Medium modifications of vector mesons

International Nuclear Information System (INIS)

Pant, L.M.

2004-01-01

The omega photoproduction in nuclear medium with the ELSA facility at Bonn and the present status of the HADES collaboration to investigate the in-medium hadron properties in proton, heavy ions and hadron induced reactions at GSI, Darmstadt are presented. Efforts are under way to utilise the electron beam at Indore for experimental hadron physics in order to step into the intermediate energy nuclear physics regime. The skeletal outline of the high energy electron beam now available at CAT, Indore is discussed

Medium-range dielectric order in systems with collectivized electrons

International Nuclear Information System (INIS)

Ismagilov, A.M.; Kopaev, Yu.V.

1993-01-01

The problem of formation of a medium-range dielectric order (on a scale much larger than the interatomic one) due to electron-electron correlations and to scattering by an impurity in a system near a phase transition into a long-range order state is solved by a microscopic approach. It is shown that for a weak impurity potential the effect of medium-range order formation is stronger than the effect of long-range order suppression related to scattering by an impurity. The influence of medium-range order on the one-particle excitation spectrum and on the density of states is considered. It is found that since the medium-range order in a system is due to correlations of electron and hole states open-quotes coupledclose quotes by a continuous set of inhomogeneity vectors (in contrast to the long-range order formed on a discrete set of such vectors), the density of states varies on an energy scale determined by the mean absolute value of these vectors. Therefore in a system undergoing phase transition into an inhomogeneous state with the modulus q 0 of inhomogeneity vectors the medium-range order forms in the density of states a pseudogap of scale length v F q 0 (v F is the Fermi velocity). This distinguishes such a system substantially from one, which tends to a phase transition into a homogeneous state (q 0 ≡0), where the medium-range order forms a pseudogap of scale length v F /ξ much-lt v F q 0 (ξ is the correlation length). The possible role of medium dielectric order effects in high-T c superconductors is discussed. 30 refs., 6 figs

The Electronic Flux in Chemical Reactions. Insights on the Mechanism of the Maillard Reaction

Science.gov (United States)

Flores, Patricio; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Silva, Eduardo; Toro-Labbé, Alejandro

2007-11-01

The electronic transfer that occurs during a chemical process is analysed in term of a new concept, the electronic flux, that allows characterizing the regions along the reaction coordinate where electron transfer is actually taking place. The electron flux is quantified through the variation of the electronic chemical potential with respect to the reaction coordinate and is used, together with the reaction force, to shed light on reaction mechanism of the Schiff base formation in the Maillard reaction. By partitioning the reaction coordinate in regions in which different process might be taking place, electronic reordering associated to polarization and transfer has been identified and found to be localized at specific transition state regions where most bond forming and breaking occur.

A pulse radiolysis study of the electron reaction with DNA in aqueous solution and ice

International Nuclear Information System (INIS)

Verberne, J.B.

1981-01-01

Research is described into some aspects of the interaction of ionizing radiation with DNA, the main emphasis being on the indirect effect where the radiation causes the formation of intermediates in the surrounding medium which then interact with the DNA. Experiments are described which have been carried out to examine the dependence of the reaction rate constant on ionic strength and counterion charge. They show that for double stranded DNA (dsDNA) the reaction rate constant increases with ionic strength. To see whether quantitative agreement can be obtained between the observations and a physical interpretation the author combines a model for reaction kinetics and a refined model for the electrostatic potential into one to obtain a theoretical rate constant for reaction with a cylindrical polyelectrolyte. Optical absorption spectra of the electron adducts of ss- and dsDNA are shown to exist and they differ significantly from the spectra of the H and OH adducts. The spectra of the electron adducts of the nucleotides have been measured. Experiments are also described devoted to the precursor of the hydrated electron: the thermalized, dry electron. Although from a radiation chemical point of view the experiments yielded a lot of information (a direct observation of the dry electron, the kinetics of electron localization, the role of ice defects in the solvation process, etc.), they proved also that the dry electron does not react with DNA in an ice matrix. (Auth.)

Nuclear reactions of high energy deuterons with medium mass targets

International Nuclear Information System (INIS)

Numajiri, Masaharu; Miura, Taichi; Oki, Yuichi

1994-01-01

Formation cross sections of product nuclides in the nuclear reactions of medium mass targets by 10 GeV deuterons were measured with a gamma-ray spectroscopy. The measured data were compared with the cross sections of 12 GeV protons. (author)

PEG-400 as an efficient and recyclable reaction medium for the synthesis of polyhydroquinolines via Hantzsch reaction

Directory of Open Access Journals (Sweden)

Shitole Nana Vikram

2013-01-01

Full Text Available Polyhydroquinoline derivatives have been prepared efficiently in a one-pot synthesis via Hantzsch condensation using PEG-400 as reaction medium. The present method does not involve any hazardous organic solvents or toxic catalysts. The present methodology offers several advantages such as simple procedure, excellent yields with shorter reaction times and purification of products by non-chromatographic methods.

Electron transfer reactions of metal complexes in solution

International Nuclear Information System (INIS)

Sutin, N.

1977-01-01

A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

International Nuclear Information System (INIS)

Hoffman, M.Z.

1985-01-01

Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

Chemical potential and reaction electronic flux in symmetry controlled reactions.

Science.gov (United States)

Vogt-Geisse, Stefan; Toro-Labbé, Alejandro

2016-07-15

In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the Cs enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA'(ξ) and JA'' (ξ). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Evaluating the Benefits of Electronic Commerce in Small and Medium Enterprises

Directory of Open Access Journals (Sweden)

Peter Marshall

2002-05-01

Full Text Available This paper outlines and analyses the behaviours of small and medium enterprises with respect to the evaluation of electronic commerce investments, and the subsequent realisation of the anticipated benefits from those investments. The responses of executives who participated in the study suggested that on-going involvement in electronic commerce did not come cheaply. Nonetheless, our study suggests that there were generally ad hoc approaches to evaluation of the proposed electronic commerce investments, almost non-existent post-implementation reviews, few measures of success, and generally speaking, there was little evidence of there being proactive management of the realisation of benefits of those investments. Perhaps not surprisingly, the group interviewed seemed somewhat disappointed with the outcomes of their electronic commerce initiatives. The implications of these findings are discussed, particularly for countries where small and medium enterprises contribute a large proportion of total economic activity, and where thus it is vital for small and medium enterprises to successfully engage in electronic commerce if the country is to derive the benefits of the new economy.

Reaction of electron-transfer flavoprotein with electron-transfer flavoprotein-ubiquinone oxidoreductase

International Nuclear Information System (INIS)

Beckmann, J.D.; Frerman, F.E.

1985-01-01

The oxidative half-reaction of electron-transfer flavoprotein (ETF), electron transfer from ETF to electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO), is dependent on complementary surface charges on the two proteins. ETF is the positively charged member of the redox pair. The evidence is based on the pH and ionic strength dependencies of the comproportionation of oxidized ETF and ETF hydroquinone catalyzed by ETF-QO and on the effects of chemical modification of ETF on the comproportionation reaction. Acetylation of one and five epsilon-amino groups of lysyl residues results in 3- and 13-fold increases, respectively, in the K/sub m/ of ETF-QO for ETF but no change in V/sub max/. Amidination, which maintains positive charge at modified loci, has no effect on steady-state kinetic constants. These chemical modifications have no effect on the equilibrium constant for equilibration of ETF redox states. The K/sub m/ of ETF-QO for ETF is pH dependent above pH 8.5, suggesting titration of lysyl residues. The ionic strength dependence of TN/KmETF for the reaction follows the limiting Bronsted equation. The ETF-QO-catalyzed comproportionation reaction exhibits a primary deuterium isotope effect in D 2 O, perhaps indicating the participation of solvent water in the electron-transfer reaction

Reaction kinetics of nitrous acid with acetohydroxamic acid in HClO4 and HNO3 medium

International Nuclear Information System (INIS)

Zheng Weifang; Yan Taihong; Bian Xiaoyan; Zhang Yu

2007-01-01

The presence of nitrous acid in feed solution of PUREX process is unavoidable. Owing to its effect on the valence of plutonium and other nuclides, nitrous acid should be scavenged. The kinetics of reaction of AHA with nitrous acid was studied in HClO 4 and HNO 3 medium. The reaction rate equation in HClO 4 and HNO 3 medium is obtained as. --dc(HNO 2 )/dr= k·c(HNO 2 ) 1 ·c(AHA) 0.75 ·c(HClO 4 ) 0.5 and --dc(HNO 2 )/dt=k·c(HNO 2 ) 1 ·c(AHA) 0.25 .· c(HNO 3 ) 1 , respectively. In HClO 4 medium, the reaction rate constant (k) is found to be (2.37±0.21) L 1.25 /(mol 1.25 ·s) at θ=5 degree C, I=0.5 mol/kg. Reaction rate constant is increased slightly with the increased ion strength in the range of 0.5-2.0 mol/kg. In HNO 3 medium, the reaction rate constant (k) is found to be (0.482±0.048) L 1.25 /(mol 1.25 ·s) at θ=10 degree C and I= 0.5 mol/kg. Reaction rate constant is also increased slightly with the increased ion strength in the range of 0.5-3.0 mol/kg. The effect of temperature to the reaction rate is also studied. The results show that with the increase of temperature, the reaction rate increases quickly. And the activation energy is found to be 99.0 kJ/mol and 46.9 kJ/mol respectively in HNO 3 . (authors)

Transient Exciplex Formation Electron Transfer Mechanism

Directory of Open Access Journals (Sweden)

Michael G. Kuzmin

2011-01-01

Full Text Available Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for conventional long-range ET mechanism, especially for endergonic reactions, and provides the possibility for medium reorganization concatenated to gradual charge shift in contrast to conventional preliminary medium and reactants reorganization. Experimental criteria for transient exciplex formation (concatenated mechanism of excited-state electron transfer are considered. Available experimental data show that this mechanism dominates for endergonic ET reactions and provides a natural explanation for a lot of known paradoxes of ET reactions.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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

Science.gov (United States)

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

2013-12-21

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

Photon induced reactions

International Nuclear Information System (INIS)

Mecking, B.A.

1982-04-01

Various aspects of medium energy nuclear reactions induced by real photons are reviewed. Special emphasis is put on high accuracy experiments that will become possible with the next generation of electron accelerators. (orig.)

Inter-satellite calibration of FengYun 3 medium energy electron fluxes with POES electron measurements

Science.gov (United States)

Zhang, Yang; Ni, Binbin; Xiang, Zheng; Zhang, Xianguo; Zhang, Xiaoxin; Gu, Xudong; Fu, Song; Cao, Xing; Zou, Zhengyang

2018-05-01

We perform an L-shell dependent inter-satellite calibration of FengYun 3 medium energy electron measurements with POES measurements based on rough orbital conjunctions within 5 min × 0.1 L × 0.5 MLT. By comparing electron flux data between the U.S. Polar Orbiting Environmental Satellites (POES) and Chinese sun-synchronous satellites including FY-3B and FY-3C for a whole year of 2014, we attempt to remove less reliable data and evaluate systematic uncertainties associated with the FY-3B and FY-3C datasets, expecting to quantify the inter-satellite calibration factors for the 150-350 keV energy channel at L = 2-7. Compared to the POES data, the FY-3B and FY-3C data generally exhibit a similar trend of electron flux variations but more or less underestimate them within a factor of 5 for the medium electron energy 150-350 keV channel. Good consistency in the flux conjunctions after the inter-calibration procedures gives us certain confidence to generalize our method to calibrate electron flux measurements from various satellite instruments.

Effect of electrostatic interactions on electron-transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

Fast reactions of electron transfer are studied by pulsed radiolysis. By this technique radicals and ionic radicals with high redox potentials are created homogeneously in the solution in about 10 -8 second. For solvated electron effect of electrostatic interaction on kinetics of reactions limited by diffusion is obtained with a good approximation by the Debye equation when ion mobility is known. Deviation from the theory occurs in ion pair formation, which is evidenced experimentally in reactions between anions when cations are complexed by a cryptate. Slow reactions k 8 M -1 s -1 are more sensitive to electrostatic interactions than reactions limited by diffusion. When there is no ion pair formation the velocity constant depends upon dielectric constant of the solvent and reaction distance. 17 refs

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-12-21

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

Effects of electrostatic interactions on electron transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

The fast reactions of electron transfer are studied by pulse radiolysis. This technique allows the creation in about 10 -8 second radicals and radical ions with high redox potentials. For solvated electrons electrostatic interaction on the kinetics of reactions limited by diffusion is described by Debye's equation when ion mobility is known. Deviation from theory can occur in ion pairs formation. This is evidenced experimentally for anions by cation complexation with a cryptate. Relatively slow reactions are more sensitive to electrostatic interactions than limited by diffusion. If ion pairs are not formed kinetics constant depends on dielectric constant of solvent and reaction radius. Experimentally is studied the effect of electrostatic interaction on the rate constants of solvated electrons with anions and cations in water-ethanol mixtures where the dielectric constant change from 80 to 25 at room temperature. 17 refs

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

Science.gov (United States)

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

2013-12-01

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the

Spin effects in medium-energy electron-3He scattering

International Nuclear Information System (INIS)

van den Brand, J.F.J.; Alarcon, R.; Bauer, T.

1998-01-01

New physics can be accessed by scattering polarized electrons from a polarized 3 He internal gas target. It is discussed how the asymmetries for the reactions 3 vector He(vector e,e'), 3 vector He(vector e,e'p), 3 vector He(vector e,e'n), 3 vector He(vector e,e'd), and 3 vector He(vector e,e'pn) may provide precise information on the S' and the D-wave parts of the 3 He ground-state wave function, the neutron form factors, and the role of spin-dependent reaction mechanism effects. The experiment uses up to 900 MeV (polarized) electrons from the AmPS storage ring in Amsterdam, Netherlands, in combination with large acceptance electron and hadron detectors. (orig.)

