIPT) leading to a dual fluorescence behaviour of a biologically important, naturally occurring, polyhydroxyflavone, fisetin (3,3',4',7-tetrahydroxyflavone), has been investigated. The normal fluorescence band, in particular, is extremely sensitive to solvent polarity with νmax shifting from 24 510 cm -1 in dioxane ( ET(30)=36.0) to 20 790 cm -1 in methanol ( ET(30)=55.5). This is rationalized in terms of solvent dipolar relaxation process, which also accounts for the red edge excitation shifts (REES) observed in viscous environments such as glycerol at low temperatures. Significant solvent dependence of the tautomer fluorescence properties ( νmax, yield and decay kinetics) reveals the influence of external hydrogen bonding perturbation on the internal hydrogen bond of the molecule. These excited-state relaxation phenomena and their relevant parameters have been used to probe the microenvironment of fisetin in a membrane mimetic system, namely AOT reverse micelles in n-heptane at different water/surfactant molar ratio ( w0).

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

    Science.gov (United States)

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

    2008-08-01

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

  7. Dynamics of Chemical and Charge Transfer Reactions of Molecular Dications: IV. Proton Transfer and Reactions of Dication Isomers in the CHCl2+ +D2 System

    Czech Academy of Sciences Publication Activity Database

    Roithová, Jana; Žabka, Ján; Hrušák, Jan; Thissen, R.; Herman, Zdeněk

    2003-01-01

    Roč. 107, - (2003), s. 7347-7354 ISSN 1089-5639 R&D Projects: GA ČR GA203/00/0632; GA AV ČR KJB4040302 Grant - others:Barrande(FR) 2002-013-1 Institutional research plan: CEZ:AV0Z4040901 Keywords : dynamics of chemical * molecular dications * proton transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.792, year: 2003

  8. Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

    KAUST Repository

    Hong, Miao

    2016-01-18

    This contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition–proton transfer–NHC release fundamental steps. This study examines the monomer and catalyst scopes as well as the fundamental steps involved in the overall HTP mechanism. DMAs having six different types of linkages connecting the two methacrylates have been polymerized into the corresponding unsaturated polyesters. The most intriguing unsaturated polyester of the series is that based on the biomass-derived furfuryl dimethacrylate, which showed a unique self-curing ability Four MeO– and Cl–substituted TPT (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) derivatives as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure/reactivity relationship study revealed that OMe2TPT, being both a strong nucleophile and a good leaving group, exhibits the highest HTP activity and also produced the polyester with the highest Mn, while the Cl–substituted TPT derivatives are least active and efficient. Computational studies have provided mechanistic insights into the tail-to-tail dimerization coupling step as a suitable model for the propagation cycle of the HTP. The extensive energy profile was mapped out and the experimentally observed unicity of the TPT-based catalysts was satisfactorily explained with the thermodynamic formation of key spirocyclic species.

  9. Theoretical studies of charge transfer and proton transfer complex formation between 3,5-dinitrobenzic acid and 1,2-dimethylimidazole

    Science.gov (United States)

    Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

    2018-05-01

    Natural atomic charge analysis and molecular electrostatic potential (MEP) surface analysis of hydrogen bonded charge transfer (HBCT) and proton transfer (PT) complex of 3,5-dinitrobenzoic acid (DNBA) and 1,2-dimethylimidazole (DMI) have been investigated by theoretical modelling using widely employed DFT/B3LYP/6-311G(d,p) level of theory. Along with this analysis, Hirshfeld surface study of the intermolecular interactions and associated 2D finger plot for reported PT complex between DNBA and DMI have been explored.

  10. Excited-state intramolecular proton transfer of 2-acetylindan-1,3-dione studied by ultrafast absorption and fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Pramod Kumar Verma

    2016-03-01

    Full Text Available We employ transient absorption from the deep-UV to the visible region and fluorescence upconversion to investigate the photoinduced excited-state intramolecular proton-transfer dynamics in a biologically relevant drug molecule, 2-acetylindan-1,3-dione. The molecule is a ß-diketone which in the electronic ground state exists as exocyclic enol with an intramolecular H-bond. Upon electronic excitation at 300 nm, the first excited state of the exocyclic enol is initially populated, followed by ultrafast proton transfer (≈160 fs to form the vibrationally hot endocyclic enol. Subsequently, solvent-induced vibrational relaxation takes place (≈10 ps followed by decay (≈390 ps to the corresponding ground state.

  11. [Two-dimensional model of a double-well potential: proton transfer when a hydrogen bond is deformed].

    Science.gov (United States)

    Krasilnikov, P M

    2014-01-01

    The potential energy cross-section profile along a hydrogen bond may contain two minima in certain conditions; it is so-called a double well potential. The H-bond double well potential is essential for proton transfer along this hydrogen bond. We have considered the two-dimensional model of such double well potential in harmonic approximation, and we have also investigated the proton tunneling in it. In real environments thermal motion of atoms or conformational changes may cause reorientation and relative shift of molecule fragment forming the hydrogen bond and, as a result, the hydrogen bond isdeformed. This deformation is liable to change the double well potential form and, hence, the probability of the proton tunneling is changed too. As it is shown the characteristic time of proton tunneling is essentially increased by even small relative shift of heavy atoms forming the H-bond and also rotational displacement of covalent bond generated by one of heavy atoms and the proton (hydrogen atom). However, it is also shown, at the certain geometry of the H-bond deformation the opposite effect occurred, i.e., the characteristic time is not increased and even decreased. Notice that such its behavior arises from two-dimensionality of potential wells; this and other properties of our model are discussed in detail.

  12. Conserved phosphoryl transfer mechanisms within kinase families and the role of the C8 proton of ATP in the activation of phosphoryl transfer

    Directory of Open Access Journals (Sweden)

    Kenyon Colin P

    2012-03-01

    Full Text Available Abstract Background The kinome is made up of a large number of functionally diverse enzymes, with the classification indicating very little about the extent of the conserved kinetic mechanisms associated with phosphoryl transfer. It has been demonstrated that C8-H of ATP plays a critical role in the activity of a range of kinase and synthetase enzymes. Results A number of conserved mechanisms within the prescribed kinase fold families have been identified directly utilizing the C8-H of ATP in the initiation of phosphoryl transfer. These mechanisms are based on structurally conserved amino acid residues that are within hydrogen bonding distance of a co-crystallized nucleotide. On the basis of these conserved mechanisms, the role of the nucleotide C8-H in initiating the formation of a pentavalent intermediate between the γ-phosphate of the ATP and the substrate nucleophile is defined. All reactions can be clustered into two mechanisms by which the C8-H is induced to be labile via the coordination of a backbone carbonyl to C6-NH2 of the adenyl moiety, namely a "push" mechanism, and a "pull" mechanism, based on the protonation of N7. Associated with the "push" mechanism and "pull" mechanisms are a series of proton transfer cascades, initiated from C8-H, via the tri-phosphate backbone, culminating in the formation of the pentavalent transition state between the γ-phosphate of the ATP and the substrate nucleophile. Conclusions The "push" mechanism and a "pull" mechanism are responsible for inducing the C8-H of adenyl moiety to become more labile. These mechanisms and the associated proton transfer cascades achieve the proton transfer via different family-specific conserved sets of amino acids. Each of these mechanisms would allow for the regulation of the rate of formation of the pentavalent intermediate between the ATP and the substrate nucleophile. Phosphoryl transfer within kinases is therefore a specific event mediated and regulated via the

  13. Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Taipale, R.

    2011-07-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in

  14. Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S2CR){PhP(CH2CH2PPh2)2}](+) (R = Me, Et, Bu(n) or Ph).

    Science.gov (United States)

    Alwaaly, Ahmed; Clegg, William; Henderson, Richard A; Probert, Michael R; Waddell, Paul G

    2015-02-21

    The complexes [Ni(S2CR)(triphos)]BPh4 (R = Me, Et, Bu(n) or Ph; triphos = PhP{CH2CH2PPh2}2) have been prepared and characterised. X-ray crystallography (for R = Et, Ph, C6H4Me-4, C6H4OMe-4 and C6H4Cl-4) shows that the geometry of the five-coordinate nickel in the cation is best described as distorted trigonal bipyramidal, containing a bidentate carboxydithioate ligand with the two sulfur atoms spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)](+) with mixtures of HCl and Cl(-) in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)](2+) have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves at least two coupled equilibria. The first step involves the rapid association between [Ni(S2CR)(triphos)](+) and HCl to form the hydrogen-bonded precursor, {[Ni(S2CR)(triphos)](+)HCl} (K) and this is followed by the intramolecular proton transfer (k) to produce [Ni(SH(S)CR)(triphos)](2+). In the reaction of [Ni(S2CMe)(triphos)](+) the rate law is consistent with the carboxydithioate ligand undergoing chelate ring-opening after protonation. It seems likely that chelate ring-opening occurs for all [Ni(S2CR)(triphos)](+), but only with [Ni(S2CMe)(triphos)](+) is the protonation step sufficiently fast that chelate ring-opening is rate-limiting. With all other systems, proton transfer is rate-limiting. DFT calculations indicate that protonation can occur at either sulfur atom, but only protonation at the equatorial sulfur results in chelate ring-opening. The ways in which protonation of either sulfur atom complicates the analyses and interpretation of the kinetics are discussed.

  15. Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

    Science.gov (United States)

    Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

    2017-10-26

    Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

  16. Sterics level the rates of proton transfer to [Ni(XPh){PhP(CH₂CH₂PPh₂)₂}]⁺ (X = O, S or Se).

    Science.gov (United States)

    Alwaaly, Ahmed; Henderson, Richard A

    2014-09-04

    Rates of proton transfers between lutH(+) (lut = 2,6-dimethylpyridine) and [Ni(XPh)(PhP{CH2CH2PPh2}2)](+) (X = O, S or Se) are slow and show little variation (k(O) : k(S) : k(Se) = 1 : 12 : 9). This unusual behaviour is a consequence of sterics affecting the optimal interaction between the reactants prior to proton transfer.

  17. Influence of Hydration on Proton Transfer in the Guanine-Cytosine Radical Cation (G•+-C) Base Pair: A Density Functional Theory Study

    Science.gov (United States)

    Kumar, Anil; Sevilla, Michael D.

    2009-01-01

    On one-electron oxidation all molecules including DNA bases become more acidic in nature. For the GC base pair experiments suggest that a facile proton transfer takes place in the G•+-C base pair from N1 of G•+ to N3 of cytosine. This intra-base pair proton transfer reaction has been extensively considered using theoretical methods for the gas phase and it is predicted that the proton transfer is slightly unfavorable in disagreement with experiment. In the present study, we consider the effect of the first hydration layer on the proton transfer reaction in G•+-C by the use of density functional theory (DFT), B3LYP/6-31+G** calculations of the G•+-C base pair in the presence of 6 and 11 water molecules. Under the influence of hydration of 11 waters, a facile proton transfer from N1 of G•+ to N3 of C is predicted. The zero point energy (ZPE) corrected forward and backward energy barriers, for the proton transfer from N1 of G•+ to N3 of C, was found to be 1.4 and 2.6 kcal/mol, respectively. The proton transferred G•-(H+)C + 11H2O was found to be 1.2 kcal/mol more stable than G•+-C + 11H2O in agreement with experiment. The present calculation demonstrates that the inclusion of the first hydration shell around G•+-C base pair has an important effect on the internal proton transfer energetics. PMID:19485319

  18. HETC-3STEP calculations of proton induced nuclide production cross sections at incident energies between 20 MeV and 5 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Takada, Hiroshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Yoshizawa, Nobuaki; Ishibashi, Kenji

    1996-08-01

    For the OECD/NEA code intercomparison, nuclide production cross sections of {sup 16}O, {sup 27}Al, {sup nat}Fe, {sup 59}Co, {sup nat}Zr and {sup 197}Au for the proton incidence with energies of 20 MeV to 5 GeV are calculated with the HETC-3STEP code based on the intranuclear cascade evaporation model including the preequilibrium and high energy fission processes. In the code, the level density parameter derived by Ignatyuk, the atomic mass table of Audi and Wapstra and the mass formula derived by Tachibana et al. are newly employed in the evaporation calculation part. The calculated results are compared with the experimental ones. It is confirmed that HETC-3STEP reproduces the production of the nuclides having the mass number close to that of the target nucleus with an accuracy of a factor of two to three at incident proton energies above 100 MeV for {sup nat}Zr and {sup 197}Au. However, the HETC-3STEP code has poor accuracy on the nuclide production at low incident energies and the light nuclide production through the fragmentation process induced by protons with energies above hundreds of MeV. Therefore, further improvement is required. (author)

  19. HETC-3STEP calculations of proton induced nuclide production cross sections at incident energies between 20 MeV and 5 GeV

    International Nuclear Information System (INIS)

    Takada, Hiroshi; Yoshizawa, Nobuaki; Ishibashi, Kenji.

    1996-08-01

    For the OECD/NEA code intercomparison, nuclide production cross sections of 16 O, 27 Al, nat Fe, 59 Co, nat Zr and 197 Au for the proton incidence with energies of 20 MeV to 5 GeV are calculated with the HETC-3STEP code based on the intranuclear cascade evaporation model including the preequilibrium and high energy fission processes. In the code, the level density parameter derived by Ignatyuk, the atomic mass table of Audi and Wapstra and the mass formula derived by Tachibana et al. are newly employed in the evaporation calculation part. The calculated results are compared with the experimental ones. It is confirmed that HETC-3STEP reproduces the production of the nuclides having the mass number close to that of the target nucleus with an accuracy of a factor of two to three at incident proton energies above 100 MeV for nat Zr and 197 Au. However, the HETC-3STEP code has poor accuracy on the nuclide production at low incident energies and the light nuclide production through the fragmentation process induced by protons with energies above hundreds of MeV. Therefore, further improvement is required. (author)

  20. Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

    Science.gov (United States)

    Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

    2013-12-18

    Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

  1. Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models.

    Science.gov (United States)

    Marin, Pricila; Borba, Carlos Eduardo; Módenes, Aparecido Nivaldo; Espinoza-Quiñones, Fernando R; de Oliveira, Silvia Priscila Dias; Kroumov, Alexander Dimitrov

    2014-01-01

    Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

  2. Analyzing powers and proton spin transfer coefficients in the elastic scattering of 800 MeV polarized protons from an L-type polarized deuteron target at small momentum transfers

    International Nuclear Information System (INIS)

    Adams, D.L.

    1986-10-01

    Analyzing powers and spin transfer coefficients which describe the elastic scattering of polarized protons from a polarized deuteron target have been measured. The energy of the proton beam was 800 MeV and data were taken at laboratory scattering angles of 7, 11, 14, and 16.5 degrees. One analyzing power was also measured at 180 degrees. Three linearly independent orientations of the beam polarization were used and the target was polarized parallel and antiparallel to the direction of the beam momentum. The data were taken with the high resolution spectrometer at the Los Alamos Meson Physics Facility (experiment 685). The results are compared with multiple scattering predictions based on Dirac representations of the nucleon-nucleon scattering matrices. 27 refs., 28 figs., 4 tabs

  3. A Ratio-Analysis Method to the Dynamics of Excited State Proton Transfer: Pyranine in Water and Micelles.

    Science.gov (United States)

    Sahu, Kalyanasis; Nandi, Nilanjana; Dolai, Suman; Bera, Avisek

    2018-06-05

    Emission spectrum of a fluorophore undergoing excited state proton transfer (ESPT) often exhibits two distinct bands each representing emissions from protonated and deprotonated forms. The relative contribution of the two bands, best represented by an emission intensity ratio (R) (intensity maximum of the protonated band / intensity maximum of the deprotonated band), is an important parameter which usually denotes feasibility or promptness of the ESPT process. However, the use of ratio is only limited to the interpretation of steady-state fluorescence spectra. Here, for the first time, we exploit the time-dependence of the ratio (R(t)), calculated from time-resolved emission spectra (TRES) at different times, to analyze ESPT dynamics. TRES at different times were fitted with a sum of two lognormal-functions representing each peaks and then, the peak intensity ratio, R(t) was calculated and further fitted with an analytical function. Recently, a time-resolved area-normalized emission spectra (TRANES)-based analysis was presented where the decay of protonated emission or the rise of deprotonated emission intensity conveniently accounts for the ESPT dynamics. We show that these two methods are equivalent but the new method provides more insights on the nature of the ESPT process.

  4. QTES-DFTB dynamics study on the effect of substrate motion on quantum proton transfer in soybean lipoxygenase-1

    Science.gov (United States)

    Mazzuca, James; Garashchuk, Sophya; Jakowski, Jacek

    2014-03-01

    It has been shown that the proton transfer in the enzymatic active site of soybean lipoxygenase-1 (SLO-1) occurs largely by a quantum tunneling mechanism. This study examined the role of local substrate vibrations on this proton tunneling reaction. We employ an approximate quantum trajectory (QT) dynamics method with linear quantum force. The electronic structure (ES) was calculated on-the-fly with a density functional tight binding (DFTB) method. This QTES-DFTB method scales linearly with number of trajectories, and the calculation of the quantum force is a small addition to the overall cost of trajectory dynamics. The active site was represented as a 44-atom system. Quantum effects were included only for the transferring proton, and substrate nuclei were treated classically. The effect of substrate vibrations was evaluated by freezing or relaxing the substrate nuclei. Trajectory calculations were performed at several temperatures ranging from 250-350 K, and rate constants were calculated through the quantum mechanical flux operator which depends on time-dependent correlation functions. It was found that the substrate motion reliably increases the rate constants, as well as the P/D kinetic isotope effect, by approximately 10% across all temperatures examined. NSF Grant No. CHE-1056188, APRA-NSF-EPS-0919436, and CHE-1048629, NICS Teragrid/Xsede TG-DMR110037.

  5. Simultaneous and sequential transfer of proton and alpha-particle in the elastic 11B+16O scattering

    International Nuclear Information System (INIS)

    Kamys, B.; Rudy, Z.; Kisiel, J.; Kwasniewicsz, E.; Wolter, H.H.

    1992-01-01

    We have developed a method to treat multi-nucleon transfer as the transfer of two - possible different - subclusters, as e.g. with ' 5 Li'=(α,p). As a consequence we take into account two reaction mechanisms, the one-step simultaneous and the two-step sequential transfer of the two clusters. We formulate the method of calculation of the simultaneous transfer form factor for two non-identifical particles and also of the two-cluster spectroscopic amplitudes from shell model wave functions. We apply the method to the elastic transfer reaction 11 B( 16 O, 11 B) 11 O together with the single α and p transfer reaction 11 B( 16 O, 15 N) 12 C for E lab between 30 and 60 MeV. We obtain a consistently good description of all the data by reasonable adjustment of the spectroscopic amplitudes. In particular we find that the simultaneous (αp) transfer is considerably more important than the sequential transfer indicating strong five-nucleon correlations in these light nuclei. (orig.)

  6. The mechanism of electron gating in proton pumping cytochrome c oxidase: the effect of pH and temperature on internal electron transfer.

    Science.gov (United States)

    Brzezinski, P; Malmström, B G

    1987-10-29

    Electron-transfer reactions following flash photolysis of the mixed-valence cytochrome oxidase-CO complex have been measured at 445, 598 and 830 nm between pH 5.2 and 9.0 in the temperature range of 0-25 degrees C. There is a rapid electron transfer from the cytochrome a3-CuB pair to CuA (time constant: 14200 s-1), which is followed by a slower electron transfer to cytochrome a. Both the rate and the amplitude of the rapid phase are independent of pH, and the rate in the direction from CuA to cytochrome a3-CuB is practically independent of temperature. The second phase depends strongly on pH due to the titration of an acid-base group with pKa = 7.6. The equilibrium at pH 7.4 corresponds to reduction potentials of 225 and 345 mV for cytochrome a and a3, respectively, from which it is concluded that the enzyme is in a different conformation compared to the fully oxidized form. The results have been used to suggest a series of reaction steps in a cycle of the oxidase as a proton pump. Application of the electron-transfer theory to the temperature-dependence data suggests a mechanism for electron gating in the pump. Reduction of both cytochrome a and CuA leads to a conformational change, which changes the structure of cytochrome a3-CuB in such a way that the reorganizational barrier for electron transfer is removed and the driving force is increased.

  7. One dimensional transient numerical study of the mass heat and charge transfer in a proton exchange membrane for PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, Djamel; Benmoussa, Hocine [Laboratory (LESEI), Faculty of Engineering, University of Batna (Algeria); Bourmada, Noureddine; Oulmi, Kafia [Laboratory LCCE, Faculty of Science, University of Batna (Algeria); Mahmah, Bouziane; Belhamel, Maiouf [CDER, BP, 62 Avenue-Observatoire, Bouzareah, Alger (Algeria)

    2009-06-15

    The objective of our study is to quantify the mass water transferred by various modes: diffusion, convection and migration. For the water transfer, the principal forces considered in the model are, the convection force, the osmotic force (i.e. diffusion) and the electric force (migration). The first of these forces results from a pressure gradient, the second of a concentration gradient and the third of a protons' migration from the anode to the cathode, which has an effect on the dipole of the water molecules (resistance force to the advancement). The numerical tool used to solve the equations' system is the finite element method. The results obtained numerically considering this method are concentration profiles and concentration variation with time and membrane thickness. These results illustrate the contribution of each mass transfer mode. (author)

  8. Quasi-four-body treatment of charge transfer in the collision of protons with atomic helium: I. Thomas related mechanisms

    Science.gov (United States)

    Safarzade, Zohre; Fathi, Reza; Shojaei Akbarabadi, Farideh; Bolorizadeh, Mohammad A.

    2018-04-01

    The scattering of a completely bare ion by atoms larger than hydrogen is at least a four-body interaction, and the charge transfer channel involves a two-step process. Amongst the two-step interactions of the high-velocity single charge transfer in an anion-atom collision, there is one whose amplitude demonstrates a peak in the angular distribution of the cross sections. This peak, the so-called Thomas peak, was predicted by Thomas in a two-step interaction, classically, which could also be described through three-body quantum mechanical models. This work discusses a four-body quantum treatment of the charge transfer in ion-atom collisions, where two-step interactions illustrating a Thomas peak are emphasized. In addition, the Pauli exclusion principle is taken into account for the initial and final states as well as the operators. It will be demonstrated that there is a momentum condition for each two-step interaction to occur in a single charge transfer channel, where new classical interactions lead to the Thomas mechanism.

  9. Phylogenetic detection of horizontal gene transfer during the step-wise genesis of Mycobacterium tuberculosis

    Directory of Open Access Journals (Sweden)

    Turenne Christine

    2009-08-01

    Full Text Available Abstract Background In the past decade, the availability of complete genome sequence data has greatly facilitated comparative genomic research aimed at addressing genetic variability within species. More recently, analysis across species has become feasible, especially in genera where genome sequencing projects of multiple species have been initiated. To understand the genesis of the pathogen Mycobacterium tuberculosis within a genus where the majority of species are harmless environmental organisms, we have used genome sequence data from 16 mycobacteria to look for evidence of horizontal gene transfer (HGT associated with the emergence of pathogenesis. First, using multi-locus sequence analysis (MLSA of 20 housekeeping genes across these species, we derived a phylogeny that serves as the basis for HGT assignments. Next, we performed alignment searches for the 3989 proteins of M. tuberculosis H37Rv against 15 other mycobacterial genomes, generating a matrix of 59835 comparisons, to look for genetic elements that were uniquely found in M. tuberculosis and closely-related pathogenic mycobacteria. To assign when foreign genes were likely acquired, we designed a bioinformatic program called mycoHIT (mycobacterial homologue investigation tool to analyze these data in conjunction with the MLSA-based phylogeny. Results The bioinformatic screen predicted that 137 genes had been acquired by HGT at different phylogenetic strata; these included genes coding for metabolic functions and modification of mycobacterial lipids. For the majority of these genes, corroborating evidence of HGT was obtained, such as presence of phage or plasmid, and an aberrant GC%. Conclusion M. tuberculosis emerged through vertical inheritance along with the step-wise addition of genes acquired via HGT events, a process that may more generally describe the evolution of other pathogens.

  10. MASS TRANSFER CONTROL OF A BACKWARD-FACING STEP FLOW BY LOCAL FORCING- EFFECT OF REYNOLDS NUMBER

    Directory of Open Access Journals (Sweden)

    Zouhaier MEHREZ

    2011-01-01

    Full Text Available The control of fluid mechanics and mass transfer in separated and reattaching flow over a backward-facing step by a local forcing, is studied using Large Eddy Simulation (LES.To control the flow, the local forcing is realized by a sinusoidal oscillating jet at the step edge. The Reynolds number is varied in the range 10000 ≤ Re≤ 50000 and the Schmidt number is fixed at 1.The found results show that the flow structure is modified and the local mass transfer is enhanced by the applied forcing. The observed changes depend on the Reynolds number and vary with the frequency and amplitude of the local forcing. For the all Reynolds numbers, the largest recirculation zone size reduction is obtained at the optimum forcing frequency St = 0.25. At this frequency the local mass transfer enhancement attains the maximum.

  11. Using an isomorphic problem pair to learn introductory physics: Transferring from a two-step problem to a three-step problem

    Directory of Open Access Journals (Sweden)

    Shih-Yin Lin

    2013-10-01

    Full Text Available In this study, we examine introductory physics students’ ability to perform analogical reasoning between two isomorphic problems which employ the same underlying physics principles but have different surface features. 382 students from a calculus-based and an algebra-based introductory physics course were administered a quiz in the recitation in which they had to learn from a solved problem provided and take advantage of what they learned from it to solve another isomorphic problem (which we call the quiz problem. The solved problem provided has two subproblems while the quiz problem has three subproblems, which is known from previous research to be challenging for introductory students. In addition to the solved problem, students also received extra scaffolding supports that were intended to help them discern and exploit the underlying similarities of the isomorphic solved and quiz problems. The data analysis suggests that students had great difficulty in transferring what they learned from a two-step problem to a three-step problem. Although most students were able to learn from the solved problem to some extent with the scaffolding provided and invoke the relevant principles in the quiz problem, they were not necessarily able to apply the principles correctly. We also conducted think-aloud interviews with six introductory students in order to understand in depth the difficulties they had and explore strategies to provide better scaffolding. The interviews suggest that students often superficially mapped the principles employed in the solved problem to the quiz problem without necessarily understanding the governing conditions underlying each principle and examining the applicability of the principle in the new situation in an in-depth manner. Findings suggest that more scaffolding is needed to help students in transferring from a two-step problem to a three-step problem and applying the physics principles appropriately. We outline a few

  12. Using an isomorphic problem pair to learn introductory physics: Transferring from a two-step problem to a three-step problem

    Science.gov (United States)

    Lin, Shih-Yin; Singh, Chandralekha

    2013-12-01

    In this study, we examine introductory physics students’ ability to perform analogical reasoning between two isomorphic problems which employ the same underlying physics principles but have different surface features. 382 students from a calculus-based and an algebra-based introductory physics course were administered a quiz in the recitation in which they had to learn from a solved problem provided and take advantage of what they learned from it to solve another isomorphic problem (which we call the quiz problem). The solved problem provided has two subproblems while the quiz problem has three subproblems, which is known from previous research to be challenging for introductory students. In addition to the solved problem, students also received extra scaffolding supports that were intended to help them discern and exploit the underlying similarities of the isomorphic solved and quiz problems. The data analysis suggests that students had great difficulty in transferring what they learned from a two-step problem to a three-step problem. Although most students were able to learn from the solved problem to some extent with the scaffolding provided and invoke the relevant principles in the quiz problem, they were not necessarily able to apply the principles correctly. We also conducted think-aloud interviews with six introductory students in order to understand in depth the difficulties they had and explore strategies to provide better scaffolding. The interviews suggest that students often superficially mapped the principles employed in the solved problem to the quiz problem without necessarily understanding the governing conditions underlying each principle and examining the applicability of the principle in the new situation in an in-depth manner. Findings suggest that more scaffolding is needed to help students in transferring from a two-step problem to a three-step problem and applying the physics principles appropriately. We outline a few possible strategies

  13. Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Sode, Olaseni; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, Institute for Biophysical Dynamics, Computation Institute, The University of Chicago, Chicago, Illinois 60637, USA and Computing, Environment and Life Sciences, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2014-12-14

    Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A{sup 2−}, a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A{sup 2-} by closing a cavity that could otherwise fill with water near the proximal Fe of the active site.

  14. Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

    International Nuclear Information System (INIS)

    Sode, Olaseni; Voth, Gregory A.

    2014-01-01

    Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A 2− , a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A 2- by closing a cavity that could otherwise fill with water near the proximal Fe of the active site

  15. A phenomenological biological dose model for proton therapy based on linear energy transfer spectra.

    Science.gov (United States)

    Rørvik, Eivind; Thörnqvist, Sara; Stokkevåg, Camilla H; Dahle, Tordis J; Fjaera, Lars Fredrik; Ytre-Hauge, Kristian S

    2017-06-01

    The relative biological effectiveness (RBE) of protons varies with the radiation quality, quantified by the linear energy transfer (LET). Most phenomenological models employ a linear dependency of the dose-averaged LET (LET d ) to calculate the biological dose. However, several experiments have indicated a possible non-linear trend. Our aim was to investigate if biological dose models including non-linear LET dependencies should be considered, by introducing a LET spectrum based dose model. The RBE-LET relationship was investigated by fitting of polynomials from 1st to 5th degree to a database of 85 data points from aerobic in vitro experiments. We included both unweighted and weighted regression, the latter taking into account experimental uncertainties. Statistical testing was performed to decide whether higher degree polynomials provided better fits to the data as compared to lower degrees. The newly developed models were compared to three published LET d based models for a simulated spread out Bragg peak (SOBP) scenario. The statistical analysis of the weighted regression analysis favored a non-linear RBE-LET relationship, with the quartic polynomial found to best represent the experimental data (P = 0.010). The results of the unweighted regression analysis were on the borderline of statistical significance for non-linear functions (P = 0.053), and with the current database a linear dependency could not be rejected. For the SOBP scenario, the weighted non-linear model estimated a similar mean RBE value (1.14) compared to the three established models (1.13-1.17). The unweighted model calculated a considerably higher RBE value (1.22). The analysis indicated that non-linear models could give a better representation of the RBE-LET relationship. However, this is not decisive, as inclusion of the experimental uncertainties in the regression analysis had a significant impact on the determination and ranking of the models. As differences between the models were

  16. Analytical linear energy transfer model including secondary particles: calculations along the central axis of the proton pencil beam

    International Nuclear Information System (INIS)

    Marsolat, F; De Marzi, L; Mazal, A; Pouzoulet, F

    2016-01-01

    In proton therapy, the relative biological effectiveness (RBE) depends on various types of parameters such as linear energy transfer (LET). An analytical model for LET calculation exists (Wilkens’ model), but secondary particles are not included in this model. In the present study, we propose a correction factor, L sec , for Wilkens’ model in order to take into account the LET contributions of certain secondary particles. This study includes secondary protons and deuterons, since the effects of these two types of particles can be described by the same RBE-LET relationship. L sec was evaluated by Monte Carlo (MC) simulations using the GATE/GEANT4 platform and was defined by the ratio of the LET d distributions of all protons and deuterons and only primary protons. This method was applied to the innovative Pencil Beam Scanning (PBS) delivery systems and L sec was evaluated along the beam axis. This correction factor indicates the high contribution of secondary particles in the entrance region, with L sec values higher than 1.6 for a 220 MeV clinical pencil beam. MC simulations showed the impact of pencil beam parameters, such as mean initial energy, spot size, and depth in water, on L sec . The variation of L sec with these different parameters was integrated in a polynomial function of the L sec factor in order to obtain a model universally applicable to all PBS delivery systems. The validity of this correction factor applied to Wilkens’ model was verified along the beam axis of various pencil beams in comparison with MC simulations. A good agreement was obtained between the corrected analytical model and the MC calculations, with mean-LET deviations along the beam axis less than 0.05 keV μm −1 . These results demonstrate the efficacy of our new correction of the existing LET model in order to take into account secondary protons and deuterons along the pencil beam axis. (paper)

  17. Anomalous H/D isotope effect in hydrogen bonded systems: H-bonded cyclic structures and transfers of protons

    International Nuclear Information System (INIS)

    Marechal, Y.

    1993-01-01

    The systematic H/D substitution is a precious tool to obtain information on the dynamics of H-bonds. It is particularly useful in IR spectroscopy where H-bonds are at the origin of particularly intense and specific bands and where the particularly great value for the m D /m H ratio ensures strongly marked effects. In most H-bonded systems the effects of these substitutions are normal, in the sense that they are at the origin of bands having intensities, centers (of intensity) and widths smaller in D-bonds by a factor close to √2 as compared to H-bonds. In some systems as carboxylic acid dimers, however, anomalous ratios of intensities are found upon such a substitution. Their origin is still obscure. Experimental results suggest that such anomalous ratios have much to do with the cyclic structure of these systems. It leads to stressing an important property of H-bonded cyclic structures which is that they seem necessary for having transfers of protons between molecules through H-bonds in a neutral aqueous medium (p H =7) at room temperature. The mechanism of such transfers of protons is still poorly known, but these transfers are now suspected to play a fundamental role in such widespread reactions as hydrolysis, peptide synthesis, etc... which may make them soon appear as being a crucial basic mechanism for reactivity of aqueous systems, particularly biological systems

  18. How Formaldehyde Inhibits Hydrogen Evolution by [FeFe]-Hydrogenases: Determination by ¹³C ENDOR of Direct Fe-C Coordination and Order of Electron and Proton Transfers.

    Science.gov (United States)

    Bachmeier, Andreas; Esselborn, Julian; Hexter, Suzannah V; Krämer, Tobias; Klein, Kathrin; Happe, Thomas; McGrady, John E; Myers, William K; Armstrong, Fraser A

    2015-04-29

    Formaldehyde (HCHO), a strong electrophile and a rapid and reversible inhibitor of hydrogen production by [FeFe]-hydrogenases, is used to identify the point in the catalytic cycle at which a highly reactive metal-hydrido species is formed. Investigations of the reaction of Chlamydomonas reinhardtii [FeFe]-hydrogenase with formaldehyde using pulsed-EPR techniques including electron-nuclear double resonance spectroscopy establish that formaldehyde binds close to the active site. Density functional theory calculations support an inhibited super-reduced state having a short Fe-(13)C bond in the 2Fe subsite. The adduct forms when HCHO is available to compete with H(+) transfer to a vacant, nucleophilic Fe site: had H(+) transfer already occurred, the reaction of HCHO with the Fe-hydrido species would lead to methanol, release of which is not detected. Instead, Fe-bound formaldehyde is a metal-hydrido mimic, a locked, inhibited form analogous to that in which two electrons and only one proton have transferred to the H-cluster. The results provide strong support for a mechanism in which the fastest pathway for H2 evolution involves two consecutive proton transfer steps to the H-cluster following transfer of a second electron to the active site.

  19. Measurements of the Proton Elastic-Form-Factor Ratio μpGEp/GMp at Low Momentum Transfer

    International Nuclear Information System (INIS)

    Ron, G.; Piasetzky, E.; Pomerantz, I.; Shneor, R.; Glister, J.; Lee, B.; Choi, Seonho; Kang, H.; Oh, Y.; Song, J.; Yan, X.; Allada, K.; Dutta, C.; Armstrong, W.; Meziani, Z.-E.; Yao, H.; Arrington, J.; Solvignon, P.; Beck, A.; May-Tal Beck, S.

    2007-01-01

    High-precision measurements of the proton elastic form-factor ratio, μ p G E p /G M p , have been made at four-momentum transfer, Q 2 , values between 0.2 and 0.5 GeV 2 . The new data, while consistent with previous results, clearly show a ratio less than unity and significant differences from the central values of several recent phenomenological fits. By combining the new form-factor ratio data with an existing cross-section measurement, one finds that in this Q 2 range the deviation from unity is primarily due to G E p being smaller than expected

  20. Study of coupled heat and water transfer in proton exchange membrane fuel cells by the way of internal measurements

    International Nuclear Information System (INIS)

    Thomas, A; Maranzana, G; Didierjean, S; Dillet, J; Lottin, O

    2012-01-01

    Measurements of electrode temperatures within a proton exchange membrane fuel cell were performed using platinum wires. A temperature difference of 7°C between the electrodes and the bipolar plates was observed for a cell operating at a current density of 1.5 A.cm −2 . These measurements show a strong non-uniformity of the temperature profile through membrane electrode assembly (MEA) that future phenomenological models must take into account. In addition, the simultaneous measurements of heat and water flux through the MEA leads to the conclusion that produced water crosses the diffusion layer in vapor phase. A very simple heat transfer model is proposed.

  1. Coherent pulse and environmental characteristics of the intramolecular proton-transfer lasers based on 3-hydroxyflavone and fisetin

    Science.gov (United States)

    Parthenopoulos, Dimitri A.; Kasha, Michael

    1988-04-01

    Coherent stimulated emission and laser beams of good quality are reported for 3-hydroxyfiavone (3-HF) and a polyhydroxyfiavone, risetin, acting as intramolecular proton-transfer lasers. The laser beam quality of these materials is comparable to that observed for rhodamine-6G. Studies of amplified spontaneous emission of 3-hydroxyflavone in highly polar solvents are also reported. The very large changes in dipole moment upon electronic excitation of 3-HF expected according to ZINDO semiempirical molecular orbital calculations fail to give rise to spectral shifts in the high dielectric constant solvents. The results are interpreted as a masking spectral effect caused by specific hydrogen bonding by the solvent.

  2. Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.

    1985-01-01

    A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

  3. Measurement of Lactate Content and Amide Proton Transfer Values in the Basal Ganglia of a Neonatal Piglet Hypoxic-Ischemic Brain Injury Model Using MRI.

    Science.gov (United States)

    Zheng, Y; Wang, X-M

    2017-04-01

    As amide proton transfer imaging is sensitive to protein content and intracellular pH, it has been widely used in the nervous system, including brain tumors and stroke. This work aimed to measure the lactate content and amide proton transfer values in the basal ganglia of a neonatal piglet hypoxic-ischemic brain injury model by using MR spectroscopy and amide proton transfer imaging. From 58 healthy neonatal piglets (3-5 days after birth; weight, 1-1.5 kg) selected initially, 9 piglets remained in the control group and 43 piglets, in the hypoxic-ischemic brain injury group. Single-section amide proton transfer imaging was performed at the coronal level of the basal ganglia. Amide proton transfer values of the bilateral basal ganglia were measured in all piglets. The ROI of MR spectroscopy imaging was the right basal ganglia, and the postprocessing was completed with LCModel software. After hypoxic-ischemic insult, the amide proton transfer values immediately decreased, and at 0-2 hours, they remained at their lowest level. Thereafter, they gradually increased and finally exceeded those of the control group at 48-72 hours. After hypoxic-ischemic insult, the lactate content increased immediately, was maximal at 2-6 hours, and then gradually decreased to the level of the control group. The amide proton transfer values were negatively correlated with lactate content ( r = -0.79, P < .05). This observation suggests that after hypoxic-ischemic insult, the recovery of pH was faster than that of lactate homeostasis. © 2017 by American Journal of Neuroradiology.

  4. Constructing a proton titration curve from ion-step measurements, applied to a membrane with adsorbed protein

    NARCIS (Netherlands)

    Eijkel, Jan C.T.; Bosch, Coen; Olthuis, Wouter; Bergveld, Piet

    1997-01-01

    A new measuring method is described for obtaining a proton titration curve. The curve is obtained from a microporous composite membrane, consisting of polystyrene beads in an agarose matrix, with lysozyme molecules adsorbed to the bead surface. The membrane is incorporated into a sensor system by

  5. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    Energy Technology Data Exchange (ETDEWEB)

    Kajikawa, Takao; Kataoka, Kunishige [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan); Sakurai, Takeshi, E-mail: tsakurai@se.kanazawa-u.ac.jp [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan)

    2012-05-25

    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  6. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Science.gov (United States)

    Matasović, Brunislav; Bonifačić, Marija

    2011-06-01

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

  7. A Normalized Transfer Matrix Method for the Free Vibration of Stepped Beams: Comparison with Experimental and FE(3D Methods

    Directory of Open Access Journals (Sweden)

    Tamer Ahmed El-Sayed

    2017-01-01

    Full Text Available The exact solution for multistepped Timoshenko beam is derived using a set of fundamental solutions. This set of solutions is derived to normalize the solution at the origin of the coordinates. The start, end, and intermediate boundary conditions involve concentrated masses and linear and rotational elastic supports. The beam start, end, and intermediate equations are assembled using the present normalized transfer matrix (NTM. The advantage of this method is that it is quicker than the standard method because the size of the complete system coefficient matrix is 4 × 4. In addition, during the assembly of this matrix, there are no inverse matrix steps required. The validity of this method is tested by comparing the results of the current method with the literature. Then the validity of the exact stepped analysis is checked using experimental and FE(3D methods. The experimental results for stepped beams with single step and two steps, for sixteen different test samples, are in excellent agreement with those of the three-dimensional finite element FE(3D. The comparison between the NTM method and the finite element method results shows that the modal percentage deviation is increased when a beam step location coincides with a peak point in the mode shape. Meanwhile, the deviation decreases when a beam step location coincides with a straight portion in the mode shape.

  8. Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation

    Energy Technology Data Exchange (ETDEWEB)

    Nocera, Daniel G. [Harvard Univ., Cambridge, MA (United States)

    2013-03-15

    -innocence. The program was expanded to include other macrocycles with a focus on corroles. The photophyscial and electrochemical properties of a number of new metal- and free-base corroles were defined. Finally, the reaction chemistry of a new platform designed for oxygen evolution and reduction reactions. The hexacarboxamide cryptands was shown to be an ideal binucleating ligand for studies of oxygen. The electron transfer reaction of native oxygen in the absence of protons and metals was enabled for the first time, thus allowing us to observe new reactions of reduced oxygen with carbon dioxide. These results have had important consequence in shedding light on Li air batteries, and why these batteries cannot be recharged. This is the key issue impeding the technology development of Li-air batteries and therefore these results should be enlightening to the commercial development of Li-air batteries. Together, this portfolio of experiments provides a powerful insight to the crucial steps for the efficient conversion of small molecules to fuels and their subsequent use. To this end, the research program provides basic science to enable the low cost solar production of hydrogen from water and the reverse fuel cell reaction.

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

    Science.gov (United States)

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

    2017-04-01

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

  10. Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

    Science.gov (United States)

    2016-07-08

    actuated) by a counterbalanced hydrogen bond located farther away. To realize such goals, it is necessary to study this effect further. In particular, if...Thus in direct analogy to photoconductivity in a semiconductor, one arrives at a proton photoconductivity effect . We have exploited this analogy to

  11. Patterns of Failure After Proton Therapy in Medulloblastoma; Linear Energy Transfer Distributions and Relative Biological Effectiveness Associations for Relapses

    International Nuclear Information System (INIS)

    Sethi, Roshan V.; Giantsoudi, Drosoula; Raiford, Michael; Malhi, Imran; Niemierko, Andrzej; Rapalino, Otto; Caruso, Paul; Yock, Torunn I.; Tarbell, Nancy J.; Paganetti, Harald; MacDonald, Shannon M.

    2014-01-01

    Purpose: The pattern of failure in medulloblastoma patients treated with proton radiation therapy is unknown. For this increasingly used modality, it is important to ensure that outcomes are comparable to those in modern photon series. It has been suggested this pattern may differ from photons because of variations in linear energy transfer (LET) and relative biological effectiveness (RBE). In addition, the use of matching fields for delivery of craniospinal irradiation (CSI) may influence patterns of relapse. Here we report the patterns of failure after the use of protons, compare it to that in the available photon literature, and determine the LET and RBE values in areas of recurrence. Methods and Materials: Retrospective review of patients with medulloblastoma treated with proton radiation therapy at Massachusetts General Hospital (MGH) between 2002 and 2011. We documented the locations of first relapse. Discrete failures were contoured on the original planning computed tomography scan. Monte Carlo calculation methods were used to estimate the proton LET distribution. Models were used to estimate RBE values based on the LET distributions. Results: A total of 109 patients were followed for a median of 38.8 months (range, 1.4-119.2 months). Of the patients, 16 experienced relapse. Relapse involved the supratentorial compartment (n=8), spinal compartment (n=11), and posterior fossa (n=5). Eleven failures were isolated to a single compartment; 6 failures in the spine, 4 failures in the supratentorium, and 1 failure in the posterior fossa. The remaining patients had multiple sites of disease. One isolated spinal failure occurred at the spinal junction of 2 fields. None of the 70 patients treated with an involved-field-only boost failed in the posterior fossa outside of the tumor bed. We found no correlation between Monte Carlo-calculated LET distribution and regions of recurrence. Conclusions: The most common site of failure in patients treated with protons for

  12. 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.

  13. Magnetization transfer from macromolecules to water protons in murine dental tissues as revealed by 500 MHz 1H-NMR

    International Nuclear Information System (INIS)

    Nakamura, Koji; Era, Seiichi; Nagai, Naoki; Sogami, Masaru; Takasaki, Akihiko; Kato, Kazuo.

    1997-01-01

    Although much is known about magnetization transfer phenomena in biological soft tissues, little is known about those in hard tissues. Using a 500 MHz 1 H-NMR spectrometer, we studied the spin-lattice relaxation time (T 1 (H 2 O)) and the intermolecular cross-relaxation times (T IS (H 2 O)) from irradiated macromolecular protons to observed water protons in murine lower incisors (hard tissue) and compared with those in murine lens tissue (soft tissue). Mean values for the water content (%) of murine lower incisors and lens tissue were 16.02±2.39 (n=14) and 67.20±4.60 (n=15), respectively. These findings were consistent with the large different in water content between soft tissues and hard tissues. T IS (H 2 O) values obtained by f 2 -irradiation at 7.13 or -4.00 ppm showed no significant difference between lower incisors and lens tissue. Plots of 1/T IS (H 2 O) values vs. tissue dry weight (W(%)) for lower incisor tissue approximated a straight line with slope approximately equal for that obtained for lens tissue. These results suggest that the state of water in hard tissue may be similar to that in soft tissues, in spite of the significant difference in water content. Thus, saturation transfer NMR techniques such as measurement of T IS (H 2 O) values may be applicable to the study of water-macromolecule interactions in both biological soft and hard tissues. (author)

  14. Sequential Proton Loss Electron Transfer in Deactivation of Iron(IV) Binding Protein by Tyrosine Based Food Components.

    Science.gov (United States)

    Tang, Ning; Skibsted, Leif H

    2017-08-02

    The iron(IV) binding protein ferrylmyoglobin, MbFe(IV)═O, was found to be reduced by tyrosine based food components in aqueous solution through a sequential proton loss electron transfer reaction mechanism without binding to the protein as confirmed by isothermal titration calorimetry. Dopamine and epinephrine are the most efficient food components reducing ferrylmyoglobin to oxymyoglobin, MbFe(II)O 2 , and metmyoglobin, MbFe(III), as revealed by multivariate curve resolution alternating least-squares with second order rate constants of 33.6 ± 2.3 L/mol/s (ΔH ⧧ of 19 ± 5 kJ/mol, ΔS ⧧ of -136 ± 18 J/mol K) and 228.9 ± 13.3 L/mol/s (ΔH ⧧ of 110 ± 7 kJ/mol, ΔS ⧧ of 131 ± 25 J/mol K), respectively, at pH 7.4 and 25 °C. The other tyrosine based food components were found to reduce ferrylmyoglobin to metmyoglobin with similar reduction rates at pH 7.4 and 25 °C. These reduction reactions were enhanced by protonation of ferrylmyoglobin and facilitated proton transfer at acidic conditions. Enthalpy-entropy compensation effects were observed for the activation parameters (ΔH ⧧ and ΔS ⧧ ), indicating the common reaction mechanism. Moreover, principal component analysis combined with heat map were performed to understand the relationship between density functional theory calculated molecular descriptors and kinetic data, which was further modeled by partial least squares for quantitative structure-activity relationship analysis. In addition, a three tyrosine residue containing protein, lysozyme, was also found to be able to reduce ferrylmyoglobin with a second order rate constant of 66 ± 28 L/mol/s as determined by a competitive kinetic method.

  15. Skill Transfer and Virtual Training for IND Response Decision-Making: Project Summary and Next Steps

    Science.gov (United States)

    2016-04-12

    Lincoln Laboratory MASSACHUSETTS INSTITUTE OF TECHNOLOGY LEXINGTON, MASSACHUSETTS Technical Report 1209 Skill Transfer and Virtual ...specifically authorized by the U.S. Government may violate any copyrights that exist in this work. Skill Transfer and Virtual Training for IND Response...lns:ull of lmme<lla:e 0 evacua!lon). but many aspects are the same (such as !’laVIng fresh water . knowing evacua:Jon routn. and tlavtng a

  16. Measurement of the free neutron-proton analyzing power and spin transfer parameters in the charge exchange region at 790 MeV

    International Nuclear Information System (INIS)

    Ransome, R.D.

    1981-07-01

    The free neutron-proton analyzing power and the spin transfer parameters (K/sub NN/, K/sub SS/, K/sub SL/, and K/sub LL/) were measured at the Los Alamos Meson Physics Facility at 790 MeV between 165 0 and 180 0 center of mass. A 40% polarized neutron beam incident on a liquid hydrogen target was used. The recoil protons were momentum analyzed with a magnetic spectrometer to isolate elastic scatters. A large solid angle carbon polarimeter was used to measure the proton polarization. The measurements are the first at this energy and are in basic agreement with pre-existing phase shift solutions. The proton-carbon analyzing power was measured between 500 and 750 MeV. An empirical fit to the proton-carbon analyzing power between 100 and 750 MeV was done

  17. Neutron-proton elastic diffusion study at low transfer between 400-1000 MeV

    International Nuclear Information System (INIS)

    Wellers, F.

    1986-01-01

    This thesis presents the first complete results of forward differential cross-section, over the entire range of the intermediate energies, in the neutron-proton system. The neutron beam is produced with the synchrotron Saturne II, using the reaction of deuteron break-up, which gives it a relatively high intensity and a small energy dispersion. The experimental apparatus is a drift ionization chamber, IKAR, filled with high pressure gas which plays the double role of target and detector of the recoil proton. The use of a neutral beam requires new procedures in the analysis, more elaborate than in the case of charged projectiles, where scattered particles were detected in coincidence in wire chambers. The results are then normalized and discussed, using a phenomenological parametrization, and integrated in a continuously energy-dependent phase-shifts analysis. An entirely analytic Glauber calculation allows us to estimate the validity of the normalization method [fr

  18. Heat-transfer and pressure distributions for laminar separated flows downstream of rearward-facing steps with and without mass suction

    Science.gov (United States)

    Brown, R. D.; Jakubowski, A. K.

    1974-01-01

    Heat-transfer and pressure distributions were measured for laminar separated flows downstream of rearward-facing steps with and without mass suction. The flow conditions were such that the boundary-layer thickness was comparable to or larger than the step height. For both suction and no-suction cases, an increase in the step height resulted in a sharp decrease in the initial heat-transfer rates behind the step. Downstream, however, the heat transfer gradually recovered back to less than or near attached-flow values. Mass suction from the step base area increased the local heat-transfer rates; however, this effect was relatively weak for the laminar flows considered. Even removal of the entire approaching boundary layer raised the post-step heat-transfer rates only about 10 percent above the flatplate values. Post-step pressure distributions were found to depend on the entrainment conditions at separation. In the case of the solid-faced step, a sharp pressure drop behind the step was followed by a very short plateau and relatively fast recompression. For the slotted-step connected to a large plenum but without suction, the pressure drop at the base was much smaller and the downstream recompression more gradual than that for solid-faced step.

  19. Developing a clinical proton accelerator facility: Consortium-assisted technology transfer

    International Nuclear Information System (INIS)

    Slater, J.M.; Miller, D.W.; Slater, J.W.

    1991-01-01

    A hospital-based proton accelerator facility has emerged from the efforts of a consortium of physicists, engineers and physicians from several high-energy physics laboratories, industries and universities, working together to develop the requirements and conceptual design for a clinical program. A variable-energy medical synchrotron for accelerating protons to a prescribed energy, intensity and beam quality, has been placed in a hospital setting at Loma Linda University Medical Center for treating patients with localized cancer. Treatments began in October 1990. Scientists from Fermi National Accelerator Laboratory; Harvard Cyclotron Laboratory; Lawrence Berkeley Laboratories; the Paul Scherrer Institute; Uppsala, Sweden; Argonne, Brookhaven and Los Alamos National Laboratories; and Loma Linda University, all cooperated to produce the conceptual design. Loma Linda University contracted with Fermi National Accelerator Laboratory to design and build a 250 MeV synchrotron and beam transport system, the latter to guide protons into four treatment rooms. Lawrence Berkeley Laboratories consulted with Loma Linda University on the design of the beam delivery system (nozzle). A gantry concept devised by scientists at Harvard Cyclotron Laboratory, was adapted and fabricated by Science Applications International Corporation. The control and safety systems were designed and developed by Loma Linda University Radiation Research Laboratory. Presently, the synchrotron, beam transport system and treatment room hardware have been installed and tested and are operating satisfactorily

  20. The effect of oxygen transfer mechanism on the cathode performance based on proton-conducting solid oxide fuel cells

    KAUST Repository

    Hou, Jie

    2015-01-01

    Two types of proton-blocking composites, La2NiO4+δ-LaNi0.6Fe0.4O3-δ (LNO-LNF) and Sm0.2Ce0.8O2-δ-LaNi0.6Fe0.4O3-δ (SDC-LNF), were evaluated as cathode materials for proton-conducting solid oxide fuel cells (H-SOFCs) based on the BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte, in order to compare and investigate the influence of two different oxygen transfer mechanism on the performance of the cathode for H-SOFCs. The X-ray diffraction (XRD) results showed that the chemical compatibility of the components in both compounds was excellent up to 1000°C. Electrochemical studies revealed that LNO-LNF showed lower area specific polarization resistances in symmetrical cells and better electrochemical performance in single cell tests. The single cell with LNO-LNF cathode generated remarkable higher maximum power densities (MPDs) and lower interfacial polarization resistances (Rp) than that with SDC-LNF cathode. Correspondingly, the MPDs of the single cell with the LNO-LNF cathode were 490, 364, 266, 180 mW cm-2 and the Rp were 0.103, 0.279, 0.587, 1.367 Ω cm2 at 700, 650, 600 and 550°C, respectively. Moreover, after the single cell with LNO-LNF cathode optimized with an anode functional layer (AFL) between the anode and electrolyte, the power outputs reached 708 mW cm-2 at 700°C. These results demonstrate that the LNO-LNF composite cathode with the interstitial oxygen transfer mechanism is a more preferable alternative for H-SOFCs than SDC-LNF composite cathode with the oxygen vacancy transfer mechanism.

  1. Direct Measurements of Energy Transfer between Hot Protons and He+ via EMIC Waves Observed by MMS in the Outer Magnetosphere

    Science.gov (United States)

    Kitamura, N.; Kitahara, M.; Shoji, M.; Miyoshi, Y.; Hasegawa, H.; Nakamura, S.; Katoh, Y.; Saito, Y.; Yokota, S.; Gershman, D. J.; Vinas, A. F.; Giles, B. L.; Moore, T. E.; Paterson, W.; Pollock, C. J.; Russell, C. T.; Strangeway, R. J.; Fuselier, S. A.; Burch, J. L.

    2017-12-01

    Wave-particle interactions have been suggested to play a crucial role in energy transfer in collisionless space plasmas in which the motion of charged particles is controlled by electromagnetic fields. Using an electromagnetic ion cyclotron (EMIC) wave event observed by MMS, we investigate energy transfer between ions and EMIC waves via cyclotron type interactions. To directly detect energy exchange between ions and EMIC waves, we apply the Wave-Particle Interaction Analyzer (WPIA) method that is to calculate the dot product between the wave electric field (Ewave) and ion current perpendicular to the background magnetic field (j). In the cases of resonance, this current is called the resonant current. Near the beginning of the wave event, 15-second averages of j • Ewave reached -0.3 pW/m3 for ions with energies of 14-30 keV and pitch angles of 33.25°-78.75°. The negative value in this pitch angle range indicates that the perpendicular energy of ions was being transferred to the EMIC waves propagating toward Southern higher latitudes at the MMS location by cyclotron resonance. Ion data show non-gyrotropic distributions around the resonance velocity, and that is consistent with the nonlinear trapping of protons by the wave and formation of an electromagnetic proton hole. Near the beginning of the same wave event, strongly phase bunched He+ up to 2 keV with pitch angles slightly larger than 90° were also detected. A positive j • Ewave for the phase bunched He+ indicates that the He+ was being accelerated by the electric field of the EMIC waves. The observed feature of He+ ions is consistent with non-resonant interaction with the wave but is inconsistent with cyclotron resonance. Significantly non-gyrotropic distributions observed in this event demonstrate that different particle populations can strongly couple through wave-particle interactions in the collisionless plasma.

  2. Charge-exchange breakup of the deuteron with the production of two protons and spin structure of the amplitude of the nucleon charge transfer reaction

    International Nuclear Information System (INIS)

    Glagolev, V.V.; Lyuboshits, V.L.; Lyuboshits, V.V.; Piskunov, N.M.

    1999-01-01

    In the framework of the impulse approximation, the relation between the effective cross section of the charge-exchange breakup of a fast deuteron d + a → (pp) + b and the effective cross section of the charge transfer process n + a → p + b is discussed. In doing so, the effects of the proton identity (Fermi-statistics) and of the Coulomb and strong interactions of protons in the final state are taken into account. The distribution over relative momenta of the protons, produced in the charge-exchange process d + p → (pp) + n in the forward direction, is investigated. At the transfer momenta being close to zero the effective cross section of the charge-exchange breakup of a fast deuteron, colliding with the proton target, is determined only by the spin-flip part of the amplitude of the charge transfer reaction n + p → p + n at the zero angle. It is shown that the study of the process d + p → (pp) + n in a beam of the polarized (aligned) deuterons allows one, in principle, to separate two spin-dependent terms in the amplitude of the charge transfer reaction n + p → p + n, one of which does not conserve and the other one conserves the projection of the nucleon spin onto the direction of momentum at the transition of the neutron into the proton

  3. Modeling and analysis of all the positron emitters simulation steps generated during the treatment phase in proton-therapy - from the beam to the PET camera - for the follow-up of the irradiations

    International Nuclear Information System (INIS)

    Ty, C.V.N.

    2012-01-01

    The proton-therapy is an innovative technique for cancer treatment in critical areas, such as the eye or the head. Even though the interaction of protons with human tissues is a well-known physical phenomenon which gives rise to the proton-therapy, there are uncertainties on the proton trajectory due to heterogeneities in the irradiated tissue, the calculation of the beam parameters in the planning treatment affects the theoretical benefits of the protons and the chosen dose delivery process. Thus, methods for irradiation quality control have been suggested. Most of them rely on utilizing the mapping of the positron emitters generated during the irradiation. They are detectable and quantifiable thanks to the use of the PET (positron emitter tomography), a medical imaging technique mainly used for the cancer expansion assessment. PET acquisitions were proposed and then realized on phantoms and patients after proton-therapy. The quality control relies on comparing the measured radioactive distribution to the simulated β + distribution. The modeling of the positron activity generated by protons in the irradiated area can be divided into three steps: the simulation of the proton beam, the modeling of the proton interactions in the irradiated object and the modeling of the PET acquisition. Different ways of simulating these steps are possible. This PhD work suggests different ways of modeling the three steps and evaluates theirs benefits for the irradiation quality control. We have restrained our evaluation to the verification of the proton range and to the uncertainties related to the proton range. This research work utilizes on irradiations in homogenous and inhomogeneous areas in a head model. We have compared the uncertainties on the proton range measured thanks to the following β + distributions: 1) A β + distribution obtained by modeling the irradiation with a proton beam simulated analytically and simulated using the complete Monte Carlo method; 2) A Monte

  4. Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects

    International Nuclear Information System (INIS)

    Engdahl, K.A.; Bivehed, H.; Ahlberg, P.; Saunders, W.H. Jr.

    1983-01-01

    Primary and secondary deuterium isotope effects have been measured by polarimetry, and primary isotope effects have been calculated for the classical bifunctional catalysis: 2-pyridinone-catalyzed mutarotation of 2,3,4,6-tetra-O-methyl-α-D-glucopyranose (α-TMG) in benzene. From the positively curved plot of the specific rate of epimerization vs. the mole fraction of 2 H in the ''pool'' of OH and NH hydrogens, the isotope effects k/sub HH//k/sub DD/ = 3.66 +/- 0.09, k/sub HH//k/sub DH/ = 1.5, and k/sub HH//k/sub HD/ = 2.4 have been calculated. A secondary isotope effect of 1.14 +/- 0.02 has been measured by using α-TMG and (1- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(l- 2 H)-α-TMG], the synthesis of which is described in detail, together with those for (N- 2 H)-2-pyridinone and (1-O- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(1-O- 2 H)-α-TMG]. The rate data obtained have also been analyzed by fractionation theory, yielding approximately equal fractionation factors (0.5). The interpretation of the results has been assisted by calculations of the primary deuterium isotope effects using the BEBOVIB IV program. Two models involving small and considerable coupling, respectively, of the transferring protons to heavy-atom motion have been considered. In the favored structure for the transition state of the rate-limiting step, two protons are in transit, and their motion is governed either by a potential with a barrier or by one without. Their motion is considerably coupled to the heavy-atom motion (i.e., the breakage of the ring C-O bond), and tunnel corrections to the isotope effects are found to be negligible

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

    International Nuclear Information System (INIS)

    Karl, T.

    2000-02-01

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

  6. Single-step azide introduction in proteins via an aqueous diazo transfer

    NARCIS (Netherlands)

    van Dongen, S.F.M.; Teeuwen, R.L.M.; Nallani, M.; van Berkel, S.S.; Cornelissen, J.J.L.M.; Nolte, R.J.M.; van Hest, J.C.M.

    The controlled introduction of azides in proteins provides targetable handles for selective protein manipulation. We present here an efficient diazo transfer protocol that can be applied in an aqueous solution, leading to the facile introduction of azides in the side chains of lysine residues and at

  7. Single-Step Azide Introduction in Proteins via an Aqueous Diazo Transfer

    NARCIS (Netherlands)

    van Dongen, Stijn; Teeuwen, R.L.M.; Nallani, Madhavan; van Berkel, S.S; Cornelissen, Jeroen Johannes Lambertus Maria; Nolte, Roeland; van Hest, Jan

    2009-01-01

    The controlled introduction of azides in proteins provides targetable handles for selective protein manipulation. We present here an efficient diazo transfer protocol that can be applied in an aqueous solution, leading to the facile introduction of azides in the side chains of lysine residues and at

  8. Charge transfer and ionization occurring in proton- and helium ion-atom collisions

    International Nuclear Information System (INIS)

    DuBois, R.D.

    1985-12-01

    Two examples are presented where specific channels have been identified that are responsible for single and double target ionization via direct coulomb ionization or charge transfer processes. Using ratios of absolute cross sections that have been measured for these processes it was shown that an independent electron model should be appropriate for calculating direct double target ionization but generally appears to be inadequate in calculating charge transfer plus ionization and double charge transfer cross sections. At present such detailed information can be obtained only in limited cases. However cross sections with detailed final charge state information should provide stringent tests for present and future theoretical work. 22 refs., 2 figs

  9. 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.

  10. Natural printed silk substrate circuit fabricated via surface modification using one step thermal transfer and reduction graphene oxide

    Science.gov (United States)

    Cao, Jiliang; Huang, Zhan; Wang, Chaoxia

    2018-05-01

    Graphene conductive silk substrate is a preferred material because of its biocompatibility, flexibility and comfort. A flexible natural printed silk substrate circuit was fabricated by one step transfer of graphene oxide (GO) paste from transfer paper to the surface of silk fabric and reduction of the GO to reduced graphene oxide (RGO) using a simple hot press treatment. The GO paste was obtained through ultrasonic stirring exfoliation under low temperature, and presented excellent printing rheological properties at high concentration. The silk fabric was obtained a surface electric resistance as low as 12.15 KΩ cm-1, in the concentration of GO 50 g L-1 and hot press at 220 °C for 120 s. Though the whiteness and strength decreased with the increasing of hot press temperature and time slowly, the electric conductivity of RGO surface modification silk substrate improved obviously. The surface electric resistance of RGO/silk fabrics increased from 12.15 KΩ cm-1 to 18.05 KΩ cm-1, 28.54 KΩ cm-1 and 32.53 KΩ cm-1 after 10, 20 and 30 washing cycles, respectively. The results showed that the printed silk substrate circuit has excellent washability. This process requires no chemical reductant, and the reduction efficiency and reduction degree of GO is high. This time-effective and environmentally-friendly one step thermal transfer and reduction graphene oxide onto natural silk substrate method can be easily used to production of reduced graphene oxide (RGO) based flexible printed circuit.

  11. Size-Induced Segregation in the Stepwise Microhydration of Hydantoin and Its Role in Proton-Induced Charge Transfer

    Science.gov (United States)

    Calvo, Florent; Bacchus-Montabonel, Marie-Christine

    2018-01-01

    Recent photochemistry experiments provided evidence for the formation of hydantoin by irradiation of interstellar ice analogues. The significance of these results and the importance of hydantoin in prebiotic chemistry and polypeptide synthesis motivate the present theoretical investigation, in which we analyzed the effects of stepwise hydration on the electronic and thermodynamical properties of the structure of microhydrated hydantoin using a variety of computational approaches. We generally find microhydration to proceed around the hydantoin heterocycle until 5 water molecules are reached, at which stage hydration becomes segregated with a water cluster forming aside the heterocycle. The reactivity of microhydrated hydantoin caused by an impinging proton was evaluated through charge transfer collision cross sections for microhydrated compounds but also for hydantoin on icy grains modeled using a cluster approach mimicking the true hexagonal ice surface. The effects of hydration on charge transfer efficiency are mostly significant when few water molecules are present, and they progressively weaken and stabilize in larger clusters. On the ice substrate, charge transfer essentially contributes to a global increase in the cross sections.

  12. Neutron pair and proton pair transfer reactions between identical cores in the sulfur region

    International Nuclear Information System (INIS)

    Mermaz, M.C.

    1995-12-01

    Optical model and exact finite range distorted-wave Born approximation analyses were performed on neutron pair exchange between identical cores for 32 S and 34 S nuclei and on proton pair exchange between identical cores for 30 Si and 32 S. The extracted spectroscopic factors were compared with theoretical ones deduced from Hartree-Fock calculations on these pair of nuclei. The enhancement of the experimental cross sections with respect to the theoretical ones strongly suggests evidence for a nuclear Josephson effect. (author). 15 refs., 5 figs., 3 tabs

  13. Compton Scattering Cross Section on the Proton at High Momentum Transfer

    International Nuclear Information System (INIS)

    A. Danagoulian; V.H. Mamyan; M. Roedelbronn; K.A. Aniol; J.R.M. Annand; P.Y. Bertin; L. Bimbot; P. Bosted; J.R. Calarco; A. Camsonne; C.C. Chang; T.-H. Chang; J.-P. Chen; Seonho Choi; E. Chudakov; P. Degtyarenko; C.W. de Jager; A. Deur; D. Dutta; K. Egiyan; H. Gao; F. Garibaldi; O. Gayou; R. Gilman; A. Glamazdin; C. Glashausser; J. Gomez; D.J. Hamilton; J.-O. Hansen; D. Hayes; D.W. Higinbotham; W. Hinton; T. Horn; C. Howell; T. Hunyady; C.E. Hyde-Wright; X. Jiang; M.K. Jones; M. Khandaker; A. Ketikyan; V. Koubarovski; K. Kramer; G. Kumbartzki; G. Laveissiere; J. LeRose; R.A. Lindgren; D.J. Margaziotis; P. Markowitz; K. McCormick; Z.-E. Meziani; R. Michaels; P. Moussiegt; S. Nanda; A.M. Nathan; D.M. Nikolenko; V. Nelyubin; B.E. Norum; K. Paschke; L. Pentchev; C.F. Perdrisat; E. Piasetzky; R. Pomatsalyuk; V.A. Punjabi; I. Rachek; A. Radyushkin; B. Reitz; R. Roche; G. Ron; F. Sabatie; A. Saha; N. Savvinov; A. Shahinyan; Y. Shestakov; S. Sirca; K. Slifer; P. Solvignon; P. Stoler; S. Tajima; V. Sulkosky; L. Todor; B. Vlahovic; L.B. Weinstein; K. Wang; B. Wojtsekhowski; H. Voskanyan; H. Xiang; X. Zheng; L. Zhu

    2007-01-01

    Cross-section values for Compton scattering on the proton were measured at 25 kinematic settings over the range s = 5-11 and -t = 2-7 GeV2 with statistical accuracy of a few percent. The scaling power for the s-dependence of the cross section at fixed center of mass angle was found to be 8.0 +/- 0.2, strongly inconsistent with the prediction of perturbative QCD. The observed cross section values are in fair agreement with the calculations using the handbag mechanism, in which the external photons couple to a single quark

  14. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

    2011-06-15

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U{sup {center_dot}} radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 3})OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of {alpha}-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

  15. Coupled quantum treatment of vibrationally inelastic and vibronic charge transfer in proton-O2 collisions

    International Nuclear Information System (INIS)

    Gianturco, F.A.; Palma, A.; Semprini, E.; Stefani, F.; Baer, M.

    1990-01-01

    A three-dimensional quantum-mechanical study of vibrational, state-resolved differential cross sections (DCS) for the direct inelastic and for the charge-transfer scattering channels has been carried out for the H + +O 2 system. The collision energy considered was E c.m. =23.0 eV, which is the same as that examined by Noll and Toennies in their experiments [J. Chem. Phys. 85, 3313 (1986)]. The scattering treatment employed was the charge-transfer infinite-order sudden approximation (CT IOSA) with the vibrational states correctly expanded over the relevant adiabatic basis for each of the two electronic channels. The state-to-state DCS are found to follow closely the behavior of the experimental quantities, both in the inelastic and the charge-transfer channels. Moreover, a careful comparison between the measured relative probabilities and computed values allows us to test in minute detail the efficiency of the scattering model and the reliability of the potential-energy surfaces employed. It is found that vibrational energy transfer is overestimated in the vibrational inelastic channels while in the charge-transfer inelastic channels the same energy transfer is slightly underestimated by the calculations. The total flux distribution, however, is found to be in very good accord with experiments. Angular distributions are also well reproduced both by the DCS and by the average energy-transfer values. The study of some of the CT IOSA quantities also allows us to establish clearly the importance of nonadiabatic transitions in enhancing vibrational inelasticity in the present system

  16. Study of the proton structure by measurements of polarization transfers in real Compton scattering at J Lab

    International Nuclear Information System (INIS)

    Fanelli, C.; Salme, G.; Cisbani, E.; Hamilton, D.; Wojtsekhowski, B.

    2014-01-01

    A preliminary analysis of polarization-transfer data at large scattering angle (70 degrees), obtained in an experiment of real Compton scattering on proton, performed in Hall-C of Jefferson Lab, is presented. It is also discussed the relevance of this kind of experiments for shedding light on the non-perturbative structure of the proton, at low energy, and on the transition from the non-perturbative regime to the perturbative one, that occurs at high energy. Moreover, the possibility to extract Compton form factors and the Generalized Parton Distributions (GPD), one of the most promising theoretical tool to determine the total angular momentum contribution of quarks and gluons to nucleon spin, is emphasized. The preliminary results appear consistent with GPD's based and Regge predictions. This is not sufficient yet to exclude pQCD COZ (Chernyak-Oglobin-Zhitnistsky) model, but it is another preliminary indication that the handbag approach seems to be the dominant mechanism at the energy of the experiment

  17. The H2 + + He proton transfer reaction: quantum reactive differential cross sections to be linked with future velocity mapping experiments

    Science.gov (United States)

    Hernández Vera, Mario; Wester, Roland; Gianturco, Francesco Antonio

    2018-01-01

    We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ion {{{H}}}2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

  18. Proton-transfer compounds of 8-hydroxy-7-iodoquinoline-5-sulfonic acid (ferron) with 4-chloroaniline and 4-bromoaniline.

    Science.gov (United States)

    Smith, Graham; Wermuth, Urs D; Healy, Peter C

    2007-07-01

    The crystal structures of the proton-transfer compounds of ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid) with 4-chloroaniline and 4-bromoaniline, namely 4-chloroanilinium 8-hydroxy-7-iodoquinoline-5-sulfonate monohydrate, C(6)H(7)ClN(+) x C(9)H(5)INO(4)S(-) x H(2)O, and 4-bromoanilinium 8-hydroxy-7-iodoquinoline-5-sulfonate monohydrate, C(6)H(7)BrN(+) x C(9)H(5)INO(4)S(-) x H(2)O, have been determined. The compounds are isomorphous and comprise sheets of hydrogen-bonded cations, anions and water molecules which are extended into a three-dimensional framework structure through centrosymmetric R(2)(2)(10) O-H...N hydrogen-bonded ferron dimer interactions.

  19. Experimental test of a four-level kinetic model for excited-state intramolecular proton transfer dye lasers

    Energy Technology Data Exchange (ETDEWEB)

    Costela, A; Munnoz, J M; Douhal, A; Figuera, J M; Acuna, A U [Inst. de Quimica Fisica ' ' Rocasolano' ' , C.S.I.C., Madrid (Spain)

    1989-11-01

    The nanosecond pulses of a dye laser oscillator based on the excited-state intramolecular proton-transfer reaction (IPT) of salicylamide and 2'-hydroxylphenyl benzimidazole dyes have been studied as a function of several experimental parameters. To explain the operation of this laser a numerical four-level kinetic model was developed until the lasing properties of these dyes, in the presence of a variable oxygen concentration and pumped with a double pulse technique, could be reproduced. This was possible only by assuming that the efficiency of the laser is controlled by the absorption cross-section of a transient state with a lifetime in the nanosecond-picosecond range, which was tentatively identified as a ground state tautomeric species. (orig.).

  20. Structural, thermal, morphological and biological studies of proton-transfer complexes formed from 4-aminoantipyrine with quinol and picric acid

    Science.gov (United States)

    Adam, Abdel Majid A.

    2013-03-01

    4-Aminoantipyrine (4AAP) is widely used in the pharmaceutical industry, biochemical experiments and environmental monitoring. However, residual amounts of 4AAP in the environment may pose a threat to human health. To provide basic data that can be used to extract or eliminate 4AAP from the environment, the proton-transfer complexes of 4AAP with quinol (QL) and picric acid (PA) were synthesized and spectroscopically investigated. The interactions afforded two new proton-transfer salts named 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium-4-hydroxyphenolate and 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium-2,4,6-trinitrophenolate for QL and PA, respectively, via a 1:1 stoichiometry. Elemental analysis (CHN), electronic absorption, spectrophotometric titration, IR, Raman, 1H NMR and X-ray diffraction were used to characterize the new products. The thermal stability of the synthesized CT complexes was investigated using thermogravimetric (TG) analyses, and the morphology and particle size of these complexes were obtained from scanning electron microscopy (SEM). It was found that PA and 4AAP immediately formed a yellow precipitate with a remarkable sponge-like morphology and good thermal stability up to 180 °C. Finally, the biological activities of the newly synthesized CT complexes were tested for their antibacterial and antifungal activities. The results indicated that the [(4AAP)(QL)] complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared with standard drugs.

  1. Vibrationally resolved charge transfer for proton collisions with CO and H collisions with CO+

    International Nuclear Information System (INIS)

    Lin, C. Y.; Stancil, P. C.; Li, Y.; Gu, J. P.; Liebermann, H. P.; Buenker, R. J.; Kimura, M.

    2007-01-01

    Electron capture by protons following collisions with carbon monoxide, and the reverse process, is studied with a quantal molecular-orbital coupled-channel method utilizing the infinite order sudden approximation for collision energies between 0.5 and 1000 eV/u. The potential surfaces and couplings, computed with the multireference single- and double-excitation method for a range of H + -CO orientation angles and C-O separations, are adopted in the scattering calculations. Results including vibrationally resolved and orientation-angle-dependent cross sections are presented for a range of CO and CO + vibrational levels. Comparison with experiment is made where possible and the relevance of the reaction in astrophysics and atmospheric physics is discussed

  2. Eddy covariance emission and deposition flux measurements using proton transfer reaction – time of flight – mass spectrometry (PTR-TOF-MS): comparison with PTR-MS measured vertical gradients and fluxes

    NARCIS (Netherlands)

    Park, J.H.; Goldstein, A.H.; Timkovsky, J|info:eu-repo/dai/nl/330541676; Fares, S.; Weber, R.; Karlik, J.; Holzinger, R.|info:eu-repo/dai/nl/337989338

    2013-01-01

    During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data

  3. Maintenance of heartburn relief after step-down from twice-daily proton pump inhibitor to once-daily dexlansoprazole modified release.

    Science.gov (United States)

    Fass, Ronnie; Inadomi, John; Han, Cong; Mody, Reema; O'Neil, Janet; Perez, M Claudia

    2012-03-01

    Many patients with gastroesophageal reflux disease (GERD) take a proton pump inhibitor (PPI) twice daily to control symptoms. Once-daily dexlansoprazole modified release (MR) has a dual-delayed release formulation, making it attractive for step-down management of patients whose symptoms are well controlled on twice-daily PPIs. We investigated whether step-down to once-daily dexlansoprazole controls heartburn in patients with GERD who were receiving twice-daily PPI therapy. Patients 18 years and older taking a twice-daily PPI for symptom control were enrolled (n = 178) in a single-blind, multicenter study; 163 patients completed the study and 142 patients met criteria for the efficacy analysis. During the 6-week screening and treatment periods, patients recorded the presence of heartburn symptoms twice daily in electronic diaries. Patients' heartburn was considered well controlled if they had an average of 1 symptom or fewer per week during the last 4 weeks of screening and treatment. After screening, qualified patients were switched to masked dexlansoprazole MR 30 mg and placebo for 6 weeks. The primary efficacy end point was the proportion of patients whose heartburn remained well controlled after step-down. GERD-related symptoms and quality of life (QOL) also were evaluated using the Patient Assessment of Upper Gastrointestinal Disorders Symptom Severity Index (PAGI-SYM) and the PAGI-QOL questionnaires, respectively. After step-down to once-daily dexlansoprazole MR 30 mg, heartburn remained well controlled in 88% of patients (125 of 142). These patients were able to maintain their GERD-related symptom severity and QOL, indicated by marginal changes in the PAGI-SYM and PAGI-QOL total and subscale scores, respectively. Most patients with GERD who take twice-daily PPI to control heartburn are able to successfully step down to once-daily dexlansoprazole 30 mg. Copyright © 2012 AGA Institute. Published by Elsevier Inc. All rights reserved.

  4. Molecular simulations in electrochemistry : Electron and proton transfer reactions mediated by flavins in different molecular environments

    NARCIS (Netherlands)

    Kılıç, M.

    2014-01-01

    The aim of this thesis is to address specific questions about the role of solvent reorganization on electron transfer in different environments and about the calculation of acidity constant, as well. Particularly, we focus on molecular simulation of flavin in water and different protein (BLUF and

  5. Preparation of catalyst coated membrane by modified decal transfer method for proton exchange membrane fuel cell

    Science.gov (United States)

    Indriyati; Irmawati, Y.; Prihandoko, B.

    2017-07-01

    A new catalyst coated membrane (CCM) was prepared by modified decal transfer method. A structure of ionomer/catalyst/carbon/substrate was used to facilitate the transfer of catalyst layer from decal substrate to the membrane at quite low hot-pressing temperature (120 °C) for 8 min. Several decal substrates were tested to select a proper substrate, namely PTFE cloth, PTFE film, aluminium foil, and OHP transparent sheet. The transfer degree of catalyst layer was estimated. Elemental analysis and SEM-mapping were performed to evaluate the residue, whereas contact angle measurement was conducted to characterize the hydrophobicity of decal substrates. The results showed that PTFE cloth and PFTE film transferred approximately 90% of catalyst layer onto the membrane, while the other two substrates were around 70%. Furthermore, the elemental analysis of the residue on the substrate revealed that it was mainly composed of carbon and fluorine for PTFE cloth and PTFE film. This result supports other findings that PTFE cloth and PTFE film are suitable as decal substrate at low temperature hot pressing for fabricating CCM.

  6. Photorelaxation of imidazole and adenine via electron-driven proton transfer along H2O wires

    Czech Academy of Sciences Publication Activity Database

    Szabla, Rafal; Gora, R.W.; Janicki, M.; Šponer, Jiří

    2016-01-01

    Roč. 195, č. 2016 (2016), s. 237-251 E-ISSN 1364-5498 R&D Projects: GA ČR(CZ) GA14-12010S Institutional support: RVO:68081707 Keywords : excited-state deactivation * induced charge-transfer Subject RIV: BO - Biophysics

  7. New results on kaon-proton elastic scattering at large momentum transfers

    International Nuclear Information System (INIS)

    Asa'd, Z.; Coupland, M.; Davis, D.G.; Duff, B.G.; Fearnley, T.; Heymann, F.F.; Imrie, D.C.; Lowndes, R.; Lush, G.J.; Phillips, M.; Baglin, C.; Guillaud, J.P.; Poulet, M.; Yvert, M.; Hansen, J.D.; Myrheim, J.; Brobakken, K.; Buran, T.; Buzzo, A.; Ferroni, S.; Gracco, V.; Helgaker, P.; Kirsebom, K.; Santroni, A.; Skjevling, G.; Soerensen, S.O.

    1983-01-01

    Measurements of the K - p and K 8 p elastic differential cross sections at 20 and 50 GeV/c, respectively, have been made in the momentum transfer range 0.7< vertical stroketvertical stroke<8.0 GeV/c. (orig.)

  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

  9. Multi-step optimization strategy for fuel-optimal orbital transfer of low-thrust spacecraft

    Science.gov (United States)

    Rasotto, M.; Armellin, R.; Di Lizia, P.

    2016-03-01

    An effective method for the design of fuel-optimal transfers in two- and three-body dynamics is presented. The optimal control problem is formulated using calculus of variation and primer vector theory. This leads to a multi-point boundary value problem (MPBVP), characterized by complex inner constraints and a discontinuous thrust profile. The first issue is addressed by embedding the MPBVP in a parametric optimization problem, thus allowing a simplification of the set of transversality constraints. The second problem is solved by representing the discontinuous control function by a smooth function depending on a continuation parameter. The resulting trajectory optimization method can deal with different intermediate conditions, and no a priori knowledge of the control structure is required. Test cases in both the two- and three-body dynamics show the capability of the method in solving complex trajectory design problems.

  10. GAKER-KIRA, Energy Transfer of Protons in H2O or Polyethylene and Deuterons in D2O

    International Nuclear Information System (INIS)

    Stammler, R.J.J.

    1965-01-01

    1 - Nature of physical problem solved: Evaluation of the energy transfer matrix and its first, second and third Legendre components for protons bound in water or polyethylene, and for deuterons bound in heavy water. Further output, the isotropic scattering matrix with diagonal elements corrected for first order anisotropy, scattering and transport cross sections, nth moment of energy transfer mn(e) (n=1,2,3), and Maxwellian averages of these moments, of the transport mean free path and of the scattering cross sections. 2 - Method of solution: For down-scattering the elements of the matrix are calculated directly from the analytical formulae (BNL 5826, p 69 FF (1961)). For scattering in the same speed (energy) group, a linear average is taken of four terms, scattering from the typical speed point of that group to four equidistant points in that same interval. Up-scattering elements are computed from detailed balance. The Bessel functions that appear are calculated following an algorithm due to Stegun and Abramowitz (see references). The anisotropic version of GAKER, which is due to Koppel and Young (see references) is also included in GAKER-KIRA, and the integration over the orientation angles is done by a 5-points Gauss quadrature. 3 - Restrictions on the complexity of the problem: A maximum number of 55 speed groups is permitted

  11. Encapsulation of 3-hydroxyflavone and fisetin in β-cyclodextrins: Excited state proton transfer fluorescence and molecular mechanics studies

    Science.gov (United States)

    Banerjee, Anwesha; Sengupta, Pradeep K.

    2006-06-01

    Excited-state intramolecular proton-transfer (ESIPT) and dual emission properties (emission profile, anisotropy and decay kinetics) of 3-hydroxyflavone (a synthetic, model flavonol) and fisetin (3,7,3',4'-OH-flavone, a therapeutically active plant flavonol) have been exploited to study their encapsulation in nano-cavities comprising of natural and chemically modified β-cyclodextrins. In the presence of β-CDs, both the flavonols show significantly enhanced relative yields (along with changes in other emission parameters) of the tautomer emission. In addition, for fisetin, large blue shifts are observed for the normal emission (which has significant charge transfer character). From these we infer that the flavonols are encaged in predominantly hydrophobic micro-environments, where external hydrogen bonding perturbations (interfering with the intrinsic ESIPT), and dipolar relaxation effects, are minimized. This is further explained from results of molecular mechanics calculations which indicate selectivity in orientation of the encapsulated flavonols. Moreover, chemical modification of the β-CDs is found to profoundly influence the binding affinities of the guest flavonols.

  12. Dual fluorescence of excited state intra-molecular proton transfer of HBFO: mechanistic understanding, substituent and solvent effects.

    Science.gov (United States)

    Yang, Wenjing; Chen, Xuebo

    2014-03-07

    A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.

  13. Electron and Oxygen Atom Transfer Chemistry of Co(II) in a Proton Responsive, Redox Active Ligand Environment.

    Science.gov (United States)

    Cook, Brian J; Pink, Maren; Pal, Kuntal; Caulton, Kenneth G

    2018-05-21

    The bis-pyrazolato pyridine complex LCo(PEt 3 ) 2 serves as a masked form of three-coordinate Co II and shows diverse reactivity in its reaction with several potential outer sphere oxidants and oxygen atom transfer reagents. N-Methylmorpholine N-oxide (NMO) oxidizes coordinated PEt 3 from LCo(PEt 3 ) 2 , but the final cobalt product is still divalent cobalt, in LCo(NMO) 2 . The thermodynamics of a variety of oxygen atom transfer reagents, including NMO, are calculated by density functional theory, to rank their oxidizing power. Oxidation of LCo(PEt 3 ) 2 with AgOTf in the presence of LiCl as a trapping nucleophile forms the unusual aggregate [LCo(PEt 3 ) 2 Cl(LiOTf) 2 ] 2 held together by Li + binding to very nucleophilic chloride on Co(III) and triflate binding to those Li + . In contrast, Cp 2 Fe + effects oxidation to trivalent cobalt, to form (HL)Co(PEt 3 ) 2 Cl + ; proton and the chloride originate from solvent in a rare example of CH 2 Cl 2 dehydrochlorination. An unexpected noncomplementary redox reaction is reported involving attack by 2e reductant PEt 3 nucleophile on carbon of the 1e oxidant radical Cp 2 Fe + , forming a P-C bond and H + ; this reaction competes in the reaction of LCo(PEt 3 ) 2 with Cp 2 Fe + .

  14. Exogenous ROS-induced cell sheet transfer based on hematoporphyrin-polyketone film via a one-step process.

    Science.gov (United States)

    Koo, Min-Ah; Lee, Mi Hee; Kwon, Byeong-Ju; Seon, Gyeung Mi; Kim, Min Sung; Kim, Dohyun; Nam, Ki Chang; Park, Jong-Chul

    2018-04-01

    To date, most of invasive cell sheet harvesting methods have used culture surface property variations, such as wettability, pH, electricity, and magnetism, to induce cell detachment. These methods that rely on surface property changes are effective when cell detachment prior to application is necessary, but of limited use when used for cell sheet transfer to target regions. The study reports a new reactive oxygen species (ROS)-induced strategy based on hematoporphyrin-incorporated polyketone film (Hp-PK film) to transfer cell sheets directly to target areas without an intermediate harvesting process. After green LED (510 nm) irradiation, production of exogenous ROS from the Hp-PK films induces cell sheet detachment and transfer. The study suggests that ROS-induced cell detachment property of the Hp-PK film is closely related to conformational changes of extracellular matrix (ECM) proteins. Also, this strategy with the Hp-PK film can be applied by regulating production rate of exogenous ROS in various types of cells, including fibroblasts, mesenchymal stem cells and keratinocytes. In conclusion, ROS-induced method using the Hp-PK film can be used for one-step cell sheet transplantation and has potential in biomedical applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Rapid Stencil Mask Fabrication Enabled One-Step Polymer-Free Graphene Patterning and Direct Transfer for Flexible Graphene Devices.

    Science.gov (United States)

    Yong, Keong; Ashraf, Ali; Kang, Pilgyu; Nam, SungWoo

    2016-04-27

    We report a one-step polymer-free approach to patterning graphene using a stencil mask and oxygen plasma reactive-ion etching, with a subsequent polymer-free direct transfer for flexible graphene devices. Our stencil mask is fabricated via a subtractive, laser cutting manufacturing technique, followed by lamination of stencil mask onto graphene grown on Cu foil for patterning. Subsequently, micro-sized graphene features of various shapes are patterned via reactive-ion etching. The integrity of our graphene after patterning is confirmed by Raman spectroscopy. We further demonstrate the rapid prototyping capability of a stretchable, crumpled graphene strain sensor and patterned graphene condensation channels for potential applications in sensing and heat transfer, respectively. We further demonstrate that the polymer-free approach for both patterning and transfer to flexible substrates allows the realization of cleaner graphene features as confirmed by water contact angle measurements. We believe that our new method promotes rapid, facile fabrication of cleaner graphene devices, and can be extended to other two dimensional materials in the future.

  16. Modeling heat and mass transfer in the heat treatment step of yerba maté processing

    Directory of Open Access Journals (Sweden)

    J. M. Peralta

    2007-03-01

    Full Text Available The aim of this research was to estimate the leaf and twig temperature and moisture content of yerba maté branches (Ilex paraguariensis Saint Hilaire during heat treatment, carried out in a rotary kiln dryer. These variables had to be estimated (modeling the heat and mass transfer due to the difficulty of experimental measurement in the dryer. For modeling, the equipment was divided into two zones: the flame or heat treatment zone and the drying zone. The model developed fit well with the experimental data when water loss took place only in leaves. In the first zone, leaf temperature increased until it reached 135°C and then it slowly decreased to 88°C at the exit, despite the gas temperature, which varied in this zone from 460°C to 120°C. Twig temperature increased in the two zones from its inlet temperature (25°C up to 75°C. A model error of about 3% was estimated based on theoretical and experimental data on leaf moisture content.

  17. Mass transfer with complex chemical reactions in gas–liquid systems : two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas Bhat, R.D.; Kuipers, J.A.M.; Versteeg, G.F.

    2000-01-01

    An absorption model to study gas–liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

  18. Mass transfer with complex chemical reactions in gas-liquid systems: two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas bhat, R.D.; Kuipers, J.A.M.; Versteeg, Geert

    2000-01-01

    An absorption model to study gas¿liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

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

    Science.gov (United States)

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

    2018-05-01

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

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

    Science.gov (United States)

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

    2016-10-24

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

  1. Theoretical Investigation of the Enzymatic Phosphoryl Transfer of β-phosphoglucomutase: Revisiting Both Steps of the Catalytic Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Elsasser, Brigitta M.; Dohmeier-Fischer, Silvia; Fels, Gregor

    2012-07-12

    Enzyme catalyzed phosphate transfer is a part of almost all metabolic processes. Such reactions are of central importance for the energy balance in all organisms and play important roles in cellular control at all levels. Mutases transfer a phosphoryl group while nucleases cleave the phosphodiester linkages between two nucleotides. The subject of our present study is the Lactococcus lactis β-phosphoglucomutase (β-PGM), which effectively catalyzes the interconversion of β-D-glucose-1-phosphate (β-G1P) to β- D-glucose-6-phosphate (β-G6P) and vice versa via stabile intermediate β-D-glucose-1,6-(bis)phosphate (β-G1,6diP) in the presence of Mg2+. In this paper we revisited the reaction mechanism of the phosphoryl transfer starting from the bisphosphate β-G1,6diP in both directions (toward β-G1P and β-G6P) combining docking techniques and QM/MM theoretical method at the DFT/PBE0 level of theory. In addition we performed NEB (nudged elastic band) and free energy calculations to optimize the path and to identify the transition states and the energies involved in the catalytic cycle. Our calculations reveal that both steps proceed via dissociative pentacoordinated phosphorane, which is not a stabile intermediate but rather a transition state. In addition to the Mg2+ ion, Ser114 and Lys145 also play important roles in stabilizing the large negative charge on the phosphate through strong coordination with the phosphate oxygens and guiding the phosphate group throughout the catalytic process. The calculated energy barrier of the reaction for the β-G1P to β-G1,6diP step is only slightly higher than for the β-G1,6diP to β-G6P step (16.10 kcal mol-1 versus 15.10 kcal mol-1) and is in excellent agreement with experimental findings (14.65 kcal mol-1).

  2. 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

    Science.gov (United States)

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

    2015-05-01

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

  3. Step size of the rotary proton motor in single FoF1-ATP synthase from a thermoalkaliphilic bacterium by DCO-ALEX FRET

    Science.gov (United States)

    Hammann, Eva; Zappe, Andrea; Keis, Stefanie; Ernst, Stefan; Matthies, Doreen; Meier, Thomas; Cook, Gregory M.; Börsch, Michael

    2012-02-01

    Thermophilic enzymes operate at high temperatures but show reduced activities at room temperature. They are in general more stable during preparation and, accordingly, are considered to be more rigid in structure. Crystallization is often easier compared to proteins from bacteria growing at ambient temperatures, especially for membrane proteins. The ATP-producing enzyme FoF1-ATP synthase from thermoalkaliphilic Caldalkalibacillus thermarum strain TA2.A1 is driven by a Fo motor consisting of a ring of 13 c-subunits. We applied a single-molecule Förster resonance energy transfer (FRET) approach using duty cycle-optimized alternating laser excitation (DCO-ALEX) to monitor the expected 13-stepped rotary Fo motor at work. New FRET transition histograms were developed to identify the smaller step sizes compared to the 10-stepped Fo motor of the Escherichia coli enzyme. Dwell time analysis revealed the temperature and the LDAO dependence of the Fo motor activity on the single molecule level. Back-and-forth stepping of the Fo motor occurs fast indicating a high flexibility in the membrane part of this thermophilic enzyme.

  4. A mechano-chemiosmotic model for the coupling of electron and proton transfer to ATP synthesis in energy-transforming membranes: a personal perspective.

    Science.gov (United States)

    Kasumov, Eldar A; Kasumov, Ruslan E; Kasumova, Irina V

    2015-01-01

    ATP is synthesized using ATP synthase by utilizing energy either from the oxidation of organic compounds, or from light, via redox reactions (oxidative- or photo phosphorylation), in energy-transforming membranes of mitochondria, chloroplasts, and bacteria. ATP synthase undergoes several changes during its functioning. The generally accepted model for ATP synthesis is the well-known rotatory model (see e.g., Junge et al., Nature 459:364-370, 2009; Junge and Müller, Science 333:704-705, 2011). Here, we present an alternative modified model for the coupling of electron and proton transfer to ATP synthesis, which was initially developed by Albert Lester Lehninger (1917-1986). Details of the molecular mechanism of ATP synthesis are described here that involves cyclic low-amplitude shrinkage and swelling of mitochondria. A comparison of the well-known current model and the mechano-chemiosmotic model is also presented. Based on structural, and other data, we suggest that ATP synthase is a Ca(2+)/H(+)-K(+) Cl(-)-pump-pore-enzyme complex, in which γ-subunit rotates 360° in steps of 30°, and 90° due to the binding of phosphate ions to positively charged amino acid residues in the N-terminal γ-subunit, while in the electric field. The coiled coil b 2-subunits are suggested to act as ropes that are shortened by binding of phosphate ions to positively charged lysines or arginines; this process is suggested to pull the α 3 β 3-hexamer to the membrane during the energization process. ATP is then synthesized during the reverse rotation of the γ-subunit by destabilizing the phosphated N-terminal γ-subunit and b 2-subunits under the influence of Ca(2+) ions, which are pumped over from storage-intermembrane space into the matrix, during swelling of intermembrane space. In the process of ATP synthesis, energy is first, predominantly, used in the delivery of phosphate ions and protons to the α 3 β 3-hexamer against the energy barrier with the help of C-terminal alpha

  5. R1 correction in amide proton transfer imaging: indication of the influence of transcytolemmal water exchange on CEST measurements.

    Science.gov (United States)

    Li, Hua; Li, Ke; Zhang, Xiao-Yong; Jiang, Xiaoyu; Zu, Zhongliang; Zaiss, Moritz; Gochberg, Daniel F; Gore, John C; Xu, Junzhong

    2015-12-01

    Amide proton transfer (APT) imaging may potentially detect mobile proteins/peptides non-invasively in vivo, but its specificity may be reduced by contamination from other confounding effects such as asymmetry of non-specific magnetization transfer (MT) effects and spin-lattice relaxation with rate R1 (=1/T1). Previously reported spillover, MT and R1 correction methods were based on a two-pool model, in which the existence of multiple water compartments with heterogeneous relaxation properties in real tissues was ignored. Such simple models may not adequately represent real tissues, and thus such corrections may be unreliable. The current study investigated the effectiveness and accuracy of correcting for R1 in APT imaging via simulations and in vivo experiments using tumor-bearing rats subjected to serial injections of Gd-DTPA that produced different tissue R1 values in regions of blood-brain-barrier breakdown. The results suggest that conventional measurements of APT contrast (such as APT* and MTRasym ) may be significantly contaminated by R1 variations, while the R1 -corrected metric AREX* was found to be relatively unaffected by R1 changes over a broad range (0.4-1 Hz). Our results confirm the importance of correcting for spin-lattice relaxation effects in quantitative APT imaging, and demonstrate the reliability of using the observed tissue R1 for corrections to obtain more specific and accurate measurements of APT contrast in vivo. The results also indicate that, due to relatively fast transcytolemmal water exchange, the influence of intra- and extracellular water compartments on CEST measurements with seconds long saturation time may be ignored in tumors. Copyright © 2015 John Wiley & Sons, Ltd.

  6. On the solution of fluid flow and heat transfer problem in a 2D channel with backward-facing step

    Directory of Open Access Journals (Sweden)

    Alexander A. Fomin

    2017-06-01

    Full Text Available The stable stationary solutions of the test problem of hydrodynamics and heat transfer in a plane channel with the backward-facing step have been considered in the work for extremely high Reynolds numbers and expansion ratio of the stream $ER$. The problem has been solved by numerical integration of the 2D Navier–Stokes equations in ‘velocity-pressure’ formulation and the heat equation in the range of Reynolds number $500 \\leqslant \\mathrm{ Re} \\leqslant 3000$ and expansion ratio $1.43 \\leqslant ER \\leqslant 10$ for Prandtl number $\\mathrm{ Pr} = 0.71$. Validity of the results has been confirmed by comparing them with literature data. Detailed flow patterns, fields of stream overheating, and profiles of horizontal component of velocity and relative overheating of flow in the cross section of the channel have been presented. Complex behaviors of the coefficients of friction, hydrodynamic resistance and heat transfer (Nusselt number along the channel depending on the problem parameters have been analyzed.

  7. A new heat transfer analysis in machining based on two steps of 3D finite element modelling and experimental validation

    Science.gov (United States)

    Haddag, B.; Kagnaya, T.; Nouari, M.; Cutard, T.

    2013-01-01

    Modelling machining operations allows estimating cutting parameters which are difficult to obtain experimentally and in particular, include quantities characterizing the tool-workpiece interface. Temperature is one of these quantities which has an impact on the tool wear, thus its estimation is important. This study deals with a new modelling strategy, based on two steps of calculation, for analysis of the heat transfer into the cutting tool. Unlike the classical methods, considering only the cutting tool with application of an approximate heat flux at the cutting face, estimated from experimental data (e.g. measured cutting force, cutting power), the proposed approach consists of two successive 3D Finite Element calculations and fully independent on the experimental measurements; only the definition of the behaviour of the tool-workpiece couple is necessary. The first one is a 3D thermomechanical modelling of the chip formation process, which allows estimating cutting forces, chip morphology and its flow direction. The second calculation is a 3D thermal modelling of the heat diffusion into the cutting tool, by using an adequate thermal loading (applied uniform or non-uniform heat flux). This loading is estimated using some quantities obtained from the first step calculation, such as contact pressure, sliding velocity distributions and contact area. Comparisons in one hand between experimental data and the first calculation and at the other hand between measured temperatures with embedded thermocouples and the second calculation show a good agreement in terms of cutting forces, chip morphology and cutting temperature.

  8. Beam transfer functions for relativistic proton bunches with beam–beam interaction

    Energy Technology Data Exchange (ETDEWEB)

    Görgen, P., E-mail: goergen@temf.tu-darmstadt.de [Institut für Theorie Elektromagnetischer Felder (TEMF), Technische Universität Darmstadt, Schloßgartenstr. 8 64289 Darmstadt (Germany); Boine-Frankenheim, O. [Institut für Theorie Elektromagnetischer Felder (TEMF), Technische Universität Darmstadt, Schloßgartenstr. 8 64289 Darmstadt (Germany); Fischer, W. [Brookhaven National Laboratory, Upton, NY 11973 (United States)

    2015-03-21

    We present a method for the recovery of the transverse tune spread directly from the beam transfer function (BTF). The model is applicable for coasting beams and bunched beams at high energy with a tune spread from transverse nonlinearities induced by the beam–beam effect or by an electron lens. Other sources of tune spread can be added. A method for the recovery of the incoherent tune spread without prior knowledge of the nonlinearity is presented. The approach is based on the analytic model for BTFs of coasting beams, which agrees very well with simulations results for bunched beams at relativistic energies with typically low synchrotron tune. A priori the presented tune spread recovery method is usable only in the absence of coherent modes, but additional simulation data shows its applicability even in the presence of coherent beam–beam modes. Finally agreement of both the analytic and simulation models with measurement data obtained at RHIC is presented. The proposed method successfully recovers the tune spread from analytic, simulated and measured BTF.

  9. Quality control of meat using proton-transfer-reaction-mass-spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Mayr, D.; Hartungen, E.; Maerk, T.D.; Margesin, R.; Schinner, F.

    2002-01-01

    Full text: Numerous food scandals which happened during the last few years make food safety controls more and more important. The method currently used for determining the status of meat, with respect to spoilage, is analysis of the counts of total viable bacteria and/or specific spoilage bacteria. An obvious drawback of this bacteriological method is the long incubation period of 1-3 days that is required for colony formation. Therefore we develop a novel method for meat quality control using PTR-MS which does not have this drawback. We measured the emitted volatile organic compounds (VOCs) of meat (beef and pork) using PTR-MS as a function of storage time. At the same time a bacteriological examination of these meat samples was carried out. We found strong correlations (about 99 %) between some VOCs and bacteriological contamination. This is a first step to replace the time-consuming bacteriological method by fast headspace air measurements to facilitate the investigation of a huge number of pieces of meat in very short time and to determine the maximum storage time and storage temperature from the emissions. We will also use this method to investigate the growth of various bacteria, the changes in the microbial composition and the influence of various environmental conditions such as temperature, pH, chemical and microbial preservation techniques. (author)

  10. Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC.

    Science.gov (United States)

    Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel; Gauci, Vincent

    2015-10-01

    Proton transfer reaction mass spectrometry (PTR-MS) is a well-established technique for real-time analysis of volatile organic compounds (VOCs). Although it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of detection monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilised. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here, we introduce a sensitive, near-to-real-time method for plant monoterpene research-PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

  11. Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

    Directory of Open Access Journals (Sweden)

    Rocha Reginaldo C.

    2001-01-01

    Full Text Available Iron and ruthenium complexes of the type [M-LH]n (where M = RuII,III(NH35(2+,3+, RuII,III(edta2-,- [edta = ethylenedinitrilotetraacetate], or FeII,III(CN5(3-,2- and LH = benzotriazole or benzimidazole were prepared and characterized in aqueous solutions by means of electrochemical and spectroelectrochemical methods. Special emphasis was given to the pH-dependent redox processes, exhibited by all the investigated complexes. From their related Pourbaix diagrams, which displayed a typically Nernstian behavior, the pKa and formal reduction potential values were extracted. In addition, these E1/2 versus pH curves were also used to illustrate the partitioning relationship concerning the redox and acid-base species, and their interconversion equilibria. The active area in which the dependence of the M III/M II couple on the pH takes place, as delimited by pKaIII and pKaII, was taken into account in order to evaluate the usefulness of such simple complexes as models for proton-coupled electron transfer (PCET. The results were interpreted in terms of the acceptor/donor electronic character of the ligands and sigma,pi-metal-ligand interactions in both redox states of the metal ion.

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  13. Assessment of space proton radiation-induced charge transfer inefficiency in the CCD204 for the Euclid space observatory

    International Nuclear Information System (INIS)

    Gow, J P D; Murray, N J; Holland, A D; Hall, D J; Cropper, M; Burt, D; Hopkinson, G; Duvet, L

    2012-01-01

    Euclid is a medium class European Space Agency mission candidate for launch in 2019 with a primary goal to study the dark universe using the weak lensing and baryonic acoustic oscillations techniques. Weak lensing depends on accurate shape measurements of distant galaxies. Therefore it is beneficial that the effects of radiation-induced charge transfer inefficiency (CTI) in the Euclid CCDs over the course of the 5 year mission at L2 are understood. This will allow, through experimental analysis and modelling techniques, the effects of radiation induced CTI on shape to be decoupled from those of mass inhomogeneities along the line-of-sight. This paper discusses a selection of work from the study that has been undertaken using the e2v CCD204 as part of the initial proton radiation damage assessment for Euclid. The experimental arrangement and procedure are described followed by the results obtained, thereby allowing recommendations to be made on the CCD operating temperature, to provide an insight into CTI effects using an optical background, to assess the benefits of using charge injection on CTI recovery and the effect of the use of two different methods of serial clocking on serial CTI. This work will form the basis of a comparison with a p-channel CCD204 fabricated using the same mask set as the n-channel equivalent. A custom CCD has been designed, based on this work and discussions between e2v technologies plc. and the Euclid consortium, and designated the CCD273.

  14. Excited-state proton transfer of 4-hydroxyl-1, 8-naphthalimide derivatives: A combined experimental and theoretical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Zongjin; Li, Peng; Zhang, Xuexiang; Wang, Endong; Wang, Yanni; Zhou, Panwang, E-mail: pwzhou@dicp.ac.cn

    2016-09-15

    The photophysical properties of N-butyl-4-hydroxyl-1, 8-naphthalimide (BOH) and N-(morpholinoethyl)−4-hydroxy-1, 8-naphthalimide (MOH) in various solvents are presented and the density functional theory (DFT)/time-dependent density functional theory (TDDFT) methods at the B3LYP/TZVP theoretical level are adopted to investigate the UV–visible absorption and emission data. An efficient intermolecular excited-state proton transfer (ESPT) reaction occurs for both compounds in DMSO, methanol and water. In aqueous solution, both BOH and MOH can be used as ratiometric pH probes and perform as strong photoacids with pKa*=−2.2, −2.4, respectively. Most interestingly, in the steady-state fluorescence spectra of BOH and MOH in concentrated HCl, an unexpected blue-shifted band is observed and assumed to originate from the contact ion pair (CIP) formed by hydronium ion and the anionic form of the photoacid resulted from ESPT. Theoretical calculations are used to simulate the CIP in the case of BOH, which afford reasonable results compared with the experimental data.

  15. Internal proton transfer and H2 rotations in the H5(+) cluster: a marked influence on its thermal equilibrium state.

    Science.gov (United States)

    de Tudela, Ricardo Pérez; Barragán, Patricia; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

    2011-03-31

    Classical and path integral Monte Carlo (CMC, PIMC) "on the fly" calculations are carried out to investigate anharmonic quantum effects on the thermal equilibrium structure of the H5(+) cluster. The idea to follow in our computations is based on using a combination of the above-mentioned nuclear classical and quantum statistical methods, and first-principles density functional (DFT) electronic structure calculations. The interaction energies are computed within the DFT framework using the B3(H) hybrid functional, specially designed for hydrogen-only systems. The global minimum of the potential is predicted to be a nonplanar configuration of C(2v) symmetry, while the next three low-lying stationary points on the surface correspond to extremely low-energy barriers for the internal proton transfer and to the rotation of the H2 molecules, around the C2 axis of H5(+), connecting the symmetric C(2v) minima in the planar and nonplanar orientations. On the basis of full-dimensional converged PIMC calculations, results on the quantum vibrational zero-point energy (ZPE) and state of H5(+) are reported at a low temperature of 10 K, and the influence of the above-mentioned topological features of the surface on its probability distributions is clearly demonstrated.

  16. Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

    Science.gov (United States)

    Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

    2008-01-01

    The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

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

    International Nuclear Information System (INIS)

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

    1981-01-01

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

  18. Computing Wigner distributions and time correlation functions using the quantum thermal bath method: application to proton transfer spectroscopy.

    Science.gov (United States)

    Basire, Marie; Borgis, Daniel; Vuilleumier, Rodolphe

    2013-08-14

    Langevin dynamics coupled to a quantum thermal bath (QTB) allows for the inclusion of vibrational quantum effects in molecular dynamics simulations at virtually no additional computer cost. We investigate here the ability of the QTB method to reproduce the quantum Wigner distribution of a variety of model potentials, designed to assess the performances and limits of the method. We further compute the infrared spectrum of a multidimensional model of proton transfer in the gas phase and in solution, using classical trajectories sampled initially from the Wigner distribution. It is shown that for this type of system involving large anharmonicities and strong nonlinear coupling to the environment, the quantum thermal bath is able to sample the Wigner distribution satisfactorily and to account for both zero point energy and tunneling effects. It leads to quantum time correlation functions having the correct short-time behavior, and the correct associated spectral frequencies, but that are slightly too overdamped. This is attributed to the classical propagation approximation rather than the generation of the quantized initial conditions themselves.

  19. Linear Energy Transfer Painting With Proton Therapy: A Means of Reducing Radiation Doses With Equivalent Clinical Effectiveness

    International Nuclear Information System (INIS)

    Fager, Marcus; Toma-Dasu, Iuliana; Kirk, Maura; Dolney, Derek; Diffenderfer, Eric S.; Vapiwala, Neha; Carabe, Alejandro

    2015-01-01

    Purpose: The purpose of this study was to propose a proton treatment planning method that trades physical dose (D) for dose-averaged linear energy transfer (LET d ) while keeping the radiobiologically weighted dose (D RBE ) to the target the same. Methods and Materials: The target is painted with LET d by using 2, 4, and 7 fields aimed at the proximal segment of the target (split target planning [STP]). As the LET d within the target increases with increasing number of fields, D decreases to maintain the D RBE the same as the conventional treatment planning method by using beams treating the full target (full target planning [FTP]). Results: The LET d increased 61% for 2-field STP (2STP) compared to FTP, 72% for 4STP, and 82% for 7STP inside the target. This increase in LET d led to a decrease of D with 5.3 ± 0.6 Gy for 2STP, 4.4 ± 0.7 Gy for 4STP, and 5.3 ± 1.1 Gy for 7STP, keeping the DRBE at 90% of the volume (DRBE, 90) constant to FTP. Conclusions: LET d painting offers a method to reduce prescribed dose at no cost to the biological effectiveness of the treatment

  20. Linear Energy Transfer Painting With Proton Therapy: A Means of Reducing Radiation Doses With Equivalent Clinical Effectiveness

    Energy Technology Data Exchange (ETDEWEB)

    Fager, Marcus, E-mail: Marcus.Fager@UPHS.UPenn.edu [Department of Radiation Oncology, School of Medicine, University of Pennsylvania, Philadelphia, Pennsylvania (United States); Medical Radiation Physics, Stockholm University, Stockholm (Sweden); Toma-Dasu, Iuliana [Medical Radiation Physics, Stockholm University and Karolinska Institutet, Stockholm (Sweden); Kirk, Maura; Dolney, Derek; Diffenderfer, Eric S.; Vapiwala, Neha [Department of Radiation Oncology, School of Medicine, University of Pennsylvania, Philadelphia, Pennsylvania (United States); Carabe, Alejandro, E-mail: Alejandro.Carabe-Fernandez@UPHS.UPenn.edu [Department of Radiation Oncology, School of Medicine, University of Pennsylvania, Philadelphia, Pennsylvania (United States)

    2015-04-01

    Purpose: The purpose of this study was to propose a proton treatment planning method that trades physical dose (D) for dose-averaged linear energy transfer (LET{sub d}) while keeping the radiobiologically weighted dose (D{sub RBE}) to the target the same. Methods and Materials: The target is painted with LET{sub d} by using 2, 4, and 7 fields aimed at the proximal segment of the target (split target planning [STP]). As the LET{sub d} within the target increases with increasing number of fields, D decreases to maintain the D{sub RBE} the same as the conventional treatment planning method by using beams treating the full target (full target planning [FTP]). Results: The LET{sub d} increased 61% for 2-field STP (2STP) compared to FTP, 72% for 4STP, and 82% for 7STP inside the target. This increase in LET{sub d} led to a decrease of D with 5.3 ± 0.6 Gy for 2STP, 4.4 ± 0.7 Gy for 4STP, and 5.3 ± 1.1 Gy for 7STP, keeping the DRBE at 90% of the volume (DRBE, 90) constant to FTP. Conclusions: LET{sub d} painting offers a method to reduce prescribed dose at no cost to the biological effectiveness of the treatment.

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

    Science.gov (United States)

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

    2017-10-15

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile fingerprints were affected by the origin of the meat. The classification of the origin of the lamb was achieved by examining the calculated and recorded fingerprints in combination with chemometrics. Four different partial least squares discriminant analysis (PLS-DA) models were fitted to the data to classify lamb meat and fat samples into "region of origin" (six different regions) and "origin" (Karoo vs. Non-Karoo). The estimation models classified samples 100% correctly. Validation of the first two models gave 42% (fat) and 58% (meat) correct classification of region, while the second two models performed better with 92% (fat) and 83% (meat) correct classification of origin. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2015-01-01

    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water

  3. Estimates of the astrophysical S-factors for proton radiative capture by 10B and 24Mg nuclei using the ANCs from proton transfer reactions

    International Nuclear Information System (INIS)

    Artemov, S.V.; Igamov, S.B.; Karakhodzhaev, A.A.; Nie, G.K.; Yarmukhamedov, R.; Zaparov, E.A.; Burtebaev, N.; Rehm, K.E.

    2010-01-01

    The contribution of the direct radiative capture of protons by 10 B and 24 Mg nuclei at low energies to the astrophysical S-factors in the reactions 10 B(p,γ) 11 C and 24 Mg(p,γ) 25 Al have been calculated within the R-matrix formalism by using empirical proton asymptotical normalization coefficients (ANC). The ANCs for bound proton configurations { 10 B+p} and { 24 Mg+p} were obtained from the analysis of the reactions ( 3 He, d). The ANCs were also estimated from the values of the neutron ANCs in the mirror nucleus 25 Mg following the suggestion that the neutron and the proton in the mirror states have equivalent nuclear potentials. It has been found that the S-factor for the reaction 10 B(p,γ) 11 C extrapolated to zero energy contributes ~100 keV b to the radiative capture to the ground state of 11 C. For the reaction 24 Mg(p,γ) 25 Al the value S(0) gives 58 keV b with a direct capture contribution of 41 keV b. (author)

  4. Rates of proton transfer to Fe-S-based clusters: comparison of clusters containing {MFe(mu(2)-S)(2)}n+ and {MFe(3)(mu(3)-S)(4)}n+ (M = Fe, Mo, or W) cores.

    Science.gov (United States)

    Bates, Katie; Garrett, Brendan; Henderson, Richard A

    2007-12-24

    The rates of proton transfer from [pyrH]+ (pyr = pyrrolidine) to the binuclear complexes [Fe2S2Cl4]2- and [S2MS2FeCl2]2- (M = Mo or W) are reported. The reactions were studied using stopped-flow spectrophotometry, and the rate constants for proton transfer were determined from analysis of the kinetics of the substitution reactions of these clusters with the nucleophiles Br- or PhS- in the presence of [pyrH]+. In general, Br- is a poor nucleophile for these clusters, and proton transfer occurs before Br- binds, allowing direct measure of the rate of proton transfer from [pyrH]+ to the cluster. In contrast, PhS- is a better nucleophile, and a pathway in which PhS- binds preferentially to the cluster prior to proton transfer from [pyrH]+ usually operates. For the reaction of [Fe2S2Cl4]2- with PhS- in the presence of [pyrH]+ both pathways are observed. Comparison of the results presented in this paper with analogous studies reported earlier on cuboidal Fe-S-based clusters allows discussion of the factors which affect the rates of proton transfer in synthetic clusters including the nuclearity of the cluster core, the metal composition, and the nature of the terminal ligands. The possible relevance of these findings to the protonation sites of natural Fe-S-based clusters, including FeMo-cofactor from nitrogenase, are presented.

  5. Sugar Radical Formation by a Proton Coupled Hole Transfer in 2′-Deoxyguanosine Radical Cation (2′-dG•+): A Theoretical Treatment

    Science.gov (United States)

    Kumar, Anil; Sevilla, Michael D.

    2009-01-01

    Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084

  6. Proton-Coupled Electron Transfer and a Tyrosine-Histidine Pair in a Photosystem II-Inspired β-Hairpin Maquette: Kinetics on the Picosecond Time Scale.

    Science.gov (United States)

    Pagba, Cynthia V; McCaslin, Tyler G; Chi, San-Hui; Perry, Joseph W; Barry, Bridgette A

    2016-02-25

    Photosystem II (PSII) and ribonucleotide reductase employ oxidation and reduction of the tyrosine aromatic ring in radical transport pathways. Tyrosine-based reactions involve either proton-coupled electron transfer (PCET) or electron transfer (ET) alone, depending on the pH and the pKa of tyrosine's phenolic oxygen. In PSII, a subset of the PCET reactions are mediated by a tyrosine-histidine redox-driven proton relay, YD-His189. Peptide A is a PSII-inspired β-hairpin, which contains a single tyrosine (Y5) and histidine (H14). Previous electrochemical characterization indicated that Peptide A conducts a net PCET reaction between Y5 and H14, which have a cross-strand π-π interaction. The kinetic impact of H14 has not yet been explored. Here, we address this question through time-resolved absorption spectroscopy and 280-nm photolysis, which generates a neutral tyrosyl radical. The formation and decay of the neutral tyrosyl radical at 410 nm were monitored in Peptide A and its variant, Peptide C, in which H14 is replaced by cyclohexylalanine (Cha14). Significantly, both electron transfer (ET, pL 11, L = lyonium) and PCET (pL 9) were accelerated in Peptide A and C, compared to model tyrosinate or tyrosine at the same pL. Increased electronic coupling, mediated by the peptide backbone, can account for this rate acceleration. Deuterium exchange gave no significant solvent isotope effect in the peptides. At pL 9, but not at pL 11, the reaction rate decreased when H14 was mutated to Cha14. This decrease in rate is attributed to an increase in reorganization energy in the Cha14 mutant. The Y5-H14 mechanism in Peptide A is reminiscent of proton- and electron-transfer events involving YD-H189 in PSII. These results document a mechanism by which proton donors and acceptors can regulate the rate of PCET reactions.

  7. Advantages of chemical exchange-sensitive spin-lock (CESL) over chemical exchange saturation transfer (CEST) for hydroxyl- and amine-water proton exchange studies.

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-11-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, the sensitivity is not optimal and, more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the properties of CEST signals are compared with those of a CE-sensitive spin-lock (CESL) technique irradiating at the labile proton frequency. First, using a higher power and shorter irradiation in CE-MRI, we obtain: (i) an increased selectivity to faster CE rates via a higher sensitivity to faster CEs and a lower sensitivity to slower CEs and magnetization transfer processes; and (ii) a decreased in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Second, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with an asymmetric population approximation, which can be used for quantitative CE-MRI and validated by simulations of Bloch-McConnell equations and phantom experiments. Finally, the in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 = 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of intermediate exchange protons. Copyright © 2014 John Wiley & Sons, Ltd.

  8. Advantages of Chemical Exchange-Sensitive Spin-Lock (CESL) Over Saturation Transfer (CEST) for Hydroxyl- and Amine-Water Proton Exchange Studies

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-01-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange (IMEX) processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, its sensitivity is not optimal, and more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the property of CEST signals is compared to a CE-sensitive spin-locking (CESL) technique irradiating at the labile proton frequency. Firstly, using a higher power and shorter irradiation in CE-MRI yields i) increasing selectivity to faster chemical exchange rates by higher sensitivity to faster exchanges and less sensitivity to slower CE and magnetization transfer processes, and ii) decreasing in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher-power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Secondly, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with asymmetric population approximation (CEAPA), which can be used for quantitative CE-MRI, and validated by simulations of Bloch-McConnell equations and phantom experiments. Lastly, in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 of 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of IMEX protons. PMID:25199631

  9. Synthesis, spectroscopic characterization and structural studies of a new proton transfer (H-bonded) complex of o-phenylenediamine with L-tartaric acid

    Science.gov (United States)

    Khan, Ishaat M.; Ahmad, Afaq

    2013-10-01

    A proton transfer or H-bonded (CT) complex of o-phenylenediamine (OPD) as donor with L-tartaric acid (TART) as acceptor was synthesized and characterized by spectral techniques such as FTIR, 1H NMR, elemental analysis, TGA-TDA, X-ray crystallography and spectrophotometric studies. The structural investigations exhibit that the cation [OPD+] and anion [TART-] are linked together through strong N+-H⋯O- type hydrogen bonds due to transfer of proton from acceptor to donor. Formed H-bonded complex exhibits well resolved proton transfer bands in the regions where neither donor nor acceptor has any absorption. The stoichiometry of the H-bonded complex (HBC) was found to be 1:1, determined by straight line methods. Spectrophotometric studies have been performed at room temperature and Benesi-Hildebrand equation was used to determine formation constant (KCT), molar extinction coefficient (ɛCT) and also transition energy (ECT) of the H-bonded complex. Spectrophotomeric and crystallographic studies have ascertained the formation of 1:1 H-bonded complex. Thermal analysis (TGA-DTA) was also used to confirm the thermal fragmentation and the stability of the synthesized H-bonded complex.

  10. Molecular mechanisms controlling proton pumping by bacteriorhodopsin. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Crouch, Rosalie K.; Ebrey, Thomas G.

    2000-02-10

    Bacteriorhodopsin (bR) is the simplest biological system for the transduction of light energy. Light energy is directly converted to transmembrane proton gradient by a single, small membrane protein. The extraordinary stability of bR makes it an outstanding subject for bioenergetic studies. This project has focused on the role of interactions between key residues of the pigment involved in light-induced proton transfer. Methods to estimate the strength of these interactions and their correlation with the rate and efficiency of proton transfer have been developed. The concept of the coupling of the protonation states of key groups has been applied to individual steps of the proton transfer with the ultimate goal of understanding on the molecular level the driving forces for proton transport and the pathway of the transported proton in bT. The mechanism of light-induced proton release, uptake and the mechanism of recovery of initial state of bT has been examined. The experiments were performed with genetically engineered, site-specific mutants of bR. This has enabled us to characterize the role of individual amino acid residues in bR. Time resolved and low temperature absorption spectroscopy and light-induced photocurrent measurements were used in order to study the photochemical cycle and proton transfer in mutant pigments. Chemical modification and crosslinking of both the specific amino acids to the chromophore or to other amino acids were used to elucidate the role of light-induced conformational changes in the photocycle and the structure of the protein in the ground state. The results of this project provided new knowledge on the architecture of the proton transfer pathways inside the protein, on the mechanism of proton release in bR, and on the role of specific amino acid residues in the structure and function of bR.

  11. 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

  12. Exploration of conformational changes in lactose permease upon sugar binding and proton transfer through coarse-grained simulations.

    Science.gov (United States)

    Jewel, Yead; Dutta, Prashanta; Liu, Jin

    2017-10-01

    Escherichia coli lactose permease (LacY) actively transports lactose and other galactosides across cell membranes through lactose/H + symport process. Lactose/H + symport is a highly complex process that involves sugar translocation, H + transfer, and large-scale protein conformational changes. The complete picture of lactose/H + symport is largely unclear due to the complexity and multiscale nature of the process. In this work, we develop the force field for sugar molecules compatible with PACE, a hybrid and coarse-grained force field that couples the united-atom protein models with the coarse-grained MARTINI water/lipid. After validation, we implement the new force field to investigate the binding of a β-d-galactopyranosyl-1-thio- β-d-galactopyranoside (TDG) molecule to a wild-type LacY. Results show that the local interactions between TDG and LacY at the binding pocket are consistent with the X-ray experiment. Transitions from inward-facing to outward-facing conformations upon TDG binding and protonation of Glu269 have been achieved from ∼5.5 µs simulations. Both the opening of the periplasmic side and closure of the cytoplasmic side of LacY are consistent with double electron-electron resonance and thiol cross-linking experiments. Our analysis suggests that the conformational changes of LacY are a cumulative consequence of interdomain H-bonds breaking at the periplasmic side, interdomain salt-bridge formation at the cytoplasmic side, and the TDG orientational changes during the transition. © 2017 Wiley Periodicals, Inc.

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

    Directory of Open Access Journals (Sweden)

    E. C. Fortner

    2009-01-01

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

  14. Estimating side-chain order in methyl-protonated, perdeuterated proteins via multiple-quantum relaxation violated coherence transfer NMR spectroscopy

    International Nuclear Information System (INIS)

    Sun Hechao; Godoy-Ruiz, Raquel; Tugarinov, Vitali

    2012-01-01

    Relaxation violated coherence transfer NMR spectroscopy (Tugarinov et al. in J Am Chem Soc 129:1743–1750, 2007) is an established experimental tool for quantitative estimation of the amplitudes of side-chain motions in methyl-protonated, highly deuterated proteins. Relaxation violated coherence transfer experiments monitor the build-up of methyl proton multiple-quantum coherences that can be created in magnetically equivalent spin-systems as long as their transverse magnetization components relax with substantially different rates. The rate of this build-up is a reporter of the methyl-bearing side-chain mobility. Although the build-up of multiple-quantum 1 H coherences is monitored in these experiments, the decay of the methyl signal during relaxation delays occurs when methyl proton magnetization is in a single-quantum state. We describe a relaxation violated coherence transfer approach where the relaxation of multiple-quantum 1 H– 13 C methyl coherences during the relaxation delay period is quantified. The NMR experiment and the associated fitting procedure that models the time-dependence of the signal build-up, are applicable to the characterization of side-chain order in [ 13 CH 3 ]-methyl-labeled, highly deuterated protein systems up to ∼100 kDa in molecular weight. The feasibility of extracting reliable measures of side-chain order is experimentally verified on methyl-protonated, perdeuterated samples of an 8.5-kDa ubiquitin at 10°C and an 82-kDa Malate Synthase G at 37°C.

  15. Excited-state inter- and intramolecular proton transfer in methyl 3-hydroxy-2-quinoxalinate: effects of solvent and acid or base concentrations

    International Nuclear Information System (INIS)

    Dogra, S.K.

    2005-01-01

    Absorption, fluorescence excitation and fluorescence spectroscopy, combined with time-dependent spectroscopy and semi-empirical (AM1) and density functional theory using Gaussian 98 program calculations have been used to study the effects of solvent and acid or base concentration on the spectral characteristics of methyl 3-hydroxy-2-quinoxalinate (M3HQ). M3HQ is present as enol in less polar solvents and as keto in polar media. In non-polar solvents, large Stokes shifted fluorescence band is assigned to the phototautomer, formed by the excited-state intramolecular proton transfer, whereas fluorescence is only observed from keto in the polar solvents. In aqueous and polar solvents the monocation (MC5/MC6) is formed by protonating the carbonyl oxygen atom in the ground (S 0 ) and the first excited singlet states (S 1 ). Dication is formed by protonating one of ?N- atom of MC5/MC6. Monoanion is formed by deprotonating the phenolic proton of enol in the basic solution. pK a values for different prototropic equilibriums were determined in S 0 and S 1 states and discussed

  16. Quantitative chemical exchange saturation transfer (qCEST) MRI--RF spillover effect-corrected omega plot for simultaneous determination of labile proton fraction ratio and exchange rate.

    Science.gov (United States)

    Sun, Phillip Zhe; Wang, Yu; Dai, ZhuoZhi; Xiao, Gang; Wu, Renhua

    2014-01-01

    Chemical exchange saturation transfer (CEST) MRI is sensitive to dilute proteins and peptides as well as microenvironmental properties. However, the complexity of the CEST MRI effect, which varies with the labile proton content, exchange rate and experimental conditions, underscores the need for developing quantitative CEST (qCEST) analysis. Towards this goal, it has been shown that omega plot is capable of quantifying paramagnetic CEST MRI. However, the use of the omega plot is somewhat limited for diamagnetic CEST (DIACEST) MRI because it is more susceptible to direct radio frequency (RF) saturation (spillover) owing to the relatively small chemical shift. Recently, it has been found that, for dilute DIACEST agents that undergo slow to intermediate chemical exchange, the spillover effect varies little with the labile proton ratio and exchange rate. Therefore, we postulated that the omega plot analysis can be improved if RF spillover effect could be estimated and taken into account. Specifically, simulation showed that both labile proton ratio and exchange rate derived using the spillover effect-corrected omega plot were in good agreement with simulated values. In addition, the modified omega plot was confirmed experimentally, and we showed that the derived labile proton ratio increased linearly with creatine concentration (p plot for quantitative analysis of DIACEST MRI. Copyright © 2014 John Wiley & Sons, Ltd.

  17. FT-IR investigation of proton transfer in irradiated ice at 90 K in the absence of mobile bjerrum defects

    International Nuclear Information System (INIS)

    Devlin, J.P.; Richardson, H.H.

    1984-01-01

    Samples of cubic and amorphous ice containing isolated D 2 O molecules have been prepared using established methods. Radiolysis with 1.7 MeV electrons at 90 K has been observed to convert the D 2 O in H 2 O cubic ice to primarily coupled HOD pairs (HOD) 2 rather than isolated HOD. Based on the assumption that radiolysis produces an abundance of mobile protons but relatively few mobile orientational defects this result was predictable, i.e., the motion of protons through D 2 O sites converts the D 2 O to coupled (HOD) 2 , while extensive conversion of (HOD) 2 units to isolated HOD requires the passage of orientational defects. Thus, the vanishingly small amount of isolated HOD formed during irradiation has been interpreted as evidence that no significant number of mobile orientational defects are produced by radiolysis. The ability to observe (HOD) 2 as a dominant spectroscopic species has added to the credibility of an earlier thermal study of the kinetics of proton motion in ice that was dependent on the quantitative determination of the (HOD) 2 concentration as a function of reaction time. Furthermore, the observation that protons produced radiolytically fall rapidly into shallow traps, from which they are released by modest warming (to approx.130 K), supports a suggestion by Warman that, for a brief period following a radiolysis pulse, mobile protons are in pseudoequilibrium with protons immobilized by association with L defects. The D 2 O isolated in amorphous ice was similarly converted to HOD by mobile protons produced during radiolysis. However, the broader infrared bands of the amorphous samples have prevented assigning the HOD to a particular form [(HOD) 2 or isolated HOD]. The interesting result was the indication that the proton mobility in amorphous ice is comparable to that for cubic ice

  18. Moving protons with pendant amines: proton mobility in a nickel catalyst for oxidation of hydrogen.

    Science.gov (United States)

    O'Hagan, Molly; Shaw, Wendy J; Raugei, Simone; Chen, Shentan; Yang, Jenny Y; Kilgore, Uriah J; DuBois, Daniel L; Bullock, R Morris

    2011-09-14

    Proton transport is ubiquitous in chemical and biological processes, including the reduction of dioxygen to water, the reduction of CO(2) to formate, and the production/oxidation of hydrogen. In this work we describe intramolecular proton transfer between Ni and positioned pendant amines for the hydrogen oxidation electrocatalyst [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+) (P(Cy)(2)N(Bn)(2) = 1,5-dibenzyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane). Rate constants are determined by variable-temperature one-dimensional NMR techniques and two-dimensional EXSY experiments. Computational studies provide insight into the details of the proton movement and energetics of these complexes. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+), which have N-H bonds but no Ni-H bonds. For these two isomers, with pendant amines positioned endo to the Ni, the rate constants for proton exchange range from 10(4) to 10(5) s(-1) at 25 °C, depending on isomer and solvent. No exchange is observed for protons on pendant amines positioned exo to the Ni. Analysis of the exchange as a function of temperature provides a barrier for proton exchange of ΔG(‡) = 11-12 kcal/mol for both isomers, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting metal-mediated intramolecular proton transfers between nitrogen atoms, with chair-to-boat isomerizations as the rate-limiting steps. Because of the fast rate of proton movement, this catalyst may be considered a metal center surrounded by a cloud of exchanging protons. The high intramolecular proton mobility provides information directly pertinent to the ability of pendant amines to accelerate proton transfers during catalysis of hydrogen oxidation. These results may also have broader implications for proton movement in

  19. Amide Proton Transfer Magnetic Resonance Imaging of Alzheimer′s Disease at 3.0 Tesla: A Preliminary Study

    Directory of Open Access Journals (Sweden)

    Rui Wang

    2015-01-01

    Full Text Available Background: Amide proton transfer (APT imaging has recently emerged as an important contrast mechanism for magnetic resonance imaging (MRI in the field of molecular and cellular imaging. The aim of this study was to evaluate the feasibility of APT imaging to detect cerebral abnormality in patients with Alzheimer′s disease (AD at 3.0 Tesla. Methods: Twenty AD patients (9 men and 11 women; age range, 67-83 years and 20 age-matched normal controls (11 men and 9 women; age range, 63-82 years underwent APT and traditional MRI examination on a 3.0 Tesla MRI system. The magnetic resonance ratio asymmetry (MTR asym values at 3.5 ppm of bilateral hippocampi (Hc, temporal white matter regions, occipital white matter regions, and cerebral peduncles were measured on oblique axial APT images. MTR asym (3.5 ppm values of the cerebral structures between AD patients and control subjects were compared with independent samples t-test. Controlling for age, partial correlation analysis was used to investigate the associations between mini-mental state examination (MMSE and the various MRI measures among AD patients. Results: Compared with normal controls, MTR asym (3.5 ppm values of bilateral Hc were significantly increased in AD patients (right 1.24% ± 0.21% vs. 0.83% ± 0.19%, left 1.18% ± 0.18% vs. 0.80%± 0.17%, t = 3.039, 3.328, P = 0.004, 0.002, respectively. MTR asym (3.5 ppm values of bilateral Hc were significantly negatively correlated with MMSE (right r = −0.559, P = 0.013; left r = −0.461, P = 0.047. Conclusions: Increased MTR asym (3.5 ppm values of bilateral Hc in AD patients and its strong correlations with MMSE suggest that APT imaging could potentially provide imaging biomarkers for the noninvasive molecular diagnosis of AD.

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

    International Nuclear Information System (INIS)

    Bodrogi, F.B.M.

    2003-11-01

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

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

    Directory of Open Access Journals (Sweden)

    Filomena Morisco

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

  2. Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

    Science.gov (United States)

    Pappas, Iraklis; Chirik, Paul J

    2016-10-03

    The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

  3. A statistical analysis of volatile organic compounds observed during the TEXAQS2000 air quality study at LaPorte, Tx, using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Kuster, B.; Williams, E.; Fehsenfeld, F.; Jobson, T.; Fall, R.; Lindinger, W.; Karl, T.

    2002-01-01

    Statistical analysis of online VOC measurements obtained by proton-transfer-reaction mass spectrometry (PTR-MS) during the TEXAQS2000 intensive period is presented. The experiment was based at the La Porte site, near the Houston ship channel (HSC), and deployed for continuous long-term monitoring. Multivariate techniques helped to identify various VOC sources in the vicinity of HSC and distinguish between different anthropogenic emissions. An assessment is given of the selectivity and interpretation of mass scans from this online technique in complex urban and industrial VOC matrix. (author)

  4. Protonation mechanism and location of rate-determining steps for the Ascaris suum nicotinamide adenine dinucleotide-malic enzyme reaction from isotope effects and pH studies

    International Nuclear Information System (INIS)

    Kiick, D.M.; Harris, B.G.; Cook, P.F.

    1986-01-01

    The pH dependence of the kinetic parameters and the primary deuterium isotope effects with nicotinamide adenine dinucleotide (NAD) and also thionicotinamide adenine dinucleotide (thio-NAD) as the nucleotide substrates were determined in order to obtain information about the chemical mechanism and location of rate-determining steps for the Ascaris suum NAD-malic enzyme reaction. The maximum velocity with thio-NAD as the nucleotide is pH-independent from pH 4.2 to 9.6, while with NAD, V decreases below a pK of 4.8. V/K for both nucleotides decreases below a pK of 5.6 and above a pK of 8.9. Both the tartronate pKi and V/Kmalate decrease below a pK of 4.8 and above a pK of 8.9. Oxalate is competitive vs. malate above pH 7 and noncompetitive below pH 7 with NAD as the nucleotide. The oxalate Kis increases from a constant value above a pK of 4.9 to another constant value above a pK of 6.7. The oxalate Kii also increases above a pK of 4.9, and this inhibition is enhanced by NADH. In the presence of thio-NAD the inhibition by oxalate is competitive vs. malate below pH 7. For thio-NAD, both DV and D(V/K) are pH-independent and equal to 1.7. With NAD as the nucleotide, DV decreases to 1.0 below a pK of 4.9, while D(V/KNAD) and D(V/Kmalate) are pH-independent. Above pH 7 the isotope effects on V and the V/K values for NAD and malate are equal to 1.45, the pH-independent value of DV above pH 7. Results indicate that substrates bind to only the correctly protonated form of the enzyme. Two enzyme groups are necessary for binding of substrates and catalysis. Both NAD and malate are released from the Michaelis complex at equal rates which are equal to the rate of NADH release from E-NADH above pH 7. Below pH 7 NADH release becomes more rate-determining as the pH decreases until at pH 4.0 it completely limits the overall rate of the reaction

  5. Walk This Way: Detailed Steps for Transferring Born-Digital Content from Media You Can Read In-House

    Science.gov (United States)

    Barrera-Gomez, Julianna; Erway, Ricky

    2013-01-01

    This document is a companion to the report, "You've Got to Walk before You Can Run: First Steps for Managing Born-Digital Content Received on Physical Media." Like the "First Steps" report, the intended audience is those who are just starting to manage born-digital materials, from those wondering where to begin, to those who…

  6. Faster proton transfer dynamics of water on SnO2 compared to TiO2.

    Science.gov (United States)

    Kumar, Nitin; Kent, Paul R C; Bandura, Andrei V; Kubicki, James D; Wesolowski, David J; Cole, David R; Sofo, Jorge O

    2011-01-28

    Proton jump processes in the hydration layer on the iso-structural TiO(2) rutile (110) and SnO(2) cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  7. Towards a thermodynamic definition of efficacy in partial agonism: The thermodynamics of efficacy and ligand proton transfer in a G protein-coupled receptor of the rhodopsin class.

    Science.gov (United States)

    Broadley, Kenneth J; Sykes, Shane C; Davies, Robin H

    2010-11-15

    The thermodynamic binding profiles of agonist and antagonist complexes of the 4-hydroxypropanolamine partial agonist, prenalterol, on the chronotropic adrenergic response in guinea-pig right atria were determined over a 15 °C temperature range. The tissue response was compared with data on the ethanolamine agonist, isoprenaline, given by binding studies in a number of rat tissues. Utilising the residue conservatism surrounding the known active conformers bound to either of two aspartate residues (α-helices II, III) in both receptors (β(1), β(2)) and species (guinea-pig, rat and human), no significant deformation in the extended side chain could be found in prenalterol's agonist binding compared to isoprenaline. Antagonist binding gave a highly favourable entropy contribution at 30.0 °C of -4.7±1.2 kcal/mol. The enthalpy change between bound agonist and antagonist complexes, a function of the efficacy alone, was -6.4±1.1 kcal/mol, coincident with the calculated intrinsic preference of a primary/secondary amine-aspartate interaction for a neutral hydrogen-bonded form over its ion pair state, giving values of 6.3-6.6 kcal/mol with calculations of good quality, a figure expected to be close to that shown within a hydrophobic environment. Delivery of a proton to a conserved aspartate anion (α-helix II) becomes the critical determinant for agonist action with resultant proton transfer stabilisation dominating the enthalpy change. A proposed monocation-driven ligand proton pumping mechanism within the ternary complex is consistent with the data, delivery between two acid groups being created by the movement of the cation and the counter-movement of the ligand protonated amine moving from Asp 138 (α-helix III) to Asp 104 (α-helix II). Copyright © 2010 Elsevier Inc. All rights reserved.

  8. SU-F-BRD-14: Dose Weighted Linear Energy Transfer Analysis of Critical Structures in Proton Therapy of Pediatric Brain Tumor Patients

    Energy Technology Data Exchange (ETDEWEB)

    Pirlepesov, F.; Shin, J.; Moskvin, V. P.; Gray, J.; Hua, C.; Gajjar, A.; Krasin, M. J.; Merchant, T. E.; Farr, J. B. [St. Jude Children’s Research Hospital, Memphis, TN (United States); Li, Z. [University of Florida Proton Therapy Institute, Jacksonville, FL (United States)

    2015-06-15

    Purpose: Dose weighted Linear Energy Transfer (LETd) analysis of critical structures may be useful in understanding the side effects of the proton therapy. The objective is to analyze the differences between LETd and dose distributions in brain tumor patients receiving double scattering proton therapy, to quantify LETd variation in critical organs, and to identify beam arrangements contributing to high LETd in critical organs. Methods: Monte Carlo simulations of 9 pediatric brain tumor patients were performed. The treatment plans were reconstructed with the TOPAS Monte Carlo code to calculate LETd and dose. The beam data were reconstructed proximal to the aperture of the double scattering nozzle. The dose and LETd to target and critical organs including brain stem, optic chiasm, lens, optic nerve, pituitary gland, and hypothalamus were computed for each beam. Results: Greater variability in LETd compared to dose was observed in the brainstem for patients with a variety of tumor types including 5 patients with tumors located in the posterior fossa. Approximately 20%–44% brainstem volume received LETd of 5kev/µm or greater from beams within gantry angles 180°±30° for 5 patients treated with a 3 beam arrangement. Critical organs received higher LETd when located in the vicinity of the beam distal edge. Conclusion: This study presents a novel strategy in the evaluation of the proton treatment impact on critical organs. While the dose to critical organs is confined below the required limits, the LETd may have significant variation. Critical organs in the vicinity of beam distal edge receive higher LETd and depended on beam arrangement, e.g. in posterior fossa tumor treatment, brainstem receive higher LETd from posterior-anterior beams. This study shows importance of the LETd analysis of the radiation impact on the critical organs in proton therapy and may be used to explain clinical imaging observations after therapy.

  9. TH-CD-201-03: A Real-Time Method to Simultaneously Measure Linear Energy Transfer and Dose for Proton Therapy Using Organic Scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Alsanea, F; Therriault-Proulx, F; Sawakuchi, G; Beddar, S [UT MD Anderson Cancer Center, Houston, TX (United States)

    2016-06-15

    Purpose: The light generated in organic scintillators depends on both the radiation dose and the linear energy transfer (LET). The LET dependence leads to an under-response of the detector in the Bragg peak of proton beams. This phenomenon, called ionization quenching, must be corrected to obtain accurate dose measurements of proton beams. This work exploits the ionization quenching phenomenon to provide a method of measuring LET and auto correcting quenching. Methods: We exposed simultaneously four different organic scintillators (BCF-12, PMMA, PVT, and LSD; 1mm in diameter) and a plane parallel ionization chamber in passively scattered proton beams to doses between 32 and 43 cGy and fluence averaged LET values from 0.47 to 1.26 keV/µm. The LET values for each irradiation condition were determined using a validated Monte Carlo model of the beam line. We determined the quenching parameter in the Birk’s equation for scintillation in BCF-12 for dose measurements. One set of irradiation conditions was used to correlate the scintillation response ratio to the LET values and plot a scintillation response ratio versus LET calibration curve. Irradiation conditions independent from the calibration ones were used to validate this method. Comparisons to the expected values were made on both the basis of dose and LET. Results: Among all the scintillators investigated, the ratio of PMMA to BCF-12 provided the best correlation to LET values and was used as the LET calibration curve. The expected LET values in the validation set were within 2%±6%, which resulted in dose accuracy of 1.5%±5.8% for the range of LET values investigated in this work. Conclusion: We have demonstrated the feasibility of using the ratio between the light output of two organic scintillators to simultaneously measure LET and dose of therapeutic proton beams. Further studies are needed to verify the response in higher LET values.

  10. Rapid Convergence of Energy and Free Energy Profiles with Quantum Mechanical Size in Quantum Mechanical-Molecular Mechanical Simulations of Proton Transfer in DNA.

    Science.gov (United States)

    Das, Susanta; Nam, Kwangho; Major, Dan Thomas

    2018-03-13

    In recent years, a number of quantum mechanical-molecular mechanical (QM/MM) enzyme studies have investigated the dependence of reaction energetics on the size of the QM region using energy and free energy calculations. In this study, we revisit the question of QM region size dependence in QM/MM simulations within the context of energy and free energy calculations using a proton transfer in a DNA base pair as a test case. In the simulations, the QM region was treated with a dispersion-corrected AM1/d-PhoT Hamiltonian, which was developed to accurately describe phosphoryl and proton transfer reactions, in conjunction with an electrostatic embedding scheme using the particle-mesh Ewald summation method. With this rigorous QM/MM potential, we performed rather extensive QM/MM sampling, and found that the free energy reaction profiles converge rapidly with respect to the QM region size within ca. ±1 kcal/mol. This finding suggests that the strategy of QM/MM simulations with reasonably sized and selected QM regions, which has been employed for over four decades, is a valid approach for modeling complex biomolecular systems. We point to possible causes for the sensitivity of the energy and free energy calculations to the size of the QM region, and potential implications.

  11. Anion-selective interaction and colorimeter by an optical metalloreceptor based on ruthenium(II) 2,2'-biimidazole: hydrogen bonding and proton transfer.

    Science.gov (United States)

    Cui, Ying; Mo, Hao-Jun; Chen, Jin-Can; Niu, Yan-Li; Zhong, Yong-Rui; Zheng, Kang-Cheng; Ye, Bao-Hui

    2007-08-06

    A new anion sensor [Ru(bpy)2(H2biim)](PF6)2 (1) (bpy = 2,2'-bipyridine and H2biim = 2,2'-biimidazole) has been developed, in which the Ru(II)-bpy moiety acts as a chromophore and the H2biim ligand as an anion receptor via hydrogen bonding. A systematic investigation shows that 1 is an eligible sensor for various anions. It donates protons for hydrogen bonding to Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, and OAc- anions and further actualizes monoproton transfer to the OAc- anion, changing color from yellow to orange brown. The fluoride ion has a high affinity toward the N-H group of the H2biim ligand for proton transfer, rather than hydrogen bonding, because of the formation of the highly stable HF2- anion, resulting in stepwise deprotonation of the two N-H fragments. These processes are signaled by vivid color changes from yellow to orange brown and then to violet because of second-sphere donor-acceptor interactions between Ru(II)-H2biim and the anions. The significant color changes can be distinguished visually. The processes are not only determined by the basicity of anion but also by the strength of hydrogen bonding and the stability of the anion-receptor complexes. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of anion sensors.

  12. Photophysical properties of 1-acetoxy-8-hydroxy-1,4,4a,9a-tetrahydroanthraquinone: Evidence for excited state proton transfer reaction

    International Nuclear Information System (INIS)

    Singh, Rupashree Balia; Mahanta, Subrata; Guchhait, Nikhil

    2007-01-01

    The photophysical properties of 1-acetoxy-8-hydroxy-1,4,4a,9a-tetrahydroanthraquinone (HTHQ) have been investigated by steady state and time resolved spectroscopy in combination with quantum chemical calculations. The effects of various parameters such as the nature of solvent and pH of the medium on the spectral properties confirm the existence of different neutral and ionic species in the ground and excited states. In the ground state, HTHQ exists as intramolecularly hydrogen bonded closed conformer in non-polar and polar aprotic solvents. Apart from the closed conformer, the intermolecular hydrogen bonded solvated species and the anion of HTHQ are present in hydroxylic solvents. The closed conformer shows excited state intramolecular proton transfer in all solvents and the solvent polarity independent red shifted emission indicates only keto-enol tautomerism. Evaluation of the potential energy surfaces by quantum chemical calculation using density functional theory point towards the possibility of proton transfer reaction in the first excited state but not in the ground state

  13. Evidence for excited-state intramolecular proton transfer in 4-chlorosalicylic acid from combined experimental and computational studies: Quantum chemical treatment of the intramolecular hydrogen bonding interaction

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India)

    2012-07-25

    Highlights: Black-Right-Pointing-Pointer Experimental and computational studies on the photophysics of 4-chlorosalicylic acid. Black-Right-Pointing-Pointer Spectroscopically established ESIPT reaction substantiated by theoretical calculation. Black-Right-Pointing-Pointer Quantum chemical treatment of IMHB unveils strength, nature and directional nature. Black-Right-Pointing-Pointer Superiority of quantum chemical treatment of H-bond over geometric criteria. Black-Right-Pointing-Pointer Role of H-bond as a modulator of aromaticity. -- Abstract: The photophysical study of a pharmaceutically important chlorine substituted derivative of salicylic acid viz., 4-chlorosalicylic acid (4ClSA) has been carried out by steady-state absorption, emission and time-resolved emission spectroscopy. A large Stokes shifted emission band with negligible solvent polarity dependence marks the spectroscopic signature of excited-state intramolecular proton transfer (ESIPT) reaction in 4ClSA. Theoretical calculation by ab initio and Density Functional Theory methods yields results consistent with experimental findings. Theoretical potential energy surfaces predict the occurrence of proton transfer in S{sub 1}-state. Geometrical and energetic criteria, Atoms-In-Molecule topological parameters, Natural Bond Orbital population analysis have been exploited to evaluate the intramolecular hydrogen bond (IMHB) interaction and to explore its directional nature. The inter-correlation between aromaticity and resonance assisted H-bond is also discussed in this context. Our results unveil that the quantum chemical treatment is a more accurate tool to assess hydrogen bonding interaction in comparison to geometrical criteria.

  14. Proton polarization above 70% by DNP using photo-excited triplet states, a first step towards a broadband neutron spin filter

    International Nuclear Information System (INIS)

    Eichhorn, T.R.; Niketic, N.; Brandt, B. van den; Filges, U.; Panzner, T.; Rantsiou, E.; Wenckebach, W.Th.; Hautle, P.

    2014-01-01

    The use of polarized protons as neutron spin filter is an attractive alternative to the well established neutron polarization techniques, as the large, spin-dependent neutron scattering cross-section for protons is useful up to the sub-MeV region. Employing optically excited triplet states for the dynamic nuclear polarization (DNP) of the protons relieves the stringent requirements of classical DNP schemes, i.e low temperatures and strong magnetic fields, making technically simpler systems with open geometries possible. Using triplet DNP a record polarization of 71% has been achieved in a pentacene doped naphthalene single crystal at a field of 0.36 T using a simple helium flow cryostat for cooling. Furthermore, by placing the polarized crystal in a neutron optics focus and de-focus scheme, the actual sample cross-section could be increased by a factor 35 corresponding to an effective spin filter cross-section of 18×18mm 2

  15. Proton polarization above 70% by DNP using photo-excited triplet states, a first step towards a broadband neutron spin filter

    Energy Technology Data Exchange (ETDEWEB)

    Eichhorn, T.R. [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Laboratory of Functional and Metabolic Imaging, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland); Niketic, N.; Brandt, B. van den; Filges, U.; Panzner, T.; Rantsiou, E.; Wenckebach, W.Th. [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Hautle, P., E-mail: patrick.hautle@psi.ch [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland)

    2014-08-01

    The use of polarized protons as neutron spin filter is an attractive alternative to the well established neutron polarization techniques, as the large, spin-dependent neutron scattering cross-section for protons is useful up to the sub-MeV region. Employing optically excited triplet states for the dynamic nuclear polarization (DNP) of the protons relieves the stringent requirements of classical DNP schemes, i.e low temperatures and strong magnetic fields, making technically simpler systems with open geometries possible. Using triplet DNP a record polarization of 71% has been achieved in a pentacene doped naphthalene single crystal at a field of 0.36 T using a simple helium flow cryostat for cooling. Furthermore, by placing the polarized crystal in a neutron optics focus and de-focus scheme, the actual sample cross-section could be increased by a factor 35 corresponding to an effective spin filter cross-section of 18×18mm{sup 2}.

  16. Proton-proton bremsstrahlung

    International Nuclear Information System (INIS)

    Fearing, H.W.

    1990-01-01

    We summarize some of the information about the nucleon-nucleon force which has been obtained by comparing recent calculations of proton-proton bremsstrahlung with cross section and analyzing power data from the new TRIUMF bremsstrahlung experiment. Some comments are made as to how these results can be extended to neutron-proton bremsstrahlung. (Author) 17 refs., 6 figs

  17. The impact of dihydrogen phosphate anions on the excited-state proton transfer of harmane. Effect of β-cyclodextrin on these photoreactions.

    Science.gov (United States)

    Reyman, Dolores; Viñas, Montserrat H; Tardajos, Gloria; Mazario, Eva

    2012-01-12

    Photoinduced proton transfer reactions of harmane (1-methyl-9H-pyrido[3,4-b]indole) (HAR) in the presence of a proton donor/acceptor such as dihydrogen phosphate anions in aqueous solution have been studied by stationary and time-resolved fluorescence spectroscopy. The presence of high amounts of dihydrogen phosphate ions modifies the acid/base properties of this alkaloid. Thus, by keeping the pH constant at pH 8.8 and by increasing the amount of NaH(2)PO(4) in the solution, it is possible to reproduce the same spectral profiles as those obtained in high alkaline solutions (pH >12) in the absence of NaH(2)PO(4). Under these conditions, a new fluorescence profile appears at around 520 nm. This result could be related to the results of a recent investigation which suggests that a high intake of phosphates may promote skin tumorigenesis. The presence of β-cyclodextrin (β-CD) avoids the proton transfer reactions in this alkaloid by means the formation of an inclusion complex between β-CD and HAR. The formation of this complex originates a remarkable enhancement of the emission intensity from the neutral form in contrast to the cationic and zwitterionic forms. A new lifetime was obtained at 360 nm (2.5 ns), which was associated with the emission of this inclusion complex. At this wavelength, the fluorescence intensity decay of HAR can be described by a linear combination of two exponentials. From the ratio between the pre-exponential factors, we have obtained a value of K = 501 M for the equilibrium of formation of this complex.

  18. Reaction pathways of proton transfer in hydrogen-bonded phenol-carboxylate complexes explored by combined UV-vis and NMR spectroscopy.

    Science.gov (United States)

    Koeppe, Benjamin; Tolstoy, Peter M; Limbach, Hans-Heinrich

    2011-05-25

    Combined low-temperature NMR/UV-vis spectroscopy (UVNMR), where optical and NMR spectra are measured in the NMR spectrometer under the same conditions, has been set up and applied to the study of H-bonded anions A··H··X(-) (AH = 1-(13)C-2-chloro-4-nitrophenol, X(-) = 15 carboxylic acid anions, 5 phenolates, Cl(-), Br(-), I(-), and BF(4)(-)). In this series, H is shifted from A to X, modeling the proton-transfer pathway. The (1)H and (13)C chemical shifts and the H/D isotope effects on the latter provide information about averaged H-bond geometries. At the same time, red shifts of the π-π* UV-vis absorption bands are observed which correlate with the averaged H-bond geometries. However, on the UV-vis time scale, different tautomeric states and solvent configurations are in slow exchange. The combined data sets indicate that the proton transfer starts with a H-bond compression and a displacement of the proton toward the H-bond center, involving single-well configurations A-H···X(-). In the strong H-bond regime, coexisting tautomers A··H···X(-) and A(-)···H··X are observed by UV. Their geometries and statistical weights change continuously when the basicity of X(-) is increased. Finally, again a series of single-well structures of the type A(-)···H-X is observed. Interestingly, the UV-vis absorption bands are broadened inhomogeneously because of a distribution of H-bond geometries arising from different solvent configurations.

  19. Quasi-four-body treatment of charge transfer in the collision of protons with atomic helium: II. Second-order non-Thomas mechanisms and the cross sections

    Science.gov (United States)

    Safarzade, Zohre; Akbarabadi, Farideh Shojaei; Fathi, Reza; Brunger, Michael J.; Bolorizadeh, Mohammad A.

    2018-05-01

    A fully quantum mechanical four-body treatment of charge transfer collisions between energetic protons and atomic helium is developed here. The Pauli exclusion principle is applied to both the wave function of the initial and final states as well as the operators involved in the interaction. Prior to the collision, the helium atom is assumed as a two-body system composed of the nucleus, He2+, and an electron cloud composed of two electrons. Nonetheless, four particles are assumed in the final state. As the double interactions contribute extensively in single charge transfer collisions, the Faddeev-Lovelace-Watson scattering formalism describes it best physically. The treatment of the charge transfer cross section, under this quasi-four-body treatment within the FWL formalism, showed that other mechanisms leading to an effect similar to the Thomas one occur at the same scattering angle. Here, we study the two-body interactions which are not classically described but which lead to an effect similar to the Thomas mechanism and finally we calculate the total singlet and triplet amplitudes as well as the angular distributions of the charge transfer cross sections. As the incoming projectiles are assumed to be plane waves, the present results are calculated for high energies; specifically a projectile energy of 7.42 MeV was assumed as this is where experimental results are available in the literature for comparison. Finally, when possible we compare the present results with the other available theoretical data.

  20. Proton and α particles transfer in 16 O + 63,65 Cu for energies near the Coulomb barrier

    International Nuclear Information System (INIS)

    Ramirez, Giancarlos; Massmann, Herbert; Pereira, D.; Chamon, L.

    1996-01-01

    Full text: Experimental and theoretical studies have been performed on induced transfer reactions for one oxygen beam in two copper isotopes. An isotopic difference had been found in the cross section of the experimental transfer, which will be correlated with the systems Q values

  1. Transfer

    DEFF Research Database (Denmark)

    Wahlgren, Bjarne; Aarkrog, Vibe

    Bogen er den første samlede indføring i transfer på dansk. Transfer kan anvendes som praksis-filosofikum. Den giver en systematisk indsigt til den studerende, der spørger: Hvordan kan teoretisk viden bruges til at reflektere over handlinger i situationer, der passer til min fremtidige arbejdsplads?...

  2. The Theory and Practice of the Six-Step Method in EFL and Its Transferability to Engineering Programmes

    Science.gov (United States)

    Ntombela, Berrington X. S.

    2013-01-01

    This paper outlines the theory of the six-step method developed by personnel in the Language and Learning department at Caledonian College of Engineering, Oman. The paper further illustrates the application of this method in teaching Project, Listening, Reading, Writing, and Speaking & Debate at Foundation level. The assumption in applying the…

  3. Proton transfer and hydrogen bonding in the organic solid state: a combined XRD/XPS/ssNMR study of 17 organic acid-base complexes.

    Science.gov (United States)

    Stevens, Joanna S; Byard, Stephen J; Seaton, Colin C; Sadiq, Ghazala; Davey, Roger J; Schroeder, Sven L M

    2014-01-21

    The properties of nitrogen centres acting either as hydrogen-bond or Brønsted acceptors in solid molecular acid-base complexes have been probed by N 1s X-ray photoelectron spectroscopy (XPS) as well as (15)N solid-state nuclear magnetic resonance (ssNMR) spectroscopy and are interpreted with reference to local crystallographic structure information provided by X-ray diffraction (XRD). We have previously shown that the strong chemical shift of the N 1s binding energy associated with the protonation of nitrogen centres unequivocally distinguishes protonated (salt) from hydrogen-bonded (co-crystal) nitrogen species. This result is further supported by significant ssNMR shifts to low frequency, which occur with proton transfer from the acid to the base component. Generally, only minor chemical shifts occur upon co-crystal formation, unless a strong hydrogen bond is formed. CASTEP density functional theory (DFT) calculations of (15)N ssNMR isotropic chemical shifts correlate well with the experimental data, confirming that computational predictions of H-bond strengths and associated ssNMR chemical shifts allow the identification of salt and co-crystal structures (NMR crystallography). The excellent agreement between the conclusions drawn by XPS and the combined CASTEP/ssNMR investigations opens up a reliable avenue for local structure characterization in molecular systems even in the absence of crystal structure information, for example for non-crystalline or amorphous matter. The range of 17 different systems investigated in this study demonstrates the generic nature of this approach, which will be applicable to many other molecular materials in organic, physical, and materials chemistry.

  4. Selenium-72 formation via {sup nat}Br(p,x) induced by 100 MeV Protons: Steps towards a novel {sup 72}Se/{sup 72}As generator system

    Energy Technology Data Exchange (ETDEWEB)

    Ballard, B. [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Wycoff, D. [Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211 (United States); Birnbaum, E.R.; John, K.D. [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Lenz, J.W. [John Lenz and Associates, East Lansing, MI 48823 (United States); Jurisson, S.S. [Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211 (United States); Cutler, C.S. [Missouri University Research Reactor Center, University of Missouri-Columbia, Columbia, MO 65211 (United States); Nortier, F.M.; Taylor, W.A. [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Fassbender, M.E., E-mail: mifa@lanl.gov [Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2012-04-15

    Selenium-72 production by the proton bombardment of a natural NaBr target has been successfully demonstrated at the Los Alamos National Laboratory Isotope Production Facility (LANL-IPF). Arsenic-72 (half life 26 h) is a medium-lived positron emitting radionuclide with the major advantage of being formed as the daughter of another 'generator' radioisotope (Se-72, 8.5 d). A {sup 72}Se/{sup 72}As generator would be the preferred mechanism for clinical utilization of {sup 72}As for positron emission tomography (PET). No portable {sup 72}Se/{sup 72}As generator system has been demonstrated for convenient, repeated {sup 72}As elution ('milking'). In this work, we describe {sup 72}Se production and recovery from irradiated NaBr targets using a 100 MeV proton beam. We also introduce an {sup 72}As generator principle based on {sup 72}Se chelation followed by liquid-liquid extraction, which will be transferred to a solid-phase sorption/elution system. - Highlights: Black-Right-Pointing-Pointer A bulk production and processing method for {sup 72}Se using low-toxic NaBr in a high-energy proton beam has been developed. Black-Right-Pointing-Pointer A chelation based principle for a {sup 72}Se/{sup 72}As generator has been demonstrated. Black-Right-Pointing-Pointer Comparison of experimental yields to theoretical predictions resulted in good agreement.

  5. Fluorescence ratiometric sensing of polyols by phenylboronic acid complexes with ligands exhibiting excited-state intramolecular proton transfer in aqueous micellar media

    Energy Technology Data Exchange (ETDEWEB)

    Trejo-Huizar, Karla Elisa; Jiménez-Sánchez, Arturo; Martínez-Aguirre, Mayte A.; Yatsimirsky, Anatoly K., E-mail: anatoli@unam.mx

    2016-11-15

    2-Phenyl-3-hydroxy-4(1H)-quinolone possessing dual fluorescence due to excited-state intramolecular proton transfer (ESIPT) forms stable complex with phenylboronic acid with blue shifted emission maximum in micellar medium of a cationic surfactant even though the compound lacks required for complexation with boronic acids cis-diol structure. No complexation is observed in the presence of neutral or anionic surfactants. Titrations of this complex with polyols including sugars and nucleotides at pH 8 displace free quinolone showing ratiometric response, which allows determination of polyols with detection limits 0.05–1 mM and unusually wide linear dynamic ranges. Another ESIPT dye 2-(2′-hydroxyphenyl)−1H-benzimidazole also lacking cis-diol structure forms equally stable complex with phenylboronic acid and allows ratiometric determination of polyols with similar characteristics. The results of this study demonstrate that blocking ESIPT of signaling molecule by complexation of the receptor with the proton donor group eliminates the low energy emission from tautomeric form but strongly enhances the high energy emission typical for “normal” form of signaling molecule creating a possibility of ratiometric sensing.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

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

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  8. From bismuth oxide/hydroxide precursor clusters towards stable oxides: Proton transfer reactions and structural reorganization govern the stability of [Bi18O13(OH)10]-nitrate clusters

    Science.gov (United States)

    Walther, M.; Zahn, D.

    2018-01-01

    Structural relaxation and stability of a Bi18-cluster as obtained from association of [Bi6O4(OH)4](NO3)6 precursor clusters in DMSO solution is investigated from a combination of quantum chemical calculations and μs-scale molecular dynamics simulations using empirical interaction potentials. The Bi18-cluster undergoes a OH⋯OH proton transfer reaction, followed by considerable structural relaxation. While the aggregation of the Bi18-cluster is induced by the dissociation of a single nitrate ion leading to [Bi6O4(OH)4](NO3)5+ as an activated precursor species that can bind two more Bi6-clusters, we find the [Bi18O13(OH)10](NO3)18-x+x species (explored for x = 1-6) rather inert against either nitrate dissociation, collision with Bi6-precursors or combinations thereof.

  9. Benzothiazole-Based AIEgen with Tunable Excited-State Intramolecular Proton Transfer and Restricted Intramolecular Rotation Processes for Highly Sensitive Physiological pH Sensing.

    Science.gov (United States)

    Li, Kai; Feng, Qi; Niu, Guangle; Zhang, Weijie; Li, Yuanyuan; Kang, Miaomiao; Xu, Kui; He, Juan; Hou, Hongwei; Tang, Ben Zhong

    2018-04-23

    In this work, a benzothiazole-based aggregation-induced emission luminogen (AIEgen) of 2-(5-(4-carboxyphenyl)-2-hydroxyphenyl)benzothiazole (3) was designed and synthesized, which exhibited multifluorescence emissions in different dispersed or aggregated states based on tunable excited-state intramolecular proton transfer (ESIPT) and restricted intramolecular rotation (RIR) processes. 3 was successfully used as a ratiometric fluorescent chemosensor for the detection of pH, which exhibited reversible acid/base-switched yellow/cyan emission transition. More importantly, the pH jump of 3 was very precipitous from 7.0 to 8.0 with a midpoint of 7.5, which was well matched with the physiological pH. This feature makes 3 very suitable for the highly sensitive detection of pH fluctuation in biosamples and neutral water samples. 3 was also successfully used as a ratiometric fluorescence chemosensor for the detection of acidic and basic organic vapors in test papers.

  10. Reoriention of diprotonated DABCO (1,4-Diazabicyclo[2.2.2]octane) cation and proton transfer in organic ferroelectric adduct DABCO-2(2-Chlorobenzoic acid)

    Science.gov (United States)

    Asaji, Tetsuo

    2018-05-01

    Temperature dependences of 1H NMR as well as 35Cl NQR spin-lattice relaxation times T1 were investigated of a ferroelectric molecular adduct with Tc = 323 K, in which 1,4-diazabicyclo[2.2.2]octane (DABCO) is sandwiched between two 2-chlorobenzoic acid (2-ClBA). The NQR frequencies clearly show that proton transfer from 2-ClBA to DABCO is occurred and the molecular adduct consists of diprotonated DABCO cation and two 2-chlorobenzoate anions. The correlation time of reorientational motion of the diprotonated DABCO molecule was determined as a function of temperature. The activation energy Ea of the motion was estimated as 22 kJ mol-1 below Tc. The steep decrease of the NQR T1 with Ea = 50 kJ mol-1, observed above ca. 280 K in the ferroelectric phase, suggests a slow fluctuation of electric field gradient at chlorine nucleus.

  11. Cooperative Electrocatalytic O 2 Reduction Involving Co(salophen) with p- Hydroquinone as an Electron–Proton Transfer Mediator

    Energy Technology Data Exchange (ETDEWEB)

    Anson, Colin W. [Department of Chemistry, University of Wisconsin−Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States; Stahl, Shannon S. [Department of Chemistry, University of Wisconsin−Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States

    2017-12-01

    The molecular cobalt complex, Co(salophen), and para-hydroquinone (H2Q) serve as effective cocatalysts for the electrochemical reduction of O2 to water. Mechanistic studies reveal redox cooperativity between Co(salophen) and H2Q. H2Q serves as an electron-proton transfer mediator (EPTM) that enables electrochemical O2 reduction at higher potentials and with faster rates than is observed with Co(salophen) alone. Replacement of H2Q with the higher potential EPTM, 2-chloro-H2Q, allows for faster O2 reduction rates at higher applied potential. These results demonstrate a unique strategy to achieve improved performance with molecular electrocatalyst systems.

  12. Top-Down Charge Transfer Dissociation (CTD) of Gas-Phase Insulin: Evidence of a One-Step, Two-Electron Oxidation Mechanism

    Science.gov (United States)

    Li, Pengfei; Kreft, Iris; Jackson, Glen P.

    2018-02-01

    Top-down analyses of protonated insulin cations of charge states of 4+, 5+, or 6+ were performed by exposing the isolated precursor ions to a beam of helium cations with kinetic energy of more than 6 keV, in a technique termed charge transfer dissociation (CTD). The 100 ms charge transfer reaction resulted in approximately 20% conversion efficiency to other intact charge exchange products (CTnoD), and a range of low abundance fragment ions. To increase backbone and sulfide cleavages, and to provide better structural information than straightforward MS2 CTD, the CTnoD oxidized products were isolated and subjected to collisional activation at the MS3 level. The MS3 CTD/CID reaction effectively broke the disulfide linkages, separated the two chains, and yielded more structurally informative fragment ions within the inter-chain cyclic region. CTD also provided doubly oxidized intact product ions at the MS2 level, and resonance ejection of the singly oxidized product ion revealed that the doubly oxidized product originates directly from the isolated precursor ion and not from consecutive CTD reactions of a singly oxidized intermediate. MS4 experiments were employed to help identify potential radical cations and diradical cations, but the results were negative or inconclusive. Nonetheless, the two-electron oxidation process is a demonstration of the very large potential energy (>20 eV) available through CTD, and is a notable capability for a 3D ion trap platform.

  13. Evidence for a Proton Transfer Network and a Required Persulfide-Bond-Forming Cysteine Residue in Ni-Containing Carbon Monoxide Dehydrogenases

    International Nuclear Information System (INIS)

    Eun Jin Kim; Jian Feng; Bramlett, Matthew R.; Lindahl, Paul A.

    2004-01-01

    OAK-B135 Carbon monoxide dehydrogenase from Moorella thermoacetica catalyzes the reversible oxidation of CO to CO2 at a nickel-iron-sulfur active-site called the C-cluster. Mutants of a proposed proton transfer pathway and of a cysteine residue recently found to form a persulfide bond with the C-cluster were characterized. Four semi-conserved histidine residues were individually mutated to alanine. His116 and His122 were essential to catalysis, while His113 and His119 attenuated catalysis but were not essential. Significant activity was ''rescued'' by a double mutant where His116 was replaced by Ala and His was also introduced at position 115. Activity was also rescued in double mutants where His122 was replaced by Ala and His was simultaneously introduced at either position 121 or 123. Activity was also ''rescued'' by replacing His with Cys at position 116. Mutation of conserved Lys587 near the C-cluster attenuated activity but did not eliminate it. Activity was virtually abolished in a double mutant where Lys587 and His113 were both changed to Ala. Mutations of conserved Asn284 also attenuated activity. These effects suggest the presence of a network of amino acid residues responsible for proton transfer rather than a single linear pathway. The Ser mutant of the persulfide-forming Cys316 was essentially inactive and displayed no EPR signals originating from the C-cluster. Electronic absorption and metal analysis suggests that the C-cluster is absent in this mutant. The persulfide bond appears to be essential for either the assembly or stability of the C-cluster, and/or for eliciting the redox chemistry of the C-cluster required for catalytic activity

  14. Use of Proton-Transfer-Reaction Mass Spectrometry to Characterize Volatile Organic Compound Sources at the La Porte Super Site During the Texas Air Quality Study 2000

    Energy Technology Data Exchange (ETDEWEB)

    Karl, Thomas G.; Jobson, B Tom T.; Kuster, W. C.; Williams, Eric; Stutz, Jochen P.; Shetter, Rick; Hall, Samual R.; Goldan, P. D.; Fehsenfeld, Fred C.; Lindinger, Werner

    2003-08-19

    Proton-transfer-reaction mass spectrometry (PTR-MS) was deployed for continuous real-time monitoring of volatile organic compounds (VOCs) at a site near the Houston Ship Channel during the Texas Air Quality Study 2000. Overall, 28 ions dominated the PTR-MS mass spectra and were assigned as anthropogenic aromatics (e.g., benzene, toluene, xylenes) and hydrocarbons (propene, isoprene), oxygenated compounds (e.g., formaldehyde, acetaldehyde, acetone, methanol, C7 carbonyls), and three nitrogencontaining compounds (e.g., HCN, acetonitrile and acrylonitrile). Biogenic VOCs were minor components at this site. Propene was the most abundant lightweight hydrocarbon detected by this technique with concentrations up to 100+ nmol mol-1, and was highly correlated with its oxidation products, formaldehyde (up to ~40 nmol mol-1) and acetaldehyde (up to ~80 nmol/mol), with typical ratios close to 1 in propene-dominated plumes. In the case of aromatic species the high time resolution of the obtained data set helped in identifying different anthropogenic sources (e.g., industrial from urban emissions) and testing current emission inventories. A comparison with results from complimentary techniques (gas chromatography, differential optical absorption spectroscopy) was used to assess the selectivity of this on-line technique in a complex urban and industrial VOC matrix and give an interpretation of mass scans obtained by ‘‘soft’’ chemical ionization using proton-transfer via H3O+. The method was especially valuable in monitoring rapidly changing VOC plumes which passed over the site, and when coupled with meteorological data it was possible to identify likely sources.

  15. Treatment for the recoil effects of the multi-step heavy-ion nucleon transfers with the orthogonalized coupled-reaction-channel theory

    International Nuclear Information System (INIS)

    Misono, S.; Imanishi, B.

    1997-02-01

    We have investigated recoil effects in heavy-ion reactions for the nucleon transfers, and the validity of the spatially local approximation for the non-local transfer interaction defined by the orthogonalized coupled-reaction-channel (OCRC) theory. This approximation makes it easier to treat multi-step transfer processes with the coupled channel method and makes it possible to define the nucleon molecular orbitals with the inclusion of the recoil effects. The transfer interaction is expanded in a power series of the momentum operator, and is approximated by the first order term, i.e., the spatially local term. The numerical calculation for the core-symmetric systems 12 C+ 13 C and 16 O+ 17 O with this approximation shows that the recoil effects are well included in the results at energies lower than a few MeV/nucleon. Furthermore, the OCRC formalism allows us even to employ the complete no-recoil approximation for the calculation of cross sections, even though it is not adequate to use this approximation in the distorted wave Born approximation (DWBA) method. As to polarization, however, the no-recoil approximation is not good even in the OCRC formalism. We discuss the recoil effects on nucleon molecular-orbital states. It is shown that states of the covalent molecular orbitals of the valence (transferred) nucleon are little affected by the recoil effects, as already suggested by Korotky et al. in the full finite-range DWBA analysis of the transfer reaction, 13 C( 13 C, 12 C) 14 C. (author). 59 refs

  16. SU-E-T-515: Investigating the Linear Energy Transfer Dependency of Different PRESAGE Formulations in a Proton Beam

    Energy Technology Data Exchange (ETDEWEB)

    Carroll, M [University of Texas MD Anderson Cancer Center, Houston, TX (United States); Alqathami, M; Blencowe, A [The University of South Australia, South Australia, SA (Australia); Ibbott, G [UT MD Anderson Cancer Center, Houston, TX (United States)

    2015-06-15

    Purpose Previous studies have reported an under-response of PRESAGE in a proton beam as a Result of the extremely high LET in the distal end of the spread out Bragg peak (SOBP). This work is a preliminary investigation to quantify the effect of the formulation, specifically the concentration of halocarbon radical initiator relative to leuco dye, on radical recombination resulting in LET dependence. Methods The traditional PRESAGE formulation developed by Heuris Pharma was altered to constitute radical initiator concentrations of 5, 15, and 30% (low, medium, and high) by weight with all other components balanced to maintain proportionality. Chloroform was specifically examined in this study and all dosimeters were made in-house. Cylindrical PRESAGE dosimeters (3.5cm diameter and 6cm length) were made for each formulation and irradiated by a 200-MeV proton beam to 500 cGy across a 2cm SOBP. Dosimeters were read out using the DMOS optical-CT scanner. The dose distributions were analyzed and dose profiles were used to compare the relative dose response to find the stability across the high-LET region of the SOBP. LET dependence was measured by the variation to ion chamber measurements for the final 25% of the SOBP (∼0.5cm) prior to the distal-90 of each profile. Results Relative to ion chamber data, all PRESAGE dosimeters showed an under-response at the distal end of the SOBP. The medium concentration formulation matched most closely with an average 8.3% under-response closely followed by the low concentration at 12.2% and then the high concentration at 22.8%. In all three cases, the highest points of discrepancy were in the distal most regions. Conclusion The radical initiator concentration in PRESAGE can be tailored to reduce the LET dependence in a proton beam. This warrants further study to quantify comprehensively the effect of concentration of different halocarbon radical initiators on LET dependency. Grant number 5RO1CA100835.

  17. SU-E-T-515: Investigating the Linear Energy Transfer Dependency of Different PRESAGE Formulations in a Proton Beam

    International Nuclear Information System (INIS)

    Carroll, M; Alqathami, M; Blencowe, A; Ibbott, G

    2015-01-01

    Purpose Previous studies have reported an under-response of PRESAGE in a proton beam as a Result of the extremely high LET in the distal end of the spread out Bragg peak (SOBP). This work is a preliminary investigation to quantify the effect of the formulation, specifically the concentration of halocarbon radical initiator relative to leuco dye, on radical recombination resulting in LET dependence. Methods The traditional PRESAGE formulation developed by Heuris Pharma was altered to constitute radical initiator concentrations of 5, 15, and 30% (low, medium, and high) by weight with all other components balanced to maintain proportionality. Chloroform was specifically examined in this study and all dosimeters were made in-house. Cylindrical PRESAGE dosimeters (3.5cm diameter and 6cm length) were made for each formulation and irradiated by a 200-MeV proton beam to 500 cGy across a 2cm SOBP. Dosimeters were read out using the DMOS optical-CT scanner. The dose distributions were analyzed and dose profiles were used to compare the relative dose response to find the stability across the high-LET region of the SOBP. LET dependence was measured by the variation to ion chamber measurements for the final 25% of the SOBP (∼0.5cm) prior to the distal-90 of each profile. Results Relative to ion chamber data, all PRESAGE dosimeters showed an under-response at the distal end of the SOBP. The medium concentration formulation matched most closely with an average 8.3% under-response closely followed by the low concentration at 12.2% and then the high concentration at 22.8%. In all three cases, the highest points of discrepancy were in the distal most regions. Conclusion The radical initiator concentration in PRESAGE can be tailored to reduce the LET dependence in a proton beam. This warrants further study to quantify comprehensively the effect of concentration of different halocarbon radical initiators on LET dependency. Grant number 5RO1CA100835

  18. Redox modulation of flavin and tyrosine determines photoinduced proton-coupled electron transfer and photoactivation of BLUF photoreceptors

    NARCIS (Netherlands)

    Mathes, T.; van Stokkum, I.H.M.; Stierl, M.; Kennis, J.T.M.

    2012-01-01

    Photoinduced electron transfer in biological systems, especially in proteins, is a highly intriguing matter. Its mechanistic details cannot be addressed by structural data obtained by crystallography alone because this provides only static information on a given redox system. In combination with

  19. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Mechanisms behind the generation of protonated ions for polyaromatic hydrocarbons by atmospheric pressure photoionization.

    Science.gov (United States)

    Ahmed, Arif; Choi, Cheol Ho; Choi, Myoung Choul; Kim, Sunghwan

    2012-01-17

    In this study, the mechanism behind the generation of protonated polyaromatic hydrocarbon (PAH) ions without heteroatoms by atmospheric pressure photoionization (APPI) is investigated. Comparing data obtained by APPI of anthracene dissolved either in toluene or perdeuterated toluene suggests that toluene acts as a source of protons and that breakage of C-H bonds in the toluene molecule is important for the overall protonation reaction. Our data describing an Arrhenius-type temperature-dependent relationship between the signal intensities of molecular and protonated ions suggest a mechanistic relation between the generated molecular and protonated ions. The APPI protonation mechanism that best explains the observed phenomena is composed of two reactions: electron transfer followed by hydrogen transfer. This two-step mechanism for APPI was originally suggested by Syage (Syage, J. A. J. Am. Soc. Mass Spectrom. 2004, 15 , 1521-1533). Further quantum mechanical study shows that an energetically favorable ion-molecular complex can be generated as a result of electron transfer from toluene to PAH, which subsequently facilitates hydrogen transfer. This suggests that both electron transfer and hydrogen transfer can occur as a "concerted" reaction through the ion-molecular complex precursor state, which is consistent with experimental results. To our best knowledge, this is the first time that the dynamic nature of the APPI process is clearly revealed by combined experimental and quantum mechanical studies.

  1. Electron transfer to sulfides:

    International Nuclear Information System (INIS)

    Meneses, Ana Belen; Antonello, Sabrina; Arevalo, Maria Carmen; Maran, Flavio

    2005-01-01

    The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the C-S bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph 2 CH - . The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated C-S bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π* radical anions and those going through the intermediacy of loose σ* radical anions

  2. Experimental and Computational Studies of the Macrocyclic Effect of an Auxiliary Ligand on Electron and Proton Transfers Within Ternary Copper(II)-Histidine Complexes

    International Nuclear Information System (INIS)

    Song, Tao; Lam, Corey; Ng, Dominic C.; Orlova, G.; Laskin, Julia; Fang, De-Cai; Chu, Ivan K.

    2009-01-01

    The dissociation of [Cu II (L)His] -2+ complexes [L = diethylenetriamine (dien) or 1,4,7-triazacyclononane (9-aneN 3 )] bears a strong resemblance to the previously reported behavior of [Cu II (L)GGH] -2+ complexes. We have used low energy collision-induced dissociation experiments and density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level to study the macrocyclic effect of the auxiliary ligands on the formation of His -+ from prototypical [Cu II (L)His] -2+ systems. DFT revealed that the relative energy barriers of the same electron transfer (ET) dissociation pathways of [Cu II (9-aneN 3 )His] -2+ and [Cu II (dien)His] -2+ are very similar, with the ET reactions of [Cu II (9-aneN 3 )His] -2+ leading to the generation of two distinct His -+ species; in contrast, the proton transfer (PT) dissociation pathways of [Cu II (9-aneN 3 )His] -2+ and [Cu II (dien)His] -2+ differ considerably. The PT reactions of [Cu II (9-aneN 3 )His] -2+ are associated with substantially higher barriers (>13 kcal/mol) than those of [Cu II (dien)His] -2+ . Thus, the sterically encumbered auxiliary 9-aneN3 ligand facilitates ET reactions while moderating PT reactions, allowing the formation of hitherto non-observable histidine radical cations.

  3. Solvent effects on the excited-state double proton transfer mechanism in the 7-azaindole dimer: a TDDFT study with the polarizable continuum model.

    Science.gov (United States)

    Yu, Xue-Fang; Yamazaki, Shohei; Taketsugu, Tetsuya

    2017-08-30

    Solvent effects on the excited-state double proton transfer (ESDPT) mechanism in the 7-azaindole (7AI) dimer were investigated using the time-dependent density functional theory (TDDFT) method. Excited-state potential energy profiles along the reaction paths in a locally excited (LE) state and a charge transfer (CT) state were calculated using the polarizable continuum model (PCM) to include the solvent effect. A series of non-polar and polar solvents with different dielectric constants were used to examine the polarity effect on the ESDPT mechanism. The present results suggest that in a non-polar solvent and a polar solvent with a small dielectric constant, ESDPT follows a concerted mechanism, similar to the case in the gas phase. In a polar solvent with a relatively large dielectric constant, however, ESDPT is likely to follow a stepwise mechanism via a stable zwitterionic intermediate in the LE state on the adiabatic potential energy surface, although inclusion of zero-point vibrational energy (ZPE) corrections again suggests the concerted mechanism. In the meantime, the stepwise reaction path involving the CT state with neutral intermediates is also examined, and is found to be less competitive than the concerted or stepwise path in the LE state in both non-polar and polar solvents. The present study provides a new insight into the experimental controversy of the ESDPT mechanism of the 7AI dimer in a solution.

  4. Dissociation of protonated N-(3-phenyl-2H-chromen-2-ylidene)-benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer.

    Science.gov (United States)

    Wang, Shanshan; Dong, Cheng; Yu, Lian; Guo, Cheng; Jiang, Kezhi

    2016-01-15

    In the tandem mass spectrometry of protonated N-(3-phenyl-2H-chromen-2-ylidene)benzenesulfonamides, the precursor ions have been observed to undergo gas-phase dissociation via two competing channels: (a) the predominant channel involves migration of the sulfonyl cation to the phenyl C atom and the subsequent loss of benzenesulfinic acid along with cyclization reaction, and (b) the minor one involves dissociation of the precursor ion to give an ion/neutral complex of [sulfonyl cation/imine], followed by decomposition to afford sulfonyl cation or the INC-mediated electron transfer to give an imine radical cation. The proposed reaction channels have been supported by theoretical calculations and D-labeling experiments. The gas-phase cyclization reaction originating from the N- to C-sulfonyl cation transfer has been first reported to the best of our knowledge. For the substituted sulfonamides, the presence of electron-donating groups (R(2) -) at the C-ring effectively facilitates the reaction channel of cyclization reaction, whereas that of electron-withdrawing groups inhibits this pathway. Copyright © 2015 John Wiley & Sons, Ltd.

  5. Experimental and quantum chemical studies of a new organic proton transfer compound, 1H-imidazole-3-ium-3-hydroxy-2,4,6-trinitrophenolate

    Science.gov (United States)

    Dhamodharan, P.; Sathya, K.; Dhandapani, M.

    2018-02-01

    A new proton transfer compound, 1H-imidazole-3-ium-3-hydroxy-2,4,6-trinitrophenolate (IMHTP), was crystallized by slow evaporation-solution growth technique. 1H and 13C NMR spectral studies confirm the molecular structure of the grown crystal. Single crystal X-ray diffraction study confirms that IMHTP crystallizes in monoclinic system with space group P21/c. Thermal curves (TG/DTA) show that the material is thermally stable up to 198 °C. The crystal emits fluorescence at 510 nm, proving its utility in making green light emitting materials in optical applications. The stable molecular structure was optimized by Gaussian 09 program with B3LYP/6-311++G(d,p) level of basis set. The frontier molecular orbital study shows that the charge transfer interaction occurs within the complex. The calculated first-order hyperpolarizability value of IMHTP is 44 times higher than that the reference material, urea. The electrostatic potential map was used to probe into electrophilic and nucleophilic reactive sites present in the molecule.

  6. TRANSFER

    African Journals Online (AJOL)

    This paper reports on further studies on long range energy transfer between curcumine as donor and another thiazine dye, thionine, which is closely related to methylene blue as energy harvester (Figure 1). Since thionine is known to have a higher quantum yield of singlet oxygen sensitization than methylene blue [8], it is ...

  7. Conductive scanning probe microscopy of the semicontinuous gold film and its SERS enhancement toward two-step photo-induced charge transfer and effect of the supportive layer

    Science.gov (United States)

    Sinthiptharakoon, K.; Sapcharoenkun, C.; Nuntawong, N.; Duong, B.; Wutikhun, T.; Treetong, A.; Meemuk, B.; Kasamechonchung, P.; Klamchuen, A.

    2018-05-01

    The semicontinuous gold film, enabling various electronic applications including development of surface-enhanced Raman scattering (SERS) substrate, is investigated using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM) to reveal and investigate local electronic characteristics potentially associated with SERS generation of the film material. Although the gold film fully covers the underlying silicon surface, CAFM results reveal that local conductivity of the film is not continuous with insulating nanoislands appearing throughout the surface due to incomplete film percolation. Our analysis also suggests the two-step photo-induced charge transfer (CT) play the dominant role in the enhancement of SERS intensity with strong contribution from free electrons of the silicon support. Silicon-to-gold charge transport is illustrated by KPFM results showing that Fermi level of the gold film is slightly inhomogeneous and far below the silicon conduction band. We propose that inhomogeneity of the film workfunction affecting chemical charge transfer between gold and Raman probe molecule is associated with the SERS intensity varying across the surface. These findings provide deeper understanding of charge transfer mechanism for SERS which can help in design and development of the semicontinuous gold film-based SERS substrate and other electronic applications.

  8. 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.

  9. Using interlayer step-wise triplet transfer to achieve an efficient white organic light-emitting diode with high color-stability

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qi [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China); Department of Electrical Engineering and Computer Sciences, College of Engineering, South Dakota State University, Brookings, South Dakota 57007 (United States); Ma, Dongge, E-mail: mdg1014@ciac.jl.cn; Ding, Junqiao; Wang, Lixiang [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China); Leo, Karl [Tech. Univ. Dresden, Inst. Angew. Photophys., D-01062 Dresden (Germany); Qiao, Qiquan [Department of Electrical Engineering and Computer Sciences, College of Engineering, South Dakota State University, Brookings, South Dakota 57007 (United States); Jia, Huiping; Gnade, Bruce E. [Department of Materials Science and Engineering and Erik Jonsson School of Engineering and Computer Science, University of Texas at Dallas, Richardson, Texas 75083 (United States)

    2014-05-12

    An efficient phosphorescent white organic light emitting-diode with a red-green-blue tri-emitting-layer structure is reported. The host of the red dopant possesses a lower triplet-energy than the green dye. An interlayer step-wise triplet transfer via blue dye → green dye → red host → red dye is achieved. This mechanism allows an efficient triplet harvesting by the three dopants, thus maintaining a balanced white light and reducing energy loss. Moreover, the color stability of the device is improved significantly. The white device not only achieves a peak external quantum efficiency of 21.1 ± 0.8% and power efficiency of 37.5 ± 1.4 lm/W but shows no color shift over a wide range of voltages.

  10. At the centennial of Michaelis and Menten, competing Michaelis-Menten steps explain effect of GLP-1 on blood-brain transfer and metabolism of glucose.

    Science.gov (United States)

    Gejl, Michael; Rungby, Jørgen; Brock, Birgitte; Gjedde, Albert

    2014-08-01

    Glucagon-like peptide-1 (GLP-1) is a potent insulinotropic incretin hormone with both pancreatic and extrapancreatic effects. Studies of GLP-1 reveal significant effects in regions of brain tissue that regulate appetite and satiety. GLP-1 mimetics are used for the treatment of type 2 diabetes mellitus. GLP-1 interacts with peripheral functions in which the autonomic nervous system plays an important role, and emerging pre-clinical findings indicate a potential neuroprotective role of the peptide, for example in models of stroke and in neurodegenerative disorders. A century ago, Leonor Michaelis and Maud Menten described the steady-state enzyme kinetics that still apply to the multiple receptors, transporters and enzymes that define the biochemical reactions of the brain, including the glucose-dependent impact of GLP-1 on blood-brain glucose transfer and metabolism. This MiniReview examines the potential of GLP-1 as a molecule of interest for the understanding of brain energy metabolism and with reference to the impact on brain metabolism related to appetite and satiety regulation, stroke and neurodegenerative disorders. These effects can be understood only by reference to the original formulation of the Michaelis-Menten equation as applied to a chain of kinetically controlled steps. Indeed, the effects of GLP-1 receptor activation on blood-brain glucose transfer and brain metabolism of glucose depend on the glucose concentration and relative affinities of the steps both in vitro and in vivo, as in the pancreas. © 2014 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

  11. The role of the C8 proton of ATP in the regulation of phosphoryl transfer within kinases and synthetases

    Directory of Open Access Journals (Sweden)

    Nkosi Thokozani C

    2011-07-01

    Full Text Available Abstract Background The kinome comprises functionally diverse enzymes, with the current classification indicating very little about the extent of conserved regulatory mechanisms associated with phosphoryl transfer. The apparent Km of the kinases ranges from less than 0.4 μM to in excess of 1000 μM for ATP. It is not known how this diverse range of enzymes mechanistically achieves the regulation of catalysis via an affinity range for ATP varying by three-orders of magnitude. Results We have demonstrated a previously undiscovered mechanism in kinase and synthetase enzymes where the overall rate of reaction is regulated via the C8-H of ATP. Using ATP deuterated at the C8 position (C8D-ATP as a molecular probe it was shown that the C8-H plays a direct role in the regulation of the overall rate of reaction in a range of kinase and synthetase enzymes. Using comparative studies on the effect of the concentration of ATP and C8D-ATP on the activity of the enzymes we demonstrated that not only did C8D-ATP give a kinetic isotope effect (KIE but the KIE's obtained are clearly not secondary KIE effects as the magnitude of the KIE in all cases was at least 2 fold and in most cases in excess of 7 fold. Conclusions Kinase and synthetase enzymes utilise C8D-ATP in preference to non-deuterated ATP. The KIE obtained at low ATP concentrations is clearly a primary KIE demonstrating strong evidence that the bond to the isotopically substituted hydrogen is being broken. The effect of the ATP concentration profile on the KIE was used to develop a model whereby the C8H of ATP plays a role in the overall regulation of phosphoryl transfer. This role of the C8H of ATP in the regulation of substrate binding appears to have been conserved in all kinase and synthetase enzymes as one of the mechanisms associated with binding of ATP. The induction of the C8H to be labile by active site residues coordinated to the ATP purine ring may play a significant role in explaining the

  12. Fluorescence quenching of derivatives of anthracene by organic electron donors and acceptors in acetonitrile. Electron and proton transfer mechanism

    Science.gov (United States)

    Mac, Marek; Najbar, Jan; Wirz, Jakob

    1995-03-01

    Fluorescence quenching of anthracene derivatives by organic electron donors (amines) and acceptors was investigated using stationary fluorescence measurements. The dependence of log( kq) on Δ Get shows Rehm-Weller-type behavior. The formation of anion radicals of anthracene, bianthryl, and 9-cyanoanthracene was detected by flash photolysis in systems containing aromatic amines (aniline, 2-bromoaniline, 4-bromoaniline, N,N-dimethylaniline, 4-bromo-N,N-dimethylaniline, N,N-diethylaniline, and 1,4-diazabicyclo[2.2.2]octane). The radical yields decreased and triplet yields increased when bromo derivatives of amines were used as donor quenchers, indicating the heavy-atom effect on spin conversion within radical pairs. The importance of the heavy-atom effect decreased when the energy gap between the charge transfer and molecular triplet states was small. The formation of separated radicals decreased when primary amines were used as quenchers which indicated the existence of an additional path of deactivation of the radical pair. The behavior of amines as quenchers of bianthryl and anthracene is compared with that of inorganic anion quenchers.

  13. Spectra of the linear energy transfer measured with a track etch spectrometer in the beam of 1 GeV protons and the contribution of secondary charged particles to the dose

    International Nuclear Information System (INIS)

    Spurny, F.; Vlcek, B.; Bamblevskij, V.P.; Timoshenko, G.N.

    1999-01-01

    A spectrometer of the linear energy transfer (LET) on the base of CR-39 detector was used to establish the spectra of LET in the beam of protons with the primary energy of 1 GeV. It was found out that the LET spectra of secondary charged particles between 100 and 7000 MeV cm 2 g -1 do not depend on the radiator. The average quality factors for the LET region mentioned were obtained about 11.6 with ICRP 26 quality factors and about 14.0 with ICRP 60 quality factors. The spectra obtained permitted to calculate the contributions of these secondary charged particles to the dosimetric quantities. It was observed that these contributions were about 7.0% for the total absorbed dose of protons and close 90% in the case of the equivalent doses. It is more than it was found out for few hundred MeV protons

  14. Solvent effect on the intermolecular proton transfer of the Watson and Crick guanine-cytosine and adenine-thymine base pairs: a polarizable continuum model study.

    Science.gov (United States)

    Romero, Eduardo E; Hernandez, Florencio E

    2018-01-03

    Herein we present our results on the study of the double proton transfer (DPT) mechanism in the adenine-thymine (AT) and guanine-cytosine (GC) base pairs, both in gas phase and in solution. The latter was modeled using the polarizable continuum method (PCM) in different solvents. According to our DFT calculations, the DPT may occur for both complexes in a stepwise mechanism in condensate phase. In gas phase only the GC base pair exhibits a concerted DPT mechanism. Using the Wigner's tunneling corrections to the transition state theory we demonstrate that such corrections are important for the prediction of the rate constants of both systems in gas and in condensate phase. We also show that (i) as the polarity of the medium decreases the equilibrium constant of the DPT reaction increases in both complexes, and (ii) that the equilibrium constant in the GC complex is four orders of magnitude larger than in AT. This observation suggests that the spontaneous mutations in DNA base pairs are more probable in GC than in AT.

  15. Proton transfer dynamics in a polar nanodroplet: ESIPT of 4'-n,n-dimethylamino-3-hydroxyflavone in AOT/alkane/water reverse micelles

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Deborin [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India); Batuta, Shaikh; Begum, Naznin Ara [Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235 (India); Mandal, Debabrata, E-mail: dmandal.chemistry@gmail.com [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India)

    2017-04-15

    The excited state intramolecular proton transfer (ESIPT) of the well-known fluorophore 4'-N,N-Dimethylamino-3-hydroxyflavone (DMA3HF) was studied in AOT/n-heptane/water reverse micelle solutions. For DMA3HF molecules located inside the AOT encapsulated polar nanodroplets, ESIPT from excited enol (E*) to tautomer (T*) forms was markedly inhibited, yielding time-constants of ≥100 ps, and followed the same trend as solvent relaxation when the ratio W= [H{sub 2}O]/[AOT] was varied. At W=0, the DMA3HF molecules were attached to the ionic AOT headgroups via strong intermolecular H-bonding, which hindered ESIPT. Addition of water changes the situation radically: water molecules form stronger H-bonds with AOT headgroups, displacing the DMA3HF, which are instead engaged in intermolecular H-bonded complexes of the type [DMA3HF···water]. ESIPT of these complex-bound fluorophores involves substantial rearrangement of H-bonding, and is coupled to solvation dynamics. With increasing W-value, solvation becomes faster, and so does ESIPT, reducing the yield of E* species. At the same time, the local environment within the nanodroplets become more more polar with gradual accumulation of water, which causes a monotonic red-shift of the E* emission peak.

  16. Effects of airflow on odorants' emissions in a model pig house — A laboratory study using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Saha, Chayan Kumer; Feilberg, Anders; Zhang, Guoqiang; Adamsen, Anders Peter S.

    2011-01-01

    Identification of different factors that affect emissions of gasses, including volatile organic compounds (VOCs) is necessary to develop emission abatement technology. The objectives of this research were to quantify and study temporal variation of gas emissions from a model pig house under varying ventilation rates. The used model was a 1:12.5 scale of a section of a commercial finishing pig house. The VOC concentrations at inlet, outlet, and slurry pit of the model space were measured using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). PTR-MS can measure the temporal variations of odor compounds' emission from the slurry pit in real time. The emissions of H 2 S and 14 VOCs were lower compared to real pig buildings except for ammonia, which indicated possible other sources of those compounds than the slurry in the slurry pit. The ventilation rate affected significantly on ammonia and trimethylamine emission (p 2 S) emission was independent of the ventilation rate. VFAs' emission dependency on ventilation rate increased with the increase of carbon chain. Phenols, indoles and ketones showed the positive correlation with ventilation rate to some extent. Generally, compounds with high solubility (low Henry's constant) showed stronger correlation with ventilation rates than the compounds with high Henry's constant.

  17. Direct sampling of sub-µm atmospheric particulate organic matter in sub-ng m-3 mass concentrations by proton-transfer-reaction mass spectrometry

    Science.gov (United States)

    Armin, W.; Mueller, M.; Klinger, A.; Striednig, M.

    2017-12-01

    A quantitative characterization of the organic fraction of atmospheric particulate matter is still challenging. Herein we present the novel modular "Chemical Analysis of Aerosol Online" (CHARON) particle inlet system coupled to a new-generation proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF 6000 X2, Ionicon Analytik, Austria) that quantitatively detects organic analytes in real-time and sub-pptV levels by chemical ionization with hydronium reagent ions. CHARON consists of a gas-phase denuder for stripping off gas-phase analytes (efficiency > 99.999%), an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. With typical particle enrichment factors of around 30 for particle diameters (DP) between 120 nm and 1000 nm (somewhat reduced enrichment for 60 nm 6000) and excellent mass accuracies (< 10 ppm) chemical compositions can be assigned and included in further analyses. In addition to a detailed characterization of the CHARON PTR-TOF 6000 X2 we will present first results on the chemical composition of sub-µm particulate organic matter in the urban atmosphere in Innsbruck (Austria).

  18. Amide proton transfer imaging to discriminate between low- and high-grade gliomas: added value to apparent diffusion coefficient and relative cerebral blood volume

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yoon Seong; Ahn, Sung Soo; Lee, Seung-Koo [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, College of Medicine, Seoul (Korea, Republic of); Chang, Jong Hee; Kang, Seok-Gu [Yonsei University College of Medicine, Department of Neurosurgery, Seoul (Korea, Republic of); Kim, Se Hoon [Yonsei University College of Medicine, Department of Pathology, Seoul (Korea, Republic of); Zhou, Jinyuan [Johns Hopkins University School of Medicine, Division of MRI Research, Department of Radiology, Baltimore, MD (United States)

    2017-08-15

    To evaluate the added value of amide proton transfer (APT) imaging to the apparent diffusion coefficient (ADC) from diffusion tensor imaging (DTI) and the relative cerebral blood volume (rCBV) from perfusion magnetic resonance imaging (MRI) for discriminating between high- and low-grade gliomas. Forty-six consecutive adult patients with diffuse gliomas who underwent preoperative APT imaging, DTI and perfusion MRI were enrolled. APT signals were compared according to the World Health Organization grade. The diagnostic ability and added value of the APT signal to the ADC and rCBV for discriminating between low- and high-grade gliomas were evaluated using receiver operating characteristic (ROC) analyses and integrated discrimination improvement. The APT signal increased as the glioma grade increased. The discrimination abilities of the APT, ADC and rCBV values were not significantly different. Using both the APT signal and ADC significantly improved discrimination vs. the ADC alone (area under the ROC curve [AUC], 0.888 vs. 0.910; P = 0.007), whereas using both the APT signal and rCBV did not improve discrimination vs. the rCBV alone (AUC, 0.927 vs. 0.923; P = 0.222). APT imaging may be a useful imaging biomarker that adds value to the ADC for discriminating between low- and high-grade gliomas. (orig.)

  19. Real-time analysis of organic compounds in ship engine aerosol emissions using resonance-enhanced multiphoton ionisation and proton transfer mass spectrometry.

    Science.gov (United States)

    Radischat, Christian; Sippula, Olli; Stengel, Benjamin; Klingbeil, Sophie; Sklorz, Martin; Rabe, Rom; Streibel, Thorsten; Harndorf, Horst; Zimmermann, Ralf

    2015-08-01

    Organic combustion aerosols from a marine medium-speed diesel engine, capable to run on distillate (diesel fuel) and residual fuels (heavy fuel oil), were investigated under various operating conditions and engine parameters. The online chemical characterisation of the organic components was conducted using a resonance-enhanced multiphoton ionisation time-of-flight mass spectrometer (REMPI TOF MS) and a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS). Oxygenated species, alkenes and aromatic hydrocarbons were characterised. Especially the aromatic hydrocarbons and their alkylated derivatives were very prominent in the exhaust of both fuels. Emission factors of known health-hazardous compounds (e.g. mono- and poly-aromatic hydrocarbons) were calculated and found in higher amounts for heavy fuel oil (HFO) at typical engine loadings. Lower engine loads lead in general to increasing emissions for both fuels for almost every compound, e.g. naphthalene emissions varied for diesel fuel exhaust between 0.7 mg/kWh (75 % engine load, late start of injection (SOI)) and 11.8 mg/kWh (10 % engine load, late SOI) and for HFO exhaust between 3.3 and 60.5 mg/kWh, respectively. Both used mass spectrometric techniques showed that they are particularly suitable methods for online monitoring of combustion compounds and very helpful for the characterisation of health-relevant substances. Graphical abstract Three-dimensional REMPI data of organic species in diesel fuel and heavy fuel oil exhaust.

  20. Applying Amide Proton Transfer MR Imaging to Hybrid Brain PET/MR: Concordance with Gadolinium Enhancement and Added Value to [18F]FDG PET.

    Science.gov (United States)

    Sun, Hongzan; Xin, Jun; Zhou, Jinyuan; Lu, Zaiming; Guo, Qiyong

    2018-06-01

    The purpose of this study is to evaluate the diagnostic concordance and metric correlations of amide proton transfer (APT) imaging with gadolinium-enhanced magnetic resonance imaging (MRI) and 2-deoxy-2-[ 18 F-]fluoro-D-glucose ([ 18 F]FDG) positron emission tomography (PET), using hybrid brain PET/MRI. Twenty-one subjects underwent brain gadolinium-enhanced [ 18 F]FDG PET/MRI prospectively. Imaging accuracy was compared between unenhanced MRI, MRI with enhancement, APT-weighted (APTW) images, and PET based on six diagnostic criteria. Among tumors, the McNemar test was further used for concordance assessment between gadolinium-enhanced imaging, APT imaging, and [ 18 F]FDG PET. As well, the relation of metrics between APT imaging and PET was analyzed by the Pearson correlation analysis. APT imaging and gadolinium-enhanced MRI showed superior and similar diagnostic accuracy. APTW signal intensity and gadolinium enhancement were concordant in 19 tumors (100 %), while high [ 18 F]FDG avidity was shown in only 12 (63.2 %). For the metrics from APT imaging and PET, there was significant correlation for 13 hypermetabolic tumors (P PET in the evaluation of tumor metabolic activity during brain PET/MR studies.

  1. Grading diffuse gliomas without intense contrast enhancement by amide proton transfer MR imaging: comparisons with diffusion- and perfusion-weighted imaging

    Energy Technology Data Exchange (ETDEWEB)

    Togao, Osamu; Hiwatashi, Akio; Yamashita, Koji; Kikuchi, Kazufumi; Honda, Hiroshi [Kyushu University, Department of Clinical Radiology, Graduate School of Medical Sciences, Fukuoka (Japan); Keupp, Jochen [Philips Research, Hamburg (Germany); Yoshimoto, Koji; Kuga, Daisuke; Iihara, Koji [Kyushu University, Department of Neurosurgery, Graduate School of Medical Sciences, Fukuoka (Japan); Yoneyama, Masami [Philips Electronics Japan, Tokyo (Japan); Suzuki, Satoshi O.; Iwaki, Toru [Kyushu University, Department of Neuropathology, Graduate School of Medical Sciences, Fukuoka (Japan); Takahashi, Masaya [Advanced Imaging Research Center, UT Southwestern Medical Center, Dallas, TX (United States)

    2017-02-15

    To investigate whether amide proton transfer (APT) MR imaging can differentiate high-grade gliomas (HGGs) from low-grade gliomas (LGGs) among gliomas without intense contrast enhancement (CE). This retrospective study evaluated 34 patients (22 males, 12 females; age 36.0 ± 11.3 years) including 20 with LGGs and 14 with HGGs, all scanned on a 3T MR scanner. Only tumours without intense CE were included. Two neuroradiologists independently performed histogram analyses to measure the 90th-percentile (APT{sub 90}) and mean (APT{sub mean}) of the tumours' APT signals. The apparent diffusion coefficient (ADC) and relative cerebral blood volume (rCBV) were also measured. The parameters were compared between the groups with Student's t-test. Diagnostic performance was evaluated with receiver operating characteristic (ROC) analysis. The APT{sub 90} (2.80 ± 0.59 % in LGGs, 3.72 ± 0.89 in HGGs, P = 0.001) and APT{sub mean} (1.87 ± 0.49 % in LGGs, 2.70 ± 0.58 in HGGs, P = 0.0001) were significantly larger in the HGGs compared to the LGGs. The ADC and rCBV values were not significantly different between the groups. Both the APT{sub 90} and APT{sub mean} showed medium diagnostic performance in this discrimination. APT imaging is useful in discriminating HGGs from LGGs among diffuse gliomas without intense CE. (orig.)

  2. Synthesis, crystal growth and characterization of bioactive material: 2-amino-1H-benzo[d]imidazol-3-ium salicylate single crystal-a proton transfer molecular complex

    Science.gov (United States)

    Fathima, K. Saiadali; Anitha, K.

    2017-05-01

    The 1:1 molecular adducts 2-aminobenzimidazolium salicylate (ABIS) single crystal was synthesized and grown from 2-aminobenzimidazole (ABI) as a donor and salicylic acid (SA) as an acceptor. The cell parameter was determined using single crystal X-Ray diffraction method and the complex ABIS belongs to monoclinic system. The spectroscopic studies showed that ABIS crystal was an ion pair complex. The FTIR and Raman spectra showed that the presence of O-H, C=N, C=O vibration which confirms the proton transfer from SA to ABI. The UV-Vis spectrum exhibited a visible band at 359nm for ABIS due to the salicylate anion of the molecule. Further the antimicrobial activity of ABIS complex against Staphylococcus aureus, klebsiella pneumonia, Pseudomonas eruginos and E.coli pathogens was investigated. So the complex molecule inhibits both Gram positive and Gram negative bacterial. It is found that benzimidazole with aminogroup at position 2 increases the general antimicrobial activities of ABIS crystal.

  3. Excited-state proton transfer in confined medium. 4-methyl-7-hydroxyflavylium and β-naphthol incorporated in cucurbit[7]uril.

    Science.gov (United States)

    Basílio, Nuno; Laia, César A T; Pina, Fernando

    2015-02-12

    Excited-state proton transfer (ESPT) was studied by fluorescent emission using a mathematical model recast from the Weller theory. The titration curves can be fitted with three parameters: pK(a) (acidity constant of the ground sate), pK(ap)* (apparent acidity constant of the excited state), and η(A*), the efficiency of excited base formation from the excited acid. β-Naphthol and 4-metyhl-7-hydroxyflavylium were studied in aqueous solution and upon incorporation in cucurbit[7]uril. For all the compounds studied the interaction with the host leads to 1:1 adducts and the ground-state pK(a) increases upon incorporation. Whereas the ESPT of 4-methyl-7-hydroxyflavylium practically does not change in the presence of the host, in the case of β-naphthol it is prevented and the fluorescence emission titration curves are coincident with those taken by absorption. The position of the guest inside the host was investigated by NMR experiments and seems to determine the efficiency of the ESPT. The ESPT decreases for the guest, exhibiting a great protection of the phenol to the bulk water interaction.

  4. Investigation of the aroma of commercial peach (Prunus persica L. Batsch) types by Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and sensory analysis.

    Science.gov (United States)

    Bianchi, Tiago; Weesepoel, Yannick; Koot, Alex; Iglesias, Ignasi; Eduardo, Iban; Gratacós-Cubarsí, Marta; Guerrero, Luis; Hortós, Maria; van Ruth, Saskia

    2017-09-01

    The aim of this study was to investigate the aroma and sensory profiles of various types of peaches (Prunus persica L. Batsch.). Forty-three commercial cultivars comprising peaches, flat peaches, nectarines, and canning peaches (pavías) were grown over two consecutive harvest years. Fruits were assessed for chemical aroma and sensory profiles. Chemical aroma profile was obtained by proton transfer reaction-mass spectrometry (PTR-MS) and spectral masses were tentatively identified with PTR-Time of Flight-MS (PTR-Tof-MS). Sensory analysis was performed at commercial maturity considering seven aroma/flavor attributes. The four types of peaches showed both distinct chemical aroma and sensory profiles. Flat peaches and canning peaches showed most distinct patterns according to discriminant analysis. The sensory data were related to the volatile compounds by partial least square regression. γ-Hexalactone, γ-octalactone, hotrienol, acetic acid and ethyl acetate correlated positively, and benzeneacetaldehyde, trimethylbenzene and acetaldehyde negatively to the intensities of aroma and ripe fruit sensory scores. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Real-time monitoring of respiratory absorption factors of volatile organic compounds in ambient air by proton transfer reaction time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhonghui [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Yanli [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Yan, Qiong [Department of Respiratory Diseases, Guangzhou No. 12 People' s Hospital, Guangzhou 510620 (China); Zhang, Zhou [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Wang, Xinming, E-mail: wangxm@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China)

    2016-12-15

    Respiratory absorption factors (AFs) are essential parameters in the evaluation of human health risks from toxic volatile organic compounds (VOCs) in ambient air. A method for the real time monitoring of VOCs in inhaled and exhaled air by proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) has been developed to permit the calculation of respiratory AFs of VOCs. Isoprene was found to be a better breath tracer than O{sub 2}, CO{sub 2}, humidity, or acetone for distinguishing between the expiratory and inspiratory phases, and a homemade online breath sampling device with a buffer tube was used to optimize signal peak shapes. Preliminary tests with seven subjects exposed to aromatic hydrocarbons in an indoor environment revealed mean respiratory AFs of 55.0%, 55.9%, and 66.9% for benzene, toluene, and C8-aromatics (ethylbenzene and xylenes), respectively. These AFs were lower than the values of 90% or 100% used in previous studies when assessing the health risks of inhalation exposure to hazardous VOCs. The mean respiratory AFs of benzene, toluene and C8-aromatics were 66.5%, 70.2% and 82.3% for the three female subjects; they were noticeably much higher than that of 46.4%, 45.2% and 55.3%, respectively, for the four male subjects.

  6. External Electric Field Effects on Excited-State Intramolecular Proton Transfer in 4'-N,N-Dimethylamino-3-hydroxyflavone in Poly(methyl methacrylate) Films.

    Science.gov (United States)

    Furukawa, Kazuki; Hino, Kazuyuki; Yamamoto, Norifumi; Awasthi, Kamlesh; Nakabayashi, Takakazu; Ohta, Nobuhiro; Sekiya, Hiroshi

    2015-09-17

    The external electric field effects on the steady-state electronic spectra and excited-state dynamics were investigated for 4'-N,N-(dimethylamino)-3-hydroxyflavone (DMHF) in a poly(methyl methacrylate) (PMMA) film. In the steady-state spectrum, dual emission was observed from the excited states of the normal (N*) and tautomer (T*) forms. Application of an external electric field of 1.0 MV·cm(-1) enhanced the N* emission and reduced the T* emission, indicating that the external electric field suppressed the excited-state intramolecular proton transfer (ESIPT). The fluorescence decay profiles were measured for the N* and T* forms. The change in the emission intensity ratio N*/T* induced by the external electric field is dominated by ESIPT from the Franck-Condon excited state of the N* form and vibrational cooling in potential wells of the N* and T* forms occurring within tens of picoseconds. Three manifolds of fluorescent states were identified for both the N* and T* forms. The excited-state dynamics of DMHF in PMMA films has been found to be very different from that in solution due to intermolecular interactions in a rigid environment.

  7. Probing Proton Spin Structure: A Measurement of g2 at Four-momentum Transfer of 2 to 6 GeV2

    Energy Technology Data Exchange (ETDEWEB)

    Maxwell, James [Univ. of Virginia, Charlottesville, VA (United States); Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

    2011-12-01

    The Spin Asymmetries of the Nucleon Experiment investigated the spin structure of the proton via inclusive electron scattering at the Continuous Electron Beam Accelerator Facility at Jefferson Laboratory in Newport News, VA. A double-polarization measurement of polarized asymmetries was performed using the University of Virginia solid polarized ammonia target with target polarization aligned longitudinal and near transverse to the electron beam, allowing the extraction of the spin asymmetries A1 and A2, and spin structure functions g1 and g2. Polarized electrons of energies of 4.7 and 5.9 GeV were scattered to be viewed by a novel, non-magnetic array of detectors observing a four-momentum transfer range of 2 to 6 GeV2. This document addresses the extraction of the spin asymmetries and spin structure functions, with a focus on spin structure function g2, which we have measured as a function of x and W in four Q2 bins.

  8. Annular convective-radiative fins with a step change in thickness, and temperature-dependent thermal conductivity and heat transfer coefficient

    Science.gov (United States)

    Barforoush, M. S. M.; Saedodin, S.

    2018-01-01

    This article investigates the thermal performance of convective-radiative annular fins with a step reduction in local cross section (SRC). The thermal conductivity of the fin's material is assumed to be a linear function of temperature, and heat transfer coefficient is assumed to be a power-law function of surface temperature. Moreover, nonzero convection and radiation sink temperatures are included in the mathematical model of the energy equation. The well-known differential transformation method (DTM) is used to derive the analytical solution. An exact analytical solution for a special case is derived to prove the validity of the obtained results from the DTM. The model provided here is a more realistic representation of SRC annular fins in actual engineering practices. Effects of many parameters such as conduction-convection parameters, conduction-radiation parameter and sink temperature, and also some parameters which deal with step fins such as thickness parameter and dimensionless parameter describing the position of junction in the fin on the temperature distribution of both thin and thick sections of the fin are investigated. It is believed that the obtained results will facilitate the design and performance evaluation of SRC annular fins.

  9. FT-IR spectroelectrochemical study of the reduction of 1,4-dinitrobenzene on Au electrode: Hydrogen bonding and protonation in proton donor mixed media

    International Nuclear Information System (INIS)

    Tian Dexiang; Jin Baokang

    2011-01-01

    Highlights: → 1,4-Dinitrobenzene electrochemical reduction on the Au electrode is explored. → Radical anion (PNB· - ) is found both in aprotic media and in proton donors mixed media. → The H-bonding forming between PNB· - , PNB 2- and proton donors in low donors concentration. → The protonation of PNB 2- occurs in high concentration proton donor mixed media. - Abstract: The electrochemical behavior of 1,4-dinitrobenzene (1,4-PNB) on the Au electrode was investigated by cyclic voltammetry (CV), in situ FT-IR spectroelectrochemistry, cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. In aprotic media, 1,4-dinitrobenzene is reversibly reduced in two-step one-electron transfer. A series of IR absorption bands at 1056, 1210, 1341, 1356, 1464 and 1549 cm -1 , tracing to PNB; PNB· - and PNB 2- are observed. In the presence of proton donors mixed media, with increasing concentrations of proton donors, hydrogen-bonding and protonation process are found successively. The values of combining proton donors with per PNB 2- to form hydrogen-bonding are estimated by using electrochemical parameters. The result of forming aromatic nitroso compound is supported by tracing the change of IR absorption bands at 1149 and 1587 cm -1 at high concentration of proton donors. Based on CVA and DCVA techniques, it is clearly distinguished that the mechanisms of electrochemical reduction of PNB are elaborated in different systems.

  10. Out-and-back {sup 13}C-{sup 13}C scalar transfers in protein resonance assignment by proton-detected solid-state NMR under ultra-fast MAS

    Energy Technology Data Exchange (ETDEWEB)

    Barbet-Massin, Emeline; Pell, Andrew J. [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France); Jaudzems, Kristaps [Latvian Institute of Organic Synthesis (Latvia); Franks, W. Trent; Retel, Joren S. [Leibniz-Institut fuer Molekulare Pharmakologie (Germany); Kotelovica, Svetlana; Akopjana, Inara; Tars, Kaspars [Biomedical Research and Study Center (Latvia); Emsley, Lyndon [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France); Oschkinat, Hartmut [Leibniz-Institut fuer Molekulare Pharmakologie (Germany); Lesage, Anne; Pintacuda, Guido, E-mail: guido.pintacuda@ens-lyon.fr [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France)

    2013-08-15

    We present here {sup 1}H-detected triple-resonance H/N/C experiments that incorporate CO-CA and CA-CB out-and-back scalar-transfer blocks optimized for robust resonance assignment in biosolids under ultra-fast magic-angle spinning (MAS). The first experiment, (H)(CO)CA(CO)NH, yields {sup 1}H-detected inter-residue correlations, in which we record the chemical shifts of the CA spins in the first indirect dimension while during the scalar-transfer delays the coherences are present only on the longer-lived CO spins. The second experiment, (H)(CA)CB(CA)NH, correlates the side-chain CB chemical shifts with the NH of the same residue. These high sensitivity experiments are demonstrated on both fully-protonated and 100 %-H{sup N} back-protonated perdeuterated microcrystalline samples of Acinetobacter phage 205 (AP205) capsids at 60 kHz MAS.

  11. Investigations of chemical warfare agents and toxic industrial compounds with proton-transfer-reaction mass spectrometry for a real-time threat monitoring scenario.

    Science.gov (United States)

    Kassebacher, Thomas; Sulzer, Philipp; Jürschik, Simone; Hartungen, Eugen; Jordan, Alfons; Edtbauer, Achim; Feil, Stefan; Hanel, Gernot; Jaksch, Stefan; Märk, Lukas; Mayhew, Chris A; Märk, Tilmann D

    2013-01-30

    Security and protection against terrorist attacks are major issues in modern society. One especially challenging task is the monitoring and protection of air conditioning and heating systems of buildings against terrorist attacks with toxic chemicals. As existing technologies have low selectivity, long response times or insufficient sensitivity, there is a need for a novel approach such as we present here. We have analyzed various chemical warfare agents (CWAs) and/or toxic industrial compounds (TICs) and related compounds, namely phosgene, diphosgene, chloroacetone, chloroacetophenone, diisopropylaminoethanol, and triethyl phosphate, utilizing a high-resolution proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) instrument with the objective of finding key product ions and their intensities, which will allow a low-resolution quadrupole mass spectrometry based PTR-MS system to be used with high confidence in the assignment of threat agents in the atmosphere. We obtained high accuracy PTR-TOFMS mass spectra of the six compounds under study at two different values for the reduced electric field in the drift tube (E/N). From these data we have compiled a table containing product ions, and isotopic and E/N ratios for highly selective threat compound detection with a compact and cost-effective quadrupole-based PTR-MS instrument. Furthermore, using chloroacetophenone (tear gas), we demonstrated that this instrument's response is highly linear in the concentration range of typical Acute Exposure Guideline Levels (AEGLs). On the basis of the presented results it is possible to develop a compact and cost-effective PTR-QMS instrument that monitors air supply systems and triggers an alarm as soon as the presence of a threat agent is detected. We hope that this real-time surveillance device will help to seriously improve safety and security in environments vulnerable to terrorist attacks with toxic chemicals. Copyright © 2012 John Wiley & Sons, Ltd.

  12. Synthesis and anion binding studies of tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors: Proton transfer-induced selectivity for hydrogen sulfate over sulfate.

    Science.gov (United States)

    Khansari, Maryam Emami; Johnson, Corey R; Basaran, Ismet; Nafis, Aemal; Wang, Jing; Leszczynski, Jerzy; Hossain, Md Alamgir

    2015-01-01

    Tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors, tris([(4-cyanophenyl)amino]propyl)urea ( L1 ) and tris([(4-cyanophenyl)amino]propyl)thiourea ( L2 ), have been synthesized and their anion binding properties have been investigated for halides and oxoanions. As investigated by 1 H NMR titrations, each receptor binds an anion with a 1:1 stoichiometry via hydrogen-bonding interactions (NH⋯anion), showing the binding trend in the order of F - > H 2 PO 4 - > HCO 3 - > HSO 4 - > CH 3 COO - > SO 4 2- > Cl - > Br - > I in DMSO- d 6 . The interactions of the receptors were further studied by 2D NOESY, showing the loss of NOESY contacts of two NH resonances for the complexes of F - , H 2 PO 4 - , HCO 3 - , HSO 4 - or CH 3 COO - due to the strong NH⋯anion interactions. The observed higher binding affinity for HSO 4 - than SO 4 2- is attributed to the proton transfer from HSO 4 - to the central nitrogen of L1 or L2 which was also supported by the DFT calculations, leading to the secondary acid-base interactions. The thiourea receptor L2 has a general trend to show a higher affinity for an anion as compared to the urea receptor L1 for the corresponding anion in DMSO- d 6 . In addition, the compound L2 has been exploited for its extraction properties for fluoride in water using a liquid-liquid extraction technique, and the results indicate that the receptor effectively extracts fluoride from water showing ca. 99% efficiency (based on L2 ).

  13. Added value of amide proton transfer imaging to conventional and perfusion MR imaging for evaluating the treatment response of newly diagnosed glioblastoma

    Energy Technology Data Exchange (ETDEWEB)

    Park, Kye Jin; Kim, Ho Sung; Park, Ji Eun; Shim, Woo Hyun; Kim, Sang Joon [University of Ulsan College of Medicine, Asan Medical Center, Department of Radiology and Research Institute of Radiology, Seoul (Korea, Republic of); Smith, Seth A. [Vanderbilt University Institute of Imaging Science, Vanderbilt University, Department of Radiology and Radiological Sciences, Nashville, TN (United States)

    2016-12-15

    To determine the added value of amide proton transfer (APT) imaging to conventional and perfusion MRI for differentiating tumour progression (TP) from the treatment-related effect (TE) in patients with post-treatment glioblastomas. Sixty-five consecutive patients with enlarging contrast-enhancing lesions following concurrent chemoradiotherapy were assessed using contrast-enhanced T1-weighted MRI (CE-T1WI), 90th percentile histogram parameters of normalized cerebral blood volume (nCBV90) and APT asymmetry value (APT90). Diagnostic performance was determined using the area under the receiver operating characteristic curve (AUC) and cross validations. There were statistically significant differences in the mean APT90 between the TP and the TE groups (3.87-4.01 % vs. 1.38-1.41 %; P <.001). Compared with CE-T1WI alone, the addition of APT90 to CE-T1WI significantly improved cross-validated AUC from 0.58-0.74 to 0.89-0.91 for differentiating TP from TE. The combination of CE-T1WI, nCBV90 and APT90 resulted in greater diagnostic accuracy for differentiating TP from TE than the combination of CE-T1WI and nCBV90 (cross-validated AUC, 0.95-0.97 vs. 0.84-0.91). The inter-reader agreement between the expert and trainee was excellent for the measurements of APT90 (intraclass correlation coefficient, 0.94). Adding APT imaging to conventional and perfusion MRI improves the diagnostic performance for differentiating TP from TE. (orig.)

  14. Photophysical properties and excited state intramolecular proton transfer in 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid in homogeneous solvents and micro-heterogeneous environments

    Energy Technology Data Exchange (ETDEWEB)

    Gashnga, Pynsakhiat Miki [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India); Singh, T. Sanjoy [Department of Chemistry, Assam University, Silchar 788011, Assam (India); Baul, Tushar S. Basu [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India); Mitra, Sivaprasad, E-mail: smitra@nehu.ac.in [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India)

    2014-04-15

    A systematic study on the photophysical properties and excited state intramolecular proton transfer (ESIPT) behavior of 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid, is reported using steady-state and time-resolved fluorescence spectroscopy in homogeneous solvents as well as in different micro-heterogeneous environments. Depending on the nature of intramolecular hydrogen bond (IHB), the salicylic acid derivative may exist in two different ground state conformers (I and II). Structure I having IHB between the carbonyl oxygen and phenolic hydrogen can undergo ESIPT upon excitation as evidenced by largely Stokes-shifted fluorescence at ∼455 nm; whereas, normal fluorescence in the blue side of the spectrum (∼410 nm) is due to the spontaneous emission from conformer II. The results in homogeneous solvents were compared with those in bio-mimicking environments of β-cyclodextrin (CD) and surfactants. The intensity of the ESIPT fluorescence increases substantially upon encapsulation of the probe into the cyclodextrin as well as micellar nano-cavities. Detailed analysis of the spectroscopic data indicates that the probe forms 1:1 complex with CD in aqueous medium. Binding constant of the probe with the micelles as well as critical micelle concentration was obtained from the variation of fluorescence intensity on increasing concentration of different surfactants in aqueous medium. -- Highlights: • Steady state and time resolved fluorescence study on ESIPT in HMBA. • Dual fluorescence corresponding to the pro- and non-ESIPT structures. • Modulation of ESIPT fluorescence in micro-heterogeneous environments. • 1:1 stoichiometry for interaction with cyclodextrin. • Calculation of binding constant and other physico-chemical properties from fluorescence titration data in surfactants.

  15. In cleanroom, sub-ppb real-time monitoring of volatile organic compounds using proton-transfer reaction/time of flight/mass spectrometry

    Science.gov (United States)

    Hayeck, Nathalie; Maillot, Philippe; Vitrani, Thomas; Pic, Nicolas; Wortham, Henri; Gligorovski, Sasho; Temime-Roussel, Brice; Mizzi, Aurélie; Poulet, Irène

    2014-04-01

    Refractory compounds such as Trimethylsilanol (TMS) and other organic compounds such as propylene glycol methyl ether acetate (PGMEA) used in the photolithography area of microelectronic cleanrooms have irreversible dramatic impact on optical lenses used on photolithography tools. There is a need for real-time, continuous measurements of organic contaminants in representative cleanroom environment especially in lithography zone. Such information is essential to properly evaluate the impact of organic contamination on optical lenses. In this study, a Proton-Transfer Reaction-Time-of-Flight Mass spectrometer (PTR-TOF-MS) was applied for real-time and continuous monitoring of fugitive organic contamination induced by the fabrication process. Three types of measurements were carried out using the PTR-TOF-MS in order to detect the volatile organic compounds (VOCs) next to the tools in the photolithography area and at the upstream and downstream of chemical filters used to purge the air in the cleanroom environment. A validation and verification of the results obtained with PTR-TOF-MS was performed by comparing these results with those obtained with an off-line technique that is Automated Thermal Desorber - Gas Chromatography - Mass Spectrometry (ATD-GC-MS) used as a reference analytical method. The emerged results from the PTR-TOF-MS analysis exhibited the temporal variation of the VOCs levels in the cleanroom environment during the fabrication process. While comparing the results emerging from the two techniques, a good agreement was found between the results obtained with PTR-TOF-MS and those obtained with ATD-GC-MS for the PGMEA, toluene and xylene. Regarding TMS, a significant difference was observed ascribed to the technical performance of both instruments.

  16. Photophysical properties and excited state intramolecular proton transfer in 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid in homogeneous solvents and micro-heterogeneous environments

    International Nuclear Information System (INIS)

    Gashnga, Pynsakhiat Miki; Singh, T. Sanjoy; Baul, Tushar S. Basu; Mitra, Sivaprasad

    2014-01-01

    A systematic study on the photophysical properties and excited state intramolecular proton transfer (ESIPT) behavior of 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid, is reported using steady-state and time-resolved fluorescence spectroscopy in homogeneous solvents as well as in different micro-heterogeneous environments. Depending on the nature of intramolecular hydrogen bond (IHB), the salicylic acid derivative may exist in two different ground state conformers (I and II). Structure I having IHB between the carbonyl oxygen and phenolic hydrogen can undergo ESIPT upon excitation as evidenced by largely Stokes-shifted fluorescence at ∼455 nm; whereas, normal fluorescence in the blue side of the spectrum (∼410 nm) is due to the spontaneous emission from conformer II. The results in homogeneous solvents were compared with those in bio-mimicking environments of β-cyclodextrin (CD) and surfactants. The intensity of the ESIPT fluorescence increases substantially upon encapsulation of the probe into the cyclodextrin as well as micellar nano-cavities. Detailed analysis of the spectroscopic data indicates that the probe forms 1:1 complex with CD in aqueous medium. Binding constant of the probe with the micelles as well as critical micelle concentration was obtained from the variation of fluorescence intensity on increasing concentration of different surfactants in aqueous medium. -- Highlights: • Steady state and time resolved fluorescence study on ESIPT in HMBA. • Dual fluorescence corresponding to the pro- and non-ESIPT structures. • Modulation of ESIPT fluorescence in micro-heterogeneous environments. • 1:1 stoichiometry for interaction with cyclodextrin. • Calculation of binding constant and other physico-chemical properties from fluorescence titration data in surfactants

  17. TD-DFT investigation of the potential energy surface for Excited-State Intramolecular Proton Transfer (ESIPT) reaction of 10-hydroxybenzo[h]quinoline: Topological (AIM) and population (NBO) analysis of the intramolecular hydrogen bonding interaction

    International Nuclear Information System (INIS)

    Paul, Bijan Kumar; Guchhait, Nikhil

    2011-01-01

    Here, we report a Density Functional Theoretical (DFT) study on the photophysics of a potent Excited-State Intramolecular Proton Transfer (ESIPT) molecular system, viz., 10-hydroxybenzo[h]quinoline (HBQ). Particular emphasis has been rendered on the assessment of the proton transfer reaction in HBQ in the ground and excited-states through elucidation and a careful perusal of the potential energy surfaces (PES). The non-viability of Ground-State Intramolecular Proton Transfer (GSIPT) process is dictated by a high-energy barrier coupled with no energy minimum for the proton transferred (K-form) form at the ground-state (S 0 ) PES. Remarkable reduction of the barrier along with thermodynamic stability inversion between the enol (E-form) and the keto forms (K-form) of HBQ upon photoexcitation from S 0 to the S 1 -state advocate for the operation of ESIPT process. These findings have been cross-validated on the lexicon of analysis of optimized geometry parameters, Mulliken's charge distribution on the heavy atoms, and molecular orbitals (MO) of the E- and the K-forms of HBQ. Our computational results also corroborate to experimental observations. From the modulations in optimized geometry parameters in course of the PT process a critical assessment has been endeavoured to delve into the movement of the proton during the process. Additional stress has been placed on the analysis of the intramolecular hydrogen bonding (IMHB) interaction in HBQ. The IMHB interaction has been explored by calculation of electron density ρ(r) and the Laplacian ∇ 2 ρ(r) at the bond critical point (BCP) using Atoms-In-Molecule (AIM) method and by calculation of interaction between σ* of OH with the lone pair of the nitrogen atom using Natural Bond Orbital (NBO) analysis. - Highlights: → Theoretical modelling of the photophysics of an ESIPT probe 10-hydroxybenzo[h]quinoline (HBQ). → Calculation of intramolecular hydrogen bond (IMHB) energy. → Role of hyperconjugative charge transfer

  18. Steady-State Spectroscopic Analysis of Proton-Dependent Electron Transfer on Pyrazine-Appended Metal Dithiolenes [Ni(pdt)2], [Pd(pdt)2], and [Pt(pdt)2] (pdt = 2,3-Pyrazinedithiol).

    Science.gov (United States)

    Kennedy, Steven R; Kozar, Morgan N; Yennawar, Hemant P; Lear, Benjamin J

    2016-09-06

    We report the structural, electronic, and acid/base properties of a series of ML2 metal dithiolene complexes, where M = Ni, Pd, Pt and L = 2,3-pyrazinedithiol. These complexes are non-innocent and possess strong electronic coupling between ligands across the metal center. The electronic coupling can be readily quantified in the monoanionic mixed valence state using Marcus-Hush theory. Analysis of the intervalence charge transfer (IVCT) band reveals that that electronic coupling in the mixed valence state is 5800, 4500, and 5700 cm(-1) for the Ni, Pd, and Pt complexes, respectively. We then focus on their response to acid titration in the mixed valence state, which generates the asymmetrically protonated mixed valence mixed protonated state. For all three complexes, protonation results in severe attenuation of the electronic coupling, as measured by the IVCT band. We find nearly 5-fold decreases in electronic coupling for both Ni and Pt, while, for the Pd complex, the electronic coupling is reduced to the point that the IVCT band is no longer observable. We ascribe the reduction in electronic coupling to charge pinning induced by asymmetric protonation. The more severe reduction in coupling for the Pd complex is a result of greater energetic mismatch between ligand and metal orbitals, reflected in the smaller electronic coupling for the pure mixed valence state. This work demonstrates that the bridging metal center can be used to tune the electronic coupling in both the mixed valence and mixed valence mixed protonated states, as well as the magnitude of change of the electronic coupling that accompanies changes in protonation state.

  19. Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions.

    Science.gov (United States)

    Li, Jilai; Zhou, Shaodong; Schlangen, Maria; Weiske, Thomas; Schwarz, Helmut

    2016-10-10

    The reactivity of the cationic gold carbide [AuC] + (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC] + has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Quantitative chemical exchange saturation transfer (qCEST) MRI - omega plot analysis of RF-spillover-corrected inverse CEST ratio asymmetry for simultaneous determination of labile proton ratio and exchange rate.

    Science.gov (United States)

    Wu, Renhua; Xiao, Gang; Zhou, Iris Yuwen; Ran, Chongzhao; Sun, Phillip Zhe

    2015-03-01

    Chemical exchange saturation transfer (CEST) MRI is sensitive to labile proton concentration and exchange rate, thus allowing measurement of dilute CEST agent and microenvironmental properties. However, CEST measurement depends not only on the CEST agent properties but also on the experimental conditions. Quantitative CEST (qCEST) analysis has been proposed to address the limitation of the commonly used simplistic CEST-weighted calculation. Recent research has shown that the concomitant direct RF saturation (spillover) effect can be corrected using an inverse CEST ratio calculation. We postulated that a simplified qCEST analysis is feasible with omega plot analysis of the inverse CEST asymmetry calculation. Specifically, simulations showed that the numerically derived labile proton ratio and exchange rate were in good agreement with input values. In addition, the qCEST analysis was confirmed experimentally in a phantom with concurrent variation in CEST agent concentration and pH. Also, we demonstrated that the derived labile proton ratio increased linearly with creatine concentration (P analysis can simultaneously determine labile proton ratio and exchange rate in a relatively complex in vitro CEST system. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Influence of isovector pairing and particle-number projection effects on spectroscopic factors for one-pair like-particle transfer reactions in proton-rich even-even nuclei

    Science.gov (United States)

    Benbouzid, Y.; Allal, N. H.; Fellah, M.; Oudih, M. R.

    2018-04-01

    Isovector neutron-proton (np) pairing and particle-number fluctuation effects on the spectroscopic factors (SF) corresponding to one-pair like-particle transfer reactions in proton-rich even-even nuclei are studied. With this aim, expressions of the SF corresponding to two-neutron stripping and two-proton pick-up reactions, which take into account the isovector np pairing effect, are established within the generalized BCS approach, using a schematic definition proposed by Chasman. Expressions of the same SF which strictly conserve the particle number are also established within the Sharp-BCS (SBCS) discrete projection method. In both cases, it is shown that these expressions generalize those obtained when only the pairing between like particles is considered. First, the formalism is tested within the Richardson schematic model. Second, it is applied to study even-even proton-rich nuclei using the single-particle energies of a Woods-Saxon mean-field. In both cases, it is shown that the np pairing effect and the particle-number projection effect on the SF values are important, particularly in N = Z nuclei, and must then be taken into account.

  2. Can tautomerization of the A·T Watson-Crick base pair via double proton transfer provoke point mutations during DNA replication? A comprehensive QM and QTAIM analysis.

    Science.gov (United States)

    Brovarets, Ol'ha O; Hovorun, Dmytro M

    2014-01-01

    Trying to answer the question posed in the title, we have carried out a detailed theoretical investigation of the biologically important mechanism of the tautomerization of the A·T Watson-Crick DNA base pair, information that is hard to establish experimentally. By combining theoretical investigations at the MP2 and density functional theory levels of QM theory with quantum theory of atoms in molecules analysis, the tautomerization of the A·T Watson-Crick base pair by the double proton transfer (DPT) was comprehensively studied in vacuo and in the continuum with a low dielectric constant (ϵ = 4) corresponding to a hydrophobic interfaces of protein-nucleic acid interactions. Based on the sweeps of the electron-topological, geometric, and energetic parameters, which describe the course of the tautomerization along its intrinsic reaction coordinate (IRC), it was proved that the A·T → A(∗)·T(∗) tautomerization through the DPT is a concerted (i.e. the pathway without an intermediate) and asynchronous (i.e. protons move with a time gap) process. The limiting stage of this phenomenon is the final PT along the N6H⋯O4 hydrogen bond (H-bond). The continuum with ϵ = 4 does not affect qualitatively the course of the tautomerization reaction: similar to that observed in vacuo, it proceeds via a concerted asynchronous process with the same structure of the transition state (TS). For the first time, the nine key points along the IRC of the A·T base pair tautomerization, which could be considered as electron-topological "fingerprints" of a concerted asynchronous process of the tautomerization via the DPT, have been identified and fully characterized. These nine key points have been used to define the reactant, TS, and product regions of the DPT in the A·T base pair. Considering the energy dependence of each of the three H-bonds, which stabilize the Watson-Crick and Löwdin's base pairs, along the IRC of the tautomerization, it was found that all these H

  3. Proton therapy

    International Nuclear Information System (INIS)

    Smith, Alfred R

    2006-01-01

    Proton therapy has become a subject of considerable interest in the radiation oncology community and it is expected that there will be a substantial growth in proton treatment facilities during the next decade. I was asked to write a historical review of proton therapy based on my personal experiences, which have all occurred in the United States, so therefore I have a somewhat parochial point of view. Space requirements did not permit me to mention all of the existing proton therapy facilities or the names of all of those who have contributed to proton therapy. (review)

  4. Proton relativistic model; Modelo relativistico do proton

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Wilson Roberto Barbosa de

    1996-12-31

    In this dissertation, we present a model for the nucleon, which is composed by three relativistic quarks interacting through a contract force. The nucleon wave-function was obtained from the Faddeev equation in the null-plane. The covariance of the model under kinematical null-plane boots is discussed. The electric proton form-factor, calculated from the Faddeev wave-function, was in agreement with the data for low-momentum transfers and described qualitatively the asymptotic region for momentum transfers around 2 GeV. (author) 42 refs., 22 figs., 1 tab.

  5. Ultrafast proton shuttling in Psammocora cyan fluorescent protein.

    Science.gov (United States)

    Kennis, John T M; van Stokkum, Ivo H M; Peterson, Dayna S; Pandit, Anjali; Wachter, Rebekka M

    2013-09-26

    involving a short hydrogen bond. At any time in the reaction, the proton is localized on either the chromophore or Glu-167, which implies that most likely no low-barrier hydrogen bond exists between these molecular groups. This work supports the notion that proton transfer in biological systems, be it in an electronic excited or ground state, can be an intrinsically fast process that occurs on a 100 fs time scale. PsamFP488 represents an attractive model system that poses an ultrafast proton transfer regime in discrete steps. It constitutes a valuable model system in addition to wild type GFP, where proton transfer is relatively slow, and the S65T/H148D GFP mutant, where the effects of low-barrier hydrogen bonds dominate.

  6. Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer

    Science.gov (United States)

    Ma, Yan; Diao, Yiwei; Zhang, Bingjie; Wang, Weiwei; Ren, Xinrong; Yang, Dongsen; Wang, Ming; Shi, Xiaowen; Zheng, Jun

    2016-12-01

    A proton transfer reaction ion-drift chemical ionization mass spectrometer (PTR-ID-CIMS) equipped with a hydronium (H3+O) ion source was developed and deployed near an industrial zone in the Yangtze River Delta (YRD) region of China in spring 2015 to investigate industry-related emissions of volatile organic compounds (VOCs). Air pollutants including formaldehyde (HCHO), aromatics, and other trace gases (O3 and CO) were simultaneously measured. Humidity effects on the sensitivity of the PTR-ID-CIMS for HCHO detection were investigated and quantified. The performances of the PTR-ID-CIMS were also validated by intercomparing with offline HCHO measurement technique using 2,4-dinitrophenylhydrazone (DNPH) cartridges and the results showed fairly good agreement (slope = 0.81, R2 = 0.80). The PTR-ID-CIMS detection limit of HCHO (10 s, three-duty-cycle averages) was determined to be 0.9-2.4 (RH = 1-81.5 %) parts per billion by volume (ppbv) based on 3 times the standard deviations of the background signals. During the field study, observed HCHO concentrations ranged between 1.8 and 12.8 ppbv with a campaign average of 4.1 ± 1.6 ppbv, which was comparable with previous HCHO observations in other similar locations of China. However, HCHO diurnal profiles showed few features of secondary formation. In addition, time series of both HCHO and aromatic VOCs indicated strong influence from local emissions. Using a multiple linear regression fit model, on average the observed HCHO can be attributed to secondary formation (13.8 %), background level (27.0 %), and industry-related emissions, i.e., combustion sources (43.2 %) and chemical productions (16.0 %). Moreover, within the plumes the industry-related emissions can account for up to 69.2 % of the observed HCHO. This work has provided direct evidence of strong primary emissions of HCHO from industry-related activities. These primary HCHO sources can potentially have a strong impact on local and regional air pollution formation

  7. The primary steps of photosynthesis

    International Nuclear Information System (INIS)

    Fleming, G.R.; Van Grondelle, R.

    1996-01-01

    The two important initial steps of photosynthesis-electron transfer and energy transfer occur with great speed and efficiency. New techniques in laser optics and genetic engineering age helping us to understand why. (author). 24 refs. 8 figs

  8. A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

    International Nuclear Information System (INIS)

    Wang, Qiang; Gao, Jun; Zhang, Dongju; Liu, Chengbu

    2015-01-01

    Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome

  9. Importance of sequential two-step transfer process in a ΔS = 1 and ΔT = 1 inelastic transition of 14N(p, p')14N reaction

    International Nuclear Information System (INIS)

    Aoki, Y.; Kunori, S.; Nagano, K.; Toba, Y.; Yagi, K.

    1981-01-01

    Differential cross sections and vector analyzing powers for 14 N(p, p') and 14 N(p, d) reactions have been measured at E sub(p) = 21.0 MeV to elucidate the reaction mechanism and the effective interaction for the ΔS = ΔT = 1 transition in 14 N(p, p') 14 N(2.31 MeV) reaction. The data are analyzed in terms of finite-range distorted wave Borm approximation (DWBA) which include direct, knock-on exchange and (p, d)(d, p') two-step processes. Shell model wave functions of Cohen and Kurath are used. The data for the first excited state is reasonably well explained by introducing two-step process. The two-step process explains half of the experimental intensity. Moreover vector analyzing power can hardly be explained without introducing this two-step process. Vector analyzing power of protons leading to the second excited state in 14 N is better explained by introducing macroscopic calculation. The data for 14 N(p, d) 13 N(gs) reaction are well explained by a suitable choice of deuteron optical potential. Knock-on exchange contribution is relatively small. Importance of this two-step process for ΔS = ΔT = 1 transition is discussed up to 40 MeV. (author)

  10. Proton tunneling in solids

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, J.

    1998-10-01

    The tunneling rate of the proton and its isotopes between interstitial sites in solids is studied theoretically. The phonons and/or the electrons in the solid have two effects on the tunneling phenomenon. First, they suppress the transfer integral between two neighbouring states. Second, they give rise to a finite lifetime of the proton state. Usually the second effect is large and the tunneling probability per unit time (tunneling rate) can be defined. In some cases, however, a coherent tunneling is expected and actually observed. (author)

  11. Proton tunneling in solids

    International Nuclear Information System (INIS)

    Kondo, J.

    1998-01-01

    The tunneling rate of the proton and its isotopes between interstitial sites in solids is studied theoretically. The phonons and/or the electrons in the solid have two effects on the tunneling phenomenon. First, they suppress the transfer integral between two neighbouring states. Second, they give rise to a finite lifetime of the proton state. Usually the second effect is large and the tunneling probability per unit time (tunneling rate) can be defined. In some cases, however, a coherent tunneling is expected and actually observed. (author)

  12. Evaluation of BaZr0.1Ce0.7Y0.2O3-δ-based proton-conducting solid oxide fuel cells fabricated by a one-step co-firing process

    International Nuclear Information System (INIS)

    Sun Wenping; Wang Yanfei; Fang Shumin; Zhu Zhiwen; Yan Litao; Liu Wei

    2011-01-01

    Proton-conducting solid oxide fuel cells, incorporating BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ (BZCY) electrolyte, NiO-BZCY anode, and Sm 0.5 Sr 0.5 CoO 3-δ -Ce 0.8 Sm 0.2 O 2-δ (SSC-SDC) cathode, were successfully fabricated by a combined co-pressing and printing technique after a one-step co-firing process at 1100, 1150, or 1200 o C. Scanning electron microscope (SEM) results revealed that the co-firing temperature significantly affected not only the density of the electrolyte membrane but the grain size and porosity of the electrodes. Influences of the co-firing temperature on the electrochemical performances of the single cells were also studied in detail. Using wet hydrogen (2% H 2 O) as the fuel and static air as the oxidant, the cell co-fired at 1150 o C showed the highest maximum power density (PD max ) of 552 and 370 mW cm -2 at 700 and 650 o C, respectively, while the one co-fired at 1100 o C showed the highest PD max of 276 and 170 mWcm -2 at 600 and 550 o C, respectively. The Arrhenius equation was proposed to analyze the dependence of the PD max on the operating temperature, and revealed that PD max of the cell co-fired at a lower temperature was less dependent on operating temperature. The influences of the co-firing temperature on the resistances of the single cells, which were estimated from the electrochemical impedance spectroscopy measured under open circuit conditions, were also investigated.

  13. Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

    Science.gov (United States)

    Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

    2018-02-01

    The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Neutral pion electroproduction and virtual Compton scattering on proton with four-momentum transfer squared Q2 = 1 GeV2. Measurement of cross-sections and of generalized polarizabilities

    International Nuclear Information System (INIS)

    Laveissiere, G.

    2001-11-01

    In hadronic physics, the nucleon structure and the quarks confinement are still topical issues. The neutral pion electroproduction and virtual Compton scattering (VCS) reactions allow us to access new observables that describe this structure. This work is focussed on the VCS experiment performed at Jefferson Lab in 1998. The 4 GeV electron beam is scattered off a cryogenic hydrogen target, and the scattered electron and recoiled proton are detected in coincidence in the twin hall A spectrometers. The photon (pion) is reconstructed using a missing particle technique. The data analysis allowed to extract the cross sections relative to both process at four-momentum transfer squared Q 2 = 1 GeV 2 . The VCS cross section has been extracted for the first time in the proton resonance region (W between 1.O and 2.0 GeV) through the photon electroproduction reaction. Around the pion-production threshold up to the Delta(1232) resonance region, these results lead to the measurement of the generalized polarizabilities, that describe the proton structure in the same way as the elastic form factors. Moreover, the neutral pion electroproduction cross section measurement in the resonance region has brought new constraints on the existing phenomenological models. (author)

  15. Electron and Proton Transfer by the Grotthuss Mechanism in Aqueous Solution and in Biological Systems; Transfert d'Electrons et de Protons par le Mecanisme de Grotthuss en Solution Aqueuse et dans les Systemes Biologiques; Perenos ehlektronov i protonov mekhanizmom grotkhusa v vodnom rastvore i v biologicheskikh sistemakh; Transferencia Electronica y Protonica por el Mecanismo de Grotthuss en Soluciones Acuosas y en Sistemas Biologicos

    Energy Technology Data Exchange (ETDEWEB)

    Horne, R. A.; Courant, R. A.; Johnson, D. S. [Arthur D. Little, Inc. Cambridge, MA (United States)

    1965-10-15

    TheFe{sup ll}-Fe{sup III} electron-exchange reaction and certain long-range biological redox reactions involve the transfer of electrons by a Grotthuss-type mechanism over water bridges. The Grotthuss mechanism is also responsible for the anomalously great electrical conductivity of acidic aqueous solutions. At ordinary pressures the rate-determining step of the Grotthuss mechanism is the rotation of H{sub 2}O, or possibly H{sub 3}O+, and not the actual proton flip itself. The Grotthuss mechanism is confined to the ''free'' rotatable monomeric water between the Frank-Wen clusters in liquid water and avoids areas of relative order. The concentration dependence of protonic conduction can be represented by an equation based upon a cube root of concentration extrapolation and containing Arrhenius terms in which the activation energies are those for the rotation of and the formation of ''holes'' in the solvent water. Thus chemical energy and/or electrical energy can be transmitted rapidly over relatively great distances by the Grotthuss mechanism. Such processes are involved in a variety of phenomena of biological significance, examples being muscular contraction and the chemistry of the respiratory pigments. (author) [French] L'echange d'electrons dans Fe{sup II}-Fe{sup III} et certaines reactions biologiques d'oxydo-reduction a long terme font intervenir le transfert d'electrons par un mecanisme du type de Grotthuss sur des ponts d'eau. Le mecanisme de Grotthuss explique egalement la conductivite anormalement grande des solutions aqueuses d'acides. Sous les pressions ordinaires, l'etape du mecanisme de Grotthuss qui determine la vitesse est la rotation de H{sub 2}O ou peut-etre de H{sub 3}O+, et non pas le changement d'orientation du proton meme. Le mecanisme de Grotthuss est limite a l'eau monomerique ' libre ' , susceptible de rotation, entre les amas de Frank-Wen dans l'eau liquide et il evite les zones d'ordre relatif. On peut representer les variations de la

  16. Overvoltages transferred from a network of 220 kV to 15.65 kV level of the step-up transformer in HPP 'Bajina Bašta'

    Directory of Open Access Journals (Sweden)

    Vukelja Petar

    2011-01-01

    Full Text Available The paper presents the results of research in lightning surge waves and switching overvoltages transferred from a network of 220 kV to the 15.65 kV level of the step-up transformer in HPP 'Bajina Bašta'. Analysis of survey results lead to conclusion that transferred overvoltages can endanger 15.65 kV transformer windings and stator winding insulation. It was therefore suggested for the protection of the 15.65 kV isolation to install metal oxide surge arresters at a suitable place between the power generator bus bars and earthing.

  17. Coordinating the Structural Rearrangements Associated with Unidirectional Proton Transfer in the Bacteriorhodopsin Photocycle Induced by Deprotonation of the Proton-Release Group: A Time-Resolved Difference FTIR Spectroscopic Study†

    Science.gov (United States)

    Morgan, Joel E.; Vakkasoglu, Ahmet S.; Lanyi, Janos K.; Gennis, Robert B.; Maeda, Akio

    2014-01-01

    In the photocycle of bacteriorhodopsin at pH 7, proton release from the proton releasing group (PRG) to the extracellular medium occurs during formation of the M intermediate. This proton release is inhibited at acidic pH, below the pKa of the PRG, ∼6 in M, and instead occurs later in the cycle as the initial state is restored from the O intermediate. Here, structural changes related to deprotonation of the PRG have been investigated by time-resolved FTIR spectroscopy at 25°C. The vibrational features at 2100-1790 cm-1, 1730-1685 cm-1, 1661 cm-1, and 1130-1045 cm-1 have greater negative intensity in the pure M-minus-BR spectrum and even in the M-minus-BR spectrum, that is present earlier together with the L-minus-BR spectrum, at pH 7, than in the corresponding M-minus-BR spectra at pH 5 or pH 4. The D212N mutation abolishes the decreases in the intensities of the broad feature between 1730 and 1685 cm-1 and the band at 1661 cm-1. The 1730-1685 cm-1 feature may arise from transition dipole coupling of the backbone carbonyl groups of Glu204, Phe208, Asp212 and Lys216 interacting with Tyr57 and C15-H of the chromophore. The 1661 cm-1 band, which is insensitive to D2O substitution, may arise by interaction of the backbone carbonyl of Asp212 with C15-H. The 2100-1790 cm-1 feature with a trough at 1885 cm-1 could be due to a water cluster. Depletion of these bands upon deprotonation of the PRG is attributable to disruption of a coordinated structure, held in place by interactions of Asp212. Deprotonation of the PRG is accompanied also by disruption of the interaction of the water molecule near Arg82. The liberated Asp212 may stabilize the protonated state of Asp85, and thus confer uni-directionality to the transport. PMID:20232848

  18. Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2016-02-04

    The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is

  19. Evaluation of the radiative transfer in the core of a Pressurized Water Reactor (PWR) during the reflooding step of a Loss Of Coolant Accident (LOCA)

    International Nuclear Information System (INIS)

    Gerardin, J.

    2012-01-01

    We developed a method of resolution of radiative transfer inside a medium of vapor-droplets surrounded by hot walls, in order to couple it with a simulation of the flow at the CFD scale. The scope is the study of the cooling of the core of nuclear reactor following a Loss Of Coolant Accident (LOCA). The problem of radiative transfer can be cut into two sub problems, one concerning the evaluation of the radiative properties of the medium and a second concerning the solution of the radiative transfer equation. The radiative properties of the droplets have been computed with the use of the Mie Theory and those of the vapor have been computed with a Ck model. The medium made of vapor and droplets is an absorbing, anisotropically scattering, emissive, non grey, non homogeneous medium. Hence, owing to the possible variations of the flow properties (diameter and volumetric fraction of the droplets, temperature and pressure of the vapor), the medium can be optically thin or thick. Consequently, a method is required which solves the radiative transfer accurately, with a moderate calculation time for all of these prerequisites. The IDA has been chosen, derived from the well-known P1-approximation. Its accuracy has been checked on academical cases found in the literature and by comparison with experimental data. Simulations of LOCA flows have been conducted taking account of the radiative transfer, evaluating the radiative fluxes and showing that radiative transfer influence cannot be neglected. (author)

  20. Proton relativistic model

    International Nuclear Information System (INIS)

    Araujo, Wilson Roberto Barbosa de

    1995-01-01

    In this dissertation, we present a model for the nucleon, which is composed by three relativistic quarks interacting through a contract force. The nucleon wave-function was obtained from the Faddeev equation in the null-plane. The covariance of the model under kinematical null-plane boots is discussed. The electric proton form-factor, calculated from the Faddeev wave-function, was in agreement with the data for low-momentum transfers and described qualitatively the asymptotic region for momentum transfers around 2 GeV. (author)

  1. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  2. Spectroscopic study of 2-, 4- and 5-substituents on p Ka values of imidazole heterocycles prone to intramolecular proton-electrons transfer

    Science.gov (United States)

    Eseola, Abiodun O.; Obi-Egbedi, Nelson O.

    2010-02-01

    New 2-(1H-imidazol-2-yl)phenols ( L1Et- L8tBuPt) bearing a phenolic proton in the vicinity of the imidazole base were prepared and characterized. Experimental studies of the dependence of their protonation/deprotonation equilibrium on substituent identities and intramolecular hydrogen bonding tendencies were carried out using electronic absorption spectroscopy at varying pH values. In order to make comparison, 2-(anthracen-10-yl)-4,5-diphenyl-1H-imidazole ( L9Anthr) bearing no phenolic proton and 4,5-diphenyl-2-(4,5-diphenyl-1H-imidazol-2-yl)-1H-imidazole ( L10BisIm) bearing two symmetrical imidazole base fragments were also prepared and experimentally investigated. DFT calculations were carried out to study frontier orbitals of the investigated molecules. While electron-releasing substituents produced increase in protonation-deprotonation p Kas for the hydroxyl group, values for the imidazole base were mainly affected by polarization of the imidazole ring aromaticity across the 2-imidazole carbon and the 4,5-imidazole carbons axis of the imidazole ring. It was concluded that electron-releasing substituents on the phenol ring and/or electron-withdrawing substituents on 4,5-imidazole carbons negatively affects donor strengths/coordination chemistries of 2-(1H-imidazol-2-yl)phenols, and vice versa. Change of substituents on the phenol ring significantly altered the donor strength of the imidazole base. The understanding of p Ka variation on account of electronic effects of substituents in this work should aid the understanding of biochemical properties and substituent environments of imidazole-containing biomacromolecules.

  3. Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)(-) bonded system.

    Science.gov (United States)

    Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M

    2015-02-14

    We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

  4. Investigation of the cleanliness of transferred graphene. The first step toward its application as a window material for electron microscopy and spectroscopy

    International Nuclear Information System (INIS)

    Ma, Tao; Miyazaki, Kotaro; Ariga, Hiroko; Takakusagi, Satoru; Asakura, Kiyotaka

    2015-01-01

    The cleanliness of transferred graphene is of significant importance for its application as the window material in environmental cells used for electron microscopy and spectroscopy. We investigated the dependence of the cleanliness of graphene on transfer routes, including FeCl 3 etching, (NH 4 ) 2 S 2 O 8 etching, electrochemical delamination, and O 2 -bubbling, by means of transmission electron microscopy and X-ray photoelectron spectroscopy. It was found that electrochemical delamination provided the cleanest graphene with only a small amount of poly(methyl methacrylate) (PMMA) residue existing on the surface. (author)

  5. Electrochemical proton relay at the single-molecule level

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Medvedev, I. G.; Ulstrup, Jens

    2009-01-01

    A scheme for the experimental study of single-proton transfer events, based on proton-coupled two-electron transfer between a proton donor and a proton acceptor molecule confined in the tunneling gap between two metal leads in electrolyte solution is suggested. Expressions for the electric current...... are derived and compared with formalism for electron tunneling through redox molecules. The scheme allows studying the kinetics of proton and hydrogen atom transfer as well as kinetic isotope effects at the single-molecule level under electrochemical potential control....

  6. On adaptive time stepping for large-scale parabolic problems: Computer simulation of heat and mass transfer in vacuum freeze-drying

    Czech Academy of Sciences Publication Activity Database

    Georgiev, K.; Kosturski, N.; Margenov, S.; Starý, Jiří

    2009-01-01

    Roč. 226, č. 2 (2009), s. 268-274 ISSN 0377-0427 Institutional research plan: CEZ:AV0Z30860518 Keywords : Vacuum freeze drying * Zeolites * Heat and mass transfer * Finite element method * MIC(0) preconditioning Subject RIV: BA - General Mathematics Impact factor: 1.292, year: 2009 http://apps.isiknowledge.com

  7. Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

    Energy Technology Data Exchange (ETDEWEB)

    DeBlase, Andrew F.; Wolke, Conrad T.; Johnson, Mark A., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Weddle, Gary H. [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Department of Chemistry, Fairfield University, 1073 North Benson Road, Fairfield, Connecticut 06824 (United States); Archer, Kaye A.; Jordan, Kenneth D., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260 (United States); Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677 (United States)

    2015-10-14

    The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

  8. Effects of air exchange, temperature and slurry management on odorant emissions from pig production units and slurry tanks studied by proton-transfer-reaction mass spectrometry (PTR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Feilberg, A.; Adamsen, A.P.S.; Liu, D.; Hansen, M.J.; Bildsoe, P. [Aarhus Univ., Tjele (Denmark). Dept. of Biosystems Engineering

    2010-07-01

    The factors affecting the variability of odorant emissions from intensive pig production facilities were examined using proton-transfer-reaction mass spectrometry (PTR-MS) to monitor emissions of odorants. Quantitative and time-resolved results for protonated ions representing hydrogen sulphide (H{sub 2}S), volatile organic sulphur compounds, organic amines, volatile carboxylic acids, carbonyls, phenols and indoles can be obtained. This study presented the results from PTRMS measurements of odorant emissions from finisher pig houses and finisher manure storage tanks. The measurements were performed at an experimental full-scale pig section with mechanical ventilation and at an experimental manure storage facility with controlled air exchange. Field measurements were taken during variable air exchange rates and temperatures, during finisher growth, and during emptying of the slurry pit. The results revealed a pronounced diurnal variation in emissions of odorants from the pig section with peaks in daytime coinciding with the highest ventilation rates and highest room temperatures. The highest emission rates were observed for H{sub 2}S and carboxylic acids. Based on odour threshold values, methanethiol and 4-methylphenol were estimated to contribute considerably to the odour nuisance. Discharging of the slurry pit led to reduced H{sub 2}S emissions, but peaks of H{sub 2}S were observed during manure handling.

  9. Intramolecular, Exciplex-Mediated, Proton-Coupled, Charge-Transfer Processes in N,N-Dimethyl-3-(1-pyrenyl)propan-1-ammonium Cations: Influence of Anion, Solvent Polarity, and Temperature.

    Science.gov (United States)

    Safko, Trevor M; Faleiros, Marcelo M; Atvars, Teresa D Z; Weiss, Richard G

    2016-06-16

    An intramolecular exciplex-mediated, proton-coupled, charge-transfer (PCCT) process has been investigated for a series of N,N-dimethyl-3-(1-pyrenyl)propan-1-ammonium cations with different anions (PyS) in solvents of low to intermediate polarity over a wide temperature range. Solvent mediates both the equilibrium between conformations of the cation that place the pyrenyl and ammonium groups in proximity (conformation C) or far from each other (conformation O) and the ability of the ammonium group to transfer a proton adiabatically in the PyS excited singlet state. Thus, exciplex emission, concurrent with the PCCT process, was observed only in hydrogen-bond accepting solvents of relatively low polarity (tetrahydrofuran, ethyl acetate, and 1,4-dioxane) and not in dichloromethane. From the exciplex emission and other spectroscopic and thermodynamic data, the acidity of the ammonium group in conformation C of the excited singlet state of PyS (pKa*) has been estimated to be ca. -3.4 in tetrahydrofuran. The ratios between the intensities of emission from the exciplex and the locally excited state (IEx/ILE) appear to be much more dependent on the nature of the anion than are the rates of exciplex formation and decay, although the excited state data do not provide a quantitative measure of the anion effect on the C-O equilibrium. The activation energies associated with exciplex formation in THF are calculated to be 0.08 to 0.15 eV lower than for the neutral amine, N,N-dimethyl-3-(1-pyrenyl)propan-1-amine. Decay of the exciplexes formed from the deprotonation of PyS is hypothesized to occur through charge-recombination processes. To our knowledge, this is the first example in which photoacidity and intramolecular exciplex formation (i.e., a PCCT reaction) are coupled.

  10. Mathematic Model of Digital Control System with PID Regulator and Regular Step of Quantization with Information Transfer via the Channel of Plural Access

    Science.gov (United States)

    Abramov, G. V.; Emeljanov, A. E.; Ivashin, A. L.

    Theoretical bases for modeling a digital control system with information transfer via the channel of plural access and a regular quantization cycle are submitted. The theory of dynamic systems with random changes of the structure including elements of the Markov random processes theory is used for a mathematical description of a network control system. The characteristics of similar control systems are received. Experimental research of the given control systems is carried out.

  11. Solid-state NMR analysis of membrane proteins and protein aggregates by proton detected spectroscopy

    International Nuclear Information System (INIS)

    Zhou, Donghua H.; Nieuwkoop, Andrew J.; Berthold, Deborah A.; Comellas, Gemma; Sperling, Lindsay J.; Tang, Ming; Shah, Gautam J.; Brea, Elliott J.; Lemkau, Luisel R.; Rienstra, Chad M.

    2012-01-01

    Solid-state NMR has emerged as an important tool for structural biology and chemistry, capable of solving atomic-resolution structures for proteins in membrane-bound and aggregated states. Proton detection methods have been recently realized under fast magic-angle spinning conditions, providing large sensitivity enhancements for efficient examination of uniformly labeled proteins. The first and often most challenging step of protein structure determination by NMR is the site-specific resonance assignment. Here we demonstrate resonance assignments based on high-sensitivity proton-detected three-dimensional experiments for samples of different physical states, including a fully-protonated small protein (GB1, 6 kDa), a deuterated microcrystalline protein (DsbA, 21 kDa), a membrane protein (DsbB, 20 kDa) prepared in a lipid environment, and the extended core of a fibrillar protein (α-synuclein, 14 kDa). In our implementation of these experiments, including CONH, CO(CA)NH, CANH, CA(CO)NH, CBCANH, and CBCA(CO)NH, dipolar-based polarization transfer methods have been chosen for optimal efficiency for relatively high protonation levels (full protonation or 100 % amide proton), fast magic-angle spinning conditions (40 kHz) and moderate proton decoupling power levels. Each H–N pair correlates exclusively to either intra- or inter-residue carbons, but not both, to maximize spectral resolution. Experiment time can be reduced by at least a factor of 10 by using proton detection in comparison to carbon detection. These high-sensitivity experiments are especially important for membrane proteins, which often have rather low expression yield. Proton-detection based experiments are expected to play an important role in accelerating protein structure elucidation by solid-state NMR with the improved sensitivity and resolution.

  12. Pion-proton elastic scattering at 20 and 50 GeV/c incident momenta in the momentum transfer range 0.7 2

    International Nuclear Information System (INIS)

    Asa'd, Z.; Coupland, M.; Davis, D.G.; Duff, B.G.; Gjerpe, I.; Heymann, F.F.; Imrie, D.C.; Lowndes, R.; Lush, G.J.; Phillips, M.; Baglin, C.; Poulet, M.; Yvert, M.; Benso, S.; Buzzo, A.; Ferroni, S.; Gracco, V.; Macri, M.; Santroni, A.; Brobakken, K.; Bugge, L.; Buran, T.; Fearnley, T.; Helgaker, P.; Kirsebom, K.; Moe, A.; Soerensen, S.O.; Hansen, J.D.; Myrheim, J.; Skjevling, G.

    1982-01-01

    Measurements of the differential elastic cross sections for π - p scattering at incident momenta of 20 and 50 GeV/c and π + p at 50 GeV/c in the momentum transfer range 0.7 2 are presented. The data are compared with various models of elastic scattering. (orig.)

  13. Proton Therapy Research and Treatment Center

    Energy Technology Data Exchange (ETDEWEB)

    Goodnight, J.E. Jr. (University of California Davis Medical Center, Sacramento, CA (United States). Cancer Center); Alonso, J.R. (Lawrence Berkeley Lab., CA (United States))

    1992-05-01

    This Grant proposal outlines the steps that will be undertaken to bring the UC Davis Proton Therapy Research and Treatment, known locally as the Proton Therapy Facility (PTF), through its design and construction phases. This application concentrates on the design phase of the PTF project.

  14. First cloned Bactrian camel (Camelus bactrianus) calf produced by interspecies somatic cell nuclear transfer: A step towards preserving the critically endangered wild Bactrian camels

    Science.gov (United States)

    Vettical, Binoy S.; Hong, Seung B.

    2017-01-01

    Studies were conducted to explore the possibility of employing dromedary camel (Camelus dromedarius) oocytes as recipient cytoplasts for the development of interspecies somatic cell nuclear transfer (iSCNT) embryos using skin fibroblast cells of an adult Bactrian camel (Camelus bactrianus) and Llama (Llama glama) as donor nuclei. Also, the embryos reconstructed with Bactrian cells were transferred into the uterus of synchronized dromedary camel recipients to explore the possibility of using them as surrogate mothers. Serum-starved skin fibroblast cells were injected into the perivitelline space of enucleated mature oocytes, collected from super-stimulated dromedary camels, and fused using an Eppendorf electroporator. After activation with 5μM ionomycin and 6-dimethylaminopurine, they were cultured at 38.5°C in an atmosphere of 5% CO2, 5% O2, and 90% N2 in air. In experiment 1, Day 7 blastocysts were stained with Hoechst to count their cell numbers, while in experiment 2, they were transferred to synchronized dromedary recipients. A lower number (P < 0.05) of blastocysts were obtained from reconstructs utilizing fibroblast cells from Llama when compared with those reconstructed with dromedary and Bactrian fibroblast cells. However, no difference was observed in their cell numbers. In experiment 2, a higher (P < 0.05) proportion of blastocysts were obtained from the cleaved embryos reconstructed with Bactrian fibroblast cells when compared to those reconstructed with dromedary cells. Twenty-six Day 7 blastocysts reconstructed with Bactrian cells were transferred to 23 synchronized dromedary recipients with 5 pregnancies established on Day 30, however, only one of the pregnancies developed to term and a healthy calf weighing 33 kgs was born after completing 392 days of gestation. Unfortunately, the calf died on day 7 due to acute septicemia. In conclusion, the present study reports, for the first time, birth of a cloned Bactrian calf by iSCNT using dromedary camel

  15. First cloned Bactrian camel (Camelus bactrianus calf produced by interspecies somatic cell nuclear transfer: A step towards preserving the critically endangered wild Bactrian camels.

    Directory of Open Access Journals (Sweden)

    Nisar Ahmad Wani

    Full Text Available Studies were conducted to explore the possibility of employing dromedary camel (Camelus dromedarius oocytes as recipient cytoplasts for the development of interspecies somatic cell nuclear transfer (iSCNT embryos using skin fibroblast cells of an adult Bactrian camel (Camelus bactrianus and Llama (Llama glama as donor nuclei. Also, the embryos reconstructed with Bactrian cells were transferred into the uterus of synchronized dromedary camel recipients to explore the possibility of using them as surrogate mothers. Serum-starved skin fibroblast cells were injected into the perivitelline space of enucleated mature oocytes, collected from super-stimulated dromedary camels, and fused using an Eppendorf electroporator. After activation with 5μM ionomycin and 6-dimethylaminopurine, they were cultured at 38.5°C in an atmosphere of 5% CO2, 5% O2, and 90% N2 in air. In experiment 1, Day 7 blastocysts were stained with Hoechst to count their cell numbers, while in experiment 2, they were transferred to synchronized dromedary recipients. A lower number (P < 0.05 of blastocysts were obtained from reconstructs utilizing fibroblast cells from Llama when compared with those reconstructed with dromedary and Bactrian fibroblast cells. However, no difference was observed in their cell numbers. In experiment 2, a higher (P < 0.05 proportion of blastocysts were obtained from the cleaved embryos reconstructed with Bactrian fibroblast cells when compared to those reconstructed with dromedary cells. Twenty-six Day 7 blastocysts reconstructed with Bactrian cells were transferred to 23 synchronized dromedary recipients with 5 pregnancies established on Day 30, however, only one of the pregnancies developed to term and a healthy calf weighing 33 kgs was born after completing 392 days of gestation. Unfortunately, the calf died on day 7 due to acute septicemia. In conclusion, the present study reports, for the first time, birth of a cloned Bactrian calf by iSCNT using

  16. Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

    Science.gov (United States)

    Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

    2008-01-01

    The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical

  17. Photoinduced triplet-state electron transfer of platinum porphyrin: a one-step direct method for sensing iodide with an unprecedented detection limit

    KAUST Repository

    Masih, Dilshad

    2015-02-05

    Here, we report for the first time a one-step direct method for sensing halides in aqueous solution using phosphorescence quenching of platinum-cationic porphyrin. This method offers an easy, rapid, environmentally friendly, ultra-sensitive (with a previously unattained detection limit of 1 × 10−12 M) and economical method for the determination of iodide. To fully understand the reaction mechanism responsible for the phosphorescence quenching process, we have employed cutting-edge time-resolved laser spectroscopy with broadband capabilities.

  18. Proton decay theory

    International Nuclear Information System (INIS)

    Marciano, W.J.

    1983-01-01

    Topics include minimal SU(5) predictions, gauge boson mediated proton decay, uncertainties in tau/sub p/, Higgs scalar effects, proton decay via Higgs scalars, supersymmetric SU(5), dimension 5 operators and proton decay, and Higgs scalars and proton decay

  19. Investigation of the core-halo structure of the neutron-rich nuclei 6He and 8He by intermediate-energy elastic proton scattering at high momentum transfer

    International Nuclear Information System (INIS)

    Aksouh, F.

    2002-12-01

    The elastic proton scattering from the halo nuclei 6 He and 8 He was investigated in inverse kinematics at energies around 700 MeV/u with the aim to deduce the differential cross sections for the region of high momentum transfer, covering the first diffraction minimum. For this purpose, a liquid-hydrogen target was specially developed and used for the first time allowing to obtain low-background data as compared to commonly used targets made from C-H compounds. Previous data taken in the region of small momentum transfer were sensitive to the size and the peripheral shape of the total nuclear matter density distribution but not to the inner part. The present data allow for a more detailed insight in the structure of the alike core in 6,8 He through a better determination of the matter density distributions. Several density distributions calculated from different microscopic models were used to derive elastic scattering cross sections which are compared with the obtained data. (author)

  20. Proton therapy

    International Nuclear Information System (INIS)

    Jongen, Y.

    1995-01-01

    Ideal radiotherapy deposits a large amount of energy in the tumour volume, and none in the surrounding healthy tissues. Proton therapy comes closer to this goal because of a greater concentration of dose, well defined proton ranges and points of energy release which are precisely known - the Bragg peak1. In the past, the development of clinical proton therapy has been hampered by complexity, size, and cost. To be clinically effective, energies of several hundred MeV are required; these were previously unavailable for hospital installations, and pioneering institutions had to work with complex, inadequate equipment originally intended for nuclear physics research. Recently a number of specialist organizations and commercial companies have been working on dedicated systems for proton therapy. One, IBA of Belgium, has equipment for inhouse hospital operation which encompasses a complete therapy centre, delivered as a turnkey package and incorporating a compact, automated, higher energy cyclotron with isocentric gantries. Their system will be installed at Massachusetts General Hospital, Boston. The proton therapy system comprises: - a 235 MeV isochronous cyclotron to deliver beams of up to 1.5 microamps, but with a hardware limitation to restrict the maximum possible dose; - variable energy beam (235 to 70 MeV ) with energy spread and emittance verification; - a beam transport and switching system to connect the exit of the energy selection system to the entrances of a number of gantries and fixed beamlines. Along the beam transport system, the beam characteristics are monitored with non-interceptive multiwire ionization chambers for automatic tuning; - gantries fitted with nozzles and beamline elements for beam control; both beam scattering and beam wobbling techniques are available for shaping the beam;

  1. Tunneling Kinetics and Nonadiabatic Proton-Coupled Electron Transfer in Proteins: The Effect of Electric Fields and Anharmonic Donor-Acceptor Interactions.

    Science.gov (United States)

    Salna, Bridget; Benabbas, Abdelkrim; Russo, Douglas; Champion, Paul M

    2017-07-20

    A proper description of proton donor-acceptor (D-A) distance fluctuations is crucial for understanding tunneling in proton-coupled electron transport (PCET). The typical harmonic approximation for the D-A potential results in a Gaussian probability distribution, which does not appropriately reflect the electronic repulsion forces that increase the energetic cost of sampling shorter D-A distances. Because these shorter distances are the primary channel for thermally activated tunneling, the analysis of tunneling kinetics depends sensitively on the inherently anharmonic nature of the D-A interaction. Thus, we have used quantum chemical calculations to account for the D-A interaction and developed an improved model for the analysis of experimental tunneling kinetics. Strong internal electric fields are also considered and found to contribute significantly to the compressive forces when the D-A distance distribution is positioned below the van der Waals contact distance. This model is applied to recent experiments on the wild type (WT) and a double mutant (DM) of soybean lipoxygenase-1 (SLO). The compressive force necessary to prepare the tunneling-active distribution in WT SLO is found to fall in the ∼ nN range, which greatly exceeds the measured values of molecular motor and protein unfolding forces. This indicates that ∼60-100 MV/cm electric fields, aligned along the D-A bond axis, must be generated by an enzyme conformational interconversion that facilitates the PCET tunneling reaction. Based on the absolute value of the measured tunneling rate, and using previously calculated values of the electronic matrix element, the population of this tunneling-active conformation is found to lie in the range 10 -5 -10 -7 , indicating this is a rare structural fluctuation that falls well below the detection threshold of recent ENDOR experiments. Additional analysis of the DM tunneling kinetics leads to a proposal that a disordered (high entropy) conformation could be

  2. Transfer-free synthesis of multilayer graphene using a single-step process in an evaporator and formation confirmation by laser mode-locking

    International Nuclear Information System (INIS)

    Kim, Won-Jun; Debnath, Pulak C; Song, Yong-Won; Lee, Junsu; Lee, Ju Han; Lim, Dae-Soon

    2013-01-01

    Multilayer graphene is synthesized by a simplified process employing an evaporator in which a target substrate is deposited with a Ni catalyst layer before being heated to grow graphene directly. Carbon atoms adsorbed onto the surface of the Ni source as impurities from the atmosphere are incorporated into the catalyst layer during the deposition, and diffuse toward the catalyst/substrate interface, where they crystallize as graphene with a thickness of less than 2 nm. The need for a transfer process and external carbon supply is eliminated. The graphene is characterized by conventional analysis approaches, including nano-scale visualization and Raman spectroscopy, and utilizing photonics, graphene-functionalized passive laser mode-locking is demonstrated to confirm the successful synthesis of the graphene layer, resulting in an operating center wavelength of 1569.4 nm, a pulse duration of 1.35 ps, and a repetition rate of 31.6 MHz. (paper)

  3. Red organic light-emitting diodes based on wide band gap emitting material as the host utilizing two-step energy transfer

    International Nuclear Information System (INIS)

    Haq Khizarul; Shanpeng Liu; Khan, M A; Jiang, X Y; Zhang, Z L; Zhu, W Q

    2008-01-01

    We demonstrated efficient red organic light-emitting diodes based on a host emitting system of 9,10-di(2-naphthyl)anthracene (ADN) co-doped with 4-(dicyano-methylene)-2-t-butyle-6- (1,1,7,7-tetramethyl-julolidyl-9-enyl)-4H-pyran (DCJTB) as a red dopant and 2,3,6,7- tetrahydro-1,1,7,7-tetramethyl-1H,5H,1 1H-10(2-benzothiazolyl)-quinolizine-[9,9a,1gh] coumarin (C545T) as an assistant dopant. The typical device structure was glass substrate/ITO/4,4',4''-tris(N-3-methylphenyl-N-phenylamino) triphenylamine(m-MTDATA)/N,N'-bis-(naphthalene-1-yl)-N,N'-diphenylbenzidine (NPB)/[ADN: DCJTB: C545T/Alq 3 /LiF/Al]. It was found that C545T dopant did not emit by itself but did assist the energy transfer from the host (ADN) to the red emitting dopant. The red OLEDs realized by this approach not only enhanced the emission color, but also significantly improved the EL efficiency. The EL efficiency reached 3.5 cd A −1 at a current density of 20 mA cm −2 , which is enhanced by three times compared with devices where the emissive layer is composed of the DCJTB doped ADN. The saturated red emission was obtained with CIE coordinates (x = 0.618, y = 0.373) at 621 nm, and the device driving voltage is decreased as much as 38%. We attribute these improvements to the assistant dopant (C545T), which leads to the more efficient energy transfer from ADN to DCJTB. These results indicate that the co-doped system is a promising method for obtaining high-efficiency red OLEDs

  4. Synthesis, crystal growth and characterization of bioactive material: 2- Amino-1H-benzimidazolium pyridine-3-carboxylate single crystal- a proton transfer molecular complex

    Science.gov (United States)

    Fathima, K. Saiadali; Kavitha, P.; Anitha, K.

    2017-09-01

    The 1:1 molecular adducts 2- Amino-1H-benzimidazolium pyridine-3-carboxylate (2ABPC) was synthesized and grown as single crystal where 2-aminobenzimidazole (ABI) acts as a donor and nicotinic acid (NA) acts as an acceptor. The presence of proton and carbon were predicted using 1H and 13C NMR spectral analysis. The molecular structure of the crystal was elucidated by subjecting the grown crystals to the single crystal x-ray diffraction analysis and was refined by full matrix least-squares method to R = 0.038 for 2469 reflections. The vibrational modes of functional group have been studied using FTIR and Raman spectroscopic analysis. The UV-Vis spectrum exhibited a visible band at 246 nm for 2ABPC due to the nicotinate anion of the molecule. Further, the antimicrobial activity of 2ABPC complex against B. subtilis, klebsiella pneumonia, Pseudomonas eruginos and E. coli pathogens was investigated. Minimum Inhibitory Concentration (MIC) for this crystal was obtained using UV spectrometer against MRSA pathogen. It was found that the benzimidazole with aminogroup at position 2 increases the general antimicrobial activities of 2ABPC crystal.

  5. Liposomes and lipid disks traverse the BBB and BBTB as intact forms as revealed by two-step Förster resonance energy transfer imaging

    Directory of Open Access Journals (Sweden)

    Tongcheng Dai

    2018-03-01

    Full Text Available The blood–brain barrier (BBB and the blood–brain tumor barrier (BBTB prevent drug and nano-drug delivery systems from entering the brain. However, ligand-mediated nano-drug delivery systems have significantly enhanced the therapeutic treatment of glioma. In this study we investigated the mechanism especially the integrity of liposomes and lipid disks while traversing the BBB and BBTB both in vitro and in vivo. Fluorophores (DiO, DiI and DiD were loaded into liposomes and lipid disks to form Förster resonance energy transfer (FRET nano-drug delivery systems. Using brain capillary endothelial cells as a BBB model, we show that liposomes and disks are present in the cytoplasm as their intact forms and traverse the BBB with a ratio of 0.68‰ and 1.67‰, respectively. Using human umbilical vein endothelial cells as BBTB model, liposomes and disks remained intact and traversed the BBTB with a ratio of 2.31‰ and 8.32‰ at 3 h. Ex vivo imaging and immunohistochemical results revealed that liposomes and disks could traverse the BBB and BBTB in vivo as intact forms. In conclusion, these observations explain in part the mechanism by which nano-drug delivery systems increase the therapeutic treatment of glioma. KEY WORDS: Liposomes, Disks, Intact form, BBB, BBTB, FRET

  6. Proton radiography to improve proton therapy treatment

    NARCIS (Netherlands)

    Takatsu, J.; van der Graaf, E. R.; van Goethem, Marc-Jan; van Beuzekom, M.; Klaver, T.; Visser, Jan; Brandenburg, S.; Biegun, A. K.

    The quality of cancer treatment with protons critically depends on an accurate prediction of the proton stopping powers for the tissues traversed by the protons. Today, treatment planning in proton radiotherapy is based on stopping power calculations from densities of X-ray Computed Tomography (CT)

  7. Biological effects of proton radiation: an update

    International Nuclear Information System (INIS)

    Girdhani, S.; Hlatky, L.; Sachs, R.

    2015-01-01

    Proton radiation provides significant dosimetric advantages when compared with gamma radiation due to its superior energy deposition characteristics. Although the physical aspects of proton radiobiology are well understood, biological and clinical endpoints are understudied. The current practice to assume the relative biological effectiveness of low linear energy transfer (LET) protons to be a generic value of about 1.1 relative to photons likely obscures important unrecognised differentials in biological response between these radiation qualities. A deeper understanding of the biological properties induced by proton radiation would have both radiobiological and clinical impact. This article briefly points to some of the literature pertinent to the effects of protons on tissue-level processes that modify disease progression, such as angiogenesis, cell invasion and cancer metastasis. Recent findings hint that proton radiation may, in addition to offering improved radio-therapeutic targeting, be a means to provide a new dimension for increasing therapeutic benefits for patients by manipulating these tissue-level processes. (authors)

  8. Structure of the bacterial deacetylase LpxC bound to the nucleotide reaction product reveals mechanisms of oxyanion stabilization and proton transfer.

    Science.gov (United States)

    Clayton, Gina M; Klein, Daniel J; Rickert, Keith W; Patel, Sangita B; Kornienko, Maria; Zugay-Murphy, Joan; Reid, John C; Tummala, Srivanya; Sharma, Sujata; Singh, Sheo B; Miesel, Lynn; Lumb, Kevin J; Soisson, Stephen M

    2013-11-22

    The emergence of antibiotic-resistant strains of pathogenic bacteria is an increasing threat to global health that underscores an urgent need for an expanded antibacterial armamentarium. Gram-negative bacteria, such as Escherichia coli, have become increasingly important clinical pathogens with limited treatment options. This is due in part to their lipopolysaccharide (LPS) outer membrane components, which dually serve as endotoxins while also protecting Gram-negative bacteria from antibiotic entry. The LpxC enzyme catalyzes the committed step of LPS biosynthesis, making LpxC a promising target for new antibacterials. Here, we present the first structure of an LpxC enzyme in complex with the deacetylation reaction product, UDP-(3-O-(R-3-hydroxymyristoyl))-glucosamine. These studies provide valuable insight into recognition of substrates and products by LpxC and a platform for structure-guided drug discovery of broad spectrum Gram-negative antibiotics.

  9. Measurements of Polarization Transfers in Real Compton Scattering by a proton target at JLAB. A new source of information on the 3D shape of the nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Fanelli, Cristiano V. [Sapienza Univ. of Rome (Italy)

    2015-03-01

    In this thesis work, results of the analysis of the polarization transfers measured in real Compton scattering (RCS) by the Collaboration E07-002 at the Je fferson Lab Hall-C are presented. The data were collected at large scattering angle (theta_cm = 70deg) and with a polarized incident photon beam at an average energy of 3.8 GeV. Such a kind of experiments allows one to understand more deeply the reaction mechanism, that involves a real photon, by extracting both Compton form factors and Generalized Parton Distributions (GPDs) (also relevant for possibly shedding light on the total angular momentum of the nucleon). The obtained results for the longitudinal and transverse polarization transfers K_LL and K_LT, are of crucial importance, since they confirm unambiguously the disagreement between experimental data and pQCD prediction, as it was found in E99-114 experiment, and favor the Handbag mechanism. The E99-114 and E07-002 results can contribute to attract new interest on the great yield of the Compton scattering by a nucleon target, as demonstrated by the recent approval of an experimental proposal submitted to the Jefferson Lab PAC 42 for a Wide-angle Compton Scattering experiment, at 8 and 10 GeV Photon Energies. The new experiments approved to run with the updated 12 GeV electron beam at JLab, are characterized by much higher luminosities, and a new GEM tracker is under development to tackle the challenging backgrounds. Within this context, we present a new multistep tracking algorithm, based on (i) a Neural Network (NN) designed for a fast and efficient association of the hits measured by the GEM detector which allows the track identification, and (ii) the application of both a Kalman filter and Rauch-Tung-Striebel smoother to further improve the track reconstruction. The full procedure, i.e. NN and filtering, appears very promising, with high performances in terms of both association effciency and reconstruction accuracy, and these preliminary results will

  10. Sea-to-air flux of dimethyl sulfide in the South and North Pacific Ocean as measured by proton transfer reaction-mass spectrometry coupled with the gradient flux technique

    Science.gov (United States)

    Omori, Yuko; Tanimoto, Hiroshi; Inomata, Satoshi; Ikeda, Kohei; Iwata, Toru; Kameyama, Sohiko; Uematsu, Mitsuo; Gamo, Toshitaka; Ogawa, Hiroshi; Furuya, Ken

    2017-07-01

    Exchange of dimethyl sulfide (DMS) between the surface ocean and the lower atmosphere was examined by using proton transfer reaction-mass spectrometry coupled with the gradient flux (PTR-MS/GF) system. We deployed the PTR-MS/GF system and observed vertical gradients of atmospheric DMS just above the sea surface in the subtropical and transitional South Pacific Ocean and the subarctic North Pacific Ocean. In total, we obtained 370 in situ profiles, and of these we used 46 data sets to calculate the sea-to-air flux of DMS. The DMS flux determined was in the range from 1.9 to 31 μmol m-2 d-1 and increased with wind speed and biological activity, in reasonable accordance with previous observations in the open ocean. The gas transfer velocity of DMS derived from the PTR-MS/GF measurements was similar to either that of DMS determined by the eddy covariance technique or that of insoluble gases derived from the dual tracer experiments, depending on the observation sites located in different geographic regions. When atmospheric conditions were strongly stable during the daytime in the subtropical ocean, the PTR-MS/GF observations captured a daytime versus nighttime difference in DMS mixing ratios in the surface air overlying the ocean surface. The difference was mainly due to the sea-to-air DMS emissions and stable atmospheric conditions, thus affecting the gradient of DMS. This indicates that the DMS gradient is strongly controlled by diurnal variations in the vertical structure of the lower atmosphere above the ocean surface.

  11. Specificity and kinetics of alpha-synuclein binding to model membranes determined with fluorescent excited state intramolecular proton transfer (ESIPT) probe.

    Science.gov (United States)

    Shvadchak, Volodymyr V; Falomir-Lockhart, Lisandro J; Yushchenko, Dmytro A; Jovin, Thomas M

    2011-04-15

    Parkinson disease is characterized cytopathologically by the deposition in the midbrain of aggregates composed primarily of the presynaptic neuronal protein α-synuclein (AS). Neurotoxicity is currently attributed to oligomeric microaggregates subjected to oxidative modification and promoting mitochondrial and proteasomal dysfunction. Unphysiological binding to membranes of these and other organelles is presumably involved. In this study, we performed a systematic determination of the influence of charge, phase, curvature, defects, and lipid unsaturation on AS binding to model membranes using a new sensitive solvatochromic fluorescent probe. The interaction of AS with vesicular membranes is fast and reversible. The protein dissociates from neutral membranes upon thermal transition to the liquid disordered phase and transfers to vesicles with higher affinity. The binding of AS to neutral and negatively charged membranes occurs by apparently different mechanisms. Interaction with neutral bilayers requires the presence of membrane defects; binding increases with membrane curvature and rigidity and decreases in the presence of cholesterol. The association with negatively charged membranes is much stronger and much less sensitive to membrane curvature, phase, and cholesterol content. The presence of unsaturated lipids increases binding in all cases. These findings provide insight into the relation between membrane physical properties and AS binding affinity and dynamics that presumably define protein localization in vivo and, thereby, the role of AS in the physiopathology of Parkinson disease.

  12. Online monitoring of coffee roasting by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS): towards a real-time process control for a consistent roast profile.

    Science.gov (United States)

    Wieland, Flurin; Gloess, Alexia N; Keller, Marco; Wetzel, Andreas; Schenker, Stefan; Yeretzian, Chahan

    2012-03-01

    A real-time automated process control tool for coffee roasting is presented to consistently and accurately achieve a targeted roast degree. It is based on the online monitoring of volatile organic compounds (VOC) in the off-gas of a drum roaster by proton transfer reaction time-of-flight mass spectrometry at a high time (1 Hz) and mass resolution (5,500 m/Δm at full width at half-maximum) and high sensitivity (better than parts per billion by volume). Forty-two roasting experiments were performed with the drum roaster being operated either on a low, medium or high hot-air inlet temperature (= energy input) and the coffee (Arabica from Antigua, Guatemala) being roasted to low, medium or dark roast degrees. A principal component analysis (PCA) discriminated, for each one of the three hot-air inlet temperatures, the roast degree with a resolution of better than ±1 Colorette. The 3D space of the three first principal components was defined based on 23 mass spectral profiles of VOCs and their roast degree at the end point of roasting. This provided a very detailed picture of the evolution of the roasting process and allowed establishment of a predictive model that projects the online-monitored VOC profile of the roaster off-gas in real time onto the PCA space defined by the calibration process and, ultimately, to control the coffee roasting process so as to achieve a target roast degree and a consistent roasting.

  13. Deep-inelastic electron-proton diffraction

    International Nuclear Information System (INIS)

    Dainton, J.B.

    1995-11-01

    Recent measurements by the H1 collaboration at HERA of the cross section for deep-inelastic electron-proton scattering in which the proton interacts with minimal energy transfer and limited 4-momentum transfer squared are presented in the form of the contribution F 2 D(3) to the proton structure function F 2 . By parametrising the cross section phenomenologically in terms of a leading effective Regge pole exchange and comparing the result with a similar parametrisation of hadronic pp physics, the proton interaction is demonstrated to be dominantly of a diffractive nature. The quantitative interpretation of the parametrisation in terms of the properties of an effective leading Regge pole exchange, the pomeron (IP), shows that there is no evidence for a 'harder' BFKL-motivated IP in such deep-inelastic proton diffraction. The total contribution of proton diffraction to deep-inelastic electron-proton scattering is measured to be ∝10% and to be rather insensitive to Bjorken-x and Q 2 . A first measurement of the partonic structure of diffractive exchange is presented. It is shown to be readily interpreted in terms of the exchange of gluons, and to suggest that the bulk of diffractive momentum transfer is carried by a leading gluon. (orig.)

  14. Proton diffraction

    International Nuclear Information System (INIS)

    Den Besten, J.L.; Jamieson, D.N.; Allen, L.J.

    1998-01-01

    The Lindhard theory on ion channeling in crystals has been widely accepted throughout ion beam analysis for use in simulating such experiments. The simulations use a Monte Carlo method developed by Barret, which utilises the classical 'billiard ball' theory of ions 'bouncing' between planes or tubes of atoms in the crystal. This theory is not valid for 'thin' crystals where the planes or strings of atoms can no longer be assumed to be of infinite proportions. We propose that a theory similar to that used for high energy electron diffraction can be applied to MeV ions, especially protons, in thin crystals to simulate the intensities of transmission channeling and of RBS spectra. The diffraction theory is based on a Bloch wave solution of the Schroedinger equation for an ion passing through the periodic crystal potential. The widely used universal potential for proton-nucleus scattering is used to construct the crystal potential. Absorption due to thermal diffuse scattering is included. Experimental parameters such as convergence angle, beam tilt and scanning directions are considered in our calculations. Comparison between theory and experiment is encouraging and suggests that further work is justified. (authors)

  15. Extension of TOPAS for the simulation of proton radiation effects considering molecular and cellular endpoints

    International Nuclear Information System (INIS)

    Polster, Lisa; Schuemann, Jan; Rinaldi, Ilaria; McNamara, Aimee L; Paganetti, Harald; Burigo, Lucas; Stewart, Robert D; Attili, Andrea; Carlson, David J; Sato, Tatsuhiko; Ramos Méndez, José; Faddegon, Bruce; Perl, Joseph

    2015-01-01

    The aim of this work is to extend a widely used proton Monte Carlo tool, TOPAS, towards the modeling of relative biological effect (RBE) distributions in experimental arrangements as well as patients.TOPAS provides a software core which users configure by writing parameter files to, for instance, define application specific geometries and scoring conditions. Expert users may further extend TOPAS scoring capabilities by plugging in their own additional C++ code. This structure was utilized for the implementation of eight biophysical models suited to calculate proton RBE. As far as physics parameters are concerned, four of these models are based on the proton linear energy transfer, while the others are based on DNA double strand break induction and the frequency-mean specific energy, lineal energy, or delta electron generated track structure. The biological input parameters for all models are typically inferred from fits of the models to radiobiological experiments.The model structures have been implemented in a coherent way within the TOPAS architecture. Their performance was validated against measured experimental data on proton RBE in a spread-out Bragg peak using V79 Chinese Hamster cells.This work is an important step in bringing biologically optimized treatment planning for proton therapy closer to the clinical practice as it will allow researchers to refine and compare pre-defined as well as user-defined models. (paper)

  16. Influence of substitution on the proton donor and proton acceptor abilities of molecules. III. Study of chlorine and ftorine substitution alcohol

    International Nuclear Information System (INIS)

    Nurulloev, M.; Narziev, B.N.; Islomov, Z.; Fayzieva, M.

    2006-01-01

    This work gives the study of influence of chlorine and ftorine atoms as substitutions to proton donor and proton acceptor ability of primary, secondary and tertiary alifatic alcohol. In accordance to developed method the proton donor ability of studied substances are determined. It is shown that the quantity of proton donor ability of reactionary center of the molecules depend on substitution nature and its proton acceptor quantity. Proposed that substitution influence of these molecule mainly transferred by inductive effect

  17. The influence of the Coulomb-distortion effect on proton-proton observables

    International Nuclear Information System (INIS)

    Plessas, W.; Mathelitsch, L.

    1980-01-01

    The effect of the Coulomb distortion of the strong interaction is studied on the basis of nucleon-nucleon observables. In particular, cross sections, polarizations, spin-correlation parameters, and spin-transfer coefficients are considered for proton-proton as well as neutron-neutron scattering at laboratory kinetic energies Esub(Lab) = 10, 20, and 50 MeV. The calculations are performed for the meson-theoretical PARIS potential, the nonlocal separable GRAZ potential and also using the Arndt-Hackman-Roper parametrization of proton-proton scattering phase shifts. Important conclusions are drawn with respect to phenomenological phase-shift analyses. (Auth.)

  18. Proton imaging apparatus for proton therapy application

    International Nuclear Information System (INIS)

    Sipala, V.; Lo Presti, D.; Brianzi, M.; Civinini, C.; Bruzzi, M.; Scaringella, M.; Talamonti, C.; Bucciolini, M.; Cirrone, G.A.P.; Cuttone, G.; Randazzo, N.; Stancampiano, C.; Tesi, M.

    2011-01-01

    Radiotherapy with protons, due to the physical properties of these particles, offers several advantages for cancer therapy as compared to the traditional radiotherapy and photons. In the clinical use of proton beams, a p CT (Proton Computer Tomography) apparatus can contribute to improve the accuracy of the patient positioning and dose distribution calculation. In this paper a p CT apparatus built by the Prima (Proton Imaging) Italian Collaboration will be presented and the preliminary results will be discussed.

  19. Proton radioactivity from proton-rich nuclei

    International Nuclear Information System (INIS)

    Guzman, F.; Goncalves, M.; Tavares, O.A.P.; Duarte, S.B.; Garcia, F.; Rodriguez, O.

    1999-03-01

    Half-lives for proton emission from proton-rich nuclei have been calculated by using the effective liquid drop model of heavy-particle decay of nuclei. It is shown that this model is able to offer results or spontaneous proton-emission half-life-values in excellent agreement with the existing experimental data. Predictions of half-life-values for other possible proton-emission cases are present for null orbital angular momentum. (author)

  20. External proton and Li beams

    International Nuclear Information System (INIS)

    Schuff, Juan A.; Burlon, Alejandro A.; Debray, Mario E.; Kesque, Jose M.; Kreiner, Andres J.; Stoliar, Pablo A.; Naab, Fabian; Ozafran, Mabel J.; Vazquez, Monica E.; Perez de la Hoz, A.; Somacal, Hector; Valda, Alejandro; Canevas, S.; Ruffolo, M.; Tasat, D.R.; Muhlmann, M. C.

    2000-01-01

    In the frame of a feasibility study to introduce proton therapy in Argentina in a collaborative agreement between the Physics and Radiobiology Departments of the National Atomic Energy Commission or Argentina and the Centre de Protontherapie de Orsay, France, external proton and Li beams were produced at the TANDAR accelerator in Buenos Aires. The specific aim of this work was to start radiobiology studies on cell cultures and small laboratory animals. In particular we seek to determine here the relative biological effectiveness, RBE, for proton and Li beams as a function of energy for different tumor and normal cell lines. The 24 MeV proton beam was diffused using a 25 μm gold foil and extracted through a Kapton window to obtain a homogeneous field (constant to 95%) of about 7 cm in diameter. Measurements were carried out with quasi-monoenergetic beams (of 20.2 ± 0.07 MeV, 2.9 ± 0.10 MeV y 1.5 ± 0.1 MeV for protons and 21.4 ± 0.4 MeV for Lithium). Proton fluence and Bragg peaks were measured. The dose delivered in each case was monitored on-line with a calibrated transmission ionization chamber. Three cell lines PDV, PDVC 57 and V 79 (as a reference) were irradiated with γ-rays, proton and lithium beams with linear energy transfer (LET) from 2 to 100 keV/μm. RBE values in the range of 1.2-5.9 were obtained. In addition preliminary studies on chromosomal aberrations and viability of alveolar macrophages were carried out. (author)