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Sample records for proton transfer calculations

  1. 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.

  2. 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.

  3. 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.)

  4. 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)

  5. 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

  6. 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

  7. 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....

  8. 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

  9. 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.

  10. 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

  11. 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)

  12. 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.

  13. 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

  14. 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.

  15. 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...

  16. 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,.

  17. Histidine in Continuum Electrostatics Protonation State Calculations

    Science.gov (United States)

    Couch, Vernon; Stuchebruckhov, Alexei

    2014-01-01

    A modification to the standard continuum electrostatics approach to calculate protein pKas which allows for the decoupling of histidine tautomers within a two state model is presented. Histidine with four intrinsically coupled protonation states cannot be easily incorporated into a two state formalism because the interaction between the two protonatable sites of the imidazole ring is not purely electrostatic. The presented treatment, based on a single approximation of the interrelation between histidine’s charge states, allows for a natural separation of the two protonatable sites associated with the imidazole ring as well as the inclusion of all protonation states within the calculation. PMID:22072521

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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

  3. 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.).

  4. 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.

  5. 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)

  6. 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.)

  7. Transfer Area Mechanical Handling Calculation

    International Nuclear Information System (INIS)

    Dianda, B.

    2004-01-01

    This calculation is intended to support the License Application (LA) submittal of December 2004, in accordance with the directive given by DOE correspondence received on the 27th of January 2004 entitled: ''Authorization for Bechtel SAX Company L.L. C. to Include a Bare Fuel Handling Facility and Increased Aging Capacity in the License Application, Contract Number DE-AC--28-01R W12101'' (Arthur, W.J., I11 2004). This correspondence was appended by further Correspondence received on the 19th of February 2004 entitled: ''Technical Direction to Bechtel SAIC Company L.L. C. for Surface Facility Improvements, Contract Number DE-AC--28-OIRW12101; TDL No. 04-024'' (BSC 2004a). These documents give the authorization for a Fuel Handling Facility to be included in the baseline. The purpose of this calculation is to establish preliminary bounding equipment envelopes and weights for the Fuel Handling Facility (FHF) transfer areas equipment. This calculation provides preliminary information only to support development of facility layouts and preliminary load calculations. The limitations of this preliminary calculation lie within the assumptions of section 5 , as this calculation is part of an evolutionary design process. It is intended that this calculation is superseded as the design advances to reflect information necessary to support License Application. The design choices outlined within this calculation represent a demonstration of feasibility and may or may not be included in the completed design. This calculation provides preliminary weight, dimensional envelope, and equipment position in building for the purposes of defining interface variables. This calculation identifies and sizes major equipment and assemblies that dictate overall equipment dimensions and facility interfaces. Sizing of components is based on the selection of commercially available products, where applicable. This is not a specific recommendation for the future use of these components or their

  8. 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

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Engineering calculations in radiative heat transfer

    CERN Document Server

    Gray, W A; Hopkins, D W

    1974-01-01

    Engineering Calculations in Radiative Heat Transfer is a six-chapter book that first explains the basic principles of thermal radiation and direct radiative transfer. Total exchange of radiation within an enclosure containing an absorbing or non-absorbing medium is then described. Subsequent chapters detail the radiative heat transfer applications and measurement of radiation and temperature.

  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. 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

  3. The calculation of proton chemical shifts in hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Raymond J [Liverpool Univ. (United Kingdom). Dept. of Chemistry

    1994-12-31

    Novel extension of the CHARGE3 semi-empirical calculation of the partial atomic charges in molecules are described which allow the accurate calculation of the proton chemical shifts of a variety of acyclic alkanes. This simple scheme predicts the proton chemical shifts of all the simple alkanes, cyclohexane and methyl cyclohexanes, norbornane, trans-decalin and trans perhydrophenanthrene, comprising a range of chemical shifts from 0.3 to 2.2 {delta} with the known substituent chemical shifts of other functional groups this could allow the general prediction of proton chemical shifts in a simple and useful format. (author) 13 refs., 2 figs.

  4. 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)

  5. 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.

  6. Relativistic total and differential cross section proton--proton electron--positron pair production calculation

    International Nuclear Information System (INIS)

    Rubinstein, J.E.

    1976-01-01

    Circle Feynman diagrams for a specific permutation of variables along with their corresponding algebraic expressions are presented to evaluate [H] 2 for proton-proton electron-positron pair production. A Monte Carlo integration technique is introduced and is used to set up the multiple integral expression for the total pair production cross section. The technique is first applied to the Compton scattering problem and then to an arbitrary multiple integral. The relativistic total cross section for proton-proton electron-positron pair production was calculated for eight different values of incident proton energy. A variety of differential cross sections were calculated for the above energies. Angular differential cross section distributions are presented for the electron, positron, and proton. Invariant mass differential cross section distributions are done both with and without the presence of [H] 2 . Both WGHT and log 10 (TOTAL) distributions were also obtained. The general behavioral trends of the total and differential cross sections for proton-proton electron-positron pair production are presented. The range of validity for this calculation is from 0 to about 200 MeV

  7. 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.)

  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. Calculation of proton beam initial orbit at cyclotron central region

    International Nuclear Information System (INIS)

    Pramudita Anggraita

    2012-01-01

    A calculation of proton beam initial orbits at cyclotron central region was carried out using Scilab 5.2.0. The calculation was done in 2 dimensions in a homogeneous magnetic field of 1.66 tesla at frequency of fourth harmonics. The positions of ion source, dees, and dummy dees follow those of GE Minitrace cyclotron, peak dee voltage 30 kV. The calculation yields result comparable to those simulated at KIRAMS-13 cyclotron. (author)

  10. 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.

  11. Methods for calculating anisotropic transfer cross sections

    International Nuclear Information System (INIS)

    Cai, Shaohui; Zhang, Yixin.

    1985-01-01

    The Legendre moments of the group transfer cross section, which are widely used in the numerical solution of the transport calculation can be efficiently and accurately constructed from low-order (K = 1--2) successive partial range moments. This is convenient for the generation of group constants. In addition, a technique to obtain group-angle correlation transfer cross section without Legendre expansion is presented. (author)

  12. Analytical probabilistic proton dose calculation and range uncertainties

    Science.gov (United States)

    Bangert, M.; Hennig, P.; Oelfke, U.

    2014-03-01

    We introduce the concept of analytical probabilistic modeling (APM) to calculate the mean and the standard deviation of intensity-modulated proton dose distributions under the influence of range uncertainties in closed form. For APM, range uncertainties are modeled with a multivariate Normal distribution p(z) over the radiological depths z. A pencil beam algorithm that parameterizes the proton depth dose d(z) with a weighted superposition of ten Gaussians is used. Hence, the integrals ∫ dz p(z) d(z) and ∫ dz p(z) d(z)2 required for the calculation of the expected value and standard deviation of the dose remain analytically tractable and can be efficiently evaluated. The means μk, widths δk, and weights ωk of the Gaussian components parameterizing the depth dose curves are found with least squares fits for all available proton ranges. We observe less than 0.3% average deviation of the Gaussian parameterizations from the original proton depth dose curves. Consequently, APM yields high accuracy estimates for the expected value and standard deviation of intensity-modulated proton dose distributions for two dimensional test cases. APM can accommodate arbitrary correlation models and account for the different nature of random and systematic errors in fractionated radiation therapy. Beneficial applications of APM in robust planning are feasible.

  13. CENTRIFUGAL COMPRESSOR EFFICIENCY CALCULATION WITH HEAT TRANSFER

    Directory of Open Access Journals (Sweden)

    Valeriu Dragan

    2017-12-01

    and manner under which the efficiency itself is calculated. The paper  presents a more robust approach to measuring efficiency, regardless of the heat transfer within the turbomachinery itself. Possible applications of the study may range from cold-start regime simulation to the optimization of inter-cooling setup or even flow angle control without mechanically actuated OGV

  14. 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...

  15. 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.

  16. Calculations of proton-binding thermodynamics in proteins.

    Science.gov (United States)

    Beroza, P; Case, D A

    1998-01-01

    Computational models of proton binding can range from the chemically complex and statistically simple (as in the quantum calculations) to the chemically simple and statistically complex. Much progress has been made in the multiple-site titration problem. Calculations have improved with the inclusion of more flexibility in regard to both the geometry of the proton binding and the larger scale protein motions associated with titration. This article concentrated on the principles of current calculations, but did not attempt to survey their quantitative performance. This is (1) because such comparisons are given in the cited papers and (2) because continued developments in understanding conformational flexibility and interaction energies will be needed to develop robust methods with strong predictive power. Nevertheless, the advances achieved over the past few years should not be underestimated: serious calculations of protonation behavior and its coupling to conformational change can now be confidently pursued against a backdrop of increasing understanding of the strengths and limitations of such models. It is hoped that such theoretical advances will also spur renewed experimental interest in measuring both overall titration curves and individual pKa values or pKa shifts. Exploration of the shapes of individual titration curves (as measured by Hill coefficients and other parameters) would also be useful in assessing the accuracy of computations and in drawing connections to functional behavior.

  17. 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.

  18. Simplified shielding calculation system for high-intensity proton accelerators

    Energy Technology Data Exchange (ETDEWEB)

    Masumura, Tomomi; Nakashima, Hiroshi; Nakane, Yoshihiro; Sasamoto, Nobuo [Center for Neutron Science, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan)

    2000-06-01

    A simplified shielding calculation system is developed for applying conceptual shielding design of facilities in the joint project for high-intensity proton accelerators. The system is composed of neutron transmission calculation part for bulk shielding using simplified formulas: Moyer model and Tesch's formula, and neutron skyshine calculation part using an empirical formula: Stapleton's formula. The system is made with the Microsoft Excel software for user's convenience. This report provides a manual for the system as well as calculation conditions used in the calculation such as Moyer model's parameters. In this report preliminary results based on data at December 8, 1999, are also shown as an example. (author)

  19. DRY TRANSFER FACILITY CRITICALITY SAFETY CALCULATIONS

    International Nuclear Information System (INIS)

    C.E. Sanders

    2005-01-01

    This design calculation updates the previous criticality evaluation for the fuel handling, transfer, and staging operations to be performed in the Dry Transfer Facility (DTF) including the remediation area. The purpose of the calculation is to demonstrate that operations performed in the DTF and RF meet the nuclear criticality safety design criteria specified in the ''Project Design Criteria (PDC) Document'' (BSC 2004 [DIRS 171599], Section 4.9.2.2), the nuclear facility safety requirement in ''Project Requirements Document'' (Canori and Leitner 2003 [DIRS 166275], p. 4-206), the functional/operational nuclear safety requirement in the ''Project Functional and Operational Requirements'' document (Curry 2004 [DIRS 170557], p. 75), and the functional nuclear criticality safety requirements described in the ''Dry Transfer Facility Description Document'' (BSC 2005 [DIRS 173737], p. 3-8). A description of the changes is as follows: (1) Update the supporting calculations for the various Category 1 and 2 event sequences as identified in the ''Categorization of Event Sequences for License Application'' (BSC 2005 [DIRS 171429], Section 7). (2) Update the criticality safety calculations for the DTF staging racks and the remediation pool to reflect the current design. This design calculation focuses on commercial spent nuclear fuel (SNF) assemblies, i.e., pressurized water reactor (PWR) and boiling water reactor (BWR) SNF. U.S. Department of Energy (DOE) Environmental Management (EM) owned SNF is evaluated in depth in the ''Canister Handling Facility Criticality Safety Calculations'' (BSC 2005 [DIRS 173284]) and is also applicable to DTF operations. Further, the design and safety analyses of the naval SNF canisters are the responsibility of the U.S. Department of the Navy (Naval Nuclear Propulsion Program) and will not be included in this document. Also, note that the results for the Monitored Geologic Repository (MGR) Site specific Cask (MSC) calculations are limited to the

  20. Approaches to proton single-event rate calculations

    International Nuclear Information System (INIS)

    Petersen, E.L.

    1996-01-01

    This article discusses the fundamentals of proton-induced single-event upsets and of the various methods that have been developed to calculate upset rates. Two types of approaches are used based on nuclear-reaction analysis. Several aspects can be analyzed using analytic methods, but a complete description is not available. The paper presents an analytic description for the component due to elastic-scattering recoils. There have been a number of studies made using Monte Carlo methods. These can completely describe the reaction processes, including the effect of nuclear reactions occurring outside the device-sensitive volume. They have not included the elastic-scattering processes. The article describes the semiempirical approaches that are most widely used. The quality of previous upset predictions relative to space observations is discussed and leads to comments about the desired quality of future predictions. Brief sections treat the possible testing limitation due to total ionizing dose effects, the relationship of proton and heavy-ion upsets, upsets due to direct proton ionization, and relative proton and cosmic-ray upset rates

  1. Nodewise analytical calculation of the transfer function

    International Nuclear Information System (INIS)

    Makai, Mihaly

    1994-01-01

    The space dependence of neutron noise has so far been mostly investigated in homogeneous core models. Application of core diagnostic methods to locate a malfunction requires however that the transfer function be calculated for real, inhomogeneous cores. A code suitable for such purpose must be able to handle complex arithmetic and delta-function source. Further requirements are analytical dependence in one spatial variable and fast execution. The present work describes the TIDE program written to fulfil the above requirements. The core is subdivided into homogeneous, square assemblies. An analytical solution is given, which is a generalisation of the inhomogeneous response matrix method. (author)

  2. 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.

  3. 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

  4. 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.

  5. Calculation of fusion gain in fast ignition with magnetic target by relativistic electrons and protons

    International Nuclear Information System (INIS)

    Parvazian, A.; Javani, A.

    2010-01-01

    Fast ignition is a new method for inertial confinement fusion in which the compression and ignition steps are separated. In the first stage, fuel is compressed by laser or ion beams. In the second phase, relativistic electrons are generated by pettawat laser in the fuel. Also, in the second phase 5-35 MeV protons can be generated in the fuel. Electrons or protons can penetrate in to the ultra-dense fuel and deposit their energy in the fuel. More recently, cylindrical rather than spherical fuel chambers with magnetic control in the plasma domain have been also considered. This is called magnetized target fusion. Magnetic field has effects on relativistic electrons energy deposition rate in fuel. In this work, fast ignition method in cylindrical fuel chambers is investigated and transportation of the relativistic electrons and protons is calculated using MCNPX and FLUKA codes with 0.25 and 0.5 tesla magnetic field in single and dual hot spot. Furthermore, the transfer rate of relativistic electrons and high energy protons to the fuel and fusion gain are calculated. The results show that the presence of external magnetic field guarantees higher fusion gain, and relativistic electrons are much more appropriate objects for ignition. Magnetized target fusion in dual hot spot can be considered as an appropriate substitution for the current inertial confinement fusion techniques.

  6. Calculation of fusion gain in fast ignition with magnetic target by relativistic electrons and protons

    Directory of Open Access Journals (Sweden)

    A Parvazian

    2010-12-01

    Full Text Available Fast ignition is a new method for inertial confinement fusion (ICF in which the compression and ignition steps are separated. In the first stage, fuel is compressed by laser or ion beams. In the second phase, relativistic electrons are generated by pettawat laser in the fuel. Also, in the second phase 5-35 MeV protons can be generated in the fuel. Electrons or protons can penetrate in to the ultra-dense fuel and deposit their energy in the fuel . More recently, cylindrical rather than spherical fuel chambers with magnetic control in the plasma domain have been also considered. This is called magnetized target fusion (MTF. Magnetic field has effects on relativistic electrons energy deposition rate in fuel. In this work, fast ignition method in cylindrical fuel chambers is investigated and transportation of the relativistic electrons and protons is calculated using MCNPX and FLUKA codes with 0. 25 and 0. 5 tesla magnetic field in single and dual hot spot. Furthermore, the transfer rate of relativistic electrons and high energy protons to the fuel and fusion gain are calculated. The results show that the presence of external magnetic field guarantees higher fusion gain, and relativistic electrons are much more appropriate objects for ignition. MTF in dual hot spot can be considered as an appropriate substitution for the current ICF techniques.

  7. 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.

  8. 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...

  9. 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...

  10. Shielding calculations for a 30 MeV proton accelerator

    International Nuclear Information System (INIS)

    Nandy, Maitreyee; Sarkar, P.K.

    2003-01-01

    Full text: The thickness of the shield, made of ordinary concrete, required to reduce the equivalent dose rate below the maximum permissible limit and to ensure safe operation of a 30 MeV proton accelerator has been estimated using the Moyer model. Required double differential neutron yield from thick stopping targets has been calculated for several reactions to be used for production of 67 Ga, 111 In, 123 I and 201 Tl radioisotopes. The neutron emission at 0 deg and 90 deg angles with respect to the incident beam direction is estimated using the hybrid model code ALICE91 which considers preequilibrium and equilibrium emissions from the target+projectile composite system. From this neutron yield the equivalent neutron dose rate at unit distance is determined using the ICRP recommended flux-to-dose conversion factors

  11. Monte Carlo calculations supporting patient plan verification in proton therapy

    Directory of Open Access Journals (Sweden)

    Thiago Viana Miranda Lima

    2016-03-01

    Full Text Available Patient’s treatment plan verification covers substantial amount of the quality assurance (QA resources, this is especially true for Intensity Modulated Proton Therapy (IMPT. The use of Monte Carlo (MC simulations in supporting QA has been widely discussed and several methods have been proposed. In this paper we studied an alternative approach from the one being currently applied clinically at Centro Nazionale di Adroterapia Oncologica (CNAO. We reanalysed the previously published data (Molinelli et al. 2013, where 9 patient plans were investigated in which the warning QA threshold of 3% mean dose deviation was crossed. The possibility that these differences between measurement and calculated dose were related to dose modelling (Treatment Planning Systems (TPS vs MC, limitations on dose delivery system or detectors mispositioning was originally explored but other factors such as the geometric description of the detectors were not ruled out. For the purpose of this work we compared ionisation-chambers measurements with different MC simulations results. It was also studied some physical effects introduced by this new approach for example inter detector interference and the delta ray thresholds. The simulations accounting for a detailed geometry typically are superior (statistical difference - p-value around 0.01 to most of the MC simulations used at CNAO (only inferior to the shift approach used. No real improvement were observed in reducing the current delta-ray threshold used (100 keV and no significant interference between ion chambers in the phantom were detected (p-value 0.81. In conclusion, it was observed that the detailed geometrical description improves the agreement between measurement and MC calculations in some cases. But in other cases position uncertainty represents the dominant uncertainty. The inter chamber disturbance was not detected for the therapeutic protons energies and the results from the current delta threshold are

  12. 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.)

  13. Correlation between experimental data of protonation of aromatic compounds at (+) atmospheric pressure photoionization and theoretically calculated enthalpies.

    Science.gov (United States)

    Ahmed, Arif; Lim, Dongwon; Choi, Cheol Ho; Kim, Sunghwan

    2017-06-30

    The theoretical enthalpy calculated from the overall protonation reaction (electron transfer plus hydrogen transfer) in positive-mode (+) atmospheric-pressure photoionization (APPI) was compared with experimental results for 49 aromatic compounds. A linear relationship was observed between the calculated ΔH and the relative abundance of the protonated peak. The parameter gives reasonable predictions for all the aromatic hydrocarbon compounds used in this study. A parameter is devised by combining experimental MS data and high-level theoretical calculations. A (+) APPI Q Exactive Orbitrap mass spectrometer was used to obtain MS data for each solution. B3LYP exchange-correlation functions with the standard 6-311+G(df,2p) basis set was used to perform density functional theory (DFT) calculations. All the molecules with ΔH toluene clusters produced protonated ions, regardless of the desolvation temperature. For molecules with ΔH >0, molecular ions were more abundant at typical APPI desolvation temperatures (300°C), while the protonated ions became comparable or dominant at higher temperatures (400°C). The toluene cluster size was an important factor when predicting the ionization behavior of aromatic hydrocarbon ions in (+) APPI. The data used in this study clearly show that the theoretically calculated reaction enthalpy (ΔH) of protonation with toluene dimers can be used to predict the protonation behavior of aromatic compounds. When compounds have a negative ΔH value, the types of ions generated for aromatic compounds could be very well predicted based on the ΔH value. The ΔH can explain overall protonation behavior of compounds with ΔH values >0. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  14. 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.

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

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

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

  16. Proton dose calculation on scatter-corrected CBCT image: Feasibility study for adaptive proton therapy

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yang-Kyun, E-mail: ykpark@mgh.harvard.edu; Sharp, Gregory C.; Phillips, Justin; Winey, Brian A. [Department of Radiation Oncology, Massachusetts General Hospital and Harvard Medical School, Boston, Massachusetts 02114 (United States)

    2015-08-15

    Purpose: To demonstrate the feasibility of proton dose calculation on scatter-corrected cone-beam computed tomographic (CBCT) images for the purpose of adaptive proton therapy. Methods: CBCT projection images were acquired from anthropomorphic phantoms and a prostate patient using an on-board imaging system of an Elekta infinity linear accelerator. Two previously introduced techniques were used to correct the scattered x-rays in the raw projection images: uniform scatter correction (CBCT{sub us}) and a priori CT-based scatter correction (CBCT{sub ap}). CBCT images were reconstructed using a standard FDK algorithm and GPU-based reconstruction toolkit. Soft tissue ROI-based HU shifting was used to improve HU accuracy of the uncorrected CBCT images and CBCT{sub us}, while no HU change was applied to the CBCT{sub ap}. The degree of equivalence of the corrected CBCT images with respect to the reference CT image (CT{sub ref}) was evaluated by using angular profiles of water equivalent path length (WEPL) and passively scattered proton treatment plans. The CBCT{sub ap} was further evaluated in more realistic scenarios such as rectal filling and weight loss to assess the effect of mismatched prior information on the corrected images. Results: The uncorrected CBCT and CBCT{sub us} images demonstrated substantial WEPL discrepancies (7.3 ± 5.3 mm and 11.1 ± 6.6 mm, respectively) with respect to the CT{sub ref}, while the CBCT{sub ap} images showed substantially reduced WEPL errors (2.4 ± 2.0 mm). Similarly, the CBCT{sub ap}-based treatment plans demonstrated a high pass rate (96.0% ± 2.5% in 2 mm/2% criteria) in a 3D gamma analysis. Conclusions: A priori CT-based scatter correction technique was shown to be promising for adaptive proton therapy, as it achieved equivalent proton dose distributions and water equivalent path lengths compared to those of a reference CT in a selection of anthropomorphic phantoms.

  17. 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.

  18. 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...

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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)

  10. 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.

  11. 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

  12. 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...

  13. Distorted wave calculations for double electron transfer

    International Nuclear Information System (INIS)

    Martinez, A.E.; Rivarola, R.D.; Gayet, R.; Hanssen, J.

    1992-01-01

    The resonant double electron capture by alpha particles in helium targets is studied, at intermediate and high collision energies, using the Continuum Distorted Wave - Eikonal Initial State (CDW-EIS) model. Differential and total cross sections for capture into the He (1 s 2 ) final state are calculated in the framework of an Independent Electron Approximation (IEA). Theoretical results are compared with the experimental data available at present for capture into any final state of helium. (author)

  14. An introduction to heat transfer principles and calculations

    CERN Document Server

    Ede, A J; Ower, E

    1967-01-01

    An Introduction to Heat Transfer Principles and Calculations is an introductory text to the principles and calculations of heat transfer. The theory underlying heat transfer is described, and the principal results and formulae are presented. Available techniques for obtaining rapid, approximate solutions to complicated problems are also considered. This book is comprised of 12 chapters and begins with a brief account of some of the concepts, methods, nomenclature, and other relevant information about heat transfer. The reader is then introduced to radiation, conduction, convection, and boiling

  15. TU-AB-BRC-09: Fast Dose-Averaged LET and Biological Dose Calculations for Proton Therapy Using Graphics Cards

    International Nuclear Information System (INIS)

    Wan, H; Tseung, Chan; Beltran, C

    2016-01-01

    Purpose: To demonstrate fast and accurate Monte Carlo (MC) calculations of proton dose-averaged linear energy transfer (LETd) and biological dose (BD) on a Graphics Processing Unit (GPU) card. Methods: A previously validated GPU-based MC simulation of proton transport was used to rapidly generate LETd distributions for proton treatment plans. Since this MC handles proton-nuclei interactions on an event-by-event using a Bertini intranuclear cascade-evaporation model, secondary protons were taken into account. The smaller contributions of secondary neutrons and recoil nuclei were ignored. Recent work has shown that LETd values are sensitive to the scoring method. The GPU-based LETd calculations were verified by comparing with a TOPAS custom scorer that uses tabulated stopping powers, following recommendations by other authors. Comparisons were made for prostate and head-and-neck patients. A python script is used to convert the MC-generated LETd distributions to BD using a variety of published linear quadratic models, and to export the BD in DICOM format for subsequent evaluation. Results: Very good agreement is obtained between TOPAS and our GPU MC. Given a complex head-and-neck plan with 1 mm voxel spacing, the physical dose, LETd and BD calculations for 10"8 proton histories can be completed in ∼5 minutes using a NVIDIA Titan X card. The rapid turnover means that MC feedback can be obtained on dosimetric plan accuracy as well as BD hotspot locations, particularly in regards to their proximity to critical structures. In our institution the GPU MC-generated dose, LETd and BD maps are used to assess plan quality for all patients undergoing treatment. Conclusion: Fast and accurate MC-based LETd calculations can be performed on the GPU. The resulting BD maps provide valuable feedback during treatment plan review. Partially funded by Varian Medical Systems.

  16. TU-AB-BRC-09: Fast Dose-Averaged LET and Biological Dose Calculations for Proton Therapy Using Graphics Cards

    Energy Technology Data Exchange (ETDEWEB)

    Wan, H; Tseung, Chan; Beltran, C [Mayo Clinic, Rochester, MN (United States)

    2016-06-15

    Purpose: To demonstrate fast and accurate Monte Carlo (MC) calculations of proton dose-averaged linear energy transfer (LETd) and biological dose (BD) on a Graphics Processing Unit (GPU) card. Methods: A previously validated GPU-based MC simulation of proton transport was used to rapidly generate LETd distributions for proton treatment plans. Since this MC handles proton-nuclei interactions on an event-by-event using a Bertini intranuclear cascade-evaporation model, secondary protons were taken into account. The smaller contributions of secondary neutrons and recoil nuclei were ignored. Recent work has shown that LETd values are sensitive to the scoring method. The GPU-based LETd calculations were verified by comparing with a TOPAS custom scorer that uses tabulated stopping powers, following recommendations by other authors. Comparisons were made for prostate and head-and-neck patients. A python script is used to convert the MC-generated LETd distributions to BD using a variety of published linear quadratic models, and to export the BD in DICOM format for subsequent evaluation. Results: Very good agreement is obtained between TOPAS and our GPU MC. Given a complex head-and-neck plan with 1 mm voxel spacing, the physical dose, LETd and BD calculations for 10{sup 8} proton histories can be completed in ∼5 minutes using a NVIDIA Titan X card. The rapid turnover means that MC feedback can be obtained on dosimetric plan accuracy as well as BD hotspot locations, particularly in regards to their proximity to critical structures. In our institution the GPU MC-generated dose, LETd and BD maps are used to assess plan quality for all patients undergoing treatment. Conclusion: Fast and accurate MC-based LETd calculations can be performed on the GPU. The resulting BD maps provide valuable feedback during treatment plan review. Partially funded by Varian Medical Systems.

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

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

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

  18. 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.

  19. 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

  20. 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.

  1. Bivariational calculations for radiation transfer in an inhomogeneous participating media

    International Nuclear Information System (INIS)

    El Wakil, S.A.; Machali, H.M.; Haggag, M.H.; Attia, M.T.

    1986-07-01

    Equations for radiation transfer are obtained for dispersive media with space dependent albedo. Bivariational bound principle is used to calculate the reflection and transmission coefficients for such media. Numerical results are given and compared. (author)

  2. Method of calculating heat transfer in furnaces of small power

    Directory of Open Access Journals (Sweden)

    Khavanov Pavel

    2016-01-01

    Full Text Available This publication presents the experiences and results of generalization criterion equation of importance in the analysis of the processes of heat transfer and thermal calculations of low-power heat generators cooled combustion chambers. With generalizing depending estimated contribution of radiation and convective heat transfer component in the complex for the combustion chambers of small capacity boilers. Determined qualitative and quantitative dependence of the integrated radiative-convective heat transfer from the main factors working combustion chambers of small volume.

  3. Ab initio calculation of the neutron-proton mass difference

    Science.gov (United States)

    Borsanyi, Sz.; Durr, S.; Fodor, Z.; Hoelbling, C.; Katz, S. D.; Krieg, S.; Lellouch, L.; Lippert, T.; Portelli, A.; Szabo, K. K.; Toth, B. C.

    2015-03-01

    The existence and stability of atoms rely on the fact that neutrons are more massive than protons. The measured mass difference is only 0.14% of the average of the two masses. A slightly smaller or larger value would have led to a dramatically different universe. Here, we show that this difference results from the competition between electromagnetic and mass isospin breaking effects. We performed lattice quantum-chromodynamics and quantum-electrodynamics computations with four nondegenerate Wilson fermion flavors and computed the neutron-proton mass-splitting with an accuracy of 300 kilo-electron volts, which is greater than 0 by 5 standard deviations. We also determine the splittings in the Σ, Ξ, D, and Ξcc isospin multiplets, exceeding in some cases the precision of experimental measurements.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. Ab initio calculation of the neutron-proton mass difference

    CERN Multimedia

    CERN. Geneva

    2015-01-01

    The existence and stability of atoms relies on the fact that neutrons are more massive than protons. The mass difference is only 0.14% of the average and has significant astrophysical and cosmological implications. A slightly smaller or larger value would have led to a dramatically different universe. After an introduction to the problem and to lattice quantum chromodynamics (QCD), I will show how this difference can be computed precisely by carefully accounting for electromagnetic and mass isospin breaking effects in lattice computations. I will also report on results for splittings in the \\Sigma, \\Xi, D and \\Xi_{cc} isospin multiplets, some of which are predictions. The computations are performed in lattice QCD plus QED with four, non-degenerate quark flavors.

  13. 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.

  14. Calculation of the decay rate of the proton

    International Nuclear Information System (INIS)

    Ross, D.A.

    1980-01-01

    The SU(5) model of Georgi and Glashow is used for these calculations, being the simplist such model and since the point of unification of the strong, weak and electromagnetic interactions is very intensitive to the exact details of the model provided it obeys the desert hypothesis. The broad features of the calculation are common to all models with a dessert between the W-mass and unification

  15. 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.

  16. 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

  17. 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.

  18. Shielding calculation of slow extracted beam facility at KEK proton synchrotron

    International Nuclear Information System (INIS)

    Hirabayashi, Hiromi; Katoh, Kazuaki

    1978-01-01

    The KEK proton synchrotron has two external beam lines, i.e. a fast extracted beam line for a bubble chamber and a slow extracted beam line for counter experiments. The maximum total intensity of the slow beam is estimated as 5 x 10 12 protons per sec. For beam losses along the line, shielding calculation was made, and on the basis of these results, adequacy of the current shielding construction plans was discussed. (Mori, K.)

  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. 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.

  1. Incorporating partial shining effects in proton pencil-beam dose calculation

    International Nuclear Information System (INIS)

    Li Yupeng; Zhang Xiaodong; Lii Mingfwu; Sahoo, Narayan; Zhu, Ron X; Gillin, Michael; Mohan, Radhe

    2008-01-01

    A range modulator wheel (RMW) is an essential component in passively scattered proton therapy. We have observed that a proton beam spot may shine on multiple steps of the RMW. Proton dose calculation algorithms normally do not consider the partial shining effect, and thus overestimate the dose at the proximal shoulder of spread-out Bragg peak (SOBP) compared with the measurement. If the SOBP is adjusted to better fit the plateau region, the entrance dose is likely to be underestimated. In this work, we developed an algorithm that can be used to model this effect and to allow for dose calculations that better fit the measured SOBP. First, a set of apparent modulator weights was calculated without considering partial shining. Next, protons spilled from the accelerator reaching the modulator wheel were simplified as a circular spot of uniform intensity. A weight-splitting process was then performed to generate a set of effective modulator weights with the partial shining effect incorporated. The SOBPs of eight options, which are used to label different combinations of proton-beam energy and scattering devices, were calculated with the generated effective weights. Our algorithm fitted the measured SOBP at the proximal and entrance regions much better than the ones without considering partial shining effect for all SOBPs of the eight options. In a prostate patient, we found that dose calculation without considering partial shining effect underestimated the femoral head and skin dose

  2. A new approach for soil-plant transfer calculations

    International Nuclear Information System (INIS)

    Dorp, F. van; Eleveld, R.; Frissel, M.J.

    1979-01-01

    Models to calculate radiation doses to man caused by normal or accidental release of radionuclides from nuclear industries often include the transfer of these nuclides from soil to plant. This soil-plant transfer is mostly described with a black box approach by using concentration factors. This approach has several disadvantages, the most important being the lack of physical meaning of a concentration factor. We propose to describe the soil-plant transfer of radionuclides as a function of plant and soil parameters all having a physical meaning. The separate parameters are open to experimental determination but a realistic estimation of the parameters is also possible, or the use of a combination of both. Depending on the purpose of the calculation, realistic or conservative values of the parameters can be used and the degree of conservatism can be indicated. (author)

  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. Deep-penetration calculations in concrete and iron for shielding of proton therapy accelerators

    International Nuclear Information System (INIS)

    Sheu, Rong-Jiun; Chen, Yen-Fu; Lin, Uei-Tyng; Jiang, Shiang-Huei

    2012-01-01

    Proton accelerators in the energy range of approximately 200 MeV have become increasingly popular for cancer treatment in recent years. These proton therapy facilities usually involve bulky concrete or iron in their shielding design or accelerator structure. Simple shielding data, such as source terms or attenuation lengths for various proton energies and materials are useful in designing accelerator shielding. Understanding the appropriateness or uncertainties associated with these data, which are largely generated from Monte Carlo simulations, is critical to the quality of a shielding design. This study demonstrated and investigated the problems of deep-penetration calculations on the estimation of shielding parameters through an extensive comparison between the FLUKA and MCNPX calculations for shielding against a 200-MeV proton beam hitting an iron target. Simulations of double-differential neutron production from proton bombardment were validated by comparison with experimental data. For the concrete shielding, the FLUKA calculated depth–dose distributions were consistent with the MCNPX results, except for some discrepancies in backward directions. However, for the iron shielding, if FLUKA is used inappropriately then overestimation of neutron attenuation can be expected as shown by this work because of the multigroup treatment for low-energy neutrons in FLUKA. Two neutron energy group structures, three degrees of self-shielding correction, and two iron compositions were considered in this study. Significant variation of the resulting attenuation lengths indicated the importance of problem-dependent multigroup cross sections and proper modeling of iron composition in deep-penetration calculations.

  5. 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.

  6. Calculated neutron spectrum from 800-MeV protons incident on a copper beam stop

    International Nuclear Information System (INIS)

    Perry, D.G.

    1975-10-01

    A Monte Carlo calculation was performed to obtain the neutron spectrum generated by 800-MeV protons incident on the LAMPF main copper beam stop. The total flux is calculated to be of the order of 10 13 n/cm 2 -sec-mA at full-beam intensity of 1 mA, with flux spectra calculated for angles of 20 0 , 30 0 , 60 0 , 90 0 , 120 0 , and 150 0 . (auth)

  7. Magnetization transfer MR of cerebrovascular disorders using calculated images

    Energy Technology Data Exchange (ETDEWEB)

    Enomoto, Kyoko; Watabe, Tsuneya; Amanuma, Makoto; Heshiki, Atsuko [Saitama Medical School, Moroyama, Saitama (Japan)

    1997-06-01

    This study applied a magnetization transfer contrast method to patients with cerebrovascular disorders. A 1.5 T superconducting MR unit was used, and magnetization transfer ratio (MTR) images were calculated by evaluating two paired images before and after off-resonance gradient echo pulse sequences. The normal white matter showed the highest MTRs, CSF the lowest, and gray matter, intermediate. Cerebral ischemic patients showed two patterns according to the chronological stage of the affected area. Lesions in the acute and subacute stages revealed higher transfer rates than those in the chronic stage. Patients with cerebral hemorrhage were divided into three groups: the hyperacute group showed a low transfer pattern; the acute group presented inhomogeneous high transfer rates; and the subacute group showed remarkably low transfer rates. In the acute and subacute ischemic stages, increased macromolecules caused higher MTRs than in the chronic stage. In hemorrhagic groups, low MTRs in subacute hemorrhage reflected the transfer of methemoglobin. High MTRs in acute hemorrhage with rich deoxyhemoglobin suggested increased fibrin, plasma, and serum components of macromolecules. The MTC method provided new chronological information on cerebral hemorrhage, adding to that provided by routine MR images. (author)

  8. Available transfer capability calculation considering voltage stability margin

    International Nuclear Information System (INIS)

    Pan, Xiong; Xu, Guoyu

    2005-01-01

    To make the electricity trades carry out successfully, the calculation of available transfer capability (ATC) must coordinate the relationship between the security and economic benefits. In this paper, a model for ATC calculations accorded with trade-off mechanism in electricity market was set up. The impact of branch outage contingency on the static voltage stability margin was analyzed, and contingency ranking was performed through sensitivity indices of branch flows with respect to the loading margin. Optimal power flow based on primal-dual interior point method was applied to obtain ATC when the N-1 security constraints were included. The calculation results of IEEE 30-bus and IEEE 118-bus systems show that the proposed model and method are valid. (author) (N-1 security constraints; Electricity market; Available transfer capability; Optimal power flow; Voltage stability)

  9. 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.)

  10. 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.)

  11. Calculated secondary yields for proton broadband using DECAY TURTLE

    International Nuclear Information System (INIS)

    Sondgeroth, A.

    1995-02-01

    The calculations for the yields were done by Al Sondgeroth and Anthony Malensek. The authors used the DECAY deck called PBSEC E.DAT from the CMS DECKS library. After obtaining the run modes and calibration modes from the liaison physicist, they made individual decay runs, using DECAY TURTLE from the CMS libraries and a production spectrum subroutine which was modified by Anthony, for each particle and decay mode for all particle types coming out of the target box. Results were weighted according to branching ratios for particles with more than one decay mode. The production spectra were produced assuming beryllium as the target. The optional deuterium target available to broadband will produce slightly higher yields. It should be noted that they did not include pion yields from klong decays because they could not simulate three body decays. Pions from klongs would add a very small fraction to the total yield

  12. 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

  13. Electronic stopping power calculation for water under the Lindhard formalism for application in proton computed tomography

    Energy Technology Data Exchange (ETDEWEB)

    Guerrero, A. F., E-mail: afguerreror@uqvirtual.edu.co [Departamento de Física, Universidad Del Quindío Cra 15 # 12N Armenia, Quindío (Colombia); Mesa, J., E-mail: jmesa@ibb.unesp.br [Instituto de Biociências de Botucatu da UNESP Distrito de Rubião Jr. s/n°, 18618-000, Botucatu, SP (Brazil)

    2016-07-07

    Because of the behavior that charged particles have when they interact with biological material, proton therapy is shaping the future of radiation therapy in cancer treatment. The planning of radiation therapy is made up of several stages. The first one is the diagnostic image, in which you have an idea of the density, size and type of tumor being treated; to understand this it is important to know how the particles beam interacts with the tissue. In this work, by using de Lindhard formalism and the Y.R. Waghmare model for the charge distribution of the proton, the electronic stopping power (SP) for a proton beam interacting with a liquid water target in the range of proton energies 10{sup 1} eV - 10{sup 10} eV taking into account all the charge states is calculated.

  14. 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)

  15. 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

  16. Calculation of multi-dimensional dose distribution in medium due to proton beam incidence

    International Nuclear Information System (INIS)

    Kawachi, Kiyomitsu; Inada, Tetsuo

    1978-01-01

    The method of analyzing the multi-dimensional dose distribution in a medium due to proton beam incidence is presented to obtain the reliable and simplified method from clinical viewpoint, especially for the medical treatment of cancer. The heavy ion beam being taken out of an accelerator has to be adjusted to fit cancer location and size, utilizing a modified range modulator, a ridge filter, a bolus and a special scanning apparatus. The precise calculation of multi-dimensional dose distribution of proton beam is needed to fit treatment to a limit part. The analytical formulas consist of those for the fluence distribution in a medium, the divergence of flying range, the energy distribution itself, the dose distribution in side direction and the two-dimensional dose distribution. The fluence distribution in polystyrene in case of the protons with incident energy of 40 and 60 MeV, the energy distribution of protons at the position of a Bragg peak for various values of incident energy, the depth dose distribution in polystyrene in case of the protons with incident energy of 40 and 60 MeV and average energy of 100 MeV, the proton fluence and dose distribution as functions of depth for the incident average energy of 250 MeV, the statistically estimated percentage errors in the proton fluence and dose distribution, the estimated minimum detectable tumor thickness as a function of the number of incident protons for the different incident spectra with average energy of 250 MeV, the isodose distribution in a plane containing the central axis in case of the incident proton beam of 3 mm diameter and 40 MeV and so on are presented as the analytical results, and they are evaluated. (Nakai, Y.)

  17. Determination of intermolecular transfer integrals from DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Baumeier, Bjoern; Andrienko, Denis [Max-Planck Institute for Polymer Research, Mainz (Germany)

    2010-07-01

    Theoretical studies of charge transport in organic conducting systems pose a unique challenge since they require multiscale schemes that combine quantum-chemical, molecular dynamics and kinetic Monte-Carlo calculations. The description of the mobility of electrons and holes in the hopping regime relies on the determination of intermolecular hopping rates in large scale morphologies. Using Marcus theory these rates can be calculated from intermolecular transfer integrals and on-site energies. Here we present a detailed computational study on the accuracy and efficiency of density-functional theory based approaches to the determination of intermolecular transfer integrals. First, it is demonstrated how these can be obtained from quantum-chemistry calculations by forming the expectation value of a dimer Fock operator with frontier orbitals of two neighboring monomers based on a projective approach. We then consider the prototypical example of one pair out of a larger morphology of Tris(8-hydroxyquinolinato)aluminium (Alq3) and study the influence of computational parameters, e.g. the choice of basis sets, exchange-correlation functional, and convergence criteria, on the calculated transfer integrals. The respective accuracies and efficiencies are compared in order to derive an optimal strategy for future simulations based on the full morphology.

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

    Science.gov (United States)

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

    2015-12-01

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

  19. MRI-Based Computed Tomography Metal Artifact Correction Method for Improving Proton Range Calculation Accuracy

    International Nuclear Information System (INIS)

    Park, Peter C.; Schreibmann, Eduard; Roper, Justin; Elder, Eric; Crocker, Ian; Fox, Tim; Zhu, X. Ronald; Dong, Lei; Dhabaan, Anees

    2015-01-01

    Purpose: Computed tomography (CT) artifacts can severely degrade dose calculation accuracy in proton therapy. Prompted by the recently increased popularity of magnetic resonance imaging (MRI) in the radiation therapy clinic, we developed an MRI-based CT artifact correction method for improving the accuracy of proton range calculations. Methods and Materials: The proposed method replaces corrupted CT data by mapping CT Hounsfield units (HU number) from a nearby artifact-free slice, using a coregistered MRI. MRI and CT volumetric images were registered with use of 3-dimensional (3D) deformable image registration (DIR). The registration was fine-tuned on a slice-by-slice basis by using 2D DIR. Based on the intensity of paired MRI pixel values and HU from an artifact-free slice, we performed a comprehensive analysis to predict the correct HU for the corrupted region. For a proof-of-concept validation, metal artifacts were simulated on a reference data set. Proton range was calculated using reference, artifactual, and corrected images to quantify the reduction in proton range error. The correction method was applied to 4 unique clinical cases. Results: The correction method resulted in substantial artifact reduction, both quantitatively and qualitatively. On respective simulated brain and head and neck CT images, the mean error was reduced from 495 and 370 HU to 108 and 92 HU after correction. Correspondingly, the absolute mean proton range errors of 2.4 cm and 1.7 cm were reduced to less than 2 mm in both cases. Conclusions: Our MRI-based CT artifact correction method can improve CT image quality and proton range calculation accuracy for patients with severe CT artifacts

  20. The precision of proton range calculations in proton radiotherapy treatment planning: experimental verification of the relation between CT-HU and proton stopping power

    International Nuclear Information System (INIS)

    Schaffner, B.; Pedroni, E.

    1998-01-01

    The precision in proton radiotherapy treatment planning depends on the accuracy of the information used to calculate the stopping power properties of the tissues in the patient's body. This information is obtained from computed tomography (CT) images using a calibration curve to convert CT Hounsfield units into relative proton stopping power values. The validity of a stoichiometric method to create the calibration curve has been verified by measuring pairs of Hounsfield units and stopping power values for animal tissue samples. It was found that the agreement between measurement and calibration curve is better than 1% if beam hardening effects in the acquisition of the CT images can be neglected. The influence of beam hardening effects on the quantitative reading of the CT measurements is discussed and an estimation for the overall range precision of proton beams is given. It is expected that the range of protons in the human body can be controlled to better than ±1.1% of the water equivalent range in soft tissue and ±1.8% in bone, which translates into a range precision of about 1-3 mm in typical treatment situations. (author)

  1. Code package for calculation of damage effects of medium-energy protons in metal targets

    International Nuclear Information System (INIS)

    Coulter, C.A.

    1976-12-01

    A program package was developed to calculate radiation damage effects produced in a metal target by protons in the 100-MeV to 3.5-GeV energy range. A detailed description is given of the control cards and data cards required to use the code package

  2. 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.

  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. 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.)

  5. Conformation of antifreeze glycoproteins as determined from conformational energy calculations and fully assigned proton NMR spectra

    International Nuclear Information System (INIS)

    Bush, C.A.; Rao, B.N.N.

    1986-01-01

    The 1 H NMR spectra of AFGP's ranging in molecular weight from 2600 to 30,000 Daltons isolated from several different species of polar fish have been measured. The spectrum of AFGP 1-4 from Pagothenia borchgrevinki with an average of 30 repeating subunits has a single resonance for each proton of the glycotripeptide repeating unit, (ala-[gal-(β-1→3) galNAc-(α--O-]thr-ala)/sub n/. Its 1 H NMR spectrum including resonances of the amide protons has been completely assigned. Coupling constants and nuclear Overhauser enhancements (n.O.e.) between protons on distant residues imply conformational order. The 2600 dalton molecular weight glycopeptides (AFGP-8) have pro in place of ala at certain specific points in the sequence and AFGP-8R of Eleginus gracilis has arg in place of one thr. The resonances of pro and arg were assigned by decoupling. The resonances of the carboxy and amino terminals have distinct chemical shifts and were assigned in AFGP-8 of Boreogadus saida by titration. n.O.e. between α--protons and amide protons of the adjacent residue (sequential n.O.e.) were used in assignments of additional resonances and to assign the distinctive resonances of thr followed by pro. Conformational energy calculations on the repeating glycotripeptide subunit of AFGP show that the α--glucosidic linkage has a fixed conformation while the β--linkage is less rigid. A conformational model for AFGP 1-4, which is based on the calculations has the peptide in an extended left-handed helix with three residues per turn similar to polyproline II. The model is consistent with CD data, amide proton coupling constants, temperature dependence of amide proton chemical shifts

  6. Calculation of primary and secondary dose in proton therapy of brain tumors using Monte Carlo method

    International Nuclear Information System (INIS)

    Moghbel Esfahani, F.; Alamatsaz, M.; Karimian, A.

    2012-01-01

    High-energy beams of protons offer significant advantages for the treatment of deep-seated local tumors. Their physical depth-dose distribution in tissue is characterized by a small entrance dose and a distinct maximum - Bragg peak - near the end of range with a sharp falloff at the distal edge. Therefore, research must be done to investigate the possible negative and positive effects of using proton therapy as a treatment modality. In proton therapy, protons do account for the vast majority of dose. However, when protons travel through matter, secondary particles are created by the interactions of protons and matter en route to and within the patient. It is believed that secondary dose can lead to secondary cancer, especially in pediatric cases. Therefore, the focus of this work is determining both primary and secondary dose. Dose calculations were performed by MCNPX in tumoral and healthy parts of brain. The brain tumor has a 10 mm diameter and is located 16 cm under the skin surface. The brain was simulated by a cylindrical water phantom with the dimensions of 19 x 19cm 2 (length x diameter), with 0.5 cm thickness of plexiglass (C 4 H 6 O 2 ). Then beam characteristics were investigated to ensure the accuracy of the model. Simulations were initially validated with against packages such as SRIM/TRIM. Dose calculations were performed using different configurations to evaluate depth-dose profiles and dose 2D distributions.The results of the simulation show that the best proton energy interval, to cover completely the brain tumor, is from 152 to 154 MeV. (authors)

  7. 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.

  8. A GPU implementation of a track-repeating algorithm for proton radiotherapy dose calculations

    International Nuclear Information System (INIS)

    Yepes, Pablo P; Mirkovic, Dragan; Taddei, Phillip J

    2010-01-01

    An essential component in proton radiotherapy is the algorithm to calculate the radiation dose to be delivered to the patient. The most common dose algorithms are fast but they are approximate analytical approaches. However their level of accuracy is not always satisfactory, especially for heterogeneous anatomical areas, like the thorax. Monte Carlo techniques provide superior accuracy; however, they often require large computation resources, which render them impractical for routine clinical use. Track-repeating algorithms, for example the fast dose calculator, have shown promise for achieving the accuracy of Monte Carlo simulations for proton radiotherapy dose calculations in a fraction of the computation time. We report on the implementation of the fast dose calculator for proton radiotherapy on a card equipped with graphics processor units (GPUs) rather than on a central processing unit architecture. This implementation reproduces the full Monte Carlo and CPU-based track-repeating dose calculations within 2%, while achieving a statistical uncertainty of 2% in less than 1 min utilizing one single GPU card, which should allow real-time accurate dose calculations.

  9. 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.

  10. SU-F-BRD-09: A Random Walk Model Algorithm for Proton Dose Calculation

    International Nuclear Information System (INIS)

    Yao, W; Farr, J

    2015-01-01

    Purpose: To develop a random walk model algorithm for calculating proton dose with balanced computation burden and accuracy. Methods: Random walk (RW) model is sometimes referred to as a density Monte Carlo (MC) simulation. In MC proton dose calculation, the use of Gaussian angular distribution of protons due to multiple Coulomb scatter (MCS) is convenient, but in RW the use of Gaussian angular distribution requires an extremely large computation and memory. Thus, our RW model adopts spatial distribution from the angular one to accelerate the computation and to decrease the memory usage. From the physics and comparison with the MC simulations, we have determined and analytically expressed those critical variables affecting the dose accuracy in our RW model. Results: Besides those variables such as MCS, stopping power, energy spectrum after energy absorption etc., which have been extensively discussed in literature, the following variables were found to be critical in our RW model: (1) inverse squared law that can significantly reduce the computation burden and memory, (2) non-Gaussian spatial distribution after MCS, and (3) the mean direction of scatters at each voxel. In comparison to MC results, taken as reference, for a water phantom irradiated by mono-energetic proton beams from 75 MeV to 221.28 MeV, the gamma test pass rate was 100% for the 2%/2mm/10% criterion. For a highly heterogeneous phantom consisting of water embedded by a 10 cm cortical bone and a 10 cm lung in the Bragg peak region of the proton beam, the gamma test pass rate was greater than 98% for the 3%/3mm/10% criterion. Conclusion: We have determined key variables in our RW model for proton dose calculation. Compared with commercial pencil beam algorithms, our RW model much improves the dose accuracy in heterogeneous regions, and is about 10 times faster than MC simulations

  11. Higher order energy transfer. Quantum electrodynamical calculations and graphical representation

    International Nuclear Information System (INIS)

    Jenkins, R.D.

    2000-01-01

    In Chapter 1, a novel method of calculating quantum electrodynamic amplitudes is formulated using combinatorial theory. This technique is used throughout instead of conventional time-ordered methods. A variety of hyperspaces are discussed to highlight isomorphism between a number of A generalisation of Pascal's triangle is shown to be beneficial in determining the form of hyperspace graphs. Chapter 2 describes laser assisted resonance energy transfer (LARET), a higher order perturbative contribution to the well-known process resonance energy transfer, accommodating an off resonance auxiliary laser field to stimulate the migration. Interest focuses on energy exchanges between two uncorrelated molecular species, as in a system where molecules are randomly oriented. Both phase-weighted and standard isotropic averaging are required for the calculations. Results are discussed in terms of a laser intensity-dependent mechanism. Identifying the applied field regime where LARET should prove experimentally significant, transfer rate increases of up to 30% are predicted. General results for three-center energy transfer are elucidated in chapter 3. Cooperative and accretive mechanistic pathways are identified with theory formulated to elicit their role in a variety of energy transfer phenomena and their relative dominance. In multichromophoric the interplay of such factors is analysed with regard to molecular architectures. The alignments and magnitudes of donor and acceptor transition moments and polarisabilities prove to have profound effects on achievable pooling efficiency for linear configurations. Also optimum configurations are offered. In ionic lattices, although both mechanisms play significant roles in pooling and cutting processes, only the accretive is responsible for sensitisation. The local, microscopic level results are used to gauge the lattice response, encompassing concentration and structural effects. (author)

  12. Half-life calculation of one-proton emitters with a shell model potential

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, M. M.; Duarte, S. B. [Centro Brasileiro de Pesquisas Fisicas-CBPF/MCT Rua Dr. Xavier Sigaud, 150, 22290-180, Rio de Janeiro-RJ (Brazil); Teruya, N. [Departamento de Fisica, Universidade Federal da Paraiba - UFPB Campus de Joao Pessoa, 58051-970, Joao Pessoa - PB (Brazil)

    2013-03-25

    The accumulated amount of data for half-lives of proton emitters still remains a challenge to the ability of nuclear models to reproduce them consistently. These nuclei are far from beta stability line in a region where the validity of current nuclear models is not guaranteed. A nuclear shell model is introduced to the calculation of the nuclear barrier of less deformed proton emitters. The predictions using the proposed model are in good agreement with the data, with the advantage of have used only a single parameter in the model.

  13. 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)

  14. Calculation of the equilibrium pH in a multiple-buffered aqueous solution based on partitioning of proton buffering: a new predictive formula.

    Science.gov (United States)

    Nguyen, Minhtri K; Kao, Liyo; Kurtz, Ira

    2009-06-01

    Upon the addition of protons to an aqueous solution containing multiple buffers, the final H+ concentration ([H+]) at equilibrium is determined by the partitioning of added H+ among the various buffer components. In the analysis of acid-base chemistry, the Henderson-Hasselbalch equation and the Stewart strong ion formulation can only describe (rather than predict) the equilibrium pH following a proton load since these formulas calculate the equilibrium pH only when the reactant concentrations at equilibrium(1) 1The term "equilibrium" refers to the steady state proton and reactant concentrations when the buffering of excess protons by the various buffers is complete. are already known. In this regard, it is simpler to directly measure the equilibrium pH rather than measure the equilibrium reactant concentrations to calculate the equilibrium pH. As these formulas cannot predict the final equilibrium [H+] following a proton load to a multiple-buffered aqueous solution, we developed a new quantitative approach for predicting the equilibrium [H+] that is based on the preequilibrium(2)2 The term "preequilibrium" refers to the initial proton and reactant concentrations immediately upon addition of protons and before the buffering of excess protons by the various buffers. concentrations of all buffers in an aqueous solution. The mathematical model used to derive our equation is based on proton transfer buffer equilibria without requiring the incorporation of electroneutrality considerations. The model consists of a quartic polynomial equation that is derived based solely on the partitioning of H+ among the various buffer components. We tested the accuracy of the model using aqueous solutions with various buffers and measured the equilibrium pH values following the addition of HCl. Our results confirmed the accuracy of our new equation (r2 = 1; measured pH vs. predicted pH), indicating that it quantitatively accounts for the underlying acid-base phenomenology.

  15. Calculation of the equilibrium pH in a multiple-buffered aqueous solution based on partitioning of proton buffering: a new predictive formula

    Science.gov (United States)

    Nguyen, Minhtri K.; Kao, Liyo; Kurtz, Ira

    2009-01-01

    Upon the addition of protons to an aqueous solution containing multiple buffers, the final H+ concentration ([H+]) at equilibrium is determined by the partitioning of added H+ among the various buffer components. In the analysis of acid-base chemistry, the Henderson-Hasselbalch equation and the Stewart strong ion formulation can only describe (rather than predict) the equilibrium pH following a proton load since these formulas calculate the equilibrium pH only when the reactant concentrations at equilibrium1 1The term “equilibrium” refers to the steady state proton and reactant concentrations when the buffering of excess protons by the various buffers is complete. are already known. In this regard, it is simpler to directly measure the equilibrium pH rather than measure the equilibrium reactant concentrations to calculate the equilibrium pH. As these formulas cannot predict the final equilibrium [H+] following a proton load to a multiple-buffered aqueous solution, we developed a new quantitative approach for predicting the equilibrium [H+] that is based on the preequilibrium22The term “preequilibrium” refers to the initial proton and reactant concentrations immediately upon addition of protons and before the buffering of excess protons by the various buffers. concentrations of all buffers in an aqueous solution. The mathematical model used to derive our equation is based on proton transfer buffer equilibria without requiring the incorporation of electroneutrality considerations. The model consists of a quartic polynomial equation that is derived based solely on the partitioning of H+ among the various buffer components. We tested the accuracy of the model using aqueous solutions with various buffers and measured the equilibrium pH values following the addition of HCl. Our results confirmed the accuracy of our new equation (r2 = 1; measured pH vs. predicted pH), indicating that it quantitatively accounts for the underlying acid-base phenomenology. PMID

  16. 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 *.

  17. 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)

  18. 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.

  19. Protonation Sites, Tandem Mass Spectrometry and Computational Calculations of o-Carbonyl Carbazolequinone Derivatives.

    Science.gov (United States)

    Martínez-Cifuentes, Maximiliano; Clavijo-Allancan, Graciela; Zuñiga-Hormazabal, Pamela; Aranda, Braulio; Barriga, Andrés; Weiss-López, Boris; Araya-Maturana, Ramiro

    2016-07-05

    A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules.

  20. Sub 100 nm proton beam micromachining: theoretical calculations on resolution limits

    International Nuclear Information System (INIS)

    Kan, J.A. van; Sum, T.C.; Osipowicz, T.; Watt, F.

    2000-01-01

    Proton beam micromachining is a novel direct-write process for the production of three-dimensional (3D) microstructures. A focused beam of MeV protons is scanned in a pre-determined pattern over a suitable resist material (e.g. PMMA or SU-8) and the latent image formed is subsequently developed chemically. In this paper calculations on theoretical resolution limits of proton beam micromachined three-dimensional microstructures are presented. Neglecting the finite beam size, a Monte Carlo ion transport code was used in combination with a theoretical model describing the delta-ray (δ-ray) energy deposition to determine the lateral energy deposition distribution in PMMA resist material. The energy deposition distribution of ion induced secondary electrons (δ-rays) has been parameterized using analytical models. It is assumed that the attainable resolution is limited by a convolution of the spread of the ion beam and energy deposition of the δ-rays

  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. Single event upsets calculated from new ENDF/B-VI proton and neutron data up to 150 MeV

    International Nuclear Information System (INIS)

    Chadwick, M.B.

    1999-01-01

    Single-event upsets (SEU) in microelectronics are calculated from newly-developed silicon nuclear reaction recoil data that extend up to 150 MeV, for incident protons and neutrons. Calculated SEU cross sections are compared with measured data

  4. Proton recoil spectra in spherical proportional counters calculated with finite element and Monte Carlo methods

    Energy Technology Data Exchange (ETDEWEB)

    Benmosbah, M. [Laboratoire de Chimie Physique et Rayonnement Alain Chambaudet, UMR CEA E4, Universite de Franche-Comte, 16 route de Gray, 25030 Besancon Cedex (France); Groetz, J.E. [Laboratoire de Chimie Physique et Rayonnement Alain Chambaudet, UMR CEA E4, Universite de Franche-Comte, 16 route de Gray, 25030 Besancon Cedex (France)], E-mail: jegroetz@univ-fcomte.fr; Crovisier, P. [Service de Protection contre les Rayonnements, CEA Valduc, 21120 Is/Tille (France); Asselineau, B. [Laboratoire de Metrologie et de Dosimetrie des Neutrons, IRSN, Cadarache BP3, 13115 St Paul-lez-Durance (France); Truffert, H.; Cadiou, A. [AREVA NC, Etablissement de la Hague, DQSSE/PR/E/D, 50444 Beaumont-Hague Cedex (France)

    2008-08-11

    Proton recoil spectra were calculated for various spherical proportional counters using Monte Carlo simulation combined with the finite element method. Electric field lines and strength were calculated by defining an appropriate mesh and solving the Laplace equation with the associated boundary conditions, taking into account the geometry of every counter. Thus, different regions were defined in the counter with various coefficients for the energy deposition in the Monte Carlo transport code MCNPX. Results from the calculations are in good agreement with measurements for three different gas pressures at various neutron energies.

  5. 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.

  6. 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.

  7. Measurement and calculation of characteristic prompt gamma ray spectra emitted during proton irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Polf, J C; Peterson, S; Beddar, S [M D Anderson Cancer Center, Univeristy of Texas, Houston, TX 77030 (United States); McCleskey, M; Roeder, B T; Spiridon, A; Trache, L [Cyclotron Institute, Texas A and M University, College Station, TX 77843 (United States)], E-mail: jcpolf@mdanderson.org

    2009-11-21

    In this paper, we present results of initial measurements and calculations of prompt gamma ray spectra (produced by proton-nucleus interactions) emitted from tissue equivalent phantoms during irradiations with proton beams. Measurements of prompt gamma ray spectra were made using a high-purity germanium detector shielded either with lead (passive shielding), or a Compton suppression system (active shielding). Calculations of the spectra were performed using a model of both the passive and active shielding experimental setups developed using the Geant4 Monte Carlo toolkit. From the measured spectra it was shown that it is possible to distinguish the characteristic emission lines from the major elemental constituent atoms (C, O, Ca) in the irradiated phantoms during delivery of proton doses similar to those delivered during patient treatment. Also, the Monte Carlo spectra were found to be in very good agreement with the measured spectra providing an initial validation of our model for use in further studies of prompt gamma ray emission during proton therapy. (note)

  8. Monte carlo calculation of energy deposition and ionization yield for high energy protons

    International Nuclear Information System (INIS)

    Wilson, W.E.; McDonald, J.C.; Coyne, J.J.; Paretzke, H.G.

    1985-01-01

    Recent calculations of event size spectra for neutrons use a continuous slowing down approximation model for the energy losses experienced by secondary charged particles (protons and alphas) and thus do not allow for straggling effects. Discrepancies between the calculations and experimental measurements are thought to be, in part, due to the neglect of straggling. A tractable way of including stochastics in radiation transport calculations is via the Monte Carlo method and a number of efforts directed toward simulating positive ion track structure have been initiated employing this technique. Recent results obtained with our updated and extended MOCA code for charged particle track structure are presented here. Major emphasis has been on calculating energy deposition and ionization yield spectra for recoil proton crossers since they are the most prevalent event type at high energies (>99% at 14 MeV) for small volumes. Neutron event-size spectra can be obtained from them by numerical summing and folding techniques. Data for ionization yield spectra are presented for simulated recoil protons up to 20 MeV in sites of diameters 2-1000 nm

  9. TH-A-19A-09: Towards Sub-Second Proton Dose Calculation On GPU

    Energy Technology Data Exchange (ETDEWEB)

    Silva, J da [University of Cambridge, Cambridge, Cambridgeshire (United Kingdom)

    2014-06-15

    Purpose: To achieve sub-second dose calculation for clinically relevant proton therapy treatment plans. Rapid dose calculation is a key component of adaptive radiotherapy, necessary to take advantage of the better dose conformity offered by hadron therapy. Methods: To speed up proton dose calculation, the pencil beam algorithm (PBA; clinical standard) was parallelised and implemented to run on a graphics processing unit (GPU). The implementation constitutes the first PBA to run all steps on GPU, and each part of the algorithm was carefully adapted for efficiency. Monte Carlo (MC) simulations obtained using Fluka of individual beams of energies representative of the clinical range impinging on simple geometries were used to tune the PBA. For benchmarking, a typical skull base case with a spot scanning plan consisting of a total of 8872 spots divided between two beam directions of 49 energy layers each was provided by CNAO (Pavia, Italy). The calculations were carried out on an Nvidia Geforce GTX680 desktop GPU with 1536 cores running at 1006 MHz. Results: The PBA reproduced within ±3% of maximum dose results obtained from MC simulations for a range of pencil beams impinging on a water tank. Additional analysis of more complex slab geometries is currently under way to fine-tune the algorithm. Full calculation of the clinical test case took 0.9 seconds in total, with the majority of the time spent in the kernel superposition step. Conclusion: The PBA lends itself well to implementation on many-core systems such as GPUs. Using the presented implementation and current hardware, sub-second dose calculation for a clinical proton therapy plan was achieved, opening the door for adaptive treatment. The successful parallelisation of all steps of the calculation indicates that further speedups can be expected with new hardware, brightening the prospects for real-time dose calculation. This work was funded by ENTERVISION, European Commission FP7 grant 264552.

  10. TH-A-19A-09: Towards Sub-Second Proton Dose Calculation On GPU

    International Nuclear Information System (INIS)

    Silva, J da

    2014-01-01

    Purpose: To achieve sub-second dose calculation for clinically relevant proton therapy treatment plans. Rapid dose calculation is a key component of adaptive radiotherapy, necessary to take advantage of the better dose conformity offered by hadron therapy. Methods: To speed up proton dose calculation, the pencil beam algorithm (PBA; clinical standard) was parallelised and implemented to run on a graphics processing unit (GPU). The implementation constitutes the first PBA to run all steps on GPU, and each part of the algorithm was carefully adapted for efficiency. Monte Carlo (MC) simulations obtained using Fluka of individual beams of energies representative of the clinical range impinging on simple geometries were used to tune the PBA. For benchmarking, a typical skull base case with a spot scanning plan consisting of a total of 8872 spots divided between two beam directions of 49 energy layers each was provided by CNAO (Pavia, Italy). The calculations were carried out on an Nvidia Geforce GTX680 desktop GPU with 1536 cores running at 1006 MHz. Results: The PBA reproduced within ±3% of maximum dose results obtained from MC simulations for a range of pencil beams impinging on a water tank. Additional analysis of more complex slab geometries is currently under way to fine-tune the algorithm. Full calculation of the clinical test case took 0.9 seconds in total, with the majority of the time spent in the kernel superposition step. Conclusion: The PBA lends itself well to implementation on many-core systems such as GPUs. Using the presented implementation and current hardware, sub-second dose calculation for a clinical proton therapy plan was achieved, opening the door for adaptive treatment. The successful parallelisation of all steps of the calculation indicates that further speedups can be expected with new hardware, brightening the prospects for real-time dose calculation. This work was funded by ENTERVISION, European Commission FP7 grant 264552

  11. Comparison between calculation and measurement of energy deposited by 800 MeV protons

    International Nuclear Information System (INIS)

    Loewe, W.E.

    1980-01-01

    The High Energy Transport Code, HETC, was obtained from the Radiation Shielding Information Center (RSIC) at Oak Ridge National Laboratory and altered as necessary to run on a CDC 7600 using the LTSS software in use at LLNL. HETC was then used to obtain calculated estimates of energy deposited, for comparison with a series of benchmark experiments done by LLNL. These experiments used proton beams of various energies incident on well-defined composite targets in good geometry. In this report, two aspects of the comparison between calculated and experimental energy depositions from an 800 MeV proton beam are discussed. Both aspects involve the fact that workers at SAI had previously used their version of HETC to calculate this experiment and reported their comparison with the measured data. The first aspect addressed is that their calculated data and LLNL calculations do not agree, suggesting an error in the conversion process from the RSIC code. The second aspect is not independent of the first, but is of sufficient importance to merit separate emphasis. It is that the SAI calculations agree well with experiments at the detector plate located some distance from the shower plate, whereas the LLNL calculations show a clearcut discrepancy there in comparison with the experiment. A contract was let in January 1980 by LLNL with SAI in order to obtain full details on the two cited aspects of the comparison between calculated and experimental energy depositions from an 800 MeV proton beam. The ensuing discussion is based on the final report of that contracted work

  12. 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.

  13. 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.)

  14. 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

  15. 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

  16. 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

  17. 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 ...

  18. 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...

  19. 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

  20. 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

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  2. Transport calculation of medium-energy protons and neutrons by Monte Carlo method

    International Nuclear Information System (INIS)

    Ban, Syuuichi; Hirayama, Hideo; Katoh, Kazuaki.

    1978-09-01

    A Monte Carlo transport code, ARIES, has been developed for protons and neutrons at medium energy (25 -- 500 MeV). Nuclear data provided by R.G. Alsmiller, Jr. were used for the calculation. To simulate the cascade development in the medium, each generation was represented by a single weighted particle and an average number of emitted particles was used as the weight. Neutron fluxes were stored by the collisions density method. The cutoff energy was set to 25 MeV. Neutrons below the cutoff were stored to be used as the source for the low energy neutron transport calculation upon the discrete ordinates method. Then transport calculations were performed for both low energy neutrons (thermal -- 25 MeV) and secondary gamma-rays. Energy spectra of emitted neutrons were calculated and compared with those of published experimental and calculated results. The agreement was good for the incident particles of energy between 100 and 500 MeV. (author)

  3. Half-lives for proton emission, alpha decay, cluster radioactivity, and cold fission processes calculated in a unified theoretical framework

    International Nuclear Information System (INIS)

    Duarte, S.B.; Tavares, O.A.P.; Guzman, F.; Dimarco, A.; Garcia, F.; Goncalves, M.

    2002-01-01

    Half-life values of spontaneous nuclear decay processes are presented in the framework of the Effective Liquid Drop Model (ELDM) using the combination of varying mass asymmetry shape description for the mass transfer with Werner-Wheeler's inertia coefficient V MAS /WW. The calculated half-lives of ground-state to ground-state transitions for the proton emission, alpha decay, cluster radioactivity, and cold fission processes are compared with experimental data. Results have shown that the ELDM is a very efficient model to describe these different decay processes in a same, unified theoretical framework. A Table listing the predicted half-life values, τ c is presented for all possible cases of spontaneous nuclear break-up such that -7.30 10 τ c [S] 10 (τ/τ c ) > -17.0, where τ is the total half-life of the parent nucleus. (author)

  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. 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

  6. Time-domain calculation of sub-nanosecond pulse launched by a proton beam

    International Nuclear Information System (INIS)

    Chan, Kwok-Chi Dominic; Cooper, R.K.

    1990-01-01

    Using the finite-difference time-domain code TBCI, we have numerically calculated the radiation from a sub-nanosecond 800-MeV proton bunch as it is launched into space. The calculation is compared to measurements of the time history of the radiated fields and good agreement is found. A movie showing the development of the radiation pattern will be shown during the presentation at this conference, namely, the First Los Alamos Symposium on Ultra-Wideband Radar. 6 refs., 7 figs

  7. Calculated inclusive neutron production from 400 GeV proton-nucleus collisions

    International Nuclear Information System (INIS)

    Alsmiller, R.G. Jr.; Alsmiller, F.S.; Hermann, O.W.

    1989-08-01

    Calculated inclusive neutron production from 400 GeV proton-nucleus collisions is presented and compared with experimental data. Target nuclei H, Be, Cu, and Pb are considered and the comparisons cover the laboratory energy range of 20 to 400 GeV, and angular range 0.7 to 10 mr. Moderately good agreement between the calculated and experimental data is found, but the agreement in the case of Be, Cu and Pb is significantly better than in the case of H. 8 refs., 4 figs

  8. 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.

  9. 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.

  10. The calculation of proton and secondary electron stopping powers in liquid water

    International Nuclear Information System (INIS)

    Marouane, Abdelhak; Inchaouh, Jamal; Ouaskit, Said; Fathi, Ahmed

    2012-01-01

    The stopping power of energetic protons in liquid water has been calculated using a new model based on different theoretical and semi-empirical approaches. In this model, we consider the relativistic corrections along with the electronic and nuclear stopping power. The present work accounts for the different interactions made with electrons and nuclei inside the target. Interactions of the incident particle with the target's electrons dominate in the high energy regime; in the low energy regime, the interactions of the projectile with the target nuclei contribute importantly and are included in the calculation. We also compute the stopping cross sections and the stopping power of secondary electrons ejected from proton and hydrogen ionization impact, and generated by hydrogen electron loss processes. The consideration of secondary electrons' stopping power can contribute to the study of nano-dosimetry. Our results are in good agreement with existing experimental data. This calculation model can be useful for different applications in medical physics and space radiation health, such as hadron therapy for cancer treatment or radiation protection for astronauts. - Highlights: ► We discussed the stopping cross sections at the Bragg peak region of primary and secondary processes. ► We considered the corrections of incident particle energy focusing on the Rudds semi-empirical model. ► We calculated the electronic and nuclear stopping power, and we deduced the total stopping power. ► We calculated the stopping power of the secondary electrons.

  11. Efficiency improvement in proton dose calculations with an equivalent restricted stopping power formalism

    Science.gov (United States)

    Maneval, Daniel; Bouchard, Hugo; Ozell, Benoît; Després, Philippe

    2018-01-01

    The equivalent restricted stopping power formalism is introduced for proton mean energy loss calculations under the continuous slowing down approximation. The objective is the acceleration of Monte Carlo dose calculations by allowing larger steps while preserving accuracy. The fractional energy loss per step length ɛ was obtained with a secant method and a Gauss-Kronrod quadrature estimation of the integral equation relating the mean energy loss to the step length. The midpoint rule of the Newton-Cotes formulae was then used to solve this equation, allowing the creation of a lookup table linking ɛ to the equivalent restricted stopping power L eq, used here as a key physical quantity. The mean energy loss for any step length was simply defined as the product of the step length with L eq. Proton inelastic collisions with electrons were added to GPUMCD, a GPU-based Monte Carlo dose calculation code. The proton continuous slowing-down was modelled with the L eq formalism. GPUMCD was compared to Geant4 in a validation study where ionization processes alone were activated and a voxelized geometry was used. The energy straggling was first switched off to validate the L eq formalism alone. Dose differences between Geant4 and GPUMCD were smaller than 0.31% for the L eq formalism. The mean error and the standard deviation were below 0.035% and 0.038% respectively. 99.4 to 100% of GPUMCD dose points were consistent with a 0.3% dose tolerance. GPUMCD 80% falloff positions (R80 ) matched Geant’s R80 within 1 μm. With the energy straggling, dose differences were below 2.7% in the Bragg peak falloff and smaller than 0.83% elsewhere. The R80 positions matched within 100 μm. The overall computation times to transport one million protons with GPUMCD were 31-173 ms. Under similar conditions, Geant4 computation times were 1.4-20 h. The L eq formalism led to an intrinsic efficiency gain factor ranging between 30-630, increasing with the prescribed accuracy of simulations. The

  12. A method to calculate fission-fragment yields Y(Z,N) versus proton and neutron number in the Brownian shape-motion model. Application to calculations of U and Pu charge yields

    Energy Technology Data Exchange (ETDEWEB)

    Moeller, Peter [Los Alamos National Laboratory, Theoretical Division, Los Alamos, NM (United States); Ichikawa, Takatoshi [Kyoto University, Yukawa Institute for Theoretical Physics, Kyoto (Japan)

    2015-12-15

    We propose a method to calculate the two-dimensional (2D) fission-fragment yield Y(Z,N) versus both proton and neutron number, with inclusion of odd-even staggering effects in both variables. The approach is to use the Brownian shape-motion on a macroscopic-microscopic potential-energy surface which, for a particular compound system is calculated versus four shape variables: elongation (quadrupole moment Q{sub 2}), neck d, left nascent fragment spheroidal deformation ε{sub f1}, right nascent fragment deformation ε{sub f2} and two asymmetry variables, namely proton and neutron numbers in each of the two fragments. The extension of previous models 1) introduces a method to calculate this generalized potential-energy function and 2) allows the correlated transfer of nucleon pairs in one step, in addition to sequential transfer. In the previous version the potential energy was calculated as a function of Z and N of the compound system and its shape, including the asymmetry of the shape. We outline here how to generalize the model from the ''compound-system'' model to a model where the emerging fragment proton and neutron numbers also enter, over and above the compound system composition. (orig.)

  13. Validation of FLUKA calculated cross-sections for radioisotope production in proton-on-target collisions at proton energies around 1 GeV

    CERN Document Server

    Felcini, M

    2006-01-01

    The production cross-sections of several radioisotopes induced by 1 GeV protons impinging on different target materials have been calculated using the FLUKA Monte Carlo and compared to measured cross-sections. The emphasis of this study is on the production of alpha and beta/gamma emitters of interest for activation evaluations at a research complex, such as the EURISOL complex, using several MW power proton driver at an energy of 1 GeV. The comparisons show that in most of the cases of interest for such evaluations, the FLUKA Monte Carlo reproduces radioisotope production cross-sections within less than a factor of two with respect to the measured values. This result implies that the FLUKA calculations are adequately accurate for proton induced activation estimates at a 1 GeV high power proton driver complex.

  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. Absolute Hydration Free Energy of Proton from First Principles Electronic Structure Calculations

    International Nuclear Information System (INIS)

    Zhan, Chang-Guo; Dixon, David A.

    2001-01-01

    The absolute hydration free energy of the proton, DGhyd298(H+), is one of the fundamental quantities for the thermodynamics of aqueous systems. Its exact value remains unknown despite extensive experimental and computational efforts. We report a first-principles determination of DGhyd298(H+) by using the latest developments in electronic structure theory and massively parallel computers. DGhyd298(H+) is accurately predicted to be -262.4 kcal/mol based on high-level, first-principles solvation-included electronic structure calculations. The absolute hydration free energies of other cations can be obtained by using appropriate available thermodynamic data in combination with this value. The high accuracy of the predicted absolute hydration free energy of proton is confirmed by applying the same protocol to predict DGhyd298(Li+)

  16. A Fourier analysis on the maximum acceptable grid size for discrete proton beam dose calculation

    International Nuclear Information System (INIS)

    Li, Haisen S.; Romeijn, H. Edwin; Dempsey, James F.

    2006-01-01

    We developed an analytical method for determining the maximum acceptable grid size for discrete dose calculation in proton therapy treatment plan optimization, so that the accuracy of the optimized dose distribution is guaranteed in the phase of dose sampling and the superfluous computational work is avoided. The accuracy of dose sampling was judged by the criterion that the continuous dose distribution could be reconstructed from the discrete dose within a 2% error limit. To keep the error caused by the discrete dose sampling under a 2% limit, the dose grid size cannot exceed a maximum acceptable value. The method was based on Fourier analysis and the Shannon-Nyquist sampling theorem as an extension of our previous analysis for photon beam intensity modulated radiation therapy [J. F. Dempsey, H. E. Romeijn, J. G. Li, D. A. Low, and J. R. Palta, Med. Phys. 32, 380-388 (2005)]. The proton beam model used for the analysis was a near mono-energetic (of width about 1% the incident energy) and monodirectional infinitesimal (nonintegrated) pencil beam in water medium. By monodirection, we mean that the proton particles are in the same direction before entering the water medium and the various scattering prior to entrance to water is not taken into account. In intensity modulated proton therapy, the elementary intensity modulation entity for proton therapy is either an infinitesimal or finite sized beamlet. Since a finite sized beamlet is the superposition of infinitesimal pencil beams, the result of the maximum acceptable grid size obtained with infinitesimal pencil beam also applies to finite sized beamlet. The analytic Bragg curve function proposed by Bortfeld [T. Bortfeld, Med. Phys. 24, 2024-2033 (1997)] was employed. The lateral profile was approximated by a depth dependent Gaussian distribution. The model included the spreads of the Bragg peak and the lateral profiles due to multiple Coulomb scattering. The dependence of the maximum acceptable dose grid size on the

  17. Heavy Ion SEU Cross Section Calculation Based on Proton Experimental Data, and Vice Versa

    CERN Document Server

    Wrobel, F; Pouget, V; Dilillo, L; Ecoffet, R; Lorfèvre, E; Bezerra, F; Brugger, M; Saigné, F

    2014-01-01

    The aim of this work is to provide a method to calculate single event upset (SEU) cross sections by using experimental data. Valuable tools such as PROFIT and SIMPA already focus on the calculation of the proton cross section by using heavy ions cross-section experiments. However, there is no available tool that calculates heavy ion cross sections based on measured proton cross sections with no knowledge of the technology. We based our approach on the diffusion-collection model with the aim of analyzing the characteristics of transient currents that trigger SEUs. We show that experimental cross sections could be used to characterize the pulses that trigger an SEU. Experimental results allow yet defining an empirical rule to identify the transient current that are responsible for an SEU. Then, the SEU cross section can be calculated for any kind of particle and any energy with no need to know the Spice model of the cell. We applied our method to some technologies (250 nm, 90 nm and 65 nm bulk SRAMs) and we sho...

  18. A new calculation formula of the nuclear cross-section of therapeutic protons

    Directory of Open Access Journals (Sweden)

    Waldemar Ulmer

    2014-03-01

    Full Text Available Purpose: We have previously developed for nuclear cross-sections of therapeutic protons a calculation model, which is founded on the collective model as well as a quantum mechanical many particle problem to derive the S matrix and transition probabilities. In this communication, we show that the resonances can be derived by shifted Gaussian functions, whereas the unspecific nuclear interaction compounds can be represented by an error function, which also provides the asymptotic behavior. Method: The energy shifts can be interpreted in terms of necessary domains of energy to excite typical nuclear processes. Thus the necessary formulas referring to previous calculations of nuclear cross-sections will be represented. The mass number AN determines the strong interaction range, i.e. RStrong = 1.2·10-13·AN1/3cm. The threshold energy ETh of the energy barrier is determined by the condition Estrong = ECoulomb. Results and Conclusion: A linear combination of Gaussians, which contain additional energy shifts, and an error function incorporate a possible representation of Fermi-Dirac statistics, which is applied here to nuclear excitations and reaction with release of secondary particles. The new calculation formula provides a better understanding of different types of resonances occurring in nuclear interactions with protons. The present study is mainly a continuation of published papers.1-3--------------------------------Cite this article as: Ulmer W. A new calculation formula of the nuclear cross-section of therapeutic protons. Int J Cancer Ther Oncol 2014; 2(2:020211. DOI: 10.14319/ijcto.0202.11

  19. 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.

  20. 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.

  1. 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

  2. Charge transfer in collisions between protons and lithium atoms

    International Nuclear Information System (INIS)

    Ermolaev, A.M.

    1984-01-01

    In the first paragraph of section 4.2, p 1074, the energy at which the two-state cross sections for capture from the L and K shells of Li 0 are equal should read 60 keV CM (1 x 10 -17 cm 2 ) instead of 200 keV CM (6 x 10 -19 cm 2 ) incorrectly stated there. This will not, however, affect the general comment in the same paragraph on Olson's calculations at low impact energies. The present calculations shows that capture from the K shell constitute only 13 per cent at 50 keV lab to compare with 62 per cent according to Olsen's estimates. As the impact energy increases above 100 keV lab the presently reported K-shell cross sections converge rapidly to Olson's curve. In the view of the above correction, the penultimate line in the abstract should give 50 keV lab rather than 150 keV lab as the energy below which capture from the K shell becomes relatively unimportant. (author)

  3. Shielding calculations in support of the Spallation Neutron Source (SNS) proton beam transport system

    International Nuclear Information System (INIS)

    Johnson, Jeffrey O.; Gallmeier, Franz X.; Popova, Irina

    2002-01-01

    Determining the bulk shielding requirements for accelerator environments is generally an easy task compared to analyzing the radiation transport through the complex shield configurations and penetrations typically associated with the detailed Title II design efforts of a facility. Shielding calculations for penetrations in the SNS accelerator environment are presented based on hybrid Monte Carlo and discrete ordinates particle transport methods. This methodology relies on coupling tools that map boundary surface leakage information from the Monte Carlo calculations to boundary sources for one-, two-, and three-dimensional discrete ordinates calculations. The paper will briefly introduce the coupling tools for coupling MCNPX to the one-, two-, and three-dimensional discrete ordinates codes in the DOORS code suite. The paper will briefly present typical applications of these tools in the design of complex shield configurations and penetrations in the SNS proton beam transport system

  4. Fast pencil beam dose calculation for proton therapy using a double-Gaussian beam model

    Directory of Open Access Journals (Sweden)

    Joakim eda Silva

    2015-12-01

    Full Text Available The highly conformal dose distributions produced by scanned proton pencil beams are more sensitive to motion and anatomical changes than those produced by conventional radiotherapy. The ability to calculate the dose in real time as it is being delivered would enable, for example, online dose monitoring, and is therefore highly desirable. We have previously described an implementation of a pencil beam algorithm running on graphics processing units (GPUs intended specifically for online dose calculation. Here we present an extension to the dose calculation engine employing a double-Gaussian beam model to better account for the low-dose halo. To the best of our knowledge, it is the first such pencil beam algorithm for proton therapy running on a GPU. We employ two different parametrizations for the halo dose, one describing the distribution of secondary particles from nuclear interactions found in the literature and one relying on directly fitting the model to Monte Carlo simulations of pencil beams in water. Despite the large width of the halo contribution, we show how in either case the second Gaussian can be included whilst prolonging the calculation of the investigated plans by no more than 16%, or the calculation of the most time-consuming energy layers by about 25%. Further, the calculation time is relatively unaffected by the parametrization used, which suggests that these results should hold also for different systems. Finally, since the implementation is based on an algorithm employed by a commercial treatment planning system, it is expected that with adequate tuning, it should be able to reproduce the halo dose from a general beam line with sufficient accuracy.

  5. Calculation of proton and neutron emission spectra from proton reactions with 90Zr and 208Pb to 160 MeV with the GNASH code

    International Nuclear Information System (INIS)

    Young, P.G.; Chadwick, M.B.

    1994-01-01

    A number of modifications have been made to the reaction theory code GNASH in order the accuracy of calculations at incident particle energies up to 200 MeV. Direct reaction a level density models appropriate for higher energy calculations are now used in the code, and most importantly, improved preequilibrium models have been incorporated into the code system. The code has been used to calculate proton-induced reactions on 90 Zr and 208 Pb for the International Code and Model Intercomparison for Intermediate Energy Reactions organized by the NEA. Calculations were performed with GNASH at incident proton energies of 25, 45, 80, and 160 mev using both the exciton model and Feshbach-Kerman-Koonin theory for the preequilibrium component. The models and procedures used in the GNASH calculations with the exciton model are described here. The results are compared to experimental data and to results from the GNASH calculations with Feshbach-Kerman-Koonin preequilibrium theory

  6. 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)

  7. Evolution of calculation models for the proton-therapy dose planning software

    International Nuclear Information System (INIS)

    Vidal, Marie

    2011-01-01

    This work was achieved in collaboration between the Institut Curie Proton-therapy Center of Orsay (ICPO), the DOSIsoft company and the CREATIS laboratory, in order to develop a new dose calculation model for the new ICPO treatment room. A new accelerator and gantry room from the IBA company were installed during the up-grade project of the proton-therapy center, with the intention of enlarging the cancer localizations treated at ICPO. Developing a package of methods and new dose calculation algorithms to adapt them to the new specific characteristics of the delivered beams by the IBA system is the first goal of this PhD work. They all aim to be implemented in the DOSIsoft treatment planning software, Isogray. First, the double scattering technique is treated in taking into account major differences between the IBA system and the ICPO fixed beam lines passive system. Secondly, a model is explored for the scanned beams modality. The second objective of this work is improving the Ray-Tracing and Pencil-Beam dose calculation models already in use. For the double scattering and uniform scanning techniques, the patient personalized collimator at the end of the beam line causes indeed a patient dose distribution contamination. A reduction method of that phenomenon was set up for the passive beam system. An analytical model was developed which describes the contamination function with parameters validated through Monte-Carlo simulations on the GATE platform. It allows us to apply those methods to active scanned beams. (author) [fr

  8. Evolution of dose calculation models for proton-therapy treatment planning

    International Nuclear Information System (INIS)

    Vidal, Marie

    2011-01-01

    This work was achieved in collaboration between the Institut Curie proton-therapy Center of Orsay (ICPO), the DOSIsoft company and the CREATIS laboratory, in order to develop a new dose calculation model for the new ICPO treatment room. A new accelerator and gantry room from the IBA company were installed during the up-grade project of the proton-therapy center, with the intention of enlarging the cancer localizations treated at ICPO. Developing a package of methods and new dose calculation algorithms to adapt them to the new specific characteristics of the delivered beams by the IBA system is the first goal of this PhD work. They all aim to be implemented in the DOSIsoft treatment planning software, Isogray. First, the double scattering technique is treated in taking into account major differences between the IBA system and the ICPO fixed beam lines passive system. Secondly, a model is explored for the scanned beams modality. The second objective of this work is improving the Ray-Tracing and Pencil-Beam dose calculation models already in use. For the double scattering and uniform scanning techniques, the patient personalized collimator at the end of the beam line causes indeed a patient dose distribution contamination. A reduction method of that phenomenon was set up for the passive beam system. An analytical model was developed which describes the contamination function with parameters validated through Monte-Carlo simulations on the GATE platform. It allows us to apply those methods to active scanned beams [fr

  9. Sub-second pencil beam dose calculation on GPU for adaptive proton therapy.

    Science.gov (United States)

    da Silva, Joakim; Ansorge, Richard; Jena, Rajesh

    2015-06-21

    Although proton therapy delivered using scanned pencil beams has the potential to produce better dose conformity than conventional radiotherapy, the created dose distributions are more sensitive to anatomical changes and patient motion. Therefore, the introduction of adaptive treatment techniques where the dose can be monitored as it is being delivered is highly desirable. We present a GPU-based dose calculation engine relying on the widely used pencil beam algorithm, developed for on-line dose calculation. The calculation engine was implemented from scratch, with each step of the algorithm parallelized and adapted to run efficiently on the GPU architecture. To ensure fast calculation, it employs several application-specific modifications and simplifications, and a fast scatter-based implementation of the computationally expensive kernel superposition step. The calculation time for a skull base treatment plan using two beam directions was 0.22 s on an Nvidia Tesla K40 GPU, whereas a test case of a cubic target in water from the literature took 0.14 s to calculate. The accuracy of the patient dose distributions was assessed by calculating the γ-index with respect to a gold standard Monte Carlo simulation. The passing rates were 99.2% and 96.7%, respectively, for the 3%/3 mm and 2%/2 mm criteria, matching those produced by a clinical treatment planning system.

  10. Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach

    International Nuclear Information System (INIS)

    Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa

    2016-01-01

    In order to calculate the stopping power of protons, there are many very successful models at high energies, which are extrapolated to low-energy regions. From the point of view of application of proton beam in cancer treatment is just this low energy region the most relevant due to the dose deposition profile in depth for protons. In this work, we present a calculation of the stopping power of protons in a water target using the dielectric formalism in MELF-GOS approach. The results when compared to other models show good agreement for energies above 100 keV and lower values below this energy. This result should impact the range of values of protons and the Bragg peak position. (author)

  11. Calculation of channels for forming and transport of medical proton beams at the JINR phasotron

    International Nuclear Information System (INIS)

    Kuz'min, E.S.; Mirokhin, I.V.; Molokanov, A.G.; Obukhov, Yu.L.; Savchenko, O.V.

    1984-01-01

    Results of numerical simulation of shaping and transporting processes of therapeutic proton beams with a modified Bragg curve at the JINR phasotron are presented. The mean energy of proton beams are about 100, 130 and 200 MeV. To provide the flat-topped depth-dose distributions with a steep back slope, the method of shaping with a necessary energy spectrum from a nonmonoenergetic beam is used. It is shown by the calculations that it is possible to choose such modes of the channel operation at which clinical-physical requirements to the parameters of medical proton beams are satisfied. Extensions of flat-tops of dose peaks are 1.3 g/cm 2 , 1.7 g/cm 2 and 3.5 g/cm 2 for the 100 MeV, 130 MeV and 200 MeV beam energies, respectively. Dose rate in the peaks of modified distributions are not less than 100 rad per minute

  12. 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

  13. Calculations of the photon dose behind concrete shielding of high energy proton accelerators

    International Nuclear Information System (INIS)

    Dworak, D.; Tesch, K.; Zazula, J.M.

    1992-02-01

    The photon dose per primary beam proton behind lateral concrete shieldings was calculated by using an extension of the Monte Carlo particle shower code FLUKA. The following photon-producing processes were taken into account: capture of thermal neutrons, deexcitation of nuclei after nuclear evaporation, inelastic neutron scattering and nuclear reactions below 140 MeV, as well as photons from electromagnetic cascades. The obtained ratio of the photon dose to the neutron dose equivalent varies from 8% to 20% and it well compares with measurements performed recently at DESY giving a mean ratio of 14%. (orig.)

  14. 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.

  15. Clinical implementation of full Monte Carlo dose calculation in proton beam therapy

    International Nuclear Information System (INIS)

    Paganetti, Harald; Jiang, Hongyu; Parodi, Katia; Slopsema, Roelf; Engelsman, Martijn

    2008-01-01

    The goal of this work was to facilitate the clinical use of Monte Carlo proton dose calculation to support routine treatment planning and delivery. The Monte Carlo code Geant4 was used to simulate the treatment head setup, including a time-dependent simulation of modulator wheels (for broad beam modulation) and magnetic field settings (for beam scanning). Any patient-field-specific setup can be modeled according to the treatment control system of the facility. The code was benchmarked against phantom measurements. Using a simulation of the ionization chamber reading in the treatment head allows the Monte Carlo dose to be specified in absolute units (Gy per ionization chamber reading). Next, the capability of reading CT data information was implemented into the Monte Carlo code to model patient anatomy. To allow time-efficient dose calculation, the standard Geant4 tracking algorithm was modified. Finally, a software link of the Monte Carlo dose engine to the patient database and the commercial planning system was established to allow data exchange, thus completing the implementation of the proton Monte Carlo dose calculation engine ('DoC++'). Monte Carlo re-calculated plans are a valuable tool to revisit decisions in the planning process. Identification of clinically significant differences between Monte Carlo and pencil-beam-based dose calculations may also drive improvements of current pencil-beam methods. As an example, four patients (29 fields in total) with tumors in the head and neck regions were analyzed. Differences between the pencil-beam algorithm and Monte Carlo were identified in particular near the end of range, both due to dose degradation and overall differences in range prediction due to bony anatomy in the beam path. Further, the Monte Carlo reports dose-to-tissue as compared to dose-to-water by the planning system. Our implementation is tailored to a specific Monte Carlo code and the treatment planning system XiO (Computerized Medical Systems Inc

  16. 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.

  17. 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...

  18. Extended wave-packet model to calculate energy-loss moments of protons in matter

    Science.gov (United States)

    Archubi, C. D.; Arista, N. R.

    2017-12-01

    In this work we introduce modifications to the wave-packet method proposed by Kaneko to calculate the energy-loss moments of a projectile traversing a target which is represented in terms of Gaussian functions for the momentum distributions of electrons in the atomic shells. These modifications are introduced using the Levine and Louie technique to take into account the energy gaps corresponding to the different atomic levels of the target. We use the extended wave-packet model to evaluate the stopping power, the energy straggling, the inverse mean free path, and the ionization cross sections for protons in several targets, obtaining good agreements for all these quantities on an extensive energy range that covers low-, intermediate-, and high-energy regions. The extended wave-packet model proposed here provides a method to calculate in a very straightforward way all the significant terms of the inelastic interaction of light ions with any element of the periodic table.

  19. 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.

  20. Technical Note: On the calculation of stopping-power ratio for stoichiometric calibration in proton therapy

    Energy Technology Data Exchange (ETDEWEB)

    Ödén, Jakob [Department of Medical Physics, Karolinska University Hospital, Stockholm SE-17176, Sweden and Department of Medical Radiation Physics, Stockholm University and Karolinska Institutet, Stockholm SE-17176 (Sweden); Zimmerman, Jens; Nowik, Patrik; Poludniowski, Gavin, E-mail: gavin.poludniowski@karolinska.se [Department of Medical Physics, Karolinska University Hospital, Stockholm SE-17176 (Sweden); Bujila, Robert [Department of Medical Physics, Karolinska University Hospital, Stockholm SE-17176, Sweden and Department of Physics, Royal Institute of Technology, Stockholm SE-10691 (Sweden)

    2015-09-15

    Purpose: The quantitative effects of assumptions made in the calculation of stopping-power ratios (SPRs) are investigated, for stoichiometric CT calibration in proton therapy. The assumptions investigated include the use of the Bethe formula without correction terms, Bragg additivity, the choice of I-value for water, and the data source for elemental I-values. Methods: The predictions of the Bethe formula for SPR (no correction terms) were validated against more sophisticated calculations using the SRIM software package for 72 human tissues. A stoichiometric calibration was then performed at our hospital. SPR was calculated for the human tissues using either the assumption of simple Bragg additivity or the Seltzer-Berger rule (as used in ICRU Reports 37 and 49). In each case, the calculation was performed twice: First, by assuming the I-value of water was an experimentally based value of 78 eV (value proposed in Errata and Addenda for ICRU Report 73) and second, by recalculating the I-value theoretically. The discrepancy between predictions using ICRU elemental I-values and the commonly used tables of Janni was also investigated. Results: Errors due to neglecting the correction terms to the Bethe formula were calculated at less than 0.1% for biological tissues. Discrepancies greater than 1%, however, were estimated due to departures from simple Bragg additivity when a fixed I-value for water was imposed. When the I-value for water was calculated in a consistent manner to that for tissue, this disagreement was substantially reduced. The difference between SPR predictions when using Janni’s or ICRU tables for I-values was up to 1.6%. Experimental data used for materials of relevance to proton therapy suggest that the ICRU-derived values provide somewhat more accurate results (root-mean-square-error: 0.8% versus 1.6%). Conclusions: The conclusions from this study are that (1) the Bethe formula can be safely used for SPR calculations without correction terms; (2

  1. Technical Note: On the calculation of stopping-power ratio for stoichiometric calibration in proton therapy

    International Nuclear Information System (INIS)

    Ödén, Jakob; Zimmerman, Jens; Nowik, Patrik; Poludniowski, Gavin; Bujila, Robert

    2015-01-01

    Purpose: The quantitative effects of assumptions made in the calculation of stopping-power ratios (SPRs) are investigated, for stoichiometric CT calibration in proton therapy. The assumptions investigated include the use of the Bethe formula without correction terms, Bragg additivity, the choice of I-value for water, and the data source for elemental I-values. Methods: The predictions of the Bethe formula for SPR (no correction terms) were validated against more sophisticated calculations using the SRIM software package for 72 human tissues. A stoichiometric calibration was then performed at our hospital. SPR was calculated for the human tissues using either the assumption of simple Bragg additivity or the Seltzer-Berger rule (as used in ICRU Reports 37 and 49). In each case, the calculation was performed twice: First, by assuming the I-value of water was an experimentally based value of 78 eV (value proposed in Errata and Addenda for ICRU Report 73) and second, by recalculating the I-value theoretically. The discrepancy between predictions using ICRU elemental I-values and the commonly used tables of Janni was also investigated. Results: Errors due to neglecting the correction terms to the Bethe formula were calculated at less than 0.1% for biological tissues. Discrepancies greater than 1%, however, were estimated due to departures from simple Bragg additivity when a fixed I-value for water was imposed. When the I-value for water was calculated in a consistent manner to that for tissue, this disagreement was substantially reduced. The difference between SPR predictions when using Janni’s or ICRU tables for I-values was up to 1.6%. Experimental data used for materials of relevance to proton therapy suggest that the ICRU-derived values provide somewhat more accurate results (root-mean-square-error: 0.8% versus 1.6%). Conclusions: The conclusions from this study are that (1) the Bethe formula can be safely used for SPR calculations without correction terms; (2

  2. 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.

  3. 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)

  4. 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.

  5. Simulation and analysis of main steam control system based on heat transfer calculation

    Science.gov (United States)

    Huang, Zhenqun; Li, Ruyan; Feng, Zhongbao; Wang, Songhan; Li, Wenbo; Cheng, Jiwei; Jin, Yingai

    2018-05-01

    In this paper, after thermal power plant 300MW boiler was studied, mat lab was used to write calculation program about heat transfer process between the main steam and boiler flue gas and amount of water was calculated to ensure the main steam temperature keeping in target temperature. Then heat transfer calculation program was introduced into Simulink simulation platform based on control system multiple models switching and heat transfer calculation. The results show that multiple models switching control system based on heat transfer calculation not only overcome the large inertia of main stream temperature, a large hysteresis characteristic of main stream temperature, but also adapted to the boiler load changing.

  6. 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.

  7. 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.

  8. 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.

  9. Real-time dose calculation and visualization for the proton therapy of ocular tumours

    Energy Technology Data Exchange (ETDEWEB)

    Pfeiffer, Karsten [Medizinische Physik, Deutsches Krebsforschungszentrum, INF 280, D-69120 Heidelberg (Germany). E-mail: k.pfeiffer at dkfz.de; Bendl, Rolf [Medizinische Physik, Deutsches Krebsforschungszentrum, INF 280, D-69120 Heidelberg (Germany). E-mail: r.bendl at dkfz.de

    2001-03-01

    A new real-time dose calculation and visualization was developed as part of the new 3D treatment planning tool OCTOPUS for proton therapy of ocular tumours within a national research project together with the Hahn-Meitner Institut Berlin. The implementation resolves the common separation between parameter definition, dose calculation and evaluation and allows a direct examination of the expected dose distribution while adjusting the treatment parameters. The new tool allows the therapist to move the desired dose distribution under visual control in 3D to the appropriate place. The visualization of the resulting dose distribution as a 3D surface model, on any 2D slice or on the surface of specified ocular structures is done automatically when adapting parameters during the planning process. In addition, approximate dose volume histograms may be calculated with little extra time. The dose distribution is calculated and visualized in 200 ms with an accuracy of 6% for the 3D isodose surfaces and 8% for other objects. This paper discusses the advantages and limitations of this new approach. (author)

  10. Measured and calculated neutron yields for 100 MeV protons on thick targets of Pb and Li

    International Nuclear Information System (INIS)

    Jones, R.T.; Lone, M.A.; Okazaki, A.

    1983-01-01

    The neutron yield per proton from thick targets of lead and lithium irradiated with 100 MeV protons has been measured and calculated. The water bath method was used to measure the neutron production, and a Faraday cup for the beam current determination. Measured yields are 0.343 +- 0.021 for lead and 0.123 +- 0.007 for lithium. Corresponding yields calculated with the nucleon-meson transport code NMTC are 0.363 +- 0.002 and 0.160 +- 0.001. Measured and calculated thermal neutron distributions in the water bath are also compared

  11. 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

  12. 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.

  13. Adjusted NIEL calculations for estimating proton-induced degradation of GaInP/GaAs/Ge space solar cells

    International Nuclear Information System (INIS)

    Lu Ming; Wang Rong; Liu Yunhong; Hu Wentao; Feng Zhao; Han Zhaolei

    2011-01-01

    The non-ionizing energy loss (NIEL) values for protons in solar cells should be modified by taking into account the distribution of the Bragg damage peak in the active region to calculate the corresponding displacement damage dose. In this paper, based upon a thin target approximation, a new approach is presented to modify NIEL values for protons on a GaAs sub-cell. Adjusted NIEL values can be used to estimate the degradation induced by protons on GaInP/GaAs/Ge triple-junction space solar cells.

  14. 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...

  15. 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.

  16. 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.)

  17. 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

  18. 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

  19. 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.

  20. Parameter-free effective field theory calculation for the solar proton-fusion and hep processes

    International Nuclear Information System (INIS)

    T.S. Park; L.E. Marcucci; R. Schiavilla; M. Viviani; A. Kievsky; S. Rosati; K. Kubodera; D.P. Min; M. Rho

    2002-01-01

    Spurred by the recent complete determination of the weak currents in two-nucleon systems up to Ο(Q 3 ) in heavy-baryon chiral perturbation theory, we carry out a parameter-free calculation of the threshold S-factors for the solar pp (proton-fusion) and hep processes in an effective field theory that combines the merits of the standard nuclear physics method and systematic chiral expansion. The power of the EFT adopted here is that one can correlate in a unified formalism the weak-current matrix elements of two-, three- and four-nucleon systems. Using the tritium β-decay rate as an input to fix the only unknown parameter in the theory, we can evaluate the threshold S factors with drastically improved precision; the results are S pp (0) = 3.94 x (1 ± 0.004) x 10 -25 MeV-b and S hep (0) = (8.6 ± 1.3) x 10 -20 keV-b. The dependence of the calculated S-factors on the momentum cutoff parameter Λ has been examined for a physically reasonable range of Λ. This dependence is found to be extremely small for the pp process, and to be within acceptable levels for the hep process, substantiating the consistency of our calculational scheme

  1. 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

  2. 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

  3. 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

  4. 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....

  5. SU-E-T-470: Importance of HU-Mass Density Calibration Technique in Proton Pencil Beam Dose Calculation

    Energy Technology Data Exchange (ETDEWEB)

    Penfold, S; Miller, A [University of Adelaide, Adelaide, SA (Australia)

    2015-06-15

    Purpose: Stoichiometric calibration of Hounsfield Units (HUs) for conversion to proton relative stopping powers (RStPs) is vital for accurate dose calculation in proton therapy. However proton dose distributions are not only dependent on RStP, but also on relative scattering power (RScP) of patient tissues. RScP is approximated from material density but a stoichiometric calibration of HU-density tables is commonly neglected. The purpose of this work was to quantify the difference in calculated dose of a commercial TPS when using HU-density tables based on tissue substitute materials and stoichiometric calibrated ICRU tissues. Methods: Two HU-density calibration tables were generated based on scans of the CIRS electron density phantom. The first table was based directly on measured HU and manufacturer quoted density of tissue substitute materials. The second was based on the same CT scan of the CIRS phantom followed by a stoichiometric calibration of ICRU44 tissue materials. The research version of Pinnacle{sup 3} proton therapy was used to compute dose in a patient CT data set utilizing both HU-density tables. Results: The two HU-density tables showed significant differences for bone tissues; the difference increasing with increasing HU. Differences in density calibration table translated to a difference in calculated RScP of −2.5% for ICRU skeletal muscle and 9.2% for ICRU femur. Dose-volume histogram analysis of a parallel opposed proton therapy prostate plan showed that the difference in calculated dose was negligible when using the two different HU-density calibration tables. Conclusion: The impact of HU-density calibration technique on proton therapy dose calculation was assessed. While differences were found in the calculated RScP of bony tissues, the difference in dose distribution for realistic treatment scenarios was found to be insignificant.

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

    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.

  7. Half-lives for proton emission, alpha decay, cluster radioactivity, and cold fission processes calculated in a unified theoretical framework

    Energy Technology Data Exchange (ETDEWEB)

    Duarte, S.B.; Tavares, O.A.P.; Guzman, F.; Dimarco, A. [Centro Brasileiro de Pesquisas Fisicas (CBPF), Rio de Janeiro, RJ (Brazil); Garcia, F. [Sao Paulo Univ., SP (Brazil). Inst. de Fisica; Universidade Estadual de Santa Cruz, Ilheus, BA (Brazil). Dept. de Ciencias Exatas e Tecnologicas; Rodriguez, O. [Sao Paulo Univ., SP (Brazil). Inst. de Fisica; Instituto Superior de Ciencias e Tecnologia Nucleares, La Habana (Cuba); Goncalves, M. [Instituto de Radioprotecao e Dosimetria (IRD), Rio de Janeiro, RJ (Brazil)

    2002-01-01

    Half-life values of spontaneous nuclear decay processes are presented in the framework of the Effective Liquid Drop Model (ELDM) using the combination of varying mass asymmetry shape description for the mass transfer with Werner-Wheeler's inertia coefficient V{sub MAS}/WW. The calculated half-lives of ground-state to ground-state transitions for the proton emission, alpha decay, cluster radioactivity, and cold fission processes are compared with experimental data. Results have shown that the ELDM is a very efficient model to describe these different decay processes in a same, unified theoretical framework. A Table listing the predicted half-life values, {tau}{sub c} is presented for all possible cases of spontaneous nuclear break-up such that -7.30 <{approx_equal} log{sub 10} {tau}{sub c} [S] <{approx_equal} 27.50 and log {sub 10}({tau}/{tau}{sub c}) > -17.0, where {tau} is the total half-life of the parent nucleus. (author)

  8. Interaction of 14 MeV neutrons with hydrogenated target proton emission calculation

    International Nuclear Information System (INIS)

    Martin, G.; Perez, N.; Desdin.

    1996-01-01

    Using neutron emission data of a 14 MeV neutron generator, a paraffin target, and based on the n + H 1 → n '+ p reaction, have been obtained the characteristics of the proton emission in a proton-neutron mixed field. It was used Monte Carlo simulation and it was obtained the proton output as function of the converter width and the energy spectrum of protons corresponding to different converter thickness. Among 0.07 and 0.2 cm there is a maximum zone for the proton emission. The energy spectrum agrees with obtained on previous papers. Figures showing these results are provided

  9. 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

  10. Accurate magnetic field calculations for contactless energy transfer coils

    NARCIS (Netherlands)

    Sonntag, C.L.W.; Spree, M.; Lomonova, E.A.; Duarte, J.L.; Vandenput, A.J.A.

    2007-01-01

    In this paper, a method for estimating the magnetic field intensity from hexagon spiral windings commonly found in contactless energy transfer applications is presented. The hexagonal structures are modeled in a magneto-static environment using Biot-Savart current stick vectors. The accuracy of the

  11. Calculated L-shell x-ray line intensities for proton and helium ion impact

    International Nuclear Information System (INIS)

    Cohen, D.D.; Harrigan, M.

    1986-01-01

    Theoretical L-shell X-ray line intensities have been calculated for proton and helium bombardment of atoms from nickel (Z 2 = 28) to curium (Z 2 = 96). The ionization cross sections for the three L subshells were obtained from the recent calculations by Cohen and Harrigan in the ECPSSR theory, which uses the plane-wave Born approximation (PWBA) with corrections for energy loss (E), Coulomb deflection (C), perturbed-stationary-state (PSS), and relativistic (R) effects. The fluorescence yields and Coster-Kronig transition probabilities were taken from M. O. Krause (Phys. Chem. Ref. Data 8, 307 (1979)) and the L-subshell emission rates from S. I. Salem, S. L. Panosian, and R. A. Krause (Atomic Data and Nuclear Data Tables 14, 91 (1974)). The line intensities Ll, Lα, Leta, Lβ 1 to Lβ 6 , Lβ/sub 9,10/, and Lγ 1 to Lgg 6 are tabulated for selected ion energies from 0.2 to 10 MeV

  12. Inter-comparison of Dose Distributions Calculated by FLUKA, GEANT4, MCNP, and PHITS for Proton Therapy

    Science.gov (United States)

    Yang, Zi-Yi; Tsai, Pi-En; Lee, Shao-Chun; Liu, Yen-Chiang; Chen, Chin-Cheng; Sato, Tatsuhiko; Sheu, Rong-Jiun

    2017-09-01

    The dose distributions from proton pencil beam scanning were calculated by FLUKA, GEANT4, MCNP, and PHITS, in order to investigate their applicability in proton radiotherapy. The first studied case was the integrated depth dose curves (IDDCs), respectively from a 100 and a 226-MeV proton pencil beam impinging a water phantom. The calculated IDDCs agree with each other as long as each code employs 75 eV for the ionization potential of water. The second case considered a similar condition of the first case but with proton energies in a Gaussian distribution. The comparison to the measurement indicates the inter-code differences might not only due to different stopping power but also the nuclear physics models. How the physics parameter setting affect the computation time was also discussed. In the third case, the applicability of each code for pencil beam scanning was confirmed by delivering a uniform volumetric dose distribution based on the treatment plan, and the results showed general agreement between each codes, the treatment plan, and the measurement, except that some deviations were found in the penumbra region. This study has demonstrated that the selected codes are all capable of performing dose calculations for therapeutic scanning proton beams with proper physics settings.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. Accurate magnetic field calculations for contactless energy transfer coils

    OpenAIRE

    Sonntag, C.L.W.; Spree, M.; Lomonova, E.A.; Duarte, J.L.; Vandenput, A.J.A.

    2007-01-01

    In this paper, a method for estimating the magnetic field intensity from hexagon spiral windings commonly found in contactless energy transfer applications is presented. The hexagonal structures are modeled in a magneto-static environment using Biot-Savart current stick vectors. The accuracy of the models are evaluated by mapping the current sticks and the hexagon spiral winding tracks to a local twodimensional plane, and comparing their two-dimensional magnetic field intensities. The accurac...

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. 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

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  4. 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.

  5. 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.

  6. 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 + .

  7. Calculation of Post-Closure Natural Convection Heat and Mass Transfer in Yucca Mountain Drifts

    International Nuclear Information System (INIS)

    Webb, S.; Itamura, M.

    2004-01-01

    Natural convection heat and mass transfer under post-closure conditions has been calculated for Yucca Mountain drifts using the computational fluid dynamics (CFD) code FLUENT. Calculations have been performed for 300, 1000, 3000, and 10,000 years after repository closure. Effective dispersion coefficients that can be used to calculate mass transfer in the drift have been evaluated as a function of time and boundary temperature tilt

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. Sensitivity of relativistic impulse approximation proton-nucleus elastic scattering calculations on relativistic mean-field parameterizations

    International Nuclear Information System (INIS)

    Hojsik, M.; Gmuca, S.

    1998-01-01

    Relativistic microscopic calculations are presented for proton elastic scattering from 40 Ca at 500 MeV. The underlying target densities are calculated within the framework of the relativistic mean-field theory with several parameter sets commonly in use. The self consistency of the scalar and vector densities (and thus to relativistic mean-field parameters) is investigated. Recently, the relativistic impulse approximation (RIA) has been widely and repeatedly used for the calculations of proton-nucleus scattering at intermediate energies. These calculations have exhibited significant improvements over the nonrelativistic approaches. The relativistic impulse approximation calculations. in particular, provide a dramatically better description of the spin observables, namely the analyzing power, A y , and the spin-rotation function, Q, at least for energies higher than 400 MeV. In the relativistic impulse approximation, the Dirac optical potential is obtained by folding of the local Lorentz-invariant amplitudes with the corresponding nuclear densities. For the spin zero targets the scalar and vector terms give the dominant contributions. Thus the scalar and vector nuclear densities (both, proton and neutron ones) play the dominant role in the relativistic impulse approximation. While the proton vector densities can be obtained by unfolding from the empirically known charge densities, all other densities used rely to a great extent on theoretical models. The various recipes are used to construct the neutron vector densities and the scalar densities for both, neutrons and protons. In this paper we will study the sensitivity of the relativistic impulse approximation results on the various sets of relativistic mean-field parameters currently in use

  13. SU-E-T-37: A GPU-Based Pencil Beam Algorithm for Dose Calculations in Proton Radiation Therapy

    International Nuclear Information System (INIS)

    Kalantzis, G; Leventouri, T; Tachibana, H; Shang, C

    2015-01-01

    Purpose: Recent developments in radiation therapy have been focused on applications of charged particles, especially protons. Over the years several dose calculation methods have been proposed in proton therapy. A common characteristic of all these methods is their extensive computational burden. In the current study we present for the first time, to our best knowledge, a GPU-based PBA for proton dose calculations in Matlab. Methods: In the current study we employed an analytical expression for the protons depth dose distribution. The central-axis term is taken from the broad-beam central-axis depth dose in water modified by an inverse square correction while the distribution of the off-axis term was considered Gaussian. The serial code was implemented in MATLAB and was launched on a desktop with a quad core Intel Xeon X5550 at 2.67GHz with 8 GB of RAM. For the parallelization on the GPU, the parallel computing toolbox was employed and the code was launched on a GTX 770 with Kepler architecture. The performance comparison was established on the speedup factors. Results: The performance of the GPU code was evaluated for three different energies: low (50 MeV), medium (100 MeV) and high (150 MeV). Four square fields were selected for each energy, and the dose calculations were performed with both the serial and parallel codes for a homogeneous water phantom with size 300×300×300 mm3. The resolution of the PBs was set to 1.0 mm. The maximum speedup of ∼127 was achieved for the highest energy and the largest field size. Conclusion: A GPU-based PB algorithm for proton dose calculations in Matlab was presented. A maximum speedup of ∼127 was achieved. Future directions of the current work include extension of our method for dose calculation in heterogeneous phantoms

  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. Experimental validation of a deforming grid 4D dose calculation for PBS proton therapy

    Science.gov (United States)

    Krieger, Miriam; Klimpki, Grischa; Fattori, Giovanni; Hrbacek, Jan; Oxley, David; Safai, Sairos; Weber, Damien C.; Lomax, Antony J.; Zhang, Ye

    2018-03-01

    The aim of this study was to verify the temporal accuracy of the estimated dose distribution by a 4D dose calculation (4DDC) in comparison to measurements. A single-field plan (0.6 Gy), optimised for a liver patient case (CTV volume: 403cc), was delivered to a homogeneous PMMA phantom and measured by a high resolution scintillating-CCD system at two water equivalent depths. Various motion scenarios (no motion and motions with amplitude of 10 mm and two periods: 3.7 s and 4.4 s) were simulated using a 4D Quasar phantom and logged by an optical tracking system in real-time. Three motion mitigation approaches (single delivery, 6× layered and volumetric rescanning) were applied, resulting in 10 individual measurements. 4D dose distributions were retrospectively calculated in water by taking into account the delivery log files (retrospective) containing information on the actually delivered spot positions, fluences, and time stamps. Moreover, in order to evaluate the sensitivity of the 4DDC inputs, the corresponding prospective 4DDCs were performed as a comparison, using the estimated time stamps of the spot delivery and repeated periodical motion patterns. 2D gamma analyses and dose-difference-histograms were used to quantify the agreement between measurements and calculations for all pixels with > 5% of the maximum calculated dose. The results show that a mean gamma score of 99.2% with standard deviation 1.0% can be achieved for 3%/3 mm criteria and all scenarios can reach a score of more than 95%. The average area with more than 5% dose difference was 6.2%. Deviations due to input uncertainties were obvious for single scan deliveries but could be smeared out once rescanning was applied. Thus, the deforming grid 4DDC has been demonstrated to be able to predict the complex patterns of 4D dose distributions for PBS proton therapy with high dosimetric and geometric accuracy, and it can be used as a valid clinical tool for 4D treatment planning, motion mitigation

  16. Heat transfer calculations on the KNK II emergency cooling system

    International Nuclear Information System (INIS)

    Vossebrecker, H.; Groenefeld, G.

    1976-12-01

    The Licensing Authority had demanded that in case of the change of the KNK thermal core into a fast core the decay heat removal system must be improved by a diverse and spatially separated emergency cooling system. In order to meet this requirement an existing nitrogen system of the facility is extended in such a manner that the decay heat will be removed by a nitrogen flow passing through the gap between reactor vessel and guard vessel. The heat transport from the core to the vessel is accomplished by natural convection flow rates which are generated by density differences between the hot core subassemblies, the reflector subassemblies and other passages between the upper and the lower plenum. The calculations show that the maximum temperatures in the core do not reach the sodium boiling-point. The maximum vessel temperature is 673 deg. C. In this report the function of the emergency cooling system and the methods of calculation are described, the input data and the results are stated and it is shown that the calculated temperatures are conservative [de

  17. Calculations of Total and Differential Solid Angles for a Proton Recoil Solid State Detector

    Energy Technology Data Exchange (ETDEWEB)

    Konijn, J; Lauber, A; Tollander, B

    1963-08-15

    The solid angles have been computed for a proton recoil counter consisting of a circular hydrogenous foil viewed by an isotropic neutron point source at different distances from the target foil. Tables are given for the total subtended solid angle as well as the differential energy distribution function of the proton recoil spectrum. The influence of finite foil thickness has also been studied.

  18. Calculation codes for radiant heat transfers; Les codes de calcul de rayonnement thermique

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    This document reports on 12 papers about computerized simulation and modeling of radiant heat transfers and fluid flows in various industrial and domestic situations: space heating, metal industry (furnaces, boilers..), aerospace industry (turbojet engines, combustion chambers) etc.. This workshop was organized by the ``radiation`` section of the French society of thermal engineers. (J.S.)

  19. Calculation codes for radiant heat transfers; Les codes de calcul de rayonnement thermique

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-12-31

    This document reports on 12 papers about computerized simulation and modeling of radiant heat transfers and fluid flows in various industrial and domestic situations: space heating, metal industry (furnaces, boilers..), aerospace industry (turbojet engines, combustion chambers) etc.. This workshop was organized by the ``radiation`` section of the French society of thermal engineers. (J.S.)

  20. 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

  1. 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.

  2. ESTAR, PSTAR, ASTAR. A PC package for calculating stopping powers and ranges of electrons, protons and helium ions. Version 2

    International Nuclear Information System (INIS)

    Berger, M.J.

    1993-01-01

    A PC package is documented for calculating stopping powers and ranges of electrons, protons and helium ions in matter for energies from 1 keV up to 10 GeV. Stopping powers and ranges for electrons can be calculated for any element, compound or mixture. Stopping powers and ranges of protons and helium ions can be calculated for 74 materials (26 elements and 48 compounds and mixtures). The files are stored on two HD diskettes in compressed form. Both executable files for IBM PC and Fortran-77 source files are provided. All three programs require 5.2 Mb of disk space. This set of two diskettes with detailed documentation is available upon request, cost free, from the IAEA Nuclear Data Section. (author). 25 refs, 4 tabs

  3. Numerical fluid flow and heat transfer calculations on multiprocessor systems

    Energy Technology Data Exchange (ETDEWEB)

    Oehman, G.A.; Malen, T.E.; Kuusela, P.

    1989-01-01

    The first part of the report presents the basic principles of parallel processing, and factors influencing tbe efficiency of practical applications are discussed. In a multiprocessor computer, different parts of the program code are executed in parallel, i.e. simultaneous with respect to time, on different processors, and thus it becomes possible to decrease the overall computation time by a factor, which in the ideal case is equal to the number of processors. The application study starts from the numerical solution of the twodimesional Laplace equation, which describes the steady heat conduction in a solid plate and advances through the solution of the three dimensional Laplace equation to the case of study laminar fluid flow in a twodimensional box at Reynolds numbers up to 20. Hereby the stream function-vorticity method is first applied and the SIMPLER method. The conventional (sequential) numerical algoritms for these fluid flow and heat transfer problems are found not to be ideally suited for conversion to parallel computation, but sped-up ratios considerably above 50 % of the theoretical maximum are regularly achieved in the runs. The numerical procedures we coded in the OCCAM-2 language and the test runs were performed at who Akademi on the imperimental HATHI-computers containing 16 T4l4 and 100 INMOS T800 transputers respectively.

  4. Numerical fluid flow and heat transfer calculations on multiprocessor systems

    Energy Technology Data Exchange (ETDEWEB)

    Oehman, G.A.; Malen, T.E.; Kuusela, P.

    1989-12-31

    The first part of the report presents the basic principles of parallel processing, and factors influencing tbe efficiency of practical applications are discussed. In a multiprocessor computer, different parts of the program code are executed in parallel, i.e. simultaneous with respect to time, on different processors, and thus it becomes possible to decrease the overall computation time by a factor, which in the ideal case is equal to the number of processors. The application study starts from the numerical solution of the twodimesional Laplace equation, which describes the steady heat conduction in a solid plate and advances through the solution of the three dimensional Laplace equation to the case of study laminar fluid flow in a twodimensional box at Reynolds numbers up to 20. Hereby the stream function-vorticity method is first applied and the SIMPLER method. The conventional (sequential) numerical algoritms for these fluid flow and heat transfer problems are found not to be ideally suited for conversion to parallel computation, but sped-up ratios considerably above 50 % of the theoretical maximum are regularly achieved in the runs. The numerical procedures we coded in the OCCAM-2 language and the test runs were performed at who Akademi on the imperimental HATHI-computers containing 16 T4l4 and 100 INMOS T800 transputers respectively.

  5. 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.

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

    Science.gov (United States)

    Mohrig, Jerry R

    2013-07-16

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

  7. 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.

  8. 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

  9. 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.

  10. Calculation of local bed to wall heat transfer in a fluidized-bed

    International Nuclear Information System (INIS)

    Kilkis, B.I.

    1987-01-01

    Surface to bed heat transfer in a fluidized-bed largely depends upon its local and global hydrodynamical behavior including particle velocity, particle trajectory, gas velocity, and void fraction. In this study, a computer program was developed in order to calculate the local bed to wall heat transfer, by accounting for the local and global instantaneous hydrodynamics of the bed. This is accomplished by utilizing the CHEMFLUB computer program. This information at a given location is interpreted so that the most appropriate heat transfer model is utilized for each time increment. These instantaneous heat transfer coefficient for the given location. Repeating the procedure for different locations, a space average heat transfer coefficient is also calculated. This report briefly summarizes the various heat transfer models employed and gives sample computer results reporting the case study for Mickley - Trilling's experimental set-up. Comparisons with available experimental data and correlations are also provided in order to compare and evaluate the computer results

  11. Calculations of combined radiation and convection heat transfer in rod bundles under emergency cooling conditions

    International Nuclear Information System (INIS)

    Sun, K.H.; Gonzalez-Santalo, J.M.; Tien, C.L.

    1976-01-01

    A model has been developed to calculate the heat transfer coefficients from the fuel rods to the steam-droplet mixture typical of Boiling Water Reactors under Emergency Core Cooling System (ECCS) operation conditions during a postulated loss-of-coolant accident. The model includes the heat transfer by convection to the vapor, the radiation from the surfaces to both the water droplets and the vapor, and the effects of droplet evaporation. The combined convection and radiation heat transfer coefficient can be evaluated with respect to the characteristic droplet size. Calculations of the heat transfer coefficient based on the droplet sizes obtained from the existing literature are consistent with those determined empirically from the Full-Length-Emergency-Cooling-Heat-Transfer (FLECHT) program. The present model can also be used to assess the effects of geometrical distortions (or deviations from nominal dimensions) on the heat transfer to the cooling medium in a rod bundle

  12. 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.

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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

  1. 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...

  2. Multigroup and coupled forward-adjoint Monte Carlo calculation efficiencies for secondary neutron doses from proton beams

    International Nuclear Information System (INIS)

    Kelsey IV, Charles T.; Prinja, Anil K.

    2011-01-01

    We evaluate the Monte Carlo calculation efficiency for multigroup transport relative to continuous energy transport using the MCNPX code system to evaluate secondary neutron doses from a proton beam. We consider both fully forward simulation and application of a midway forward adjoint coupling method to the problem. Previously we developed tools for building coupled multigroup proton/neutron cross section libraries and showed consistent results for continuous energy and multigroup proton/neutron transport calculations. We observed that forward multigroup transport could be more efficient than continuous energy. Here we quantify solution efficiency differences for a secondary radiation dose problem characteristic of proton beam therapy problems. We begin by comparing figures of merit for forward multigroup and continuous energy MCNPX transport and find that multigroup is 30 times more efficient. Next we evaluate efficiency gains for coupling out-of-beam adjoint solutions with forward in-beam solutions. We use a variation of a midway forward-adjoint coupling method developed by others for neutral particle transport. Our implementation makes use of the surface source feature in MCNPX and we use spherical harmonic expansions for coupling in angle rather than solid angle binning. The adjoint out-of-beam transport for organs of concern in a phantom or patient can be coupled with numerous forward, continuous energy or multigroup, in-beam perturbations of a therapy beam line configuration. Out-of-beam dose solutions are provided without repeating out-of-beam transport. (author)

  3. A correction scheme for a simplified analytical random walk model algorithm of proton dose calculation in distal Bragg peak regions

    Science.gov (United States)

    Yao, Weiguang; Merchant, Thomas E.; Farr, Jonathan B.

    2016-10-01

    The lateral homogeneity assumption is used in most analytical algorithms for proton dose, such as the pencil-beam algorithms and our simplified analytical random walk model. To improve the dose calculation in the distal fall-off region in heterogeneous media, we analyzed primary proton fluence near heterogeneous media and propose to calculate the lateral fluence with voxel-specific Gaussian distributions. The lateral fluence from a beamlet is no longer expressed by a single Gaussian for all the lateral voxels, but by a specific Gaussian for each lateral voxel. The voxel-specific Gaussian for the beamlet of interest is calculated by re-initializing the fluence deviation on an effective surface where the proton energies of the beamlet of interest and the beamlet passing the voxel are the same. The dose improvement from the correction scheme was demonstrated by the dose distributions in two sets of heterogeneous phantoms consisting of cortical bone, lung, and water and by evaluating distributions in example patients with a head-and-neck tumor and metal spinal implants. The dose distributions from Monte Carlo simulations were used as the reference. The correction scheme effectively improved the dose calculation accuracy in the distal fall-off region and increased the gamma test pass rate. The extra computation for the correction was about 20% of that for the original algorithm but is dependent upon patient geometry.

  4. 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

  5. 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.)

  6. 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.)

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Shielding Calculations for PUSPATI TRIGA Reactor (RTP) Fuel Transfer Cask with Micro shield

    International Nuclear Information System (INIS)

    Nurhayati Ramli; Ahmad Nabil Abdul Rahim; Ariff Shah Ismail

    2011-01-01

    The shielding calculations for RTP fuel transfer cask was performed by using computer code Micro shield 7.02. Micro shield is a computer code designed to provide a model to be used for shielding calculations. The results of the calculations can be obtained fast but the code is not suitable for complex geometries with a shielding composed of more than one material. Nevertheless, the program is sufficient for As Low As Reasonable Achievable (ALARA) optimization calculations. In this calculation, a geometry based on the conceptual design of RTP fuel transfer cask was modeled. Shielding material used in the calculations were lead (Pb) and stainless steel 304 (SS304). The results obtained from these calculations are discussed in this paper. (author)

  12. The influence of CT image noise on proton range calculation in radiotherapy planning

    International Nuclear Information System (INIS)

    Chvetsov, Alexei V; Paige, Sandra L

    2010-01-01

    The purpose of this note is to evaluate the relationship between the stochastic errors in CT numbers and the standard deviation of the computed proton beam range in radiotherapy planning. The stochastic voxel-to-voxel variation in CT numbers called 'noise,' may be due to signal registration, processing and numerical image reconstruction technique. Noise in CT images may cause a deviation in the computed proton range from the physical proton range, even assuming that the error due to CT number-stopping power calibration is removed. To obtain the probability density function (PDF) of the computed proton range, we have used the continuing slowing down approximation (CSDA) and the uncorrelated white Gaussian noise along the proton path. The model of white noise was accepted because for the slice-based fan-beam CT scanner; the power-spectrum properties apply only to the axial (x, y) domain and the noise is uncorrelated in the z domain. However, the possible influence of the noise power spectrum on the standard deviation of the range should be investigated in the future. A random number generator was utilized for noise simulation and this procedure was iteratively repeated to obtain convergence of range PDF, which approached a Gaussian distribution. We showed that the standard deviation of the range, σ, increases linearly with the initial proton energy, computational grid size and standard deviation of the voxel values. The 95% confidence interval width of the range PDF, which is defined as 4σ, may reach 0.6 cm for the initial proton energy of 200 MeV, computational grid 0.25 cm and 5% standard deviation of CT voxel values. Our results show that the range uncertainty due to random errors in CT numbers may be significant and comparable to the uncertainties due to calibration of CT numbers. (note)

  13. 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

  14. Calculation of energy transfer by fission fragments from plane uranium layer to thin wire

    International Nuclear Information System (INIS)

    Pikulev, A.A.

    2006-01-01

    Energy transfer from a flat fissile uranium slab to a fine wire via fission fragments is calculated. The rate of energy transfer versus the thicknesses of the slab and protecting aluminum film, as well as the wire-slab gap, is found. An expression for the absorption coefficient of the wire is derived, and the effect the thickness of the wire has on the energy transfer process is studied. The amount of the edge effect for a finite-size uranium slab is demonstrated with calculations for vacuum conditions and for argon under a pressure of 0.25 atm [ru

  15. 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

  16. Comparison of calculated and experimental values of the yields of xenon isotopes in reactions with high-energy protons

    International Nuclear Information System (INIS)

    Shukolyukov, A.Yu.; Katargin, N.V.; Baishev, I.S.

    1989-01-01

    Calculations of the cumulative yields of isotopes of Xe have been carried out on the basis of the semi-empirical formula of Silverberg and Tsao for Ba- and Dy-targets and bombarding proton energies in the range 100-1050 MeV. Results are compared with experimental data for the yields of Xe isotopes, and domains of applicability of the semi-empirical formula are determined

  17. 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

  18. 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.

  19. 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

  20. 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.

  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. Ionization of atoms or ions by electron or proton impact; calculations with the classical three-body theory. ch. 3

    International Nuclear Information System (INIS)

    Boesten, L.G.J.

    1978-01-01

    Calculations on the threshold ionization of H, He + and Li 2+ by electrons have been performed to study the so-called 'post-collision interaction' (P.C.I.) effects which appear to affect the threshold ionization process significantly. These effects are caused by the long range Coulomb interactions between the two electrons as they move away from the nucleus. The long range interactions are fully taken into account in the classical three-body collision theory. In quantum mechanical theories, however, it is difficult to account for these interactions. This theory has been used to study the ionization of He + -ions by electron impact up to much higher energies (up till ten times the threshold energy). The results are compared with experimental results of Dolder et al. (1961) and with results of quantum mechanical calculations. Results are given for ionization of helium atoms by electron or proton impact. This collision process, in which four particles are involved, can under certain circumstances be treated as a collision process in which only three particles are involved. Calculations are performed concerning: a) cross sections for ionization of metastable helium atoms by electron impact, b) cross sections for ionization of ground-state helium atoms by fast proton impact (energy and angular distributions of ejected electrons), c) generalized oscillator strengths for ionization of helium by fast proton impact

  3. 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.

  4. 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.

  5. Calculation of proton-deuteron phase parameters including the Coulomb force

    International Nuclear Information System (INIS)

    Alt, E.O.; Sandhas, W.; Ziegelmann, H.

    1985-04-01

    A previously proposed exact method for including the Coulomb force in three-body collisions is applied to proton-deuteron scattering. We present phase shifts for angular momenta up to L=9, from elastic threshold to 50 MeV proton laboratory energy. Separable rank-one potentials are taken for the nuclear interactions. A charge-independent and a charge-symmetric choise, while leading to different neutron-deuteron and proton-deuteron phase parameters, nevertheless yields practically the same Coulomb corrections. We, moreover, investigate the question of P-wave resonances.A critical comparison of our results with those obtained in a co-ordinate space formalism is performed. Furthermore, proposals for an approximate inclusion of the Coulomb potential are tested, and found unsatisfactory. (orig.)

  6. 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

  7. 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.

  8. 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

  9. Structure evolution of mononuclear tungsten and molybdenum species in the protonation process: Insight from FPMD and DFT calculations

    Science.gov (United States)

    Zhang, Ning; Yi, Haibo; Zeng, Dewen; Zhao, Zhongwei; Wang, Wenlei; Costanzo, Francesca

    2018-03-01

    In this work, we apply static density functional theory (DFT) calculations, as well as classical and first-principles molecular dynamics (FPMD) simulations, using the free-energy perturbation method to study the protonation ability, active site and structures of W(VI) and Mo(VI) in acidic aqueous solution. Using FPMD simulations, utilizing the pKa's calculation technique, we concluded that the octahedral WO2(OH)2(H2O)2 is the true formula for tungstic acid (H2WO4), and the hydroxyl ligands are the acidic site. This aqueous structure of H2WO4 is analogous to the previously reported structure of molybdic acid (H2MoO4). The FPMD trajectories of the tungstic acid deprotonation show that the mono-protonated monotungstate ion (HWO4-) may partially exist as a five-coordinated WO3(OH)(H2O)- species except for the four-coordinated WO3(OH)- species. This result is supported by DFT calculations, with an isoenergetic point (ΔE = 1.9 kcal·mol-1) for the WO3(OH)(H2O)- and WO3(OH)- species, when explicit solvent molecules are taken into account. In contrast, for the H2MoO4 acid, FPMD trajectories during the deprotonation process show that two H2O ligands immediately escape from the first coordinated sphere of Mo(VI) to form the four-coordinated MoO3(OH)- species. This difference indicates that structural expansion of W(VI) began in the first protonated step, while that of Mo(VI) only occurs in the second step. In addition, our calculated first and second acid constants for tungstic acid are higher than previously reported values for molybdic acid. This result suggests that WO42- is more easily protonated than the MoO42- anion in the same acidic solution, which is further confirmed by DFT calculations of hydrated oxoanions and its protonated species, based upon the hydration energy.

  10. Calculation of transfer factors for the transfer of caesium-137 from feedingstuffs to the meat of farm animals

    International Nuclear Information System (INIS)

    Mirna, A.

    1979-01-01

    To calculate the radiation exposure of the population in the surroundings of nuclear technical plants, the knowledge of the transfer of emitted radionuclides to plants, animals, and food is an essential precondition. Recent data from the literature about transfer factors (food/meat) of cesium-137 (Cs-137) for calves, cattle, and pigs have revealed considerable differences between the species mentioned and the value in the 'general calculation fundaments for the determination of radiation exposure by emission of radioactive substances with waste air' (12). In the FR of Germany mainly pork is eaten, therefore, it is interesting to know if the transfer of Cs-137 in the individual animal species is so far the same that it is justified to only use the exposure path grass-cattle for calculation. The values presented here have suggested for the transfer of fall-out Cs-137 from the food into the meat a value, on an average, six times as high as had been assumed up to day. In pork meat, there was even an increase by 2 tenth powers. (orig.) [de

  11. 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.

  12. 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)

  13. 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.

  14. Calculation of nuclear data for fast neutron and proton radiotherapy: A new ICRU report

    International Nuclear Information System (INIS)

    Chadwick, M.B.

    1997-01-01

    The author discusses the determination of nuclear interaction cross sections that are needed for fast neutron and proton radiotherapy. Both nuclear theory and experimental results are used to evaluate these data. An International Commission on Radiation Units and Measurements (ICRU) report, which is expected to be issued in 1998 and which compiles these data, is described

  15. Calculation of A (x) for the Proton-Deuteron Breakup Reaction at 135 MeV

    NARCIS (Netherlands)

    Eslami-Kalantari, M.; Mehmandoost-Khajeh-Dad, A. A.; Shafaei, M. A.; Amir-Ahmadi, H. R.; Biegun, A.; Gasparic, I.; Joulaeizadeh, L.; Kalantar-Nayestanaki, N.; Kistryn, St.; Kozela, A.; Mardanpour, H.; Messchendorp, J. G.; Moeini, H.; Ramazani Moghaddam Arani, Ahmad; Shende, S. V.; Stephan, E.; Sworst, R.

    Observables in proton-deuteron scattering are sensitive probes of the nucleon-nucleon interaction and three-nucleon force effects (3NF). Several facilities in the world, including Kernfysisch Versneller Instituut (KVI), allow a detailed study a few-nucleon interaction below the pion-production

  16. Calculations and measurements of the scintillator-to-water stopping power ratio of liquid scintillators for use in proton radiotherapy

    International Nuclear Information System (INIS)

    Scott Ingram, W.; Robertson, Daniel; Beddar, Sam

    2015-01-01

    Liquid scintillators are a promising detector for high-resolution three-dimensional proton therapy dosimetry. Because the scintillator comprises both the active volume of the detector and the phantom material, an ideal scintillator will exhibit water equivalence in its radiological properties. One of the most fundamental of these is the scintillator’s stopping power. The objective of this study was to compare calculations and measurements of scintillator-to-water stopping power ratios to evaluate the suitability of the liquid scintillators BC-531 and OptiPhase HiSafe 3 for proton dosimetry. We also measured the relative scintillation output of the two scintillators. Both calculations and measurements show that the linear stopping power of OptiPhase is significantly closer to water than that of BC-531. BC-531 has a somewhat higher scintillation output. OptiPhase can be mixed with water at high concentrations, which further improves its scintillator-to-water stopping power ratio. However, this causes the solution to become cloudy, which has a negative impact on the scintillation output and spatial resolution of the detector. OptiPhase is preferred over BC-531 for proton dosimetry because its density and scintillator-to-water stopping power ratio are more water equivalent

  17. 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.

  18. 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.

  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. 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.

  3. 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).

  4. 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.

  5. 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

  6. Calculating the heat transfer coefficient of frame profiles with internal cavities

    DEFF Research Database (Denmark)

    Noyé, Peter Anders; Laustsen, Jacob Birck; Svendsen, Svend

    2004-01-01

    . The heat transfer coefficient is determined by two-dimensional numerical calculations and by measurements. Calculations are performed in Therm (LBNL (2001)), which is developed at Lawrence Berkeley National Laboratory, USA. The calculations are performed in accordance with the future European standards...... correspondence between measured and calculated values. Hence, when determining the heat transfer coefficient of frame profiles with internal cavities by calculations, it is necessary to apply a more detailed radiation exchange model than described in the prEN ISO 10077-2 standard. The ISO-standard offers......Determining the energy performance of windows requires detailed knowledge of the thermal properties of their different elements. A series of standards and guidelines exist in this area. The thermal properties of the frame can be determined either by detailed two-dimensional numerical methods...

  7. Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach; Calculo do poder de freamento de protons em agua utilizando o formalismo dieletrico na aproximacao MELF-GOS

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Botucatu, SP (Brazil)

    2016-07-01

    In order to calculate the stopping power of protons, there are many very successful models at high energies, which are extrapolated to low-energy regions. From the point of view of application of proton beam in cancer treatment is just this low energy region the most relevant due to the dose deposition profile in depth for protons. In this work, we present a calculation of the stopping power of protons in a water target using the dielectric formalism in MELF-GOS approach. The results when compared to other models show good agreement for energies above 100 keV and lower values below this energy. This result should impact the range of values of protons and the Bragg peak position. (author)

  8. 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.

  9. Dose distributions of a proton beam for eye tumor therapy: Hybrid pencil-beam ray-tracing calculations

    International Nuclear Information System (INIS)

    Rethfeldt, Ch.; Fuchs, H.; Gardey, K.-U.

    2006-01-01

    For the case of eye tumor therapy with protons, improvements are introduced compared to the standard dose calculation which implies straight-line optics and the constant-density assumption for the eye and its surrounding. The progress consists of (i) taking account of the lateral scattering of the protons in tissue by folding the entrance fluence distribution with the pencil beam distribution widening with growing depth in the tissue, (ii) rescaling the spread-out Bragg peak dose distribution in water with the radiological path length calculated voxel by voxel on ray traces through a realistic density matrix for the treatment geometry, yielding a trajectory dependence of the geometrical range. Distributions calculated for some specific situations are compared to measurements and/or standard calculations, and differences to the latter are discussed with respect to the requirements of therapy planning. The most pronounced changes appear for wedges placed in front of the eye, causing additional widening of the lateral falloff. The more accurate prediction of the dose dependence at the field borders is of interest with respect to side effects in the risk organs of the eye

  10. Mössbauer spectroscopy and DFT calculations on all protonation states of the 2Fe-2S cluster of the Rieske protein

    Science.gov (United States)

    Müller, C. S.; Auerbach, H.; Stegmaier, K.; Wolny, J. A.; Schünemann, V.; Pierik, A. J.

    2017-11-01

    The Thermus thermophilus Rieske protein ( TtRP) contains a 2Fe-2S cluster with one iron (Fe-Cys) coordinated by four sulfur atoms (2xS2- and 2xCys) and one iron (Fe-His) by two sulfur and two nitrogen atoms (2xS2-, His134 and His154). Here, the protein is investigated at three pH values (6.0, 8.5 and 10.5) in order to elucidate the protonation states of the His-ligands. Examination of the effect of protonation on the electronic structure of the cluster via Mössbauer spectroscopy gives a deeper understanding of the coupling of electron transfer to the protonation state of the His-ligands. Two components (1 referring to Fe-Cys and 2 to Fe-His) with parameters typical for a diamagnetic [2Fe-2S]2+ cluster are detected. The Mössbauer parameters and the protonation state clearly correlate: while δ remains almost pH-independent with δ 1 (pH6.0) = 0.23 (± 0.01) mms- 1 and δ 1 (pH10.5) = 0.24 (± 0.01) mms- 1 for Fe-Cys, it decreases for Fe-His from δ 2 (pH6.0) = 0.34 (± 0.01) mms- 1 to δ 2 (pH10.5) = 0.28 (± 0.01) mms- 1. Δ E Q changes from Δ E Q1 (pH6.0) = 0.57 (± 0.01) mms- 1 to Δ E Q1 (pH10.5) = 0.45 (± 0.01) mms- 1 and from Δ E Q2 (pH6.0) = 1.05 (± 0.01) mms- 1 to Δ E Q2 (pH10.5) = 0.71 (± 0.01) mms- 1. Density functional theory (DFT)-calculations based on the crystal structure (pdb 1NYK) (Hunsicker-Wang et al. Biochemistry 42, 7303, 2003) have been performed for the Rieske-cluster with different His-ligand protonation states, reproducing the experimentally observed trend.

  11. 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

  12. 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.

  13. Waste retrieval sluicing system campaign number 1 solids volume transferred calculation

    International Nuclear Information System (INIS)

    BAILEY, J.W.

    1999-01-01

    This calculation has been prepared to document the volume of sludge removed from tank 241-C-106 during Waste Retrieval Sluicing System (WRSS) Sluicing Campaign No.1. This calculation will be updated, if necessary, to incorporate new data. This calculation supports the declaration of completion of WRSS Campaign No.1 and, as such, is also the documentation for completion of Performance Agreement TWR 1.2.1 , C-106 Sluicing Performance Expectations. It documents the performance of all the appropriate tank 241-C-106 mass transfer verifications, evaluations, and appropriate adjustments discussed in HNF-SD-WM-PROC-021, Chapter 23, ''Process Engineering Calculations for Tank 241-C-106 Sluicing and Retrieval''

  14. Waste retrieval sluicing system campaign number 1 solids volume transferred calculation

    International Nuclear Information System (INIS)

    BAILEY, J.W.

    1999-01-01

    This calculation has been prepared to document the volume of sludge removed from tank 241-C-106 during Waste Retrieval Sluicing System (WRSS) Sluicing Campaign No.1. This calculation will be updated, if necessary, to incorporate new data. This calculation supports the declaration of completion of WRSS Campaign No.1 and, as such, is also the documentation for completion of Performance Agreement TWR 1.2.1 C-106 Sluicing Performance Expectations. It documents the performance of all the appropriate tank 241-C-106 mass transfer verifications, evaluations, and appropriate adjustments discussed in HNF-SD-WM-PROC-021, Chapter 23, ''Process Engineering Calculations for Tank 241-C-106 Sluicing and Retrieval''

  15. The FLUFF code for calculating finned surface heat transfer -description and user's guide

    International Nuclear Information System (INIS)

    Fry, C.J.

    1985-08-01

    FLUFF is a computer code for calculating heat transfer from finned surfaces by convection and radiation. It can also represent heat transfer by radiation to a partially emitting and absorbing medium within the fin cavity. The FLUFF code is useful not only for studying the behaviour of finned surfaces but also for deriving heat fluxes which can be applied as boundary conditions to other heat transfer codes. In this way models of bodies with finned surfaces may be greatly simplified since the fins need not be explicitly represented. (author)

  16. Light scattering by multiple spheres: comparison between Maxwell theory and radiative-transfer-theory calculations.

    Science.gov (United States)

    Voit, Florian; Schäfer, Jan; Kienle, Alwin

    2009-09-01

    We present a methodology to compare results of classical radiative transfer theory against exact solutions of Maxwell theory for a high number of spheres. We calculated light propagation in a cubic scattering region (20 x 20 x 20 microm(3)) consisting of different concentrations of polystyrene spheres in water (diameter 2 microm) by an analytical solution of Maxwell theory and by a numerical solution of radiative transfer theory. The relative deviation of differential as well as total scattering cross sections obtained by both approaches was evaluated for each sphere concentration. For the considered case, we found that deviations due to radiative transfer theory remain small, even for concentrations up to ca. 20 vol. %.

  17. [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.

  18. Wave packet methods for the direct calculation of energy-transfer moments in molecular collisions

    International Nuclear Information System (INIS)

    Bradley, K.S.; Schatz, G.C.; Balint-Kurti, G.G.

    1999-01-01

    The authors present a new wave packet based theory for the direct calculation of energy-transfer moments in molecular collision processes. This theory does not contain any explicit reference to final state information associated with the collision dynamics, thereby avoiding the need for determining vibration-rotation bound states (other than the initial state) for the molecules undergoing collision and also avoiding the calculation of state-to-state transition probabilities. The theory applies to energy-transfer moments of any order, and it generates moments for a wide range of translational energies in a single calculation. Two applications of the theory are made that demonstrate its viability; one is to collinear He + H 2 and the other to collinear He + CS 2 (with two active vibrational modes in CS 2 ). The results of these applications agree well with earlier results based on explicit calculation of transition probabilities

  19. SU-E-T-135: Assessing the Clinical Impact of Approximations in Analytical Dose Calculations for Proton Therapy

    Energy Technology Data Exchange (ETDEWEB)

    Schuemann, J; Giantsoudi, D; Grassberger, C; Paganetti, H [Massachusetts General Hospital, Boston, MA (United States)

    2015-06-15

    Purpose: To estimate the clinical relevance of approximations made in analytical dose calculation methods (ADCs) used for treatment planning on tumor coverage and tumor control probability (TCP) in proton therapy. Methods: We compared dose distributions planned with ADC to delivered dose distributions (as determined by TOPAS Monte Carlo (MC) simulations). We investigated 10 patients per site for 5 treatment sites (head-and-neck, lung, breast, prostate, liver). We evaluated differences between the two dose distributions analyzing dosimetric indices based on the dose-volume-histograms, the γ-index and the TCP. The normal tissue complication probability (NTCP) was estimated for the bladder and anterior rectum for the prostate patients. Results: We find that the target doses are overestimated by the ADC by 1–2% on average for all patients considered. All dosimetric indices (the mean dose, D95, D50 and D02, the dose values covering 95%, 50% and 2% of the target volume, respectively) are predicted within 5% of the delivered dose. A γ-index with a 3%/3mm criteria had a passing rate for target volumes above 96% for all patients. The TCP predicted by the two algorithms was up to 2%, 2.5%, 6%, 6.5%, and 11% for liver and breast, prostate, head-and-neck and lung patients, respectively. Differences in NTCP for anterior-rectum and bladder for prostate patients were less than 3%. Conclusion: We show that ADC provide adequate dose distributions for most patients, however, they can Result in underdosage of the target by as much as 5%. The TCP was found to be up to 11% lower than predicted. Advanced dose-calculation methods like MC simulations may be necessary in proton therapy to ensure target coverage for heterogeneous patient geometries, in clinical trials comparing proton therapy to conventional radiotherapy to avoid biases due to systematic discrepancies in calculated dose distributions, and, if tighter range margins are considered. Fully funded by NIH grants.

  20. Feasibility of MR-only proton dose calculations for prostate cancer radiotherapy using a commercial pseudo-CT generation method

    Science.gov (United States)

    Maspero, Matteo; van den Berg, Cornelis A. T.; Landry, Guillaume; Belka, Claus; Parodi, Katia; Seevinck, Peter R.; Raaymakers, Bas W.; Kurz, Christopher

    2017-12-01

    A magnetic resonance (MR)-only radiotherapy workflow can reduce cost, radiation exposure and uncertainties introduced by CT-MRI registration. A crucial prerequisite is generating the so called pseudo-CT (pCT) images for accurate dose calculation and planning. Many pCT generation methods have been proposed in the scope of photon radiotherapy. This work aims at verifying for the first time whether a commercially available photon-oriented pCT generation method can be employed for accurate intensity-modulated proton therapy (IMPT) dose calculation. A retrospective study was conducted on ten prostate cancer patients. For pCT generation from MR images, a commercial solution for creating bulk-assigned pCTs, called MR for Attenuation Correction (MRCAT), was employed. The assigned pseudo-Hounsfield Unit (HU) values were adapted to yield an increased agreement to the reference CT in terms of proton range. Internal air cavities were copied from the CT to minimise inter-scan differences. CT- and MRCAT-based dose calculations for opposing beam IMPT plans were compared by gamma analysis and evaluation of clinically relevant target and organ at risk dose volume histogram (DVH) parameters. The proton range in beam’s eye view (BEV) was compared using single field uniform dose (SFUD) plans. On average, a (2%, 2 mm) gamma pass rate of 98.4% was obtained using a 10% dose threshold after adaptation of the pseudo-HU values. Mean differences between CT- and MRCAT-based dose in the DVH parameters were below 1 Gy (radiotherapy, is feasible following adaptation of the assigned pseudo-HU values.

  1. The local skin dose conversion coefficients of electrons, protons and alpha particles calculated using the Geant4 code.

    Science.gov (United States)

    Zhang, Bintuan; Dang, Bingrong; Wang, Zhuanzi; Wei, Wei; Li, Wenjian

    2013-10-01

    The skin tissue-equivalent slab reported in the International Commission on Radiological Protection (ICRP) Publication 116 to calculate the localised skin dose conversion coefficients (LSDCCs) was adopted into the Monte Carlo transport code Geant4. The Geant4 code was then utilised for computation of LSDCCs due to a circular parallel beam of monoenergetic electrons, protons and alpha particles electrons and alpha particles are found to be in good agreement with the results using the MCNPX code of ICRP 116 data. The present work thus validates the LSDCC values for both electrons and alpha particles using the Geant4 code.

  2. 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

  3. On the calculation of length scales for turbulent heat transfer correlation

    Energy Technology Data Exchange (ETDEWEB)

    Barrett, M.J.; Hollingsworth, D.K.

    1999-07-01

    Turbulence length scale calculation methods were critically reviewed for their usefulness in boundary layer heat transfer correlations. Merits and deficiencies in each calculation method were presented. A rigorous method for calculating an energy-based integral scale was introduced. The method uses the variance of the streamwise velocity and a measured dissipation spectrum to calculate the length scale. Advantages and disadvantages of the new method were discussed. A principal advantage is the capability to decisively calculate length scales in a low-Reynolds-number turbulent boundary layer. The calculation method was tested with data from grid-generated, free-shear-layer, and wall-bounded turbulence. In each case, the method proved successful. The length scale is well behaved in turbulent boundary layers with momentum thickness Reynolds numbers from 400 to 2,100 and in flows with turbulent Reynolds numbers as low as 90.

  4. Numerical calculation of wall-to-bed heat transfer coefficients in gas-fluidized beds

    NARCIS (Netherlands)

    Kuipers, J.A.M.; Prins, W.; van Swaaij, W.P.M.

    1992-01-01

    A computer model for a hot gas-fluidized bed has been developed. The theoretical description is based on a two-fluid model (TFM) approach in which both phases are considered to be continuous and fully interpenetrating. Local wall-to-bed heat-transfer coefficients have been calculated by the

  5. Calculations of film boiling heat transfer above the quench front during reflooding

    International Nuclear Information System (INIS)

    Chan, K.C.; Yadigaroglu, G.

    1980-01-01

    An analytical method for calculating inverted-annular film boiling heat transfer above the quench front during the reflooding phase of a LOCA is presented. A two-fluid model comprising a laminar vapor film and a turbulent liquid-vapor mixture core is used. 12 refs

  6. 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.

  7. Structural activation calculations due to proton beam loss in the APT accelerator design

    International Nuclear Information System (INIS)

    Lee, S. K.; Beard, C. A.; Wilson, W. B.; Daemen, L. L.; Liska, D. J.; Waters, L. S.; Adams, M. L.

    1995-01-01

    For the new, high-power accelerators currently being designed, the amount of activation of the accelerator structure has become an important issue. To quantify this activation, a methodology was utilized that coupled transport and depletion codes to obtain dose rate estimates at several locations near the accelerator. This research focused on the 20 and 100 MeV sections of the Bridge-Coupled Drift Tube Linear Accelerator. The peak dose rate was found to be approximately 6 mR/hr in the 100 MeV section near the quadrupoles at a 25-cm radius for an assumed beam loss of 1 nA/m. It was determined that the activation was dominated by the proton interactions and subsequent spallation product generation, as opposed to the presence of the generated neutrons. The worst contributors were the spallation products created by proton bombardment of iron, and the worst component was the beam pipe, which consists mostly of iron. No definitive conclusions about the feasibility of hands-on maintenance can be determined, as the design is still not finalized

  8. Structural activation calculations due to proton beam loss in the APT accelerator design

    International Nuclear Information System (INIS)

    Lee, S.K.; Beard, C.A.; Wilson, W.B.; Daemen, L.L.; Liska, D.J.; Waters, L.S.; Adams, M.L.

    1994-01-01

    For the new, high-power accelerators currently being designed, the amount of activation of the accelerator structure has become an important issue. To quantify this activation, a methodology was utilized that coupled transport and depletion codes to obtain dose rate estimates at several locations near the accelerator. This research focused on the 20 and 100 MeV sections of the Bridge-Coupled Drift Tube Linear Accelerator. The peak dose rate was found to be approximately 6 mR/hr in the 100 MeV section near the quadrupoles at a 25-cm radius for an assumed beam loss of 1 nA/m. It was determined that the activation was dominated by the proton interactions and subsequent spallation product generation, as opposed to the presence of the generated neutrons. The worst contributors were the spallation products created by proton bombardment of iron, and the worst component was the beam pipe, which consists mostly of iron. No definitive conclusions about the feasibility of hands-on maintenance can be determined, as the design is still not finalized

  9. 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.

  10. A grey diffusion acceleration method for time-dependent radiative transfer calculations: analysis and application

    International Nuclear Information System (INIS)

    Nowak, P.F.

    1993-01-01

    A grey diffusion acceleration method is presented and is shown by Fourier analysis and test calculations to be effective in accelerating radiative transfer calculations. The spectral radius is bounded by 0.9 for the continuous equations, but is significantly smaller for the discretized equations, especially in the optically thick regimes characteristic to radiation transport problems. The GDA method is more efficient than the multigroup DSA method because its slightly higher iteration count is more than offset by the much lower cost per iteration. A wide range of test calculations confirm the efficiency of GDA compared to multifrequency DSA. (orig.)

  11. 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

  12. 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

  13. Studies and calculations of transverse emittance growth in high-energy proton storage rings

    International Nuclear Information System (INIS)

    Mane, S.R.; Jackson, G.

    1989-03-01

    In the operation of proton-antiproton colliders, an important goal is to maximize the integrated luminosity. During such operations in the Fermilab Tevatron, the transverse beam emittances were observed to grow unexpectedly quickly, thus causing a serious reduction of the luminosity. We have studied this phenomenon experimentally and theoretically. A formula for the emittance growth rate, due to random dipole kicks, is derived. In the experiment, RF phase noise of known amplitude was deliberately injected into the Tevatron to kick the beam randomly, via dispersion at the RF cavities. Theory and experiment are found to agree reasonably well. We also briefly discuss the problem of quadrupole kicks. 14 refs., 2 figs., 3 tabs

  14. Calculation of the mass transfer coefficient for the combustion of a carbon particle

    Energy Technology Data Exchange (ETDEWEB)

    Scala, Fabrizio [Istituto di Ricerche sulla Combustione - CNR, P.le Tecchio 80, 80125 Napoli (Italy)

    2010-01-15

    In this paper we address the calculation of the mass transfer coefficient around a burning carbon particle in an atmosphere of O{sub 2}, N{sub 2}, CO{sub 2}, CO, and H{sub 2}O. The complete set of Stefan-Maxwell equations is analytically solved under the assumption of no homogeneous reaction in the boundary layer. An expression linking the oxygen concentration and the oxygen flux at the particle surface (as a function of the bulk gas composition) is derived which can be used to calculate the mass transfer coefficient. A very simple approximate explicit expression is also given for the mass transfer coefficient, that is shown to be valid in the low oxygen flux limit or when the primary combustion product is CO{sub 2}. The results are given in terms of a correction factor to the equimolar counter-diffusion mass transfer coefficient, which is typically available in the literature for specific geometries and/or fluid-dynamic conditions. The significance of the correction factor and the accuracy of the different available expressions is illustrated for several cases of practical interest. Results show that under typical combustion conditions the use of the equimolar counter-diffusion mass transfer coefficient can lead to errors up to 10%. Larger errors are possible in oxygen-enriched conditions, while the error is generally low in oxy-combustion. (author)

  15. 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)

  16. Performance test of multicomponent quantum mechanical calculation with polarizable continuum model for proton chemical shift.

    Science.gov (United States)

    Kanematsu, Yusuke; Tachikawa, Masanori

    2015-05-21

    Multicomponent quantum mechanical (MC_QM) calculations with polarizable continuum model (PCM) have been tested against liquid (1)H NMR chemical shifts for a test set of 80 molecules. Improvement from conventional quantum mechanical calculations was achieved for MC_QM calculations. The advantage of the multicomponent scheme could be attributed to the geometrical change from the equilibrium geometry by the incorporation of the hydrogen nuclear quantum effect, while that of PCM can be attributed to the change of the electronic structure according to the polarization by solvent effects.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Calculated single-proton levels for nuclei with N equal to 152, 154, 156, 158, 160 and 162

    International Nuclear Information System (INIS)

    Moeller, P.; Nix, J.R.; Swiatecki, W.

    1986-09-01

    The decay properties of nuclei in many cases depend strongly on the quantum numbers of the single-particle levels in the vicinity of the Fermi surface. A striking illustration is the prolonged fission half-lives of odd nuclei relative to their even neighbors. The hindrance factor depends on the spin of unpaired odd particle and increases with increasing spin of the odd particle. The effect has been studied theoretically. For 257 Fm the hindrance factor is almost ten orders of magnitude. The computer code for calculating nuclear masses calculates single-particle levels at the deformations considered as one step in the calculations. We have run this code at the ground state deformation of all nuclei considered in the 1981 mass study and stored the calculated single-particle levels on permanent mass storage. A computer code has been constructed for extracting levels of nuclei that are specified to the program and plotting them. In this report we consider single-proton levels for even-N nuclei in the range 152 ≤ N ≤ 162. Six such plots are included in this report. The levels are plotted relative to the Fermi surface of each nucleus. We also include tables of the plotted single-particle levels since it is not always possible to determine the spin from an inspection of the plots, when levels are overlapping. 6 figs

  2. 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

  3. 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.

  4. MEASUREMENT OF QUENCHING INTENSITY, CALCULATION OF HEAT TRANSFER COEFFICIENT AND GLOBAL DATABASE OF LIQUID QUENCHANTS

    Directory of Open Access Journals (Sweden)

    Božidar Liščić

    2012-02-01

    Full Text Available This paper explains the need for a database of cooling intensities for liquid quenchants, in order to predict the quench hardness, microstructure, stresses and distortion, when real engineering components of complex geometry are quenched. The existing laboratory procedures for cooling intensity evaluation, using small test specimens, and Lumped-Heat-Capacity Method for calculation of heat transfer coefficient, are presented. Temperature Gradient Method for heat transfer calculation in workshop conditions, when using the Liscic/Petrofer probe, has been elaborated. Critical heat flux densities and their relation to the initial heat flux density, is explained. Specific facilities for testing quenching intensity in workshop conditions, are shown. The two phase project of the International Federation for Heat Treatment and Surface Engineering (IFHTSE, as recently approved, is mentioned.

  5. Uranium and radium in Finnsjoen - an experimental approach for calculation of transfer factors

    International Nuclear Information System (INIS)

    Evans, S.; Bergman, R.

    1981-01-01

    The radiological safety studies for underground disposal of HLW show that the future individual and collective doses to an important extent may originate from groundwater borne radium and uranium which reach the biosphere. Indications that the dispersion rates presently used give rise to overestimations of calculated doses justified an investigation for more realistic turnover rates of radium and uranium than those which now are in use. Within one of the sites selected for testing, the area around lake Finnsjoen, a small number of environmental samples were collected and analyzed with respect to radium and uranium and the new transfer coefficients between soil and lake water were derived. The dose rates obtained with the new transfer factors show a close agreement for radium and a slight increase for uranium compared with earlier calculations. (Auth.)

  6. Calculation of proton total reaction cross sections for some target nuclei in incident energy range of 10-600 MeV

    International Nuclear Information System (INIS)

    Bueyuekuslu, H.; Kaplan, A.; Aydin, A.; Tel, E.; Yildirim, G.

    2010-01-01

    In this study, proton total reaction cross sections have been investigated for some isotopes such as 12 C, 27 Al, 9 Be, 16 O, 181 Ta, 197 Au, 6 Li, and 14 N by a proton beam up to 600 MeV. Calculation of the proton total cross sections has been carried out by the analytic expression formulated by M.A. Alvi by using Coulomb-modified Glauber theory with the Helm model nuclear form factor. The obtained results have been discussed and compared with the available experimental data and found to be in agreement with each other.

  7. Design, performance, and calculated error of a Faraday cup for absolute beam current measurements of 600-MeV protons

    International Nuclear Information System (INIS)

    Beck, S.M.

    1975-04-01

    A mobile self-contained Faraday cup system for beam current measurments of nominal 600-MeV protons was designed, constructed, and used at the NASA Space Radiation Effects Laboratory. The cup is of reentrant design with a length of 106.7 cm and an outside diameter of 20.32 cm. The inner diameter is 15.24 cm and the base thickness is 30.48 cm. The primary absorber is commercially available lead hermetically sealed in a 0.32-cm-thick copper jacket. Several possible systematic errors in using the cup are evaluated. The largest source of error arises from high-energy electrons which are ejected from the entrance window and enter the cup. A total systematic error of -0.83 percent is calculated to be the decrease from the true current value. From data obtained in calibrating helium-filled ion chambers with the Faraday cup, the mean energy required to produce one ion pair in helium is found to be 30.76 +- 0.95 eV for nominal 600-MeV protons. This value agrees well, within experimental error, with reported values of 29.9 eV and 30.2 eV

  8. Design, performance, and calculated error of a Faraday cup for absolute beam current measurements of 600-MeV protons

    International Nuclear Information System (INIS)

    Beck, S.M.

    1975-04-01

    A mobile self-contained Faraday cup system for beam current measurements of nominal 600 MeV protons was designed, constructed, and used at the NASA Space Radiation Effects Laboratory. The cup is of reentrant design with a length of 106.7 cm and an outside diameter of 20.32 cm. The inner diameter is 15.24 cm and the base thickness is 30.48 cm. The primary absorber is commercially available lead hermetically sealed in a 0.32-cm-thick copper jacket. Several possible systematic errors in using the cup are evaluated. The largest source of error arises from high-energy electrons which are ejected from the entrance window and enter the cup. A total systematic error of -0.83 percent is calculated to be the decrease from the true current value. From data obtained in calibrating helium-filled ion chambers with the Faraday cup, the mean energy required to produce one ion pair in helium is found to be 30.76 +- 0.95 eV for nominal 600 MeV protons. This value agrees well, within experimental error, with reported values of 29.9 eV and 30.2 eV. (auth)

  9. W-320 waste retrieval sluicing system transfer line flushing volume and frequency calculation

    International Nuclear Information System (INIS)

    Bailey, J.W.

    1997-01-01

    The calculations contained in this analysis document establish the technical basis for the volume, frequency, and flushing fluid to be utilized for routine Waste Retrieval Sluicing System (WRSS) process line flushes. The WRSS was installed by Project W-320, Tank 241-C-106 Sluicing. The double contained pipelines being flushed have 4 inch stainless steel primary pipes. The flushes are intended to prevent hydrogen buildup in the transfer lines and to provide ALARA conditions for maintenance personnel

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Development and Application of a Numerical Framework for Improving Building Foundation Heat Transfer Calculations

    Science.gov (United States)

    Kruis, Nathanael J. F.

    Heat transfer from building foundations varies significantly in all three spatial dimensions and has important dynamic effects at all timescales, from one hour to several years. With the additional consideration of moisture transport, ground freezing, evapotranspiration, and other physical phenomena, the estimation of foundation heat transfer becomes increasingly sophisticated and computationally intensive to the point where accuracy must be compromised for reasonable computation time. The tools currently available to calculate foundation heat transfer are often either too limited in their capabilities to draw meaningful conclusions or too sophisticated to use in common practices. This work presents Kiva, a new foundation heat transfer computational framework. Kiva provides a flexible environment for testing different numerical schemes, initialization methods, spatial and temporal discretizations, and geometric approximations. Comparisons within this framework provide insight into the balance of computation speed and accuracy relative to highly detailed reference solutions. The accuracy and computational performance of six finite difference numerical schemes are verified against established IEA BESTEST test cases for slab-on-grade heat conduction. Of the schemes tested, the Alternating Direction Implicit (ADI) scheme demonstrates the best balance between accuracy, performance, and numerical stability. Kiva features four approaches of initializing soil temperatures for an annual simulation. A new accelerated initialization approach is shown to significantly reduce the required years of presimulation. Methods of approximating three-dimensional heat transfer within a representative two-dimensional context further improve computational performance. A new approximation called the boundary layer adjustment method is shown to improve accuracy over other established methods with a negligible increase in computation time. This method accounts for the reduced heat transfer

  15. 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.

  16. Toward understanding as photosynthetic biosignatures: light harvesting and energy transfer calculation

    Science.gov (United States)

    Komatsu, Y.; Umemura, M.; Shoji, M.; Shiraishi, K.; Kayanuma, M.; Yabana, K.

    2014-03-01

    Among several proposed biosignatures, red edge is a direct evidence of photosynthetic life if it is detected (Kiang et al 2007). Red edge is a sharp change in reflectance spectra of vegetation in NIR region (about 700-750 nm). The sign of red edge is observed by Earthshine or remote sensing (Wolstencroft & Raven 2002, Woolf et al 2002). But, why around 700-750 nm? The photosynthetic organisms on Earth have evolved to optimize the sunlight condition. However, if we consider about photosynthetic organism on extrasolar planets, they should have developed to utilize the spectra of its principal star. Thus, it is not strange even if it shows different vegetation spectra. In this study, we focused on the light absorption mechanism of photosynthetic organisms on Earth and investigated the fundamental properties of the light harvesting mechanisms, which is the first stage for the light absorption. Light harvesting complexes contain photosynthetic pigments like chlorophylls. Effective light absorption and the energy transfer are accomplished by the electronic excitations of collective photosynthetic pigments. In order to investigate this mechanism, we constructed an energy transfer model by using a dipole-dipole approximation for the interactions between electronic excitations. Transition moments and transition energies of each pigment are calculated at the time-dependent density functional theory (TDDFT) level (Marques & Gross 2004). Quantum dynamics simulation for the excitation energy transfer was calculated by the Liouvelle's equation. We adopted the model to purple bacteria, which has been studied experimentally and known to absorb lower energy. It is meaningful to focus on the mechanism of this bacteria, since in the future mission, M planets will become a important target. We calculated the oscillator strengths in one light harvesting complex and confirmed the validity by comparing to the experimental data. This complex is made of an inner and an outer ring. The

  17. 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.

  18. 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.

  19. 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.

  20. Numerical calculation of unsteady turbulent heat transfer in a circular tube considering for heat dissipation in a wale

    International Nuclear Information System (INIS)

    Groshev, A.I.; Slobodchuk, V.I.

    1986-01-01

    The results of numerical calculation of the conjugated problem of convective heat transfer under unsteady conditions are presented. The equations describing heat transfer take into account longitudinal heat diffusion in liquid and in a wall. The formulae for calculating local heat flows at the wall-liquid surface in the case of an arbitrary law of temperature variation at the outer wall surface along the channel length are proposed for steady-state heat transfer conditions

  1. The Calculation and Design of Fire suppression system in the proton accelerator research center

    International Nuclear Information System (INIS)

    Jeon, G. P.; Kim, J. Y.; Cho, J. H.; Min, Y. S.; Mun, K. J.; Cho, J. S.; Nam, J. M.; Park, S. S.; Joo, H. G.

    2010-01-01

    The fire protection system is composed of various fire suppression systems and fire detection and alarm systems. The primary function of the fire protection system is to protect life and property from a fire through detecting fires quickly and suppressing those fires that occur. In this paper, we described the fire suppression system only. The fire suppression system capacity for fire hydrant, the water mist system, sprinkler system and clean agent system is calculated and designed in compliance with the applicable Korean Acts that are applicable to fire protection and the NFSC code

  2. 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

  3. Comparison of the methods for calculating the interfacial heat transfer coefficient in hot stamping

    International Nuclear Information System (INIS)

    Zhao, Kunmin; Wang, Bin; Chang, Ying; Tang, Xinghui; Yan, Jianwen

    2015-01-01

    This paper presents a hot stamping experimentation and three methods for calculating the Interfacial Heat Transfer Coefficient (IHTC) of 22MnB5 boron steel. Comparison of the calculation results shows an average error of 7.5% for the heat balance method, 3.7% for the Beck's nonlinear inverse estimation method (the Beck's method), and 10.3% for the finite-element-analysis-based optimization method (the FEA method). The Beck's method is a robust and accurate method for identifying the IHTC in hot stamping applications. The numerical simulation using the IHTC identified by the Beck's method can predict the temperature field with a high accuracy. - Highlights: • A theoretical formula was derived for direct calculation of IHTC. • The Beck's method is a robust and accurate method for identifying IHTC. • Finite element method can be used to identify an overall equivalent IHTC

  4. 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

  5. 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

  6. Waste Retrieval Sluicing System Campaign Number 3 Solids Volume Transferred Calculation

    International Nuclear Information System (INIS)

    CAROTHERS, K.G.

    1999-01-01

    Waste Retrieval Sluicing System (WRSS) operations at tank 241-C-106 began on Wednesday, November 18, 1998. The purpose of this system is to retrieve and transfer the high-heat sludge from the tank for storage in double-shell tank 241-AY-102, thereby resolving the high-heat safety issue for the tank, and to demonstrate modernized past-practice retrieval technology for single-shell tank waste. Performance Agreement (PA) TWR 1.2.2, C-106 Sluicing, was established by the Department of Energy, Office of River Protection (ORP) for achieving completion of sluicing retrieval of waste from tank 241-C-106 by September 30, 1999. This level of sludge removal is defined in the PA as either removal of approximately 72 inches of sludge or removal of 172,000 gallons of sludge (approximately 62 inches) and less than 6,000 gallons (approximately 2 inches) of sludge removal per 12 hour sluice batch for three consecutive batches. Preliminary calculations of the volume of tank 241-C-106 sludge removed as of September 29, 1999 were provided to ORP documenting completion of PA TWR 1.2.2 (Allen 1999a). The purpose of this calculation is to document the final sludge volume removed from tank 241-C-106 up through September 30, 1999. Additionally, the results of an extra batch completed October 6, 1999 is included to show the total volume of sludge removed through the end of WRSS operations. The calculation of the sludge volume transferred from the tank is guided by engineering procedure HNF-SD-WM-PROC-021, Section 15.0,Rev. 3, sub-section 4.4, ''Calculation of Sludge Transferred.''

  7. Waste Retrieval Sluicing System Campaign Number 3 Solids Volume Transferred Calculation

    International Nuclear Information System (INIS)

    CAROTHERS, K.G.

    1999-01-01

    Waste Retrieval Sluicing System (WRSS) operations at tank 241-C-106 began on Wednesday, November 18,1998. The purpose of this system is to retrieve and transfer the high-heat sludge from the tank for storage in double-shell tank 241-AY-102, thereby resolving the high-heat safety issue for the tank, and to demonstrate modernized past-practice retrieval technology for single-shell tank waste. Performance Agreement (PA) TWR 1.2.2, C-106 Sluicing, was established by the Department of Energy, Office of River Protection (ORP) for achieving completion of sluicing retrieval of waste from tank 241-C-106 by September 30,1999. This level of sludge removal is defined in the PA as either removal of approximately 72 inches of sludge or removal of 172,000 gallons of sludge (approximately 62 inches) and less than 6,000 gallons (approximately 2 inches) of sludge removal per 12 hour sluice batch for three consecutive batches. Preliminary calculations of the volume of tank 241-C-106 sludge removed as of September 29, 1999 were provided to ORP documenting completion of PA TWR 1.2.2 (Allen 1999a). The purpose of this calculation is to document the final sludge volume removed from tank 241-C-106 up through September 30, 1999. Additionally, the results of an extra batch completed October 6, 1999 is included to show the total volume of sludge removed through the end of WRSS operations. The calculation of the sludge volume transferred from the tank is guided by engineering procedure HNF-SD-WM-PROC-021, Section 15.0,Rev. 3, sub-section 4.4, ''Calculation of Sludge Transferred.''

  8. 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.

  9. 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)

  10. Efficient voxel navigation for proton therapy dose calculation in TOPAS and Geant4

    Science.gov (United States)

    Schümann, J.; Paganetti, H.; Shin, J.; Faddegon, B.; Perl, J.

    2012-06-01

    A key task within all Monte Carlo particle transport codes is ‘navigation’, the calculation to determine at each particle step what volume the particle may be leaving and what volume the particle may be entering. Navigation should be optimized to the specific geometry at hand. For patient dose calculation, this geometry generally involves voxelized computed tomography (CT) data. We investigated the efficiency of navigation algorithms on currently available voxel geometry parameterizations in the Monte Carlo simulation package Geant4: G4VPVParameterisation, G4VNestedParameterisation and G4PhantomParameterisation, the last with and without boundary skipping, a method where neighboring voxels with the same Hounsfield unit are combined into one larger voxel. A fourth parameterization approach (MGHParameterization), developed in-house before the latter two parameterizations became available in Geant4, was also included in this study. All simulations were performed using TOPAS, a tool for particle simulations layered on top of Geant4. Runtime comparisons were made on three distinct patient CT data sets: a head and neck, a liver and a prostate patient. We included an additional version of these three patients where all voxels, including the air voxels outside of the patient, were uniformly set to water in the runtime study. The G4VPVParameterisation offers two optimization options. One option has a 60-150 times slower simulation speed. The other is compatible in speed but requires 15-19 times more memory compared to the other parameterizations. We found the average CPU time used for the simulation relative to G4VNestedParameterisation to be 1.014 for G4PhantomParameterisation without boundary skipping and 1.015 for MGHParameterization. The average runtime ratio for G4PhantomParameterisation with and without boundary skipping for our heterogeneous data was equal to 0.97: 1. The calculated dose distributions agreed with the reference distribution for all but the G4

  11. 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.

  12. 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

  13. 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.

  14. Time averaging procedure for calculating the mass and energy transfer rates in adiabatic two phase flow

    International Nuclear Information System (INIS)

    Boccaccini, L.V.

    1986-07-01

    To take advantages of the semi-implicit computer models - to solve the two phase flow differential system - a proper averaging procedure is also needed for the source terms. In fact, in some cases, the correlations normally used for the source terms - not time averaged - fail using the theoretical time step that arises from the linear stability analysis used on the right handside. Such a time averaging procedure is developed with reference to the bubbly flow regime. Moreover, the concept of mass that must be exchanged to reach equilibrium from a non-equilibrium state is introduced to limit the mass transfer during a time step. Finally some practical calculations are performed to compare the different correlations for the average mass transfer rate developed in this work. (orig.) [de

  15. Calculations of the electromechanical transfer processes using implicit methods of numerical integration

    Energy Technology Data Exchange (ETDEWEB)

    Pogosyan, T A

    1983-01-01

    The article is dedicated to the solution of systems of differential equations which describe the transfer processes in an electric power system (EES) by implicit methods of numerical integration. The distinguishing feature of the implicit methods (Euler's reverse method and the trapeze method) is their absolute stability and, consequently, the relatively small accumulation of errors in each step of integration. Therefore, they are found to be very convenient for solving problems of electric power engineering, when the transfer processes are described by a rigid system of differential equations. The rigidity is associated with the range of values of the time constants considered. The advantage of the implicit methods over explicit are shown in a specific example (calculation of the dynamic stability of the simplest electric power system), along with the field of use of the implicit methods and the expedience of their use in power engineering problems.

  16. Dissipative exciton transfer in donor-bridge-acceptor systems: numerical renormalization group calculation of equilibrium properties

    Energy Technology Data Exchange (ETDEWEB)

    Tornow, Sabine [Theoretische Physik III, Elektronische Korrelationen und Magnetismus, Universitaet Augsburg, 86135 Augsburg (Germany); Tong, Ning-Hua [Institut fuer Theorie der Kondensierten Materie, Universitaet Karlsruhe, 76128 Karlsruhe (Germany); Bulla, Ralf [Theoretische Physik III, Elektronische Korrelationen und Magnetismus, Universitaet Augsburg, 86135 Augsburg (Germany)

    2006-07-05

    We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.

  17. Dissipative exciton transfer in donor-bridge-acceptor systems: numerical renormalization group calculation of equilibrium properties.

    Science.gov (United States)

    Tornow, Sabine; Tong, Ning-Hua; Bulla, Ralf

    2006-07-05

    We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.

  18. Calculation code of mass and heat transfer in a pulsed column for Purex process

    International Nuclear Information System (INIS)

    Tsukada, Takeshi; Takahashi, Keiki

    1993-01-01

    A calculation code for extraction behavior analysis in a pulsed column employed at an extraction process of a reprocessing plant was developed. This code was also combined with our previously developed calculation code for axial temperature profiles in a pulsed column. The one-dimensional dispersion model was employed for both of the extraction behavior analysis and the axial temperature profile analysis. The reported values of the fluid characteristics coefficient, the transfer coefficient and the diffusivities in the pulsed column were used. The calculated concentration profiles of HNO 3 , U and Pu for the steady state have a good agreement with the reported experimental results. The concentration and temperature profiles were calculated under the operation conditions which induce the abnormal U extraction behavior, i.e. U extraction zone is moved to the bottom of the column. Thought there is slight difference between calculated and experimental value, it is appeared that our developed code can be applied to the simulation under the normal operation condition and the relatively slowly transient condition. Pu accumulation phenomena was analyzed with this code and the accumulation tendency is similar to the reported analysis results. (author)

  19. 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.)

  20. 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

  1. A Direct Radiative Transfer Equation Solver for Path Loss Calculation of Underwater Optical Wireless Channels

    KAUST Repository

    Li, Changping

    2014-11-10

    In this report, we propose a fast numerical solution for the steady state radiative transfer equation in order to calculate the path loss due to light absorption and scattering in various type of underwater channels. In the proposed scheme, we apply a direct non-uniform method to discretize the angular space and an upwind type finite difference method to discretize the spatial space. A Gauss-Seidel iterative method is then applied to solve the fully discretized system of linear equations. The accuracy and efficiency of the proposed scheme is validated by Monte Carlo simulations.

  2. A Direct Radiative Transfer Equation Solver for Path Loss Calculation of Underwater Optical Wireless Channels

    KAUST Repository

    Li, Changping; Park, Ki-Hong; Alouini, Mohamed-Slim

    2014-01-01

    In this report, we propose a fast numerical solution for the steady state radiative transfer equation in order to calculate the path loss due to light absorption and scattering in various type of underwater channels. In the proposed scheme, we apply a direct non-uniform method to discretize the angular space and an upwind type finite difference method to discretize the spatial space. A Gauss-Seidel iterative method is then applied to solve the fully discretized system of linear equations. The accuracy and efficiency of the proposed scheme is validated by Monte Carlo simulations.

  3. Experimental study and calculation of boiling heat transfer on steel plates during runout table operation

    International Nuclear Information System (INIS)

    Liu, Z.D.; Fraser, D.; Samarasekera, I.V.

    2002-01-01

    Within a hot strip steel mill, red hot steel is hot rolled into a long continuous slab that is led onto what is called the runout table. Temperatures of the steel at the beginning of this table are around 900 o C. Above and below the runout table are banks of water jets, sprays or water curtains that rapidly cool the steel slab. The heat transfer process itself may be considered one of the most complicated in the industrial world. The cooling process that occurs on the runout table is crucial and governs the final mechanical properties and flatness of a steel strip. However, very limited data of industrial conditions has been available and that which is available is poorly understood. To study heat transfer during runout table cooling, an industrial scale pilot runout table facility was constructed at the University of British Columbia (UBC). This paper describes the experimental details, data acquisition and data handling techniques for steel plates during water jet impingement cooling by one circular water jet from industrial headers. The effect of cooling water temperature and initial steel plate temperature as well as varying water jet diameters on heat transfer was systematically investigated. A two-dimensional finite element scheme based inverse heat conduction model was developed to calculate surface heat transfer coefficients along the impinging surface. Heat flux curves at the stagnation area were obtained for selected tests. A quantitative relationship between adjustable processing parameters and heat transfer coefficients along the impinging surface during runout table operation is discussed. The results of the study were used to upgrade an extensive process model developed at UBC. The model ties in the cooling rate and hence two dimensional temperature gradients to the resulting microstructure and final mechanical properties of the steel. This process model is widely used by major steel industries in Canada and the United States. (author)

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. CALCULATION REGARDING THERMAL TRANSFER THROUGH CLOSING ELEMENTS FOR A CATTLE SHELTER KEPT IN LOOSE HOUSING

    Directory of Open Access Journals (Sweden)

    Ancuţa JURCO

    2013-01-01

    Full Text Available This paper presents the calculation regarding thermal transmission due to closing elements for cattle shelter kept loose housing. The shelter is compound from 2 compartments, splitted in the middle by a cross alley. The compartments are divided in feeding area and resting area. The shelter has the opening of 16.35 m, total hall lenght is 40.95 m, with surface about 669.53 sqm and the maximum hight about 6.40 m. After analyzing the calculation of heat transfer through closing elements for a cattle shelter kept in loose housing show that the amount of heat lost through external walls with heterogeneous structure is minimal compared to the classical exterior wall with homogeneous structure.

  12. Effect of the improvement of the HITRAN database on the radiative transfer calculation

    International Nuclear Information System (INIS)

    Feng Xuan; Zhao Fengsheng; Gao Wenhua

    2007-01-01

    The line parameters of the HITRAN 2004 have been updated, as compared with the older editions (the 2000 edition and the 1996 edition). In order to know the effect of the modifications on radiative transfer calculation with high spectral resolution, comparison in optical depth and radiance spectrum have been given between different editions. Four infrared spectral regions are selected, and they cover the three bands of atmospheric infrared sounder (AIRS) and one of geosynchronous imaging fourier transform spectrometer (GIFTS). The comparison has shown that the relative difference between HITRAN 2000 and 2004 and that between HITRAN 1996 and 2004 is decreasing. But the maximal discrepancy between the latest two editions in some spectral intervals is over 1%. It is important to estimate the error of calculation with the line parameters correctly or one has to use the new edition of HITRAN

  13. Improvements in pencil beam scanning proton therapy dose calculation accuracy in brain tumor cases with a commercial Monte Carlo algorithm.

    Science.gov (United States)

    Widesott, Lamberto; Lorentini, Stefano; Fracchiolla, Francesco; Farace, Paolo; Schwarz, Marco

    2018-05-04

    validation of a commercial Monte Carlo (MC) algorithm (RayStation ver6.0.024) for the treatment of brain tumours with pencil beam scanning (PBS) proton therapy, comparing it via measurements and analytical calculations in clinically realistic scenarios. Methods: For the measurements a 2D ion chamber array detector (MatriXX PT)) was placed underneath the following targets: 1) anthropomorphic head phantom (with two different thickness) and 2) a biological sample (i.e. half lamb's head). In addition, we compared the MC dose engine vs. the RayStation pencil beam (PB) algorithm clinically implemented so far, in critical conditions such as superficial targets (i.e. in need of range shifter), different air gaps and gantry angles to simulate both orthogonal and tangential beam arrangements. For every plan the PB and MC dose calculation were compared to measurements using a gamma analysis metrics (3%, 3mm). Results: regarding the head phantom the gamma passing rate (GPR) was always >96% and on average > 99% for the MC algorithm; PB algorithm had a GPR ≤90% for all the delivery configurations with single slab (apart 95 % GPR from gantry 0° and small air gap) and in case of two slabs of the head phantom the GPR was >95% only in case of small air gaps for all the three (0°, 45°,and 70°) simulated beam gantry angles. Overall the PB algorithm tends to overestimate the dose to the target (up to 25%) and underestimate the dose to the organ at risk (up to 30%). We found similar results (but a bit worse for PB algorithm) for the two targets of the lamb's head where only two beam gantry angles were simulated. Conclusions: our results suggest that in PBS proton therapy range shifter (RS) need to be used with extreme caution when planning the treatment with an analytical algorithm due to potentially great discrepancies between the planned dose and the dose delivered to the patients, also in case of brain tumours where this issue could be underestimated. Our results also

  14. Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

    Science.gov (United States)

    Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2018-01-25

    We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

  15. Heat Transfer Coefficient at Cast-Mold Interface During Centrifugal Casting: Calculation of Air Gap

    Science.gov (United States)

    Bohacek, Jan; Kharicha, Abdellah; Ludwig, Andreas; Wu, Menghuai; Karimi-Sibaki, Ebrahim

    2018-06-01

    During centrifugal casting, the thermal resistance at the cast-mold interface represents a main blockage mechanism for heat transfer. In addition to the refractory coating, an air gap begins to form due to the shrinkage of the casting and the mold expansion, under the continuous influence of strong centrifugal forces. Here, the heat transfer coefficient at the cast-mold interface h has been determined from calculations of the air gap thickness d a based on a plane stress model taking into account thermoelastic stresses, centrifugal forces, plastic deformations, and a temperature-dependent Young's modulus. The numerical approach proposed here is rather novel and tries to offer an alternative to the empirical formulas usually used in numerical simulations for a description of a time-dependent heat transfer coefficient h. Several numerical tests were performed for different coating thicknesses d C, rotation rates Ω, and temperatures of solidus T sol. Results demonstrated that the scenario at the interface is unique for each set of parameters, hindering the possibility of employing empirical formulas without a preceding experiment being performed. Initial values of h are simply equivalent to the ratio of the coating thermal conductivity and its thickness ( 1000 Wm-2 K-1). Later, when the air gap is formed, h drops exponentially to values at least one order of magnitude smaller ( 100 Wm-2 K-1).

  16. Acoustical contribution calculation and analysis of compressor shell based on acoustic transfer vector method

    Science.gov (United States)

    Chen, Xiaol; Guo, Bei; Tuo, Jinliang; Zhou, Ruixin; Lu, Yang

    2017-08-01

    Nowadays, people are paying more and more attention to the noise reduction of household refrigerator compressor. This paper established a sound field bounded by compressor shell and ISO3744 standard field points. The Acoustic Transfer Vector (ATV) in the sound field radiated by a refrigerator compressor shell were calculated which fits the test result preferably. Then the compressor shell surface is divided into several parts. Based on Acoustic Transfer Vector approach, the sound pressure contribution to the field points and the sound power contribution to the sound field of each part were calculated. To obtain the noise radiation in the sound field, the sound pressure cloud charts were analyzed, and the contribution curves in different frequency of each part were acquired. Meanwhile, the sound power contribution of each part in different frequency was analyzed, to ensure those parts where contributes larger sound power. Through the analysis of acoustic contribution, those parts where radiate larger noise on the compressor shell were determined. This paper provides a credible and effective approach on the structure optimal design of refrigerator compressor shell, which is meaningful in the noise and vibration reduction.

  17. 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.

  18. Microscopic calculation of absolute values of two-nucleon transfer cross sections

    International Nuclear Information System (INIS)

    Potel, G.; Bayman, B. F.; Barranco, F.

    2009-01-01

    Arguably, the greatest achievement of many-body physics in the fifties was that of providing the basis for a complete description and a thorough understanding of superconductivity in metals. At the basis of it one finds BCS theory and Josephson effect. The first recognized the central role played by the appearance of a macroscopic coherent field -usually viewed as a condensate of strongly overlapping Cooper pairs-, the quasiparticle vacuum. The second realized that a true gap is not essential for such a state of matter to exist, but rather a finite expectation value of the pair field. Consequently, the specific probe to study the superconducting state is Cooper pair tunneling. Important progress in the understanding of pairing in atomic nuclei may arise from the systematic study of two-particle transfer reactions. Although this subject of research started about the time of the BCS papers, the quantitative calculation of absolute cross sections taking properly into account the full non-locality of the Cooper pairs (correlation length much larger than nuclear dimensions) is still an open problem. We present in this talk the results obtained within a second order DWBA framework for two- nucleon transfer reactions around the Coulomb barrier induced both by heavy and light ions. The calculations were done using a computer code developed for this purpose including the sequential and simultaneous contributions to the process, with microscopic form factors which take into account the relevant structure aspects of the process, such as the nature of the single-particle wavefunctions, the spectroscopic factors, and the interaction potential responsible for the transfer. Reasonable agreement with the experimental absolute values of the differential cross section is obtained without any parameter adjustment (see Figure 1).(author)

  19. 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

  20. 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

  1. 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.

  2. 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.).

  3. 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)

  4. 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.

  5. The atomic structure of protons and hydrides in Sm1.92Ca0.08Sn2O7-δ pyrochlore from DFT calculations and FTIR spectroscopy

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Eurenius, K. E. J.; Rossmeisl, Jan

    2012-01-01

    A combined density functional theory and Fourier transform infrared spectroscopy study of the structure and specific site preference of protons and hydrides in the pyrochlore Sm1.92Ca0.08Sn2O7-δ is presented. Two protonic sites of particular high stability are identified, both located on O(1......) oxygen atoms closely associated with a Ca dopant. Further, the unexpected presence of Ho hydride defects in undoped, oxygen deficient Sm2Sn2O7 is reported. Finally, the stretching frequencies and relative intensities for these and other sites are calculated. The main features of the Fourier transform...

  6. 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)

  7. Monte Carlo calculations of resonance radiative transfer through a semi-infinite atmosphere

    International Nuclear Information System (INIS)

    Slater, G.; Salpeter, E.E.; Wasserman, I.

    1982-01-01

    The results of Monte Carlo calculations of radiative transfer through a semi-infinite plane-parallel atmosphere of resonant scatterers are presented. With a photon source at optical depth tau/sub ES/ we model the semi-infinite geometry by embedding a perfectly reflecting mirror at depth tau/sub MS/+tau/sub ES/. Although some quantities characterizing the emergent photons diverge as tau/sub MS/→infinity, the mean number of scatters, N/sub ES/, and path length, L/sub ES/, accumulated between the source and the edge of the atmosphere converge. Accurate results of N/sub ES/, L/sub ES/, X/sub pk/, the most probable frequency shift of the escaping photons, and tau/sub LAST/, the mean optical depth at which they last scatter, are obtained by choosing tau/sub MS/ = 4tau/sub ES/. Approximate analytic calculations of N/sub ES/, L/sub ES/, N, the mean total number of scatters undergone by escaping photons, L, their mean total path length, and , their mean (absolute) frequency shift, are presented for a symmetric slab with αtau/sub ES/>>1 and tau/sub MS/>>tau/sub ES/. Analogous calculations for an asymmetric slab are discussed. Analytic fitting formulae for N/sub ES/, L/sub ES/, X/sub pk/, and tau/sub LAST/ are given

  8. Mathematical Calculations Of Heat Transfer For The CNC Deposition Platform Based On Chemical Thermal Method

    Science.gov (United States)

    Essa, Mohammed Sh.; Chiad, Bahaa T.; Hussein, Khalil A.

    2018-05-01

    Chemical thermal deposition techniques are highly depending on deposition platform temperature as well as surface substrate temperatures, so in this research thermal distribution and heat transfer was calculated to optimize the deposition platform temperature distribution, determine the power required for the heating element, to improve thermal homogeneity. Furthermore, calculate the dissipated thermal power from the deposition platform. Moreover, the thermal imager (thermal camera) was used to estimate the thermal destitution in addition to, the temperature allocation over 400cm2 heated plate area. In order to reach a plate temperature at 500 oC, a plate supported with an electrical heater of power (2000 W). Stainless steel plate of 12mm thickness was used as a heated plate and deposition platform and subjected to lab tests using element analyzer X-ray fluorescence system (XRF) to check its elemental composition and found the grade of stainless steel and found to be 316 L. The total heat losses calculated at this temperature was 612 W. Homemade heating element was used to heat the plate and can reach 450 oC with less than 15 min as recorded from the system.as well as the temperatures recorded and monitored using Arduino/UNO microcontroller with cold-junction-compensated K-thermocouple-to-digital converter type MAX6675.

  9. Calculations of the displacement damage and short-circuit current degradation in proton irradiated (AlGa)As-GaAs solar cells

    Science.gov (United States)

    Yeh, C. S.; Li, S. S.; Loo, R. Y.

    1987-01-01

    A theoretical model for computing the displacement damage defect density and the short-circuit current (I sub sc) degradation in proton-irradiated (AlGa)As-GaAs p-n junction solar cells is presented. Assumptions were made with justification that the radiation induced displacement defects form an effective recombination center which controls the electron and hole lifetimes in the junction space charge region and in the n-GaAs active layer of the irradiated GaAs p-n junction cells. The degradation of I sub sc in the (AlGa)As layer was found to be negligible compared to the total degradation. In order to determine the I sub sc degradation, the displacement defect density, path length, range, reduced energy after penetrating a distance x, and the average number of displacements formed by one proton scattering event were first calculated. The I sub sc degradation was calculated by using the electron capture cross section in the p-diffused layer and the hole capture cross section in the n-base layer as well as the wavelength dependent absorption coefficients. Excellent agreement was found between the researchers calculated values and the measured I sub sc in the proton irradiated GaAs solar cells for proton energies of 100 KeV to 10 MeV and fluences from 10 to the 10th power p/square cm to 10 to the 12th power p/square cm.

  10. Application of the Lion's integral to calculate heat transfer with the N2O4 turbulent flow in a tube

    International Nuclear Information System (INIS)

    Petrovich, V.Yu.; Tverkovkin, B.E.; Nesterenko, V.B.

    1976-01-01

    When carrying out engineering calculation of heat transfer in the case of turbulent flow of non-equilibrium reacting gas in a tube, it is necessary to dispose of criterion dependence to calculate Nusselt number. As a rule, dependences obtained by empirical methods are not widely adopted. It is proposed that the integral of Lion type be used for the heat transfer calculation in the form of which an expression for Nusselt number has been written under the conditions of turbulent flow with a non-equilibrium chemical reaction. On calculating turbulent fluctuations Millionshchikov two-layer model is used. A simple approximation of source-discharge of the mass of mixture components is suggested for the sake of simplification of Lion integral. The proposed theoretical dependences for the heat transfer calculation when chemical reactions are available substantially extend the field of application of Lion integral and may be used designing equipment with a chemically reacting coolant

  11. 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

  12. 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.

  13. 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

  14. 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.)

  15. Gibbs energies of protonation and complexation of platinum and vanadate metal ions with naringenin and phenolic acids: Theoretical calculations associated with experimental values

    International Nuclear Information System (INIS)

    Fazary, Ahmed E.; Alshihri, Ayed S.; Alfaifi, Mohammad Y.; Saleh, Kamel A.; Elbehairi, Serag Eldin I.; Fawy, Khaled F.; Abd-Rabboh, Hisham S.M.

    2016-01-01

    Highlights: • The experimental thermodynamic equilibrium and stability constants of vanadium and platinum complexes involving naringin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined. • The theoretical calculations of the free energy changes associated with the ligand protonation, and metal ion–ligand complex formation equilibria using density function theory calculations, providing a complete picture of the microscopic equilibria of the studied complex systems. - Abstract: The Experimental thermodynamic equilibrium (pK_a values) and stability (log β) constants of vanadium and platinum binary and mixed ligand complexes involving naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined at 310.15 K in 0.16 mol·dm"−"3 KCl aqueous solutions using pH-potentiometric technique and by means of two estimation models (HYPERQUAD 2008 and Bjerrum–Calvin). The theoretical calculations of overall protonation and stability constants of the metal complex species in solution were predicted as the free energy change associated with the ligand protonation, and metal ion–ligand complex formation equilibria (species solvation/de-solvation) using ab initio and density function theory (DFT) calculations. The usage of the experimental potentiometry technique and theoretical predictions provides a complete picture of the microscopic equilibria of the studied systems (vanadium/platinum–naringenin–phenolic acid). Specifically, this theoretically DFT predications would be useful to determine the most real protonation constants of the studied bioligands in which the binding sites changes due to the ligand protonation/deprotonation equilibria. Also, the complexing capacities of vanadium and platinum towards naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid in solutions were evaluated and discussed. From the

  16. 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

  17. The simulation calculation of acoustics energy transfer through the material structure

    Directory of Open Access Journals (Sweden)

    Zvolenský Peter

    2016-01-01

    Full Text Available The paper deals with the modification of the rail passenger coach floor design aimed at improvement of sound reduction index. Refurbishing was performed by using a new acoustic material with a filamentary microstructure. The materials proposed in research were compared by simulation calculation of acoustic energy transfer trough porous microstructure of filamentary material, and the effect of material porosity on sound reduction index and sound absorption coefficient were observed. This proposed filamentary material can be used in the railway bed structure, too. High degree of noise absorbing, resistance to climate conditions, low specific mass, enable to choose a system of low anti-noise barriers having similar properties as standard high anti-noise walls..

  18. 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.)

  19. An Algorithm to Compress Line-transition Data for Radiative-transfer Calculations

    Science.gov (United States)

    Cubillos, Patricio E.

    2017-11-01

    Molecular line-transition lists are an essential ingredient for radiative-transfer calculations. With recent databases now surpassing the billion-line mark, handling them has become computationally prohibitive, due to both the required processing power and memory. Here I present a temperature-dependent algorithm to separate strong from weak line transitions, reformatting the large majority of the weaker lines into a cross-section data file, and retaining the detailed line-by-line information of the fewer strong lines. For any given molecule over the 0.3-30 μm range, this algorithm reduces the number of lines to a few million, enabling faster radiative-transfer computations without a significant loss of information. The final compression rate depends on how densely populated the spectrum is. I validate this algorithm by comparing Exomol’s HCN extinction-coefficient spectra between the complete (65 million line transitions) and compressed (7.7 million) line lists. Over the 0.6-33 μm range, the average difference between extinction-coefficient values is less than 1%. A Python/C implementation of this algorithm is open-source and available at https://github.com/pcubillos/repack. So far, this code handles the Exomol and HITRAN line-transition format.

  20. Calculation of laminar incompressible fluid flow and heat transfer during spherical annulus filling

    International Nuclear Information System (INIS)

    Tuft, D.B.

    1979-04-01

    A method of computing laminar incompressible fluid-flow and heat transfer during the filling of a spherical annulus is presented. Transient fluid temperatures and heat flux rates in the spherical annulus are calculated for an insulated outer sphere and a constant temperature inner sphere with heated water filling the annulus from the bottom. To achieve a solution, laminar axially symmetric flow is assumed and the Marker-and-Cell (MAC) free surface computational method is applied to this problem in spherical coordinates. Changes in the standard MAC treatment are incorporated and special methods for handling the free surface are introduced. A variable mesh is used to improve resolution near the inner sphere where temperature and velocity gradients are steep and the governing equations are derived for variable fluid properties to allow an eddy viscosity turbulence model to be applied later. Calculations of velocity, temperature, and inner sphere heat flux in a spherical annulus of 139.7 mm inner radius, and 168.3 mm outer radius within an inlet tube diameter of 38.1 mm are presented

  1. 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.

  2. 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.

  3. 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.

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

    Science.gov (United States)

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

    2018-05-01

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

  5. Interaction of protons with the C{sub 60} molecule: calculation of deposited energies and electronic stopping cross sections (v{sub {<=}}5 au)

    Energy Technology Data Exchange (ETDEWEB)

    Moretto-Capelle, P. [Laboratoire CAR, IRSAMC, UMR 5589 CNRS, Universite Paul Sabatier, Toulouse (France)]. E-mail: pmc@irsamc.ups-tlse.fr; Bordenave-Montesquieu, D.; Rentenier, A.; Bordenave-Montesquieu, A. [Laboratoire CAR, IRSAMC, UMR 5589 CNRS, Universite Paul Sabatier, Toulouse (France)

    2001-09-28

    The energy deposited by a proton in a C{sub 60} molecule is calculated over a broad collision velocity range from 0.1 to 5 au, using the free-electron gas model of Lindhard and Winther (1964 Mat. Fys. Medd. K Dan. Vidensk. Selsk. 34) and the C{sub 60} electron density distribution calculated by Puska and Nieminen. The energy lost by the proton is maximum near 1.8 au collision velocity in contrast with the saturation found in the low-velocity regime, in the 0.25-0.5 au velocity range, by Kunert and Schmidt. From the impact parameter dependence we deduce the distributions of deposited energies, the averaged energy losses and the C{sub 60} electronic stopping cross sections. It is found that the C{sub 60} molecule behaves as a carbon foil giving very similar absolute stopping cross sections per atom. (author). Letter-to-the-editor.

  6. 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.

  7. Containment fan cooler heat transfer calculation during main steam line break for Maanshan PWR plant

    Energy Technology Data Exchange (ETDEWEB)

    Yuann, Yng-Ruey, E-mail: ryyuann@iner.gov.tw; Kao, Lain-Su, E-mail: lskao@iner.gov.tw

    2013-10-15

    Highlights: • Evaluate component cooling water (CCW) thermal response during MSLB for Maanshan. • Using GOTHIC to calculate CCW temperature and determine time required to boil CCW. • Both convective and condensation heat transfer from the air side are considered. • Boiling will not occur since T{sub B} is sufficiently longer than CCW pump restart time. -- Abstract: A thermal analysis has been performed for the Containment Fan Cooler Unit (FCU) during Main Steam Line Break (MSLB) accident, concurrent with loss of offsite power, for Maanshan PWR plant. The analysis is performed in order to address the waterhammer and two-phase flow issues discussed in USNRC's Generic Letter 96-06 (GL 96-06). Maanshan plant is a twin-unit Westinghouse 3-loop PWR currently operated at rated core thermal power of 2822 MWt for each unit. The design basis for containment temperature is Main Steam Line Break (MSLB) accident at power of 2830.5 MWt, which results in peak vapor temperature of 387.6 °F. The design is such that when MSLB occurs concurrent with loss of offsite power (MSLB/LOOP), both the coolant pump on the secondary side and the fan on the air side of the FCU loose power and coast down. The pump has little inertia and coasts down in 2–3 s, while the FCU fan coasts down over much longer period. Before the pump is restored through emergency diesel generator, there is potential for boiling the coolant in the cooling coils by the high-temperature air/steam mixture entering the FCU. The time to boiling depends on the operating pressure of the coolant before the pump is restored. The prediction of the time to boiling is important because it determines whether there is potential for waterhammer or two-phase flow to occur before the pump is restored. If boiling occurs then there exists steam region in the pipe, which may cause the so called condensation induced waterhammer or column closure waterhammer. In either case, a great amount of effort has to be spent to

  8. SU-E-T-553: Monte Carlo Calculation of Proton Bragg Peak Displacements in the Presence of Al2O3:C Dosimeters

    Energy Technology Data Exchange (ETDEWEB)

    Young, L; Yang, F [Univ Washington, Seattle, WA (United States)

    2015-06-15

    Purpose: The application of optically stimulated luminescence dosimeters (OSLDs) may be extended to clinical investigations verifying irradiated doses in small animal models. In proton beams, the accurate positioning of the Bragg peak is essential for tumor targeting. The purpose of this study was to estimate the displacement of a pristine Bragg peak when an Al2O3:C nanodot (Landauer, Inc.) is placed on the surface of a water phantom and to evaluate corresponding changes in dose. Methods: Clinical proton pencil beam simulations were carried out with using TOPAS, a Monte Carlo platform layered on top of GEANT4. Point-shaped beams with no energy spread were modeled for energies 100MV, 150MV, 200MV, and 250MV. Dose scoring for 100,000 particle histories was conducted within a water phantom (20cm × 20cm irradiated area, 40cm depth) with its surface placed 214.5cm away from the source. The modeled nanodot had a 4mm radius and 0.2mm thickness. Results: A comparative analysis of Monte Carlo depth dose profiles modeled for these proton pencil beams did not demonstrate an energy dependent in the Bragg peak shift. The shifts in Bragg Peak depth for water phantoms modeled with a nanodot on the phantom surface ranged between 2.7 to 3.2 mm. In all cases, the Bragg Peaks were shifted closer to the irradiation source. The peak dose in phantoms with an OSLD remained unchanged with percent dose differences less than 0.55% when compared to phantom doses without the nanodot. Conclusion: Monte Carlo calculations show that the presence of OSLD nanodots in proton beam therapy will not change the position of a pristine Bragg Peak by more than 3 mm. Although the 3.0 mm shift will not have a detrimental effect in patients receiving proton therapy, this effect may not be negligible in dose verification measurements for mouse models at lower proton beam energies.

  9. Theoretical Studies of Oxygen Reduction and Proton Transfer in SOFCs and Nerve Agents on Selected Surfaces

    Science.gov (United States)

    2015-11-19

    accurate description of the states of interest in the presence of less accurately described lower-lying states. The basis of this argument lies in the way ...energy is calculated for that vertex and a systematic variation of the parameters is carried out in a way that eliminates the worst vertex after each...Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota , K.; Fukuda, R

  10. Acceleration of radiative transfer model calculations for the retrieval of trace gases under cloudy conditions

    International Nuclear Information System (INIS)

    Efremenko, Dmitry S.; Loyola, Diego G.; Spurr, Robert J.D.; Doicu, Adrian

    2014-01-01

    In the independent pixel approximation (IPA), radiative transfer computations involving cloudy scenes require two separate calls to the radiative transfer model (RTM), one call for a clear sky scenario, the other for an atmosphere containing clouds. In this paper, clouds are considered as an optically homogeneous layer. We present two novel methods for RTM performance enhancement with particular application to trace gas retrievals under cloudy conditions. Both methods are based on reusing results from clear-sky RTM calculations to speed up corresponding calculations for the cloud-filled scenario. The first approach is numerically exact, and has been applied to the discrete-ordinate with matrix exponential (DOME) RTM. Results from the original clear sky computation can be saved in the memory and reused for the non-cloudy layers in the second computation. In addition, for the whole-atmosphere boundary-value approach to the determination of the intensity field, we can exploit a ’telescoping technique’ to reduce the dimensionality (and hence the computational effort for the solution) of the boundary value problem in the absence of Rayleigh scattering contributions for higher azimuthal components of the radiation field. The second approach is (for the cloudy scenario) to generate a spectral correction applied to the radiation field from a fast two-stream RTM. This correction is based on the use of principal-component analysis (PCA) applied to a given window of spectral optical property data, in order to exploit redundancy in the data and confine the number of full-stream multiple scatter computations to the first few EOFs (Empirical Orthogonal Functions) arising from the PCA. This method has been applied to the LIDORT RTM; although the method involves some approximation, it provides accuracy better than 0.2%, and a speed-up factor of approximately 2 compared with two calls of RTM. -- Highlights: • Reusing results from clear-sky computations for a model with a

  11. TH-C-BRD-06: A Novel MRI Based CT Artifact Correction Method for Improving Proton Range Calculation in the Presence of Severe CT Artifacts

    International Nuclear Information System (INIS)

    Park, P; Schreibmann, E; Fox, T; Roper, J; Elder, E; Tejani, M; Crocker, I; Curran, W; Dhabaan, A

    2014-01-01

    Purpose: Severe CT artifacts can impair our ability to accurately calculate proton range thereby resulting in a clinically unacceptable treatment plan. In this work, we investigated a novel CT artifact correction method based on a coregistered MRI and investigated its ability to estimate CT HU and proton range in the presence of severe CT artifacts. Methods: The proposed method corrects corrupted CT data using a coregistered MRI to guide the mapping of CT values from a nearby artifact-free region. First patient MRI and CT images were registered using 3D deformable image registration software based on B-spline and mutual information. The CT slice with severe artifacts was selected as well as a nearby slice free of artifacts (e.g. 1cm away from the artifact). The two sets of paired MRI and CT images at different slice locations were further registered by applying 2D deformable image registration. Based on the artifact free paired MRI and CT images, a comprehensive geospatial analysis was performed to predict the correct CT HU of the CT image with severe artifact. For a proof of concept, a known artifact was introduced that changed the ground truth CT HU value up to 30% and up to 5cm error in proton range. The ability of the proposed method to recover the ground truth was quantified using a selected head and neck case. Results: A significant improvement in image quality was observed visually. Our proof of concept study showed that 90% of area that had 30% errors in CT HU was corrected to 3% of its ground truth value. Furthermore, the maximum proton range error up to 5cm was reduced to 4mm error. Conclusion: MRI based CT artifact correction method can improve CT image quality and proton range calculation for patients with severe CT artifacts

  12. 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)

  13. 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)

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

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-01-01

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

  15. Replacement of unsteady heat transfer coefficient by equivalent steady-state one when calculating temperature oscillations in a thermal layer

    Science.gov (United States)

    Supel'nyak, M. I.

    2017-11-01

    Features of calculation of temperature oscillations which are damped in a surface layer of a solid and which are having a small range in comparison with range of temperature of the fluid medium surrounding the solid at heat transfer coefficient changing in time under the periodic law are considered. For the specified case the equations for approximate definition of constant and oscillating components of temperature field of a solid are received. The possibility of use of appropriately chosen steady-state coefficient when calculating the temperature oscillations instead of unsteady heat-transfer coefficient is investigated. Dependence for definition of such equivalent constant heat-transfer coefficient is determined. With its help the research of temperature oscillations of solids with canonical form for some specific conditions of heat transfer is undertaken. Comparison of the obtained data with results of exact solutions of a problem of heat conductivity by which the limits to applicability of the offered approach are defined is carried out.

  16. SU-E-T-531: Performance Evaluation of Multithreaded Geant4 for Proton Therapy Dose Calculations in a High Performance Computing Facility

    International Nuclear Information System (INIS)

    Shin, J; Coss, D; McMurry, J; Farr, J; Faddegon, B

    2014-01-01

    Purpose: To evaluate the efficiency of multithreaded Geant4 (Geant4-MT, version 10.0) for proton Monte Carlo dose calculations using a high performance computing facility. Methods: Geant4-MT was used to calculate 3D dose distributions in 1×1×1 mm3 voxels in a water phantom and patient's head with a 150 MeV proton beam covering approximately 5×5 cm2 in the water phantom. Three timestamps were measured on the fly to separately analyze the required time for initialization (which cannot be parallelized), processing time of individual threads, and completion time. Scalability of averaged processing time per thread was calculated as a function of thread number (1, 100, 150, and 200) for both 1M and 50 M histories. The total memory usage was recorded. Results: Simulations with 50 M histories were fastest with 100 threads, taking approximately 1.3 hours and 6 hours for the water phantom and the CT data, respectively with better than 1.0 % statistical uncertainty. The calculations show 1/N scalability in the event loops for both cases. The gains from parallel calculations started to decrease with 150 threads. The memory usage increases linearly with number of threads. No critical failures were observed during the simulations. Conclusion: Multithreading in Geant4-MT decreased simulation time in proton dose distribution calculations by a factor of 64 and 54 at a near optimal 100 threads for water phantom and patient's data respectively. Further simulations will be done to determine the efficiency at the optimal thread number. Considering the trend of computer architecture development, utilizing Geant4-MT for radiotherapy simulations is an excellent cost-effective alternative for a distributed batch queuing system. However, because the scalability depends highly on simulation details, i.e., the ratio of the processing time of one event versus waiting time to access for the shared event queue, a performance evaluation as described is recommended

  17. Theoretical calculations of the reaction cross-sections for proton-induced reactions on natural copper using ALICE-IPPE code

    International Nuclear Information System (INIS)

    Alharbi, A.A.; Azzam, A.

    2012-01-01

    A theoretical study of the nuclear-reaction cross sections for proton-induced reactions on 63 Cu and 65 Cu was performed in the proton energy range from threshold values up to 50 MeV. The produced nuclei were different isotopes of Zn, Cu, Ni, Co and Mn, some of which have important applications. The reaction cross-section calculations were performed using the ALICE-IPPE code, which depends on the pre-equilibrium compound nucleus model. This code is suitable for the studied energy and isotopic mass ranges. Approximately 14 excitation functions for the different reactions have been constructed from the calculated cross-section values. The excitation function curves for the proton reactions with natural copper targets have been constructed from those for enriched targets using the natural abundance of the copper isotopes. Comparisons between the calculated excitation functions with those previously experimentally measured are given whenever the experimental values were available. Some statistical parameters were introduced to control the quality of the fitting between both the experimental and the theoretical calculated cross-section values. - Highlights: ► We performed reaction cross section calculations using ALICE-IPPE code. ► We constructed 14 excitation functions for nat Cu(p,xn)Zn,Cu,Ni,Co,Mn reactions. ► The available experimental data were fitted to the performed ALICE-IPPE calculations. ► Statistical parameters were introduced to control the quality of the fitting. ► The code failed to fit the experimental data for reactions with large nucleon emissions.

  18. Comparison of depth-dose distributions of proton therapeutic beams calculated by means of logical detectors and ionization chamber modeled in Monte Carlo codes

    Energy Technology Data Exchange (ETDEWEB)

    Pietrzak, Robert [Department of Nuclear Physics and Its Applications, Institute of Physics, University of Silesia, Katowice (Poland); Konefał, Adam, E-mail: adam.konefal@us.edu.pl [Department of Nuclear Physics and Its Applications, Institute of Physics, University of Silesia, Katowice (Poland); Sokół, Maria; Orlef, Andrzej [Department of Medical Physics, Maria Sklodowska-Curie Memorial Cancer Center, Institute of Oncology, Gliwice (Poland)

    2016-08-01

    The success of proton therapy depends strongly on the precision of treatment planning. Dose distribution in biological tissue may be obtained from Monte Carlo simulations using various scientific codes making it possible to perform very accurate calculations. However, there are many factors affecting the accuracy of modeling. One of them is a structure of objects called bins registering a dose. In this work the influence of bin structure on the dose distributions was examined. The MCNPX code calculations of Bragg curve for the 60 MeV proton beam were done in two ways: using simple logical detectors being the volumes determined in water, and using a precise model of ionization chamber used in clinical dosimetry. The results of the simulations were verified experimentally in the water phantom with Marcus ionization chamber. The average local dose difference between the measured relative doses in the water phantom and those calculated by means of the logical detectors was 1.4% at first 25 mm, whereas in the full depth range this difference was 1.6% for the maximum uncertainty in the calculations less than 2.4% and for the maximum measuring error of 1%. In case of the relative doses calculated with the use of the ionization chamber model this average difference was somewhat greater, being 2.3% at depths up to 25 mm and 2.4% in the full range of depths for the maximum uncertainty in the calculations of 3%. In the dose calculations the ionization chamber model does not offer any additional advantages over the logical detectors. The results provided by both models are similar and in good agreement with the measurements, however, the logical detector approach is a more time-effective method. - Highlights: • Influence of the bin structure on the proton dose distributions was examined for the MC simulations. • The considered relative proton dose distributions in water correspond to the clinical application. • MC simulations performed with the logical detectors and the

  19. 47 CFR 54.902 - Calculation of Interstate Common Line Support for transferred exchanges.

    Science.gov (United States)

    2010-10-01

    ... filed pursuant to § 54.903(a)(4) shall reflect the transfer of exchanges. All post-transaction... transfer of exchanges. All post-transaction Interstate Common Line Support shall be subject to true up by... for transferred exchanges. 54.902 Section 54.902 Telecommunication FEDERAL COMMUNICATIONS COMMISSION...

  20. 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.

  1. Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

    International Nuclear Information System (INIS)

    Hansen, P.E.; Langgard, M.; Bolvig, S.

    1998-01-01

    Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

  2. Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    C. Spirig

    2005-01-01

    Full Text Available Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK and methacrolein (MACR were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.

  3. 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.

  4. SU-E-J-136: Investigation Into Robustness of Stopping Power Calculated by DECT and SECT for Proton Therapy Treatment Planning

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, J [University of Adelaide, Adelaide, SA (Australia); Penfold, S [University of Adelaide, Adelaide, SA (Australia); Royal Adelaide Hospital, Adelaide, SA (Australia)

    2015-06-15

    Purpose: To investigate the robustness of dual energy CT (DECT) and single energy CT (SECT) proton stopping power calibration techniques and quantify the associated errors when imaging a phantom differing in chemical composition to that used during stopping power calibration. Methods: The CIRS tissue substitute phantom was scanned in a CT-simulator at 90kV and 140kV. This image set was used to generate a DECT proton SPR calibration based on a relationship between effective atomic number and mean excitation energy. A SECT proton SPR calibration based only on Hounsfield units (HUs) was also generated. DECT and SECT scans of a second phantom of known density and chemical composition were performed. The SPR of the second phantom was calculated with the DECT approach (SPR-DECT),the SECT approach (SPR-SECT) and finally the known density and chemical composition of the phantom (SPR-ref). The DECT and SECT image sets were imported into the Pinnacle{sup 3} research release of proton therapy treatment planning. The difference in dose when exposed to a common pencil beam distribution was investigated. Results: SPR-DECT was found to be in better agreement with SPR-ref than SPR- SECT. The mean difference in SPR for all materials was 0.51% for DECT and 6.89% for SECT. With the exception of Teflon, SPR-DECT was found to agree with SPR-ref to within 1%. Significant differences in calculated dose were found when using the DECT image set or the SECT image set. Conclusion: The DECT calibration technique was found to be more robust to situations in which the physical properties of the test materials differed from the materials used during SPR calibration. Furthermore, it was demonstrated that the DECT and SECT SPR calibration techniques can Result in significantly different calculated dose distributions.

  5. 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.

  6. 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.

  7. 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)

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. Combining density functional theory (DFT) and collision cross-section (CCS) calculations to analyze the gas-phase behaviour of small molecules and their protonation site isomers.

    Science.gov (United States)

    Boschmans, Jasper; Jacobs, Sam; Williams, Jonathan P; Palmer, Martin; Richardson, Keith; Giles, Kevin; Lapthorn, Cris; Herrebout, Wouter A; Lemière, Filip; Sobott, Frank

    2016-06-20

    Electrospray ion mobility-mass spectrometry (IM-MS) data show that for some small molecules, two (or even more) ions wi