Multiple scattering in the nuclear rearrangement reactions at medium energy

International Nuclear Information System (INIS)

Tekou, A.

1980-09-01

It is shown that the multiple scattering mechanism is very important in the transfer of the large momenta involved in the nuclear rearrangement reactions at medium energy. In contrast to the usual belief, the reaction cross-section is not very sensitive to the high momenta components of the nuclear wave function. The multiple scattering mechanism is especially important in 4 He(p,d) 3 He reaction around 800 MeV. Here the collisions involving two nucleons of the target nucleus are dominant. The triple collisions contribution is also important. The four collision contribution is negligible in the forward direction and sizeable at large angles. Thus, using the K.M.T. approach in DWBA calculations, the second order term of the optical potential must be included. So, is it not well established that the second term of the K.M.T. optical potential is important for the proton elastic scattering on light nuclei. (author)

The calculation of electron depth-dose distributions in multilayer medium

International Nuclear Information System (INIS)

Wang Chuanshan; Xu Mengjie; Li Zhiliang; Feng Yongxiang; Li Panlin

1989-01-01

Energy deposition in multilayer medium and the depth dose distribution in the layers are studied. Based on semi-empirical calculation of electron energy absorption in matter with EDMULT program of Tabata and Ito, further work has been carried out to extend the computation to multilayer composite material. New program developed in this paper makes IBM-PC compatible with complicated electron dose calculations

Quenching reactions of electronically excited atoms

International Nuclear Information System (INIS)

Setser, D.W.

2001-01-01

The two-body, thermal quenching reactions of electronically excited atoms are reviewed using excited states of Ar, Kr, and Xe atoms as examples. State-specific interstate relaxation and excitation-transfer reactions with atomic colliders are discussed first. These results then are used to discuss quenching reactions of excited-state atoms with diatomic and polyatomic molecules, the latter have large cross sections, and the reactions can proceed by excitation transfer and by reactive quenching. Excited states of molecules are not considered; however, a table of quenching rate constants is given for six excited-state molecules in an appendix

Low Energy Electrons as Probing Tool for Astrochemical Reaction Mechanisms

Science.gov (United States)

Hendrik Bredehöft, Jan; Swiderek, Petra; Hamann, Thorben

The complexity of molecules found in space varies widely. On one end of the scale of molecular complexity is the hydrogen molecule H2 . Its formation from H atoms is if not understood than at least thoroughly investigated[1]. On the other side of said spectrum the precursors to biopolymers can be found, such as amino acids[2,3], sugars[4], lipids, cofactors[5], etc, and the kerogen-like organic polymer material in carbonaceous meteorites called "black stuff" [6]. These have also received broad attention in the last decades. Sitting in the middle between these two extremes are simple molecules that are observed by radio astronomy throughout the Universe. These are molecules like methane (CH4 ), methanol (CH3 OH), formaldehyde (CH2 O), hydrogen cyanide (HCN), and many many others. So far more than 40 such species have been identified.[7] They are often used in laboratory experiments to create larger complex molecules on the surface of simulated interstellar dust grains.[2,8] The mechanisms of formation of these observed starting materials for prebiotic chemistry is however not always clear. Also the exact mechanisms of formation of larger molecules in photochemical experiments are largely unclear. This is mostly due to the very complex chemistry going on which involves many different radicals and ions. The creation of radicals and ions can be studied in detail in laboratory simulations. They can be created in a setup mimicking interstellar grain chemistry using slow electrons. There is no free electron radiation in space. What can be found though is a lot of radiation of different sorts. There is electromagnetic radiation (UV light, X-Rays, rays, etc.) and there is particulate radiation as well in the form of high energy ions. This radiation can provide energy that drives chemical reactions in the ice mantles of interstellar dust grains. And while the multitude of different kinds of radiation might be a little confusing, they all have one thing in common: Upon

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

Energy Technology Data Exchange (ETDEWEB)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is `Tunneling Reaction and Quantum Medium`. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is 'Tunneling Reaction and Quantum Medium'. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

Some insights into formamide formation through gas-phase reactions in the interstellar medium

International Nuclear Information System (INIS)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

2014-01-01

We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH 3 + , NH 4 + , NH 3 OH + , and NH 2 OH + ) and neutral molecules having one carbonyl group (H 2 CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

Some Insights into Formamide Formation through Gas-phase Reactions in the Interstellar Medium

Science.gov (United States)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

2014-01-01

We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH_{3}^{+}, NH_{4}^{+}, NH3OH+, and NH2OH+) and neutral molecules having one carbonyl group (H2CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

Kinetics and Mechanism of Oxidation of Aromatic Aldehydes by Imidazolium Dichromate in Aqueous Acetic Acid Medium

Directory of Open Access Journals (Sweden)

S. Sheik Mansoor

2009-01-01

Full Text Available The kinetics of oxidation of benzaldehyde (BA and para-substituted benzaldehydes by imidazolium dichromate (IDC has been studied in aqueous acetic acid medium in the presence of perchloric acid. The reaction is first order each in [IDC], [Substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. Electron withdrawing substituents are found to increase the reaction and electron releasing substituents are found to retard the rate of the reaction and the rate data obey the Hammett relationship. The products of the oxidation are the corresponding acids. The rate decreases with the increase in the water content of the medium. A suitable mechanism is proposed.

Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

NARCIS (Netherlands)

Frissen, A.E.

1990-01-01

This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity

Some insights into formamide formation through gas-phase reactions in the interstellar medium

Energy Technology Data Exchange (ETDEWEB)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

2014-01-10

We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

The quantum dynamics of electronically nonadiabatic chemical reactions

Science.gov (United States)

Truhlar, Donald G.

1993-01-01

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

Electron transfer reactions in structural units of copper proteins

International Nuclear Information System (INIS)

Faraggi, M.

1975-01-01

In previous pulse radiolysis studies it was suggested that the reduction of the Cu(II) ions in copper proteins by the hydrated electron is a multi-step electron migration process. The technique has been extended to investigate the reduction of some structural units of these proteins. These studies include: the reaction of the hydrated electron with peptides, the reaction of the disulphide bridge with formate radical ion and radicals produced by the reduction of peptides, and the reaction of Cu(II)-peptide complex with esub(aq)sup(-) and CO 2 - . Using these results the reduction mechanism of copper and other proteins will be discussed. (author)

Studies on electron transfer reactions of Keggin-type mixed ...

Indian Academy of Sciences (India)

Administrator

(PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1: 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one elec- tron reduced heteropoly ...

Electron transfer reactions involving porphyrins and chlorophyll a

International Nuclear Information System (INIS)

Neta, P.; Scherz, A.; Levanon, H.

1979-01-01

Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

Microwave activation of palladium nanoparticles for enhanced ethanol electrocatalytic oxidation reaction in alkaline medium

CSIR Research Space (South Africa)

Rohwer, MB

2015-02-01

Full Text Available in alkaline medium (in terms of high mass activity stability and fast reaction kinetics). The remarkable microwave-induced properties on the Pd catalyst promise to revolutionize the use of microwave for catalyst activation for enhanced heterogeneous catalysis...

Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan’s upper atmosphere and the interstellar medium

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhe-Chen; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)

2016-06-07

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

Energy Technology Data Exchange (ETDEWEB)

Sailani, Riya; Bhasin, Meneka; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

2014-01-15

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be (61.67 ± 0.47) kJ mol{sup -1} and (-62.71 ± 2.48) JK{sup -1}mol{sup -1} respectively employing Eyring equation.

Effects of Reaction Medium on the Phase Synthesis and Particle Size Evolution of BaTiO3

NARCIS (Netherlands)

Stawski, Thomasz M.; Veldhuis, Sjoerd A.; Göbel, Ole; ten Elshof, Johan E.; Blank, David H.A.

2010-01-01

The low-temperature alkoxide–hydroxide precipitation synthesis of nanosized crystalline barium titanate (BaTiO3) in nonaqueous media is presented. In this report, we show the influence of the reaction medium on the nature of the product by investigating the reaction of titanium (IV) isopropoxide

Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

Science.gov (United States)

Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

2017-03-03

Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

Medium-Ring Effects on the Endo/Exo Selectivity of the Organocatalytic Intramolecular Diels-Alder Reaction.

Science.gov (United States)

Hooper, Joel F; James, Natalie C; Bozkurt, Esra; Aviyente, Viktorya; White, Jonathan M; Holland, Mareike C; Gilmour, Ryan; Holmes, Andrew B; Houk, K N

2015-12-18

The intramolecular Diels-Alder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan's imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels-Alder reaction to form the isobenzofuran core of the eunicellins.

Theoretical study of ultrarelativistic laser-electron interaction with radiation reaction

Directory of Open Access Journals (Sweden)

Seto K.

2013-11-01

Full Text Available When the laser intensity becomes higher than 1022  W/cm2, the motion of an electron becomes relativistic, and emits large amounts of radiation. This radiation energy loss transferred to the kinetic energy loss of the electron, is treated as an external force, the “radiation reaction force”. We show the new equation of motion including this radiation reaction and the simulation method, as well as results of single electron system or dual electrons system with Liénard-Wiechert field interaction.

Silver nanoparticle catalysed redox reaction: An electron relay effect

International Nuclear Information System (INIS)

Mallick, Kaushik; Witcomb, Mike; Scurrell, Mike

2006-01-01

A silver cluster shows efficient catalytic activity in a redox reaction because the cluster acts as the electron relay centre behaving alternatively as an acceptor and as a donor of electrons. An effective transfer of electrons is possible when the redox potential of the cluster is intermediate between the electron donor and electron acceptor system

Evaluation of the acute adverse reaction of contrast medium with high and moderate iodine concentration in patients undergoing computed tomography

International Nuclear Information System (INIS)

Nagamoto, Masashi; Gomi, Tatsuya; Terada, Hitoshi; Terada, Shigehiko; Kohda, Eiichi

2006-01-01

The aim of this prospective study was to evaluate and compare acute adverse reactions between contrast medium containing moderate and high concentrations of iodine in patients undergoing computed tomography (CT). A total of 945 patients undergoing enhanced CT were randomly assigned to receive one of two doses of contrast medium. We then prospectively investigated the incidence of adverse reactions. Iopamidol was used as the contrast medium, with a high concentration of 370 mgI/ml and a moderate concentration of 300 mgI/ml. The frequency of adverse reactions, such as pain at the injection site and heat sensation, were determined. Acute adverse reactions were observed in 2.4% (11/458) of the moderate-concentration group compared to 3.11% (15/482) of the high-concentration group; there was no significant difference in incidence between the two groups. Most adverse reactions were mild, and there was no significant difference in severity. One patient in the high-concentration group was seen to have a moderate adverse reaction. No correlation existed between the incidence of adverse reactions and patient characteristics such as sex, age, weight, flow amount, and flow rate. The incidence of pain was not significantly different between the two groups. In contrast, the incidence of heat sensation was significantly higher in the high-concentration group. The incidence and severity of acute adverse reactions were not significantly different between the two groups, and there were no severe adverse reactions in either group. (author)

Inverse-Electron-Demand Diels-Alder Reactions: Principles and Applications.

Science.gov (United States)

Png, Zhuang Mao; Zeng, Huining; Ye, Qun; Xu, Jianwei

2017-09-05

Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Delta-electron spectroscopy: An aid for the determination of reaction times in heavy ion reactions

International Nuclear Information System (INIS)

Skapa, H.

1983-01-01

For the systems I->Au and I->Bi at an incident energy of 6.2 MeV/u (I->Au) and 6.6 MeV/u (I->Bi) the emission probability of delta electrons was determined. In an energy range from 150 KeV to 1000 KeV electrons were spectroscoped in coincidence to elastically, quasielastically, and deep inelastically scattered ions. In deep inelastic reaction between reaction products with high and without a mean mass drift was discriminated. The contribution of the conversion electrons, determined from gamma spectra, extends in the range of deep inelastic reactions of about 60%. While the ratio of conversion electrons for deep inelastic events with large to such without mass drift shows a flat, monotoneous growth for the ratio of the measured emission probabilities a oscillation-like structure with about 400 KeV width results. An interpretation of this structure as interference effect by nuclear time delay yields for the case of large mass drift a nuclear retention time of 7.5 x 10 -21 s. (orig./HSI) [de

One-electron reduction reactions with enzymes in solution

International Nuclear Information System (INIS)

Bisby, R.H.; Cundall, R.B.; Redpath, J.L.; Adams, G.E.

1976-01-01

At pH 8 and above, hydrated electrons react with ribonuclease lysozyme and α-chymotrypsin to form transient products whose spectra resemble, but are not identical to, those for the RSSR - radical anion already known for simple disulphides. Assuming a value for the extinction coefficient similar to that for RSSR - in simple disulphides, only a fraction of the hydrated electrons are shown to react with the disulphide bridges: the remainder react at other sites in the protein molecule, such as histidine, tyrosine and, in lysozyme, tryptophan residues, giving rise to comparatively weak optical absorptions between 300 and 400 nm. This has been substantiated by studying the reaction of e - sub(aq) with subtilisin Novo (an enzyme which does not contain disulphide bridges), with enzymes in which the sulphur bridges have been oxidised and with some amino acid derivatives. On lowering the pH of the solution the intensity of the RSSR - absorption diminishes as the protonated histidine residues become the favoured reaction sites. In acid solutions (pH 2 to 3) the transient optical absoptions observed are due to reactions of hydrogen atoms with the aromatic amino acids tyrosine, tryptophan and phenylalanine. The CO - 2 radical anion is only observed to transfer an electron to disulphide groups in ribonuclease, although the effect of repeated pulsing shows that some reaction must occur elsewhere in the protein molecule. In acid solutions, protonation of the electron adduct appears to produce the RSSRH. radical, whose spectrum has a maximum at 340 nm. (author)

Influence of the medium on the reaction rate of the t-butoxyl radical with iron(II)

International Nuclear Information System (INIS)

Mihaljevic, B.; Razem, D.

2002-01-01

Complete text of publication follows. Tert-butoxyl radicals (t-BuO.) were generated by homolytic photodecomposition of di-tert-butylperoxide using ruby laser flashes at 347 nm. The reaction of t-BuO. radicals with Fe 2+ was studied under pseudo-first order conditions. The quantum yield Φ(Fe 3+ ) was determined by measuring the absorbance of Fe 3+ ion as [FeCl] 2+ complex at 360 nm 2 μs after the flash. According to the equation derived from the reaction scheme, the rate constant k 3 was obtained from the relative rate constant k r (k r =k 0 /k 3 ) and the value of k 0 ; the latter refers to the overall rate of the competing disappearance of t-BuO. radicals from the system (reaction 2), including the highest contribution of β-cleavage. The rate constant k 0 was determined using diphenylmethanol instead of Fe 2+ . The known rate constant of the reaction of t-BuO. radical with diphenylmethanol giving ketyl radicals (6.9 x 10 6 dm 3 mol -1 s -1 ) was applied. The quantum yield of ketyl radicals was determined by measuring the maximum of absorbance at 535 nm. At acid concentration of 0.023 mol dm -3 HCl the rate constant k 3 = 3.4 x 10 8 dm 3 mol -1 s -1 was determined. The relative rate constant increased with an increase of the hydrochloric acid concentration which has been ascribed to the lower stability of t-BuO. radical at higher acidity of the medium. The effect of polarity of the medium on the reaction rate was also determined. Decreasing k 3 in media of increasing polarity were explained by increasing of the β-scission rate of t-BuO. radical with increasing polarity of the medium

Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

Directory of Open Access Journals (Sweden)

Claudia Trossero

2009-01-01

Full Text Available Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC. The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II-sulfathiazole, Co(II-ST in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test, with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

Pressure effects on electron reactions and mobility in nonpolar liquids

International Nuclear Information System (INIS)

Holroyd, R.A.; Nishikawa, Masaru

2002-01-01

High pressure studies have elucidated the mechanisms of both electron reactions and electron transport in nonpolar liquids and provided information about the partial molar volumes of ions and electrons. The very large volume changes associated with electron attachment reactions have been explained as due to electrostriction by the ions, calculated with a continuum model, but modified to include the formation of a glassy shell of solvent molecules around the ion. The mobilities of electrons in cases where the electron is trapped can now be understood by comparing the trap cavity volume with the volume of electrostriction of the solvent around the cavity. In cases where the electron is quasi-free the compressibility dependent potential fluctuations are shown to be important. The isothermal compressibility is concluded to be the single most important parameter determining the behavior of excess electrons in liquids

Electron stimulated reactions of methyl iodide coadsorbed with amorphous solid water

International Nuclear Information System (INIS)

Perry, C. C.; Faradzhev, N. S.; Madey, T. E.; Fairbrother, D. H.

2007-01-01

The electron stimulated reactions of methyl iodide (MeI) adsorbed on and suspended within amorphous solid water (ice) were studied using a combination of postirradiation temperature programmed desorption and reflection absorption infrared spectroscopy. For MeI adsorbed on top of amorphous solid water (ice), electron beam irradiation is responsible for both structural and chemical transformations within the overlayer. Electron stimulated reactions of MeI result principally in the formation of methyl radicals and solvated iodide anions. The cross section for electron stimulated decomposition of MeI is comparable to the gas phase value and is only weakly dependent upon the local environment. For both adsorbed MeI and suspended MeI, reactions of methyl radicals within MeI clusters lead to the formation of ethane, ethyl iodide, and diiodomethane. In contrast, reactions between the products of methyl iodide and water dissociation are responsible for the formation of methanol and carbon dioxide. Methane, formed as a result of reactions between methyl radicals and either parent MeI molecules or hydrogen atoms, is also observed. The product distribution is found to depend on the film's initial chemical composition as well as the electron fluence. Results from this study highlight the similarities in the carbon-containing products formed when monohalomethanes coadsorbed with amorphous solid water are irradiated by either electrons or photons

Dissociative attachment reactions of electrons with gas phase superacids

International Nuclear Information System (INIS)

Liu, X.

1992-01-01

Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients β for reactions of electrons with gas phase superacids HCo(PF 3 ) 4 , HRh(PF 3 ) 4 and carbonyl hydride complexes HMn(CO) 5 , HRe(CO) 5 have been determined under thermal conditions over the approximate temperature range 300∼550 K. The superacids react relatively slowly ( max ) with free electrons in a thermal plasma, and the values of β obtained this far do not show a correlation between acidity and β. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF 3 ) 4 was found to be independent of temperature even though the β[HCo(PF 3 ) 4 ] increases with temperature. This proposes that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF 3 ) 4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) 5 and HRe(CO) 5 , react relatively rapidly (>1/4 of β max ) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition-metal species

Concentrated Aqueous Sodium Tosylate as Green Medium for Alkene Oxidation and Nucleophilic Substitution Reactions.

Science.gov (United States)

Sela, Tal; Lin, Xiaoxi; Vigalok, Arkadi

2017-11-03

A hydrotropic solution of highly concentrated sodium tosylate (NaOTs) can be used as a recyclable medium for the environmentally benign oxidation of conjugated alkenes with H 2 O 2 . Both uncatalyzed and metal-catalyzed reactions provided the corresponding oxidation products in higher yields than in pure water or many common organic solvents.

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

Effects of medium-chain triacylglycerols on Maillard reaction in bread baking.

Science.gov (United States)

Toyosaki, Toshiyuki

2018-06-01

To investigate the relationship between the fatty acid composition of medium-chain triacylglycerols (MCTs) and the Maillard reaction induced during bread baking, a comparison with various fatty acids was conducted. Saturated fatty acids had a remarkable inhibitory effect on the amount of advanced glycation end products (AGEs) generated from the Maillard reaction in bread baking compared to unsaturated fatty acids. The amount of AGEs produced by each fatty acid (mg kg -1 ) was as follows: C18:0, 18.7; C12:0, 35.2; C16:0, 21.4; C18:0, 38.2; C18:1, 68.7; C18:2, 80.1; C20:4, 80.8; C22:4, 89.8. Saturated fatty acids were possibly involved in the Maillard reaction and, as a result, acted to inhibit it. In the case of unsaturated fatty acids, amounts of AGEs during the Maillard reaction in baking tended to increase as the degree of unsaturation increased. In other words, there was a positive correlation between the degree of unsaturation and the amount of AGEs. It was also confirmed that the air pore distribution in baked bread was closely related to AGEs. These results led us to conclude that the fatty acid composition of the added lipids also influences properties that determine the tastiness of bread. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Convection and reaction in a diffusive boundary layer in a porous medium: nonlinear dynamics.

Science.gov (United States)

Andres, Jeanne Therese H; Cardoso, Silvana S S

2012-09-01

We study numerically the nonlinear interactions between chemical reaction and convective fingering in a diffusive boundary layer in a porous medium. The reaction enhances stability by consuming a solute that is unstably distributed in a gravitational field. We show that chemical reaction profoundly changes the dynamics of the system, by introducing a steady state, shortening the evolution time, and altering the spatial patterns of velocity and concentration of solute. In the presence of weak reaction, finger growth and merger occur effectively, driving strong convective currents in a thick layer of solute. However, as the reaction becomes stronger, finger growth is inhibited, tip-splitting is enhanced and the layer of solute becomes much thinner. Convection enhances the mass flux of solute consumed by reaction in the boundary layer but has a diminishing effect as reaction strength increases. This nonlinear behavior has striking differences to the density fingering of traveling reaction fronts, for which stronger chemical kinetics result in more effective finger merger owing to an increase in the speed of the front. In a boundary layer, a strong stabilizing effect of reaction can maintain a long-term state of convection in isolated fingers of wavelength comparable to that at onset of instability.

Medium Modifications of Hadrons in Photon Induced Reactions

International Nuclear Information System (INIS)

Schadmand, S.

2004-01-01

Indications for in-medium modifications of hadron properties are reported from photoabsorption and meson production experiments. Strong medium modifications are observed in inclusive photoabsorption experiments and theoretical models investigate the in-medium dynamics of baryon resonances and their coupling to mesons. Recent experiments study the in-medium behavior of scalar and vector mesons where theoretical models expect in-medium modifications of the meson spectral functions that might be connected to partial restoration of chiral symmetry

Quantum radiation reaction in head-on laser-electron beam interaction

International Nuclear Information System (INIS)

Vranic, Marija; Grismayer, Thomas; Fonseca, Ricardo A; Silva, Luis O

2016-01-01

In this paper, we investigate the evolution of the energy spread and the divergence of electron beams while they interact with different laser pulses at intensities where quantum effects and radiation reaction are of relevance. The interaction is modelled with a quantum electrodynamic (QED)-PIC code and the results are compared with those obtained using a standard PIC code with a classical radiation reaction module. In addition, an analytical model is presented that estimates the value of the final electron energy spread after the interaction with the laser has finished. While classical radiation reaction is a continuous process, in QED, radiation emission is stochastic. The two pictures reconcile in the limit when the emitted photons energy is small compared to the energy of the emitting electrons. The energy spread of the electron distribution function always tends to decrease with classical radiation reaction, whereas the stochastic QED emission can also enlarge it. These two tendencies compete in the QED-dominated regime. Our analysis, supported by the QED module, reveals an upper limit to the maximal attainable energy spread due to stochasticity that depends on laser intensity and the electron beam average energy. Beyond this limit, the energy spread decreases. These findings are verified for different laser pulse lengths ranging from short ∼30 fs pulses presently available to the long ∼150 fs pulses expected in the near-future laser facilities, and compared with a theoretical model. Our results also show that near future experiments will be able to probe this transition and to demonstrate the competition between enhanced QED induced energy spread and energy spectrum narrowing from classical radiation reaction. (paper)

The first organocatalytic, ortho-regioselective inverse-electron-demand hetero-Diels-Alder reaction.

Science.gov (United States)

Hejmanowska, Joanna; Jasiński, Marcin; Wojciechowski, Jakub; Mlostoń, Grzegorz; Albrecht, Łukasz

2017-10-17

The development of the unprecedented ortho-regioselective inverse-electron-demand hetero-Diels-Alder (IEDHDA) reaction is described. It has been demonstrated that by proper choice of reactants and reaction conditions the inverse-electron-demand hetero-Diels-Alder cycloaddition can be realized with unprecedented regioselectivity arising from the reaction between the terminal carbon atom of the dienophile and the heteroatom of the heterodiene.

Chemistry by nanocatalysis: First example of a solid-supported RAPTA complex for organic reactions in aqueous medium

KAUST Repository

García-Garrido, Sergio E.

2010-11-18

A ruthenium-arene-PTA (RAPTA) complex has been supported for the first time on an inorganic solid, that is, silica-coated ferrite nanoparticles. The resulting magnetic material proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentration, environmentally friendly water as a reaction medium, with no use at all of organic solvent during or after the reactions, and microwaves as an alternative energy source renders the synthetic processes reported herein "truly" green and sustainable. RAPTA\\'s delight: A nano-RAPTA complex supported on silica-coated ferrite nanoparticles proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentrations, water as a reaction medium, and microwaves as an energy source renders these processes green and sustainable. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calculated sputtering and atomic displacement cross-sections for applications to medium voltage analytical electron microscopy

International Nuclear Information System (INIS)

Bradley, C.R.; Zaluzec, N.J.

1987-08-01

The development of medium voltage electron microscopes having high brightness electron sources and ultra-high vacuum environments has been anticipated by the microscopy community now for several years. The advantages of such a configuration have been discussed to great lengths, while the potential disadvantages have for the most part been neglected. The most detrimental of these relative to microcharacterization are the effects of electron sputtering and atomic displacement to the local specimen composition. These effects have in the past been considered mainly in the high voltage electron microscope regime and generally were ignored in lower voltage instruments. Recent experimental measurements have shown that the effects of electron sputtering as well as radiation induced segregation can be observed in conventional transmission electron microscopes. It is, therefore, important to determine at what point the effects will begin to manifest themselves in the new generation of medium voltage analytical electron microscopes. In this manuscript we present new calculations which allow the individual experimentalist to determine the potential threshold levels for a particular elemental system and thus avoid the dangers of introducing artifacts during microanalysis. 12 refs., 3 figs

Nuclear structure and reaction studies at medium energies

International Nuclear Information System (INIS)

Hoffmann, G.W.; Ray, R.L.

1990-10-01

This document constitutes the (1988--1991) technical progress report for the ongoing medium energy physics research program supported by the US Department of Energy through special Research Grant FG05-88ER40444. The experiments discussed are conducted at the Los Alamos National Laboratory's (LANL) Clinton P. Anderson Meson Physics Facility (LAMPF), the Alternating Gradient Synchrotron (AGS) facility of the Brookhaven National Laboratory (BNL), and at the Fermi National Accelerator Laboratory (FNAL). The overall motivation for the work discussed in this document is driven by three main objectives: (1) provide hadron-nucleon and hadron-nucleus scattering data which serve to facilitate the study of effective two-body interactions, test (and possibly determine) nuclear structure, and help study reaction mechanisms and dynamics;(2) provide unique, first-of-a-kind ''exploratory'' hadron-nucleus scattering data in the hope that such data will lead to discovery of new phenomena and new physics; and (3) perform precision tests of fundamental interactions, such as rare decay searches, whose observation would imply fundamental new physics

Hydrogen abstraction reactions by amide electron adducts

International Nuclear Information System (INIS)

Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

1982-01-01

Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

Void formation in NiTi shape memory alloys by medium-voltage electron irradiation

International Nuclear Information System (INIS)

Schlossmacher, P.; Stober, T.

1995-01-01

In-situ electron irradiation experiments of NiTi shape memory alloys, using high-voltage transmission electron microscopes, result in amorphization of the intermetallic compound. In all of these experiments high-voltages more than 1.0 MeV had to be applied in order to induce the crystalline-to-amorphous transformation. To their knowledge no irradiation effects of medium-voltage electrons of e.g. 0.5 MeV have been reported in the literature. In this contribution, the authors describe void formation in two different NiTi shape memory alloys, resulting from in-situ electron irradiation, using a 300 kV electron beam in a transmission electron microscope. First evidence is presented that void formation is correlated with the total oxygen content of the alloys

Observation of muon-electron pairs in neutrino reactions

International Nuclear Information System (INIS)

Hoffmann, D.

1980-05-01

The present thesis describes the observation of muon-electron pairs in neutrino reactions. This experiment was performed using an optical multiplate spark chamber in the broad band neutrino beam of the CERN proton synchrotron. (orig.) [de

The reaction rates of electrons with native and irradiated ribonuclease

International Nuclear Information System (INIS)

Schuessler, H.; Ebert, M.; Davies, J.V.

1977-01-01

The rate of reaction of hydrated electrons with proteins depends, amongst other things, on the conformational structure of the protein, and irradiation itself causes conformational changes in proteins. A study has been made of variations in the reaction rates of hydrated electrons with RNase pre-irradiated by the Linac or by a 60 Co γ-source. The reaction rate constants varied with the pre-irradiation dose, the concentration of phosphate buffer, the enzyme concentration and also the presence of 10 -2 M ethanol. These variations serve to emphasize the importance of the tertiary structure of biological molecules in irradiation processes and have significant implications in the mathematical analysis of the inactivation of enzymes in steady-state irradiation processes. (U.K.)

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

DEFF Research Database (Denmark)

Ulstrup, Jens; Jortner, Joshua

1975-01-01

A general quantum mechanical description of exothermic electron transfer reactions is formulated by treating such reactions as the nonradiative decay of a ''supermolecule'' consisting of the electron donor, the electron acceptor, and the polar solvent. In particular, the role of the high-frequenc...

Reaction dynamics of electronically excited alkali atoms with simpler molecules

International Nuclear Information System (INIS)

Weiss, P.S.; Mestdagh, J.M.; Schmidt, H.; Vernon, M.F.; Covinsky, M.H.; Balko, B.A.; Lee, Y.T.

1985-05-01

The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(3 2 P/sub 3/2/, 4 2 D/sub 5/2/, and 5 2 S/sub 1/2/) were produced by optical pumping using single frequency dye lasers. The effects of the symmetry, and the orientation and alignment of the excited orbital on the chemical reactivity, and detailed information on the reaction dynamics were derived from measurements of the product angular and velocity distributions. 12 refs., 9 figs

Electron-transfer reactions of extremely small AgI colloids

International Nuclear Information System (INIS)

Vucemilovic, M.I.; Micic, O.I.

1988-01-01

Small colloidal AgI particles (particle diameter 20-50 A) have been prepared in water and acetonitrile, and optical effects due to size quantization have been observed. Electron transfer reactions involving electron donors and electron acceptors with AgI have been studied by pulse radiolysis techniques. Both reduction and oxidation of the colloids led to transient bleaching of semiconductor absorption. The recovery of the bleaching has been attributed to corrosion processes. Electrons injected into AgI colloids produce metallic silver and hydrogen. Hydrogen evolution is catalyzed by metallic silver formation. (author)

Model of deep centers formation and reactions in electron irradiated InP

International Nuclear Information System (INIS)

Sibille, A.; Suski, J.; Gilleron, M.

1986-01-01

We present a model of the production of deep centers and their reactions following electron irradiations in InP. We propose that the dominant hole traps in p-InP and electron traps in p + n InP junctions are complexes between shallow acceptors and a common intrinsic entity, the phosphorus interstitial or vacancy. The reactions observed below and above room temperature are then due to a local mobility of this entity, which can be obtained as well by thermal as by electronic stimulation of the reactions. This model implies the long-range migration (at least down to 16 K) of this entity, and explains the strongly different behavior of n-InP compared to p-InP samples

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents.

Science.gov (United States)

Dzhioev, Alan A; Kosov, Daniel S; von Oppen, Felix

2013-04-07

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

Diffusion of Electronic Commerce in Small and Medium Enterprises

Directory of Open Access Journals (Sweden)

Robyn Lawson

2002-05-01

Full Text Available Using the Internet for electronic business has become an area of action for the Australian Government. This paper presents research results from two regional areas which indicate that while most manufacturing SMEs use email, very few are involved in elecronic commerce activities. Major barriers are concern about security and privacy of transactions, cost of consultants, and lack of IT expertise of staff. Employing people with appropriate knowledge has been added to current training methods such as on-the-job training. Results from the two regional areas are found to be consistent. Comparisons between small and medium organisations highlight some differences.

One-electron transfer reactions of the couple NAD./NADH

International Nuclear Information System (INIS)

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

1983-01-01

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

Production of complex particles in low energy spallation and in fragmentation reactions by in-medium random clusterization

International Nuclear Information System (INIS)

Lacroix, D.; Durand, D.

2005-09-01

Rules for in-medium complex particle production in nuclear reactions are proposed. These rules have been implemented in two models to simulate nucleon-nucleus and nucleus-nucleus reactions around the Fermi energy. Our work emphasizes the effect of randomness in cluster formation, the importance of the nucleonic Fermi motion as well as the role of conservation laws. The concepts of total available phase-space and explored phase-space under constraint imposed by the reaction are clarified. The compatibility of experimental observations with a random clusterization is illustrated in a schematic scenario of a proton-nucleus collision. The role of randomness under constraint is also illustrated in the nucleus-nucleus case. (authors)

Electronic shift register memory based on molecular electron-transfer reactions

Science.gov (United States)

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

1989-01-01

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

Correlation functions of electronic and nuclear spins in a Heisenberg antiferromagnet semi-infinite medium

International Nuclear Information System (INIS)

Sarmento, E.F.

1981-01-01

Results are found for the dynamical correlation functions (or its corresponding Green's functions) among any combination including operator pairs of electronic and nuclear spins in an antiferromagnet semi-infinite medium, at low temperatures T [pt

Analytic study of the chain dark decomposition reaction of iodides - atomic iodine donors - in the active medium of a pulsed chemical oxygen-iodine laser: 1. Criteria for the development of the branching chain dark decomposition reaction of iodides

International Nuclear Information System (INIS)

Andreeva, Tamara L; Kuznetsova, S V; Maslov, Aleksandr I; Sorokin, Vadim N

2009-01-01

The scheme of chemical processes proceeding in the active medium of a pulsed chemical oxygen-iodine laser (COIL) is analysed. Based on the analysis performed, the complete system of differential equations corresponding to this scheme is replaced by a simplified system of equations describing in dimensionless variables the chain dark decomposition of iodides - atomic iodine donors, in the COIL active medium. The procedure solving this system is described, the basic parameters determining the development of the chain reaction are found and its specific time intervals are determined. The initial stage of the reaction is analysed and criteria for the development of the branching chain decomposition reaction of iodide in the COIL active medium are determined. (active media)

Medium modifications with recoil polarization

International Nuclear Information System (INIS)

Brand, J.F.J. van den; Ent, R.

1994-01-01

The authors show that the virtual Compton scattering process allows for a precise study of the off-shell electron-nucleon vertex. In a separable model, they show the sensitivity to new unconstrained structure functions of the nucleon, beyond the usual Dirac and Pauli form factors. In addition, they show the sensitivity to bound nucleon form factors using the reaction 4He(rvec e,e',rvec p) 3 H. A nucleon embedded in a nucleus represents a complex system. Firstly, the bound nucleon is necessarily off-shell and in principle a complete understanding of the dynamical structure of the nucleon is required in order to calculate its off-shell electromagnetic interaction. Secondly, one faces the possibility of genuine medium effects, such as for example quark-exchange contributions. Furthermore, the electromagnetic coupling to the bound nucleon is dependent on the nuclear dynamics through the self-energy of the nucleon in the nuclear medium

Influence of bone and fat on dose distribution in electron beams in a semi-infinite medium

International Nuclear Information System (INIS)

Sordo, A.

1983-12-01

Hitherto, physical and theoretical aspects of the influence of heterogeneities in radiotherapy by electron beams had not been enough considered. We have developped an experimental method which permitted us to analyze the effect of the hard bone and the fat on the depth dose distributions when an infinite medium is irradiated by high energy electron beams. We have incorporated the KR. HOGSTROM's algorithm in a treatment planning system (TP11; AECL). This algorithm sums the dose distribution of individual pencil beams. A comparison between calculated and measured isodose lines obtained in a heterogeneous medium, shows us the performance and limits of this algorithm [fr

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

DEFF Research Database (Denmark)

Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

2011-01-01

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

Light induced electron transfer reactions of metal complexes

International Nuclear Information System (INIS)

Sutin, N.; Creutz, C.

1980-01-01

Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

International Nuclear Information System (INIS)

Pan Yang; Zhao Junshu; Ji Yuanyuan; Yan Lei; Yu Shuqin

2006-01-01

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields 3 TMB* after rapid intersystem crossing from 1 TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), α-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property (π-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k q T values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k q S have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k q values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation

Defect reactions on the phosphorus sublattice in low-temperature electron-irradiated InP

International Nuclear Information System (INIS)

Sibille, A.; Suski, J.

1985-01-01

This Rapid Communication describes several thermally or electronically stimulated defect reactions involving the dominant deep centers in low-temperature (25--300 K) electron-irradiated InP. Some of these reactions result in an increased concentration of the centers, thereby revealing the existence of a secondary production mechanism of the related defects. Low-energy irradiations allows one to select the type of the ejected atom (P) and gives direct evidence that only a phosphorus species, interstitial or vacancy, is involved in the creation-reaction-annealing events

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...

Wakefields generated by electron beams passing through a waveguide loaded with a slightly dispersive active medium

Directory of Open Access Journals (Sweden)

Andrey V. Tyukhtin

2007-05-01

Full Text Available The wakefields of a relativistic electron beam passing through a waveguide loaded with an active medium with weak resonant dispersion are considered. For the calculations in this paper, the parameters of the medium are those of a solution of fullerene (C_{60} in a nematic liquid crystal that exhibits activity in the X-band. It is shown that several of the TM accelerating modes can be amplified for the geometries under consideration; structures in which higher order modes are amplified exhibit essential advantages as PASERs. In particular, the amplification of the highest mode occurs in a structure loaded with a rather thick active medium layer that maximizes the energy stored by the active medium.

Signatures of quantum radiation reaction in laser-electron-beam collisions

International Nuclear Information System (INIS)

Wang, H. Y.; Yan, X. Q.; Zepf, M.

2015-01-01

Electron dynamics in the collision of an electron beam with a high-intensity focused ultrashort laser pulse are investigated using three-dimensional QED particle-in-cell (PIC) simulations, and the results are compared with those calculated by classical Landau and Lifshitz PIC simulations. Significant differences are observed from the angular dependence of the electron energy distribution patterns for the two different approaches, because photon emission is no longer well approximated by a continuous process in the quantum radiation-dominated regime. The stochastic nature of photon emission results in strong signatures of quantum radiation-reaction effects under certain conditions. We show that the laser spot size and duration greatly influence these signatures due to the competition of QED effects and the ponderomotive force, which is well described in the classical approximation. The clearest signatures of quantum radiation reaction are found in the limit of large laser spots and few cycle pulse durations

One electron reduction and absorption characteristics of Cresyl violet in micellar medium

International Nuclear Information System (INIS)

Gawandi, Vijay B.; Guha, S.N.; Hari Mohan

2000-01-01

Effect of surfactant micelles on absorption characteristics of Cresyl violet (CV) and on its redox reactions have been studied. Among the various surfactants investigated anionic surfactants particularly sodium lauryl sulfate (SLS) and sodium dodecyl benzene sulfonate (SDDBS) showed marked effect on these properties. Reactions of hydrated electron in these micellar media were studied using the technique of nanosecond pulse radiolysis. Results of other surfactants, viz.BSS, CTAB and TritonX-100 have also been presented. (author)

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

Science.gov (United States)

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

High-temperature sensitivity and its acclimation for photosynthetic electron reactions of desert succulents

Energy Technology Data Exchange (ETDEWEB)

Chetti, M.B.; Nobel, P.S. (Univ. of California, Los Angeles (USA))

1987-08-01

Photosynthetic electron reactions of succulent plants from hot deserts are able to tolerate extremely high temperatures and to acclimate to seasonal increase in temperature. In this study, we report the influence of relatively long, in vivo, high-temperature treatments on electron transport reactions for two desert succulents, Agave deserti and Opuntia ficus-indica, species which can tolerate 60{degree}C. Whole chain electron transport averaged 3{degree}C more sensitive to a 1-hour high-temperature treatment than did PSII (Photosystem II) which in turn averaged 3{degree}C more sensitive than did PSI. For plants maintained at day/night air temperatures of 30{degree}C/20{degree}C, treatment at 50{degree}C cause these reactions to be inhibited an average of 39% during the first hour, an additional 31% during the next 4 hours, and 100% by 12 hours. Upon shifting the plants from 30{degree}C/20{degree}C to 45{degree}C/35{degree}C, the high temperatures where activity was inhibited 50% increased 3{degree}C to 8{degree}C for the three electron transport reactions, the half-times for acclimation averaging 5 days for A. deserti and 4 days for O. ficus-indica. For the 45{degree}C/35{degree}C plants treated at 60{degree}C for 1 hour, PSI activity was reduced by 54% for A. deserti and 36% for O. ficus-indica. Acclimation leads to a toleration of very high temperatures without substantial disruption of electron transport for these desert succulents, facilitating their survival in hot deserts. Indeed, the electron transport reactions of these species tolerate longer periods at higher temperatures than any other vascular plants so far reported.

Medium modifications with recoil polarization

Energy Technology Data Exchange (ETDEWEB)

Brand, J.F.J. van den [Nationaal Instituut voor Kernfysica en Hoge Energiefysica, Amsterdam (Netherlands); Ent, R. [CEBAF, Newport News, VA (United States)

1994-04-01

The authors show that the virtual Compton scattering process allows for a precise study of the off-shell electron-nucleon vertex. In a separable model, they show the sensitivity to new unconstrained structure functions of the nucleon, beyond the usual Dirac and Pauli form factors. In addition, they show the sensitivity to bound nucleon form factors using the reaction 4He({rvec e},e{prime},{rvec p}){sup 3}H. A nucleon embedded in a nucleus represents a complex system. Firstly, the bound nucleon is necessarily off-shell and in principle a complete understanding of the dynamical structure of the nucleon is required in order to calculate its off-shell electromagnetic interaction. Secondly, one faces the possibility of genuine medium effects, such as for example quark-exchange contributions. Furthermore, the electromagnetic coupling to the bound nucleon is dependent on the nuclear dynamics through the self-energy of the nucleon in the nuclear medium.

Capturing Chemistry in Action with Electrons: Realization of Atomically Resolved Reaction Dynamics.

Science.gov (United States)

Ischenko, Anatoly A; Weber, Peter M; Miller, R J Dwayne

2017-08-23

One of the grand challenges in chemistry has been to directly observe atomic motions during chemical processes. The depiction of the nuclear configurations in space-time to understand barrier crossing events has served as a unifying intellectual theme connecting the different disciplines of chemistry. This challenge has been cast as an imaging problem in which the technical issues reduce to achieving not only sufficient simultaneous space-time resolution but also brightness for sufficient image contrast to capture the atomic motions. This objective has been met with electrons as the imaging source. The review chronicles the first use of electron structural probes to study reactive intermediates, to the development of high bunch charge electron pulses with sufficient combined spatial-temporal resolution and intensity to literally light up atomic motions, as well as the means to characterize the electron pulses in terms of temporal brightness and image reconstruction. The use of femtosecond Rydberg spectroscopy as a novel means to use internal electron scattering within the molecular reference frame to obtain similar information on reaction dynamics is also discussed. The focus is on atomically resolved chemical reaction dynamics with pertinent references to work in other areas and forms of spectroscopy that provide additional information. Effectively, we can now directly observe the far-from-equilibrium atomic motions involved in barrier crossing and categorize chemistry in terms of a power spectrum of a few dominant reaction modes. It is this reduction in dimensionality that makes chemical reaction mechanisms transferrable to seemingly arbitrarily complex (large N) systems, up to molecules as large as biological macromolecules (N > 1000 atoms). We now have a new way to reformulate reaction mechanisms using an experimentally determined dynamic mode basis that in combination with recent theoretical advances has the potential to lead to a new conceptual basis for

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

Science.gov (United States)

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Desulfurization reaction of high sulfur content flue gas treated by electron beam

International Nuclear Information System (INIS)

Hirosawa, Shojiro; Suzuki, Ryoji; Aoki, Shinji; Kojima, Takuji; Hashimoto, Shoji

2002-01-01

Experiments of flue gas treatment by electron beam were carried out, using simulated ligniteburning flue gas containing SO 2 (5500 ppm), NO (390 ppm) and H 2 O (22%). Removal efficiency of SO 2 was more than 90% at a dose of 1-2 kGy. It shows applicability of electron beam for treatment of lignite-burning flue gas. Another removal reaction besides the radiation-induced radical reaction and the thermal reaction occurring without irradiation was suggested by the facts that removal of SO 2 by the radical reaction is only a few hundreds of ppm and the removal amounts by thermal reaction under irradiation is lower than a half of total desulfurization. The mechanism similar to thermal reaction was proposed, assuming simultaneous uptake reaction of SO 2 and NH 3 on the surface of liquid aerosol. It was suggested that ammonium nitrate having deliquescence relative humidity (DRH) of 60% at 25 deg C plays an important role in producing liquid aerosols. Decrease of DRH of ammonium nitrate with elevating temperature and with formation of double salt of ammonium sulfate results in enhancement of formation of liquid aerosols. (author)

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum

International Nuclear Information System (INIS)

Cames, B.

1997-01-01

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media (≤ 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 ≤ E ≤ 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

Electronically stimulated deep-center reactions in electron-irradiated InP: Comparison between experiment and recombination-enhancement theories

International Nuclear Information System (INIS)

Sibille, A.

1987-01-01

We present a detailed study of the recombination enhancement of several defect reactions involving the main deep centers in low-temperature electron-irradiated InP. A fairly good agreement is obtained with the Weeks-Tully-Kimerling theory for the activation energies of the enhanced process. On the other hand, a thorough investigation of a thermally and electronically stimulated defect transformation shows evidence that one major approximation (local vibrational equilibrium) fails, and that the recently proposed [H. Sumi, Phys. Rev. B 29, 4616 (1984)] mechanism of coherent recombination on deep centers is responsible for altered reaction rates at high injection levels

On the length dependence of bridge-mediated electron transfer reactions

International Nuclear Information System (INIS)

Petrov, E.G.; Shevchenko, Ye.V.; May, V.

2003-01-01

Bridge-mediated nonadiabatic donor-acceptor (D-A) electron transfer (ET) is studied for the case of a regular molecular bridge of N identical units. It is shown that the multi-exponential ET kinetics reduces to a single-exponential transfer if, and only if, the integral population of the bridge remains small (less than 10 -2 ). An analytical expression for the overall D-A ET rate is derived and the necessary and sufficient conditions are formulated at which the rate is given as a sum of a superexchange and a sequential contribution. To describe experimental data on the N-dependence of ET reactions an approximate form of the overall transfer rate is derived. This expression is used to reproduce experimental data on distant ET through polyproline chains. Finally it is noted that the obtained analytical results can also be used for the description of more complex two-electron transfer reactions if the latter comprises separate single-electron pathways

Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

Science.gov (United States)

Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

2015-01-01

Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

Chemical Reactions of Molecules Promoted and Simultaneously Imaged by the Electron Beam in Transmission Electron Microscopy.

Science.gov (United States)

Skowron, Stephen T; Chamberlain, Thomas W; Biskupek, Johannes; Kaiser, Ute; Besley, Elena; Khlobystov, Andrei N

2017-08-15

The main objective of this Account is to assess the challenges of transmission electron microscopy (TEM) of molecules, based on over 15 years of our work in this field, and to outline the opportunities in studying chemical reactions under the electron beam (e-beam). During TEM imaging of an individual molecule adsorbed on an atomically thin substrate, such as graphene or a carbon nanotube, the e-beam transfers kinetic energy to atoms of the molecule, displacing them from equilibrium positions. Impact of the e-beam triggers bond dissociation and various chemical reactions which can be imaged concurrently with their activation by the e-beam and can be presented as stop-frame movies. This experimental approach, which we term ChemTEM, harnesses energy transferred from the e-beam to the molecule via direct interactions with the atomic nuclei, enabling accurate predictions of bond dissociation events and control of the type and rate of chemical reactions. Elemental composition and structure of the reactant molecules as well as the operating conditions of TEM (particularly the energy of the e-beam) determine the product formed in ChemTEM processes, while the e-beam dose rate controls the reaction rate. Because the e-beam of TEM acts simultaneously as a source of energy for the reaction and as an imaging tool monitoring the same reaction, ChemTEM reveals atomic-level chemical information, such as pathways of reactions imaged for individual molecules, step-by-step and in real time; structures of illusive reaction intermediates; and direct comparison of catalytic activity of different transition metals filmed with atomic resolution. Chemical transformations in ChemTEM often lead to previously unforeseen products, demonstrating the potential of this method to become not only an analytical tool for studying reactions, but also a powerful instrument for discovery of materials that can be synthesized on preparative scale.

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

Science.gov (United States)

Mojica, Martha; Méndez, Francisco; Alonso, Julio A

2016-02-12

The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

Voltammetric detection of the interactions between RNO2?- and electron acceptors in aqueous medium at highly boron doped diamond electrode (HBDDE)

International Nuclear Information System (INIS)

Juliao, Murilo S. da S.; Ferreira, Elizabeth I.; Ferreira, Neidenei G.; Serrano, Silvia H.P.

2006-01-01

This paper describes the electrochemical behavior of the nitrofurazone (NFZ), in predominantly aqueous medium, in the absence and presence of glutathione (reduced form) (GSH), l-cysteine (Cys) and O 2 using a highly boron doped diamond electrode (HBDDE). In presence of [Thiol]>=3.7x10 -2 molL -1 NFZ is directly reduced to RNO-Thiol adducts in an electrochemical process involving two electrons and two protons. On the other side, O 2 acts as a RNO 2 *- scavenger and the velocity constant for the reaction, k O 2 , is 60Lmol -1 s -1 . The process is catalytic and can be used to the analytical determination of NFZ in the range of 9.9x10 -7 -bar [NFZ]-bar 1.1x10 -5 molL -1 at pH 8.0, with sensitivity of 2.2x10 6 μAmol -1 cm -2 and detection limit of 3.4x10 -7 molL -1 . The analytical parameters were similar to those obtained at pH 4.0 using the direct reduction of NFZ to the respective amine derivative in a process involving six electrons and six protons. The characterization of NFZ global reduction process in aqueous medium and at relative low scan rate, 100mVs -1 , was only possible due the intrinsic superficial characteristics of the HBDDE, which stabilize the RNO 2 ? - free radical, allowing to work in a large potential window, without losing the RNO 2 ? - oxidation signal

Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

International Nuclear Information System (INIS)

Santos, Elizabeth; Schmickler, Wolfgang

2008-01-01

A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

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

Energy Technology Data Exchange (ETDEWEB)

Sun, Yuming, E-mail: ymsun@ytu.edu.cn; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian

2016-10-20

Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C{sub 2}-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What’s more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

Pauli-blocking effect in two-body collisions dominates the in-medium effects in heavy-ion reactions near Fermi energy

Energy Technology Data Exchange (ETDEWEB)

Xing, Yong-Zhong, E-mail: yzxing@tsnu.edu.cn [Institute for the Fundamental Physics, Tianshui Normal University, Gansu, Tianshui 741000 (China); Zhang, H.F. [Institute for the Fundamental Physics, Tianshui Normal University, Gansu, Tianshui 741000 (China); School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Liu, Xiao-Bin [Institute for the Fundamental Physics, Tianshui Normal University, Gansu, Tianshui 741000 (China); Zheng, Yu-Ming [Institute for the Fundamental Physics, Tianshui Normal University, Gansu, Tianshui 741000 (China); China Institute of Atomic Energy, P.O. Box 275(18), Beijing 102413 (China)

2017-01-15

The dissipation phenomenon in the heavy-ion reaction at incident energy near Fermi energy is studied by simulating the reactions {sup 129}Xe + {sup 129}Sn and {sup 58}Ni + {sup 58}Ni with isospin-dependent quantum molecular dynamics model (IQMD). The isotropy ratio in terms of transverse and longitudinal energies of the free protons emitted in the final states of these reactions is quantitatively analyzed to explore the in-medium correlation of the binary collisions. Comparison of the calculations with the experimental data recently released by INDRA collaboration exhibits that the ratio is very sensitive to the Pauli blocking effect in two-body collisions and Pauli exclusion principle is indispensable in the theoretical simulations for the heavy-ion reactions near the Fermi energy.

Performance of a Polarized Deuterium Internal Target in a Medium-Energy Electron Storage Ring.

NARCIS (Netherlands)

Zhou, Z.L.; Ferro Luzzi, M.M.E.; van den Brand, J.F.J.; Bulten, H.J.; Alarcon, R.; van Bommel, R.; Botto, T.; Bouwhuis, M.; Buchholz, M.; Choi, S.; Comfort, J.; Doets, M.; Dolfini, S.; Ent, R.; Gaulard, C.; de Jager, C.W.; Lang, J.; de Lange, D.J.; Miller, M.A.; Passchier, E.; Passchier, I.; Poolman, H.R.; Six, E.; Steijger, J.J.M.; Unal, O.; de Vries, H.

1996-01-01

A polarized deuterium target internal to a medium-energy electron storage ring is described in the context of spindependent (e, e′d) and (e ,e′p) experiments. Tensor polarized deuterium was produced in an atomic beam source and injected into a storage cell target. A Breit-Rabi polarimeter was used

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

Science.gov (United States)

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

Directory of Open Access Journals (Sweden)

Alex Petrovici

2014-09-01

Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

Presolvated electron reactions with methyl acetoacetate: electron localization, proton-deuteron exchange, and H-atom abstraction.

Science.gov (United States)

Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D

2014-09-01

Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•--CH2-COOCH3) in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-COOCH3. The ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments.

Coherently enhanced radiation reaction effects in laser-vacuum acceleration of electron bunches

NARCIS (Netherlands)

Smorenburg, P.W.; Kamp, L.P.J.; Geloni, G.; Luiten, O.J.

2010-01-01

The effects of coherently enhanced radiation reaction on the motion of subwavelength electron bunches in interaction with intense laser pulses are analyzed. The radiation reaction force behaves as a radiation pressure in the laser beam direction, combined with a viscous force in the perpendicular

Kinetics of the reactions of hydrated electrons with metal complexes

International Nuclear Information System (INIS)

Korsse, J.

1983-01-01

The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

Directory of Open Access Journals (Sweden)

Patrice Vanelle

2002-12-01

Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

In-medium NN interactions and nucleon and meson masses studied with nucleon knockout reactions

CERN Document Server

Noro, T; Akiyoshi, H; Daito, I; Fujimura, H; Hatanaka, K; Ihara, F; Ishikawa, T; Ito, M; Kawabata, M; Kawabata, T; Maeda, Y; Matsuoka, N; Morinobu, S; Nakamura, M; Obayashi, E; Okihana, A; Sagara, K; Sakaguchi, H; Takeda, H; Taki, T; Tamii, A; Tamura, K; Yamazaki, H; Yoshida, H; Yoshimura, M; Yosoi, M

2000-01-01

Spin observables have been measured for (p, 2p) reactions aiming at studying medium effects on NN interactions in nuclear field. Observed strong density-dependent reduction of the analyzing power is consistent with a model calculation where reduction of nucleon and meson masses are taken into account. On the other hand, calculations with g-matrices in the Shroedinger framework does not predict the reduction. The spin-transfer coefficients, which data are not reproduced by the model calculation, are found to be sensitive to reduction rate of each meson mass and have a possibility to test scaling lows in mass reductions.

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

International Nuclear Information System (INIS)

Mandal, Paulami; Tiwari, Sanat Kumar; Ganguly, Tapan; Sinha, Subrata

2009-01-01

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (-1.15 eV) and charge recombination reaction (-1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.

The reactions of loaded carbon nanotubes, studied by novel electron microscope techniques

International Nuclear Information System (INIS)

Rawcliffe, A.

1999-01-01

A novel electron microscope technique, controlled environment transmission electron microscopy (CETEM), has been used to investigate the reaction of materials loaded within the internal cavities of carbon nanotubes. CETEM allows the introduction of up to 20 mbar of gas around an electron microscope sample, while maintaining a high resolution imaging capability. The microscope is stable, flexible and reliable under these conditions and high resolution images of encapsulated transmission metal oxide reduction have been recorded at 460 deg. C. Recently discovered carbon nanotubes have in theory many applications, many of which will require controlled reliable loading of the internal cavity. However, at present, there is little experimental evidence to confirm theoretical descriptions of the fundamental mechanisms which govern both the extent of loading and the state in which it is found. Similarly, reaction within the cavity and the effect of encapsulation on the nano-scale particle distribution must also be understood, and CETEM proves to be an ideal technique for the study of these processes. Nanotubes have been loaded from aqueous solution with (NH 4 ) 2 IrCI 6 and with molten MoO 3 or K 2 WO 4 /WO 3 . Bulk samples of the first salt are known to decompose spontaneously in air at 200 deg. C, and the bulk oxides are partially reduced at temperature under hydrogen to give potentially useful conducting phases. Comparing the reaction of these materials it is thus possible to: investigate the effect of loading on their reaction; compare the reaction of these materials in- and out-side the tube cavity; and assess the result of violent loading processes on the tubes themselves. Fortuitously, a spontaneous decomposition, a solid-gas reduction and a phase rearrangement were all recorded, allowing mechanistic implications of encapsulation to be considered for each of these reactions. Perhaps surprisingly, the results can be largely interpreted using the reported bulk

Picosecond pulse radiolysis study of primary reactions in solutions

International Nuclear Information System (INIS)

El-Omar, Abdel Karim

2013-01-01

Following the discovery of ionizing radiations and their chemical effects, it was important to study and comprehend the formation mechanisms of short lived free radicals and molecular products. In order to perform such studies, researchers and research groups worked on developing tools allowing both formation and detection of those species at short time scales. Nowadays, pulse radiolysis imposed itself as a fundamental and efficient tool allowing scientists to probe chemical effects as well as reaction mechanisms in studied media. The Laboratoire de Chimie Physique d'Orsay 'LCP' is an interdisciplinary laboratory hosting the platform of fast kinetics known as 'ELYSE'. Due to its femtosecond laser and its picosecond electron accelerator, we have the possibility to study chemical effects of ionizing radiations interaction with media at ultrashort times up to ∼5 ps.Knowing that we are interested in primary reactions induced in aqueous media by ionizing radiations, ELYSE represents the essential tool in performing our studies. The obtained results concern:- First direct determination of hydroxyl radical 'HO*' radiolytic yield as function of time at picosecond time scale;- Direct effect of ionizing radiation in highly concentrated aqueous solutions as well as investigation of the ultrafast electron transfer reaction between solute molecules and positive holes 'H 2 O*+' formed upon water radiolysis;- Study at room temperature of electron transfer reaction between solvated electron (electron donor) and organic solutes (electron acceptors) en viscous medium;- Study at room temperature of electron's solvation dynamics in ethylene glycol and 2-propanol. (author)

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

Science.gov (United States)

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Electron exchange reaction in anion exchangers as observed in uranium isotope separation

International Nuclear Information System (INIS)

Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

1991-01-01

The mechanism of electron exchange in an ion exchanger, as occurring between U 4+ and UO 2 2+ in uranium isotope separation, was investigated. The height of the separation unit (H q ) in the presence of metal ion catalysts, as obtained from the separation experiments, was found to be almost coincident with the theoretical value of H q as calculated on the basis of the intrasolution acceleration mechanism of the metal ion, suggesting that the electron exchange mechanism in the ion-exchanger is essentially the same as that in the solution when metal ion catalysts are present. Separation experiments with no metal ion catalyst, on the other hand, showed the electron exchange reaction in the ion exchanger to be substantially higher than that in the solution, suggesting an acceleration of the electron exchange reaction by the ion-exchanger which is due to the close existence of higher order Cl - complexes of UO 2 2+ and U 4+ in the vicinity of the ion-exchange group. (author)

Electronic nicotine delivery system (electronic cigarette) awareness, use, reactions and beliefs: a systematic review

Science.gov (United States)

Pepper, Jessica K; Brewer, Noel T

2015-01-01

Objective We sought to systematically review the literature on electronic nicotine delivery systems (ENDS, also called electronic cigarettes) awareness, use, reactions and beliefs. Data sources We searched five databases for articles published between 2006 and 1 July 2013 that contained variations of the phrases ‘electronic cigarette’, ‘e-cigarette’ and ‘electronic nicotine delivery’. Study selection Of the 244 abstracts identified, we excluded articles not published in English, articles unrelated to ENDS, dissertation abstracts and articles without original data on prespecified outcomes. Data extraction Two reviewers coded each article for ENDS awareness, use, reactions and beliefs. Data synthesis 49 studies met inclusion criteria. ENDS awareness increased from 16% to 58% from 2009 to 2011, and use increased from 1% to 6%. The majority of users were current or former smokers. Many users found ENDS satisfying, and some engaged in dual use of ENDS and other tobacco. No longitudinal studies examined whether ENDS serve as ‘gateways’ to future tobacco use. Common reasons for using ENDS were quitting smoking and using a product that is healthier than cigarettes. Self-reported survey data and prospective trials suggest that ENDS might help cigarette smokers quit, but no randomised controlled trials with probability samples compared ENDS with other cessation tools. Some individuals used ENDS to avoid smoking restrictions. Conclusions ENDS use is expanding rapidly despite experts’ concerns about safety, dual use and possible ‘gateway’ effects. More research is needed on effective public health messages, perceived health risks, validity of self-reports of smoking cessation and the use of different kinds of ENDS. PMID:24259045

Medium-energy electrons and heavy ions in Jupiter's magnetosphere - Effects of lower hybrid wave-particle interactions

Science.gov (United States)

Barbosa, D. D.

1986-01-01

A theory of medium-energy (about keV) electrons and heavy ions in Jupiter's magnetosphere is presented. Lower hybrid waves are generated by the combined effects of a ring instability of neutral wind pickup ions and the modified two-stream instability associated with transport of cool Iogenic plasma. The quasi-linear energy diffusion coefficient for lower hybrid wave-particle interactions is evaluated, and several solutions to the diffusion equation are given. Calculations based on measured wave properties show that the noise substantially modifies the particle distribution functions. The effects are to accelerate superthermal ions and electrons to keV energies and to thermalize the pickup ions on time scales comparable to the particle residence time. The S(2+)/S(+) ratio at medium energies is a measure of the relative contribution from Iogenic thermal plasma and neutral wind ions, and this important quantity should be determined from future measurements. The theory also predicts a preferential acceleration of heavy ions with an accleration time that scales inversely with the root of the ion mass. Electrons accelerated by the process contribute to further reionization of the neutral wind by electron impact, thus providing a possible confirmation of Alfven's critical velocity effect in the Jovian magnetosphere.

Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

International Nuclear Information System (INIS)

Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

1987-01-01

We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

Control of chemical reactions with electron beams; Kontrolle chemischer Reaktionen mit Elektronenstrahlung

Energy Technology Data Exchange (ETDEWEB)

Boehler, Esther

2014-03-18

Interaction between low-energy electrons and molecules can lead to dissociative electron attachment (DEA) or dissociative ionization (DI). In condensed matter, the resulting reactive fragments can attack adjacent molecules to yield larger products. In this thesis, reactions initiated by DEA to acetonitrile in condensed phase have been compared to the known gas phase fragmentation channels. Also, gas phase DEA experiments have been performed on chlorosilanes to study the effect of a variation of the organic ligands on the energy of their molecular orbitals and reactivity in DEA processes. Furthermore, hydroamination reactions induced by DI for different alkenes and amines have been investigated. A similar reaction of ammonia and carbon monoxide was shown to produce formamide (HCONH2), which is the smallest molecule to contain a peptide bond and thus represents an important building block of biologically relevant substances.

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

International Nuclear Information System (INIS)

Laursen, S.L.

1990-01-01

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom ''sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

Energy Technology Data Exchange (ETDEWEB)

Laursen, S.L.

1990-01-01

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

Science.gov (United States)

Gamov, G. A.; Zavalishin, M. N.; Usacheva, T. R.; Sharnin, V. A.

2017-05-01

Thermodynamic characteristics of the formation of the Schiff base between isoniazid and pyridoxal 5'-phosphate in an aqueous solution at different pH values of a medium are determined by means of spectrophotometry and calorimetric titration. The process kinetics is studied spectrophotometrically, and the reaction rate constants for the formation of the imine at different acidities of a medium are determined. Biochemical aspects of the binding of pyridoxal 5'-phosphate into stable compounds are discussed.

Electron transfer reactions of macrocyclic compounds of cobalt

Energy Technology Data Exchange (ETDEWEB)

Heckman, R.A.

1978-08-01

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

Nobel Prize 1992: Rudolph A. Marcus: theory of electron transfer reactions in chemical systems

International Nuclear Information System (INIS)

Ulate Segura, Diego Guillermo

2011-01-01

A review of the theory developed by Rudolph A. Marcus is presented, who for his rating to the theory of electron transfer in chemical systems was awarded the Nobel Prize in Chemistry in 1992. Marcus theory has constituted not only a good extension of the use of a spectroscopic principle, but also has provided an energy balance and the application of energy conservation for electron transfer reactions. A better understanding of the reaction coordinate is exposed in terms energetic and establishing the principles that govern the transfer of electrons, protons and some labile small molecular groups as studied at present. Also, the postulates and equations described have established predictive models of reaction time, very useful for industrial environments, biological, metabolic, and others that involve redox processes. Marcus theory itself has also constituted a large contribution to the theory of complex transition [es

Polyethylene Glycol (PEG-400: An Efficient and Recyclable Reaction Medium for the Synthesis of Pyrazolo[3,4-b]pyridin-6(7H-one Derivatives

Directory of Open Access Journals (Sweden)

Deming Wang

2013-10-01

Full Text Available A mild and efficient synthesis of pyrazolo[3,4-b]pyridine-6(7H-one derivatives via a three-component reaction of an aldehyde, Meldrum’s acid and 3-methyl-1H-pyrazol-5-amine using recyclable polyethylene glycol (PEG-400 as a reaction medium is described. This method has the advantages of accessible starting materials, good yields, mild reaction conditions and begin environmentally friendly.

Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

Science.gov (United States)

Andrés, Juan; Berski, Sławomir; Silvi, Bernard

2016-07-07

Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

International Nuclear Information System (INIS)

Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

2016-01-01

We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

DEFF Research Database (Denmark)

Olsen, Thomas; Schiøtz, Jakob

2009-01-01

A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such...... density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

Energy Technology Data Exchange (ETDEWEB)

Pan Yang [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Zhao Junshu [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Ji Yuanyuan [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yan Lei [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yu Shuqin [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China)], E-mail: sqyu@ustc.edu.cn

2006-01-05

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields {sup 3}TMB* after rapid intersystem crossing from {sup 1}TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), {alpha}-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property ({pi}-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k{sub q}{sup T} values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k{sub q}{sup S} have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k{sub q} values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation.

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

Science.gov (United States)

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

Electronic nicotine delivery system (electronic cigarette) awareness, use, reactions and beliefs: a systematic review.

Science.gov (United States)

Pepper, Jessica K; Brewer, Noel T

2014-09-01

We sought to systematically review the literature on electronic nicotine delivery systems (ENDS, also called electronic cigarettes) awareness, use, reactions and beliefs. We searched five databases for articles published between 2006 and 1 July 2013 that contained variations of the phrases 'electronic cigarette', 'e-cigarette' and 'electronic nicotine delivery'. Of the 244 abstracts identified, we excluded articles not published in English, articles unrelated to ENDS, dissertation abstracts and articles without original data on prespecified outcomes. Two reviewers coded each article for ENDS awareness, use, reactions and beliefs. 49 studies met inclusion criteria. ENDS awareness increased from 16% to 58% from 2009 to 2011, and use increased from 1% to 6%. The majority of users were current or former smokers. Many users found ENDS satisfying, and some engaged in dual use of ENDS and other tobacco. No longitudinal studies examined whether ENDS serve as 'gateways' to future tobacco use. Common reasons for using ENDS were quitting smoking and using a product that is healthier than cigarettes. Self-reported survey data and prospective trials suggest that ENDS might help cigarette smokers quit, but no randomised controlled trials with probability samples compared ENDS with other cessation tools. Some individuals used ENDS to avoid smoking restrictions. ENDS use is expanding rapidly despite experts' concerns about safety, dual use and possible 'gateway' effects. More research is needed on effective public health messages, perceived health risks, validity of self-reports of smoking cessation and the use of different kinds of ENDS. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

One-electron oxidation reactions of purine and pyrimidine bases in cellular DNA.

Science.gov (United States)

Cadet, Jean; Wagner, J Richard; Shafirovich, Vladimir; Geacintov, Nicholas E

2014-06-01

The aim of this survey is to critically review the available information on one-electron oxidation reactions of nucleobases in cellular DNA with emphasis on damage induced through the transient generation of purine and pyrimidine radical cations. Since the indirect effect of ionizing radiation mediated by hydroxyl radical is predominant in cells, efforts have been made to selectively ionize bases using suitable one-electron oxidants that consist among others of high intensity UVC laser pulses. Thus, the main oxidation product in cellular DNA was found to be 8-oxo-7,8-dihydroguanine as a result of direct bi-photonic ionization of guanine bases and indirect formation of guanine radical cations through hole transfer reactions from other base radical cations. The formation of 8-oxo-7,8-dihydroguanine and other purine and pyrimidine degradation products was rationalized in terms of the initial generation of related radical cations followed by either hydration or deprotonation reactions in agreement with mechanistic pathways inferred from detailed mechanistic studies. The guanine radical cation has been shown to be implicated in three other nucleophilic additions that give rise to DNA-protein and DNA-DNA cross-links in model systems. Evidence was recently provided for the occurrence of these three reactions in cellular DNA. There is growing evidence that one-electron oxidation reactions of nucleobases whose mechanisms have been characterized in model studies involving aqueous solutions take place in a similar way in cells. It may also be pointed out that the above cross-linked lesions are only produced from the guanine radical cation and may be considered as diagnostic products of the direct effect of ionizing radiation.

Linear-dendritic supramolecular complexes as nanoscale reaction vessels for "green" chemistry. Diels-Alder reactions between fullerene C60 and polycyclic aromatic hydrocarbons in aqueous medium.

Science.gov (United States)

Simonyan, Arsen; Gitsov, Ivan

2008-10-21

This study describes the first Diels-Alder (DA) reaction performed in aqueous medium with highly hydrophobic compounds-fullerene (C 60) as the dienophile and anthracene (An) or tetracene (Tet) as the dienes, respectively. The reactions are performed in nanocontainers, constructed by self-assembly of linear-dendritic amphiphilic copolymers with poly(ethylene glycol), PEG or poly(ethylene oxide), PEO as the hydrophilic blocks and poly(benzyl ether) monodendrons as the hydrophobic fragments: G3PEO13k, dG3 and dG2. Comparative studies under identical conditions are carried out with an amphiphilic linear-linear copolymer, poly(styrene)1800- block-PEO2100, PSt-PEO, and the nonionic surfactant Igepal CO-720, IP720. The binding affinity of supermolecules built of these amphiphiles toward the DA reagents decreases in the following order: G3PEO13k > dG3 > PSt-PEO > dG2 > IP720. The kinetic constant of binding is evaluated for tetracene and decreases in a similar fashion: 5 x 10 (-7) M/min (G3PEO13k), through 4 x 10 (-7) M/min (PSt-PEO) down to 1.5 x 10 (-7) M/min for IP720. The mobility of substrates encapsulated in the micellar core, estimated by pyrene fluorescence decay, is 95-121 ns for the micelles of the linear-dendritic copolymers and notably higher for PSt-PEO (152 ns), revealing the much denser interior of the linear analogue. The apparent kinetic constant for the DA reaction of C 60 and Tet within the G3PEO13k supermolecule in aqueous medium is markedly higher than in organic solvent (toluene), 208 vs 1.82 M /min. With G3PEO13k the conversions reach 49% for the DA reaction between C 60 and An, and 55% for C 60 and Tet. Besides the monoadduct (26.5% yield) the reaction with An produces exclusively increasing amounts of D 2 h -symmetric antipodal bis-adduct, whose yield reaches up to 22.5% after 48 h. In addition to the environmentally friendly conditions notable advantages of the synthetic strategy described are the extended stability of the linear

Some experiments on the primary electron acceptor in reaction centres from Rhodopseudomanas sphaeroides

Energy Technology Data Exchange (ETDEWEB)

Wraight, C A; Cogdell, R J; Clayton, R K

1975-01-01

The bacterial reaction center absorbance change at 450 nm (A-450), assigned to an anionic semiquinone, has been suggested as a candidate for the reduced form of the primary electron acceptor in bacterial photosynthesis. In reaction centers of Rhodopseudomonas sphaeroides we have found kinetic discrepancies between the decay of A-450 and the recovery of photochemical competence. In addition, no proton uptake is measurable on the first turnover, although subsequent ones elicit one proton bound per electron. These results are taken to indicate that the acceptor reaction after a long dark period may be different for the first turnover than for subsequent ones. It is suggested that A-450 is still a likely candidate for the acceptor function but that in reaction centers, additional quinone may act as an adventitious primary acceptor when the ''true'' primary acceptor is reduced. Alternatively, the primary acceptor may act in a ''ping-pong'' fashion with respect to subsequent photoelectrons.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

NARCIS (Netherlands)

Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-01-01

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

Science.gov (United States)

Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

2018-04-01

In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize

Plasmonic photocatalytic reactions enhanced by hot electrons in a one-dimensional quantum well

Directory of Open Access Journals (Sweden)

H. J. Huang

2015-11-01

Full Text Available The plasmonic endothermic oxidation of ammonium ions in a spinning disk reactor resulted in light energy transformation through quantum hot charge carriers (QHC, or quantum hot electrons, during a chemical reaction. It is demonstrated with a simple model that light of various intensities enhance the chemical oxidization of ammonium ions in water. It was further observed that light illumination, which induces the formation of plasmons on a platinum (Pt thin film, provided higher processing efficiency compared with the reaction on a bare glass disk. These induced plasmons generate quantum hot electrons with increasing momentum and energy in the one-dimensional quantum well of a Pt thin film. The energy carried by the quantum hot electrons provided the energy needed to catalyze the chemical reaction. The results indicate that one-dimensional confinement in spherical coordinates (i.e., nanoparticles is not necessary to provide an extra excited state for QHC generation; an 8 nm Pt thin film for one-dimensional confinement in Cartesian coordinates can also provide the extra excited state for the generation of QHC.

Pulse radiolysis study of reaction of bull serum albumin electron adduct with oxygen. Polychromatic kinetics of reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

By the method of pulse radiolysis the reaction of bull serum albumin electron adduct with oxygen is investigated. As pulsed radiation source electron linear accelerators with particle energy of 8.0 and 4.5 MeV and pulse time of 40 ns and 2.2 μs, respectively have been used. It is assumed that the disappearance of protein electron adduct occurs in the course of its interaction with oxygen adsorbed on protein globular molecule

Electron transfer reactions induced by the triplet state of thiacarbocyanine dimers

International Nuclear Information System (INIS)

Chibisov, Alexander K.; Slavnova, Tatyana D.; Goerner, Helmut

2004-01-01

The photoinduced electron transfer between either cationic 5,5 ' -dichloro-3,3 ' ,9-triethylthiacarbocyanine (1) or a structurally similar anionic dye (2) and appropriate donors, e.g. ascorbic acid, and acceptors, e.g. methyl viologen, was studied by ns-laser photolysis. In aqueous solution the dyes in the ground state are present as an equilibrated mixture of dimers and monomers, whereas the triplet state is mainly populated from dimers. The triplet states of both dimers and monomers are quenched by electron donors or acceptors and the rate constant for quenching is generally 2-4 times higher for dimers than for monomers. The kinetics of triplet decay and radical formation and decay as a result of primary and secondary electron transfer were analyzed. While the one-electron reduced dimer decays due to back reactions, the one-electron oxidized dimer rapidly dissociates into the monomer and the monomeric dye radical. For the dimeric dye/donor/acceptor systems the primary photoinduced electron transfer occurs either from the donor or to the acceptor yielding the dimeric dye radicals. The one-electron reduced dimer can be efficiently oxidized by acceptors, e.g. the rate constant for reaction of the dimeric dye radical of 1 with methyl viologen (photoreductive pathway of sensitization) is 1.6x10 9 M -1 s -1 . The photooxidative pathway of sensitization is more complicated; after dissociation of the dimeric dye radical, the monomeric dye radical is reduced in a secondary electron transfer from ascorbic acid, e.g. with a rate constant of 1x10 9 M -1 s -1 for 2, yielding the monomer. On increasing the donor concentration the photooxidative pathway of sensitization is switched to a photoreductive one

Reactions of metal-substituted myoglobins with excess electrons studied by pulse radiolysis and low-temperature gamma-radiolysis

International Nuclear Information System (INIS)

Miki, Hideho; Nakajima, Atushi; Ogasawara, Masaaki; Tamura, Mamoru

1990-01-01

Reactions of metal-substituted myoglobins with excess electrons in electron-pulse-irradiated aqueous solutions at room temperature and γ-irradiated aqueous matrices at 77 K were studied for the purpose of probing the functional role of heme iron. The rate constants for the reactions of various myoglobins with hydrated electrons were not much different from each other, and were close to those of diffusion-controlled reactions. In contrast, the reduction rates of myoglobins with dithionite depended markedly on the kind of central metals in the myoglobins. The difference was interpreted in terms of Marcus' theory for electron-transfer reactions. Effects of the 6-coordinate structure of the cobalt(III) species on the reaction with dithionite was also discussed. The steady-state optical-absorption measurements of γ-irradiated matrices containing cobaltimyoglobin at 77 K demonstrated the reduction of cobalt(III) species by excess electrons produced by the action of ionizing radiation. It was shown, by electron-spin resonance spectroscopy, that a 6-coordinated cobalt(II) species produced at 77 K transformed to a 5-coordinate one at higher temperatures, as reported previously. However, structural relaxation was not observed by optical spectroscopy either in the solutions or in the low-temperature matrices. It was concluded, therefore, that the intermediate 6-coordinate cobalt(II) species gave an optical absorption spectrum which was indistinguishable from that of the relaxed 5-coordinate cobalt(II) species. (author)

(4+2) Cycloaddition reactions with inverse electron demand of nitrogen bearing, heteroaromatic cations

International Nuclear Information System (INIS)

Ritzberger-Baumgartner, W.

1996-06-01

Three cationic, heteroaromatic diene-systems (1, 2, 3, 4-tetramethoxycarbonyl-quinolizinium-tetrafluoroborate (M), 8, 9, 10, 11-tetrarnethoxycarbonylpyrido[2,1-a]-isoquinolinium-TFB and triazolo[1,5-b]isoquinolinium-TFBs) and a cationic, non-aromatic diene (2,5,5-trimethyl-3-oxo-1, 2, 4-triazolium-TFB) were synthesized. The dienes were employed successfully in cycloaddition reactions with a number ofconjugated dienophiles (including norbornene). The mechanism underlying these cycloaddition reactions was discussed in the theoretical section. At first quantumchemical calculations of the frontier orbital energies provided the proof, that the reactions followed the pattern of reactions with inverse electron demand. Calculation of the charge distribution and of the orbital coefficients led to the conclusion, that these reactions are mainly orbital controlled. Two mechanistic variants were in discussion. Either the reactions proceed in a concerted manner resembling the Diels-Alder reaction with inverse electron demand or in two distinct steps with the formation of a cationic intermediate following the attack of the heterodienes acting as weak electrophiles at the dienophiles being weak nucleophiles. Calculations of a possible transition state of these cycloaddition reactions revealed a pronounced preference for the formation of the bond between the logical reaction centers in the first step of a two-step reaction. However, experimental and theoretical findings led to the conviction, that cationic polar cycloaddition reactions proceed exactly along the crossroad between a concerted and a two-step mechanism and depending on the electrophilic strength of the diene and the nucleophilic strength of the dienophile these reactions show more characteristics of one of the two mechanistic possibilities. The high regioselectivity as well as the high stereoselectivity could be explained satisfactory with the help of the calculated orbital coefficients. (author)

Supercritical CO2 as a reaction medium for synthesis of capsaicin analogues by lipase-catalyzed transacylation of capsaicin.

Science.gov (United States)

Kobata, Kenji; Kobayashi, Mamiko; Kinpara, Sachiyo; Watanabe, Tatsuo

2003-09-01

Capsaicin analogues having different acyl moiety were synthesized by lipase-catalyzed transacylation of capsaicin with a corresponding acyl donor in supercritical CO2 as a reaction medium. Transacylation with methyl tetradecanoate using Novozym 435 as a catalyst gave vanillyl tetradecanamide in a 54% yield at 80 degrees C and 19 MPa over 72 h. Vanillyl (Z)-9-octadecenamide, olvanil, was synthesized from triolein in a 21% yield over 7 d.

Experimental study of high spin states in low-medium mass nuclei by use of charge particle induced reactions

International Nuclear Information System (INIS)

Alenius, N.G.

1975-01-01

For the test of nuclear models the study of the properties of nuclear states of high angular momentum is especially important, because such states can often be given very simple theoretical descriptions. High spin states are easily populated by use of reactions initiated by alpha particles or heavy ions. In this thesis a number of low-medium mass nuclei have been studied, with emphasis on high spin states. (Auth.)

Photochemical and radiation chemistry investigations of reaction kinetics of dissolved electrons in water and ammonium-water mixtures

International Nuclear Information System (INIS)

Telser, T.

1986-01-01

In the reaction of hydrated electrons in aqueous alkaline solutions, an intermediate product is observed. In this work, this intermediate product was determined to be a long life photoactive product in double flash experiments, which reacts at a speed constant K = 1x10 9 M -1 s -1 in a reaction of the 2nd order. It is formed in a reaction of the 1st order with reference to the electron concentration (e aq - → X, 2X → H 2 ). The alkaline metal cations of the solution appear as reaction partners of the hydrated electrons. The hydrated metal atoms formed were observed in the UV spectrum as absorpton bands at 270 nm. Pulse radiolytic measurements confirm the conclusions of the photochemical experiments. (RB) [de

Bridge mediated two-electron transfer reactions: Analysis of stepwise and concerted pathways

International Nuclear Information System (INIS)

Petrov, E.G.; May, V.

2004-01-01

A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D -- BA with the product state DBA -- results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate K TET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D - B - A, DB -- A, D - BA - , and DB - A - , K TET is obtained as a sum of the rates K TET (step) and K TET (sup) . The first rate describes stepwise TET originated by transitions of a single electron. It starts at D -- BA and reaches DBA -- via the intermediate state D - BA - . These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D -- BA to DBA -- defines K TET (sup) . An analytic dependence of K TET (step) and K TET (sup) on the number of bridging units is presented and different regimes of D-A TET are studied

Perturbation analysis of magnetohydrodynamics oscillatory flow on convective-radiative heat and mass transfer of micropolar fluid in a porous medium with chemical reaction

Directory of Open Access Journals (Sweden)

Dulal Pal

2016-03-01

Full Text Available This paper deals with the perturbation analysis of mixed convection heat and mass transfer of an oscillatory viscous electrically conducting micropolar fluid over an infinite moving permeable plate embedded in a saturated porous medium in the presence of transverse magnetic field. Analytical solutions are obtained for the governing basic equations. The effects of permeability, chemical reaction, viscous dissipation, magnetic field parameter and thermal radiation on the velocity distribution, micro-rotation, skin friction and wall couple stress coefficients are analyzed in detail. The results indicate that the effect of increasing the chemical reaction has a tendency to decrease the skin friction coefficient at the wall, while opposite trend is seen by increasing the permeability parameter of the porous medium. Also micro-rotational velocity distribution increases with an increase in the magnetic field parameter.

In-medium behaviour of vector mesons and the longitudinal and transverse response functions in (e,e'p) reactions

International Nuclear Information System (INIS)

Soyeur, M.; Brown, G.E.; Rho, M.

1991-01-01

The electromagnetic form factors of nucleons appear dominated by vector mesons at momentum transfers small than ∼ 1 GeV/c. It is therefore expected that measurements of quantities involving the electromagnetic form factors of nucleons embedded in nuclei will be sensitive to changes in vector meson properties arising from their interaction with the medium. Longitudinal and transverse response functions measured in quasi-elastic (e,e'p) reactions provide such data for two very different operators, the charge and the current densities. We show that a decrease of vector meson masses in the medium, consistent with present expectations about chiral symmetry restoration in nuclei, produces the quenching observed in the longitudinal response of light systems ( 3 He, 4 He) and part of this quenching for heavier nuclei 40 Ca where nuclear correlations are expected to generate an additional suppression of the longitudinal response. The transverse response is almost unchanged, in agreement with the data. Difficulties in extrating very quantitative information on the in-medium behaviour of vector mesons from (e,e'p) data are pointed out

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

Science.gov (United States)

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

Reaction (γ,2e) and (e,3e) as probe of electron correlation in atoms

International Nuclear Information System (INIS)

Amusia, M.Y.

1995-01-01

Cross sections of the (γ,2e) and (e,3e) reactions contain information about the two vacancy-energy spectrum and electron-pair correlations in initial and final states of the target atom. Physical pictures of these processes are presented for two- and many-electron atoms. The simplest mechanisms are discussed, demonstrating some features which await experimental confirmation. Attention is given to high photon energy and the relativistic energy region of these reactions. The energy distribution of outgoing relativistic electrons is qualitatively different from the nonrelativistic case. The origin and types of corrections to the simplest mechanisms, and possible means of their detection, are discussed. In addition, the role of different resonances: shape, giant, autoionizational, and Feshbach-type are considered. Results of calculations are compared with experimental data, mainly on double photoionization cross sections. Different possible objects as targets for the reactions are considered, including negative ions, excited atoms, molecules, and clusters. The modification of these reactions due to photon emission is discussed. The future of the domain is outlined

Reactions (γ,2e) and (e,3e) as probes of electronic correlations in atoms

International Nuclear Information System (INIS)

Amusia, M.Ya.

1993-01-01

Cross sections of the (γ,2e) and (e,3e) reactions carry information on two vacancy energy spectrum and on electron pair correlations in initial and final states of the target atom. Physical pictures of these processes are presented for two- and many-electron atoms. Simplest mechanisms of them are discussed, demonstrating some features which are waiting for experimental confirmation. Attention is given to high photon energy and even to relativistic energy region of these reactions. The energy distribution of outgoing relativistic electrons is qualitatively different from what it is for the nonrelativistic case. Origin and types of corrections to the simplest mechanisms and possible means of their detection are discussed. Role of different resonances: shape, giant, autoionizational, and Feschbach-type are considered. Results of calculations are compared with experimental data, mainly on double photoionization cross sections. Different possible objects as targets for the reactions are mentioned, including negative ions, excited atoms, molecules and clusters. Modification of the type of these reactions due to rather probable emission of the photon is discussed. Future of the domain is outlined. (orig.)

Physics with a 15-30 GeV electron accelerator (ELFE)

International Nuclear Information System (INIS)

Frois, B.; Pire, B.

1993-01-01

Proposals for ELFE (Electron Laboratory For Europe), a 15-30 GeV high luminosity, continuous beam electron accelerator are discussed. These proposals form an extensive research program on exclusive reactions to probe the evolution of correlated quarks systems. Using the nucleus itself as a microscopic detector is one of the important ideas of this program. The same reaction is measured using nuclei of different sizes and thus the differences are observed in the evolution from quarks and gluons to hadrons in the nuclear medium. A brief overview of the physics with ELFE is presented. (R.P.) 1 tab

Electron screening effects in (p,α) reactions induced on boron isotopes studied via the Trojan Horse Method

International Nuclear Information System (INIS)

Lamia, L; Spitaleri, C; Cherubini, S; Gulino, M; Puglia, S M R; Rapisarda, G G; Romano, S; Sergi, M L; Carlin, N; Gameiro Munhoz, M; Gimenez Del Santo, M; Kiss, G G; Somorjai, E; Kroha, V; Kubono, S; La Cognata, M; Pizzone, R G; Li, C; Wen, Qungang; Mukhamedzhanov, A

2013-01-01

The Trojan Horse Method is a powerful indirect technique allowing one to measure the bare nucleus S(E)-factor and the electron screening potential for astrophysically relevant reactions without the needs of extrapolations. The case of the (p,α) reactions induced on the two boron isotopes 10,11 B is here discussed in view of the recent Trojan Horse (TH) applications to the quasi-free 10,11 B+ 2 H reactions. The comparison between the TH and the low-energy direct data allowed us to determine the electron screening potential for the 11 B(p,α) reaction, while preliminary results on the 10 B(p,α) reaction have been extracted.

Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

Science.gov (United States)

Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

2000-12-01

Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

The exothermic reaction route of a self-heatable conductive ink for rapid processable printed electronics

Science.gov (United States)

Shin, Dong-Youn; Han, Jin Wook; Chun, Sangki

2013-12-01

We report the exothermic reaction route and new capability of a self-heatable conductive ink (Ag2O and silver 2,2-dimethyloctanoate) in order to achieve both a low sintering temperature and electrical resistivity within a short sintering time for flexible printed electronics and display appliances. Unlike conventional conductive ink, which requires a costly external heating instrument for rapid sintering, self-heatable conductive ink by itself is capable of generating heat as high as 312 °C when its exothermic reaction is triggered at a temperature of 180 °C. This intensive exothermic reaction is found to result from the recursive reaction of the 2,2-dimethyloctanoate anion, which is thermally dissociated from silver 2,2-dimethyloctanoate, with silver oxide microparticles. Through this recursive reaction, a massive number of silver atoms are supplied from silver oxide microparticles, and the nucleation of silver atoms and the fusion of silver nanoparticles become the major source of heat. This exothermic reaction eventually realizes the electrical resistivity of self-heatable conductive ink as low as 27.5 μΩ cm within just 40 s by combining chemical annealing, which makes it suitable for the roll-to-roll printable electronics such as a flexible touch screen panel.We report the exothermic reaction route and new capability of a self-heatable conductive ink (Ag2O and silver 2,2-dimethyloctanoate) in order to achieve both a low sintering temperature and electrical resistivity within a short sintering time for flexible printed electronics and display appliances. Unlike conventional conductive ink, which requires a costly external heating instrument for rapid sintering, self-heatable conductive ink by itself is capable of generating heat as high as 312 °C when its exothermic reaction is triggered at a temperature of 180 °C. This intensive exothermic reaction is found to result from the recursive reaction of the 2,2-dimethyloctanoate anion, which is thermally

Handling of Environmental Related Requirements : Awareness and Ability to Act at Small and Medium Sized Electric and Electronic Companies

OpenAIRE

Lin, Han-Hsuan

2008-01-01

Environmental related product requirements are increasing worldwide from government authorities, customers and other stakeholders. For small and medium sized companies manufacturing electric and electronic products it is more difficult compared to bigger companies to meet new product related requirements due to smaller budget, resources and knowledge. This research studies the awareness and ability to act upon changes when small and medium sized companies in Sweden face environmental related ...

Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

Science.gov (United States)

Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

2017-10-01

Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

Quantifying Chemical and Electrochemical Reactions in Liquids by in situ Electron Microscopy

DEFF Research Database (Denmark)

Canepa, Silvia

and developing a robust imaging analysis method for quantitatively understand chemical and electrochemical process during in situ liquid electron microscopy. By using two custom-made liquid cells (an electrochemical scanning electron microscopy (EC-SEM) platform and Liquid Flow S/TEM holder) beam...... of electrochemical deposition of copper (Cu) by electrochemical liquid scanning electron microscopy (EC-SEM) was done in order to direct observe the formation of dendritic structures. Finally the shape evolution from solid to hollow structures through galvanic replacement reactions were observed for different silver...

Medium-Energy Nuclear Data Library (MENDLIB): Phase 1

International Nuclear Information System (INIS)

Siciliano, E.R.; Arthur, E.D.

1987-10-01

This document describes an initial step towards the formation of a computerized on-line data library, which would contain published medium-energy experimental data, and which would serve the basic and applied needs of the medium-energy nuclear physics community. The data emphasized in this project will be from measured charged-particle and meson induced nuclear scattering and reactions; an area for which no such data base presently exists. Access to the data will be through a menu-driven program in a user-friendly environment. The project is divided into three phases: Phase 1 involves compilation of Clinton P. Anderson Meson Physics Facility (LAMPF) data from nucleon and pion induced reactions, Phase 2 includes nucleon and pion data from other medium-energy facilities, and Phase 3 includes electron, light-ion, and possibly kaon and anti-nucleon data. The initial goals, the manner in which they would be pursued, and the resources needed to implement Phase 1 (the pilot phase) are discussed in detail. Possible expansion of Phase 1 to attain the envisioned goals of Phase 2 and 3 are briefly outlined. During all stages of the project, input from the community will be sought via the various facility user groups and the American Physical Society Division of Nuclear Physics. It is proposed that the Applied Nuclear Science Group (T-2) of the Los Alamos National Laboratory oversees the development and implementation of this project, and the LAMPF VAX computers be used as the host computers for on-line access

Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

Institute of Scientific and Technical Information of China (English)

Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

2005-01-01

Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

Science Requirements and Conceptual Design for a Polarized Medium Energy Electron-Ion Collider at Jlab

Energy Technology Data Exchange (ETDEWEB)

Abeyratne, S; Ahmed, S; Barber, D; Bisognano, J; Bogacz, A; Castilla, A; Chevtsov, P; Corneliussen, S; Deconinck, W; Degtiarenko, P; Delayen, J; Derbenev, Ya; DeSilva, S; Douglas, D; Dudnikov, V; Ent, R; Erdelyi, B; Evtushenko, P; Fujii, Yu; Filatov, Yury; Gaskell, D; Geng, R; Guzey, V; Horn, T; Hutton, A; Hyde, C; Johnson, R; Kim, Y; Klein, F; Kondratenko, A; Kondratenko, M; Krafft, G; Li, R; Lin, F; Manikonda, S; Marhauser, F; McKeown, R; Morozov, V; Dadel-Turonski, P; Nissen, E; Ostroumov, P; Pivi, M; Pilat, F; Poelker, M; Prokudin, A; Rimmer, R; Satogata, T; Sayed, H; Spata, M; Sullivan, M; Tennant, C; Terzic, B; Tiefenback, M; Wang, M; Wang, S; Weiss, C; Yunn, B

2012-08-01

Researchers have envisioned an electron-ion collider with ion species up to heavy ions, high polarization of electrons and light ions, and a well-matched center-of-mass energy range as an ideal gluon microscope to explore new frontiers of nuclear science. In its most recent Long Range Plan, the Nuclear Science Advisory Committee (NSAC) of the US Department of Energy and the National Science Foundation endorsed such a collider in the form of a 'half-recommendation.' As a response to this science need, Jefferson Lab and its user community have been engaged in feasibility studies of a medium energy polarized electron-ion collider (MEIC), cost-effectively utilizing Jefferson Lab's already existing Continuous Electron Beam Accelerator Facility (CEBAF). In close collaboration, this community of nuclear physicists and accelerator scientists has rigorously explored the science case and design concept for this envisioned grand instrument of science. An electron-ion collider embodies the vision of reaching the next frontier in Quantum Chromodynamics - understanding the behavior of hadrons as complex bound states of quarks and gluons. Whereas the 12 GeV Upgrade of CEBAF will map the valence-quark components of the nucleon and nuclear wave functions in detail, an electron-ion collider will determine the largely unknown role sea quarks play and for the first time study the glue that binds all atomic nuclei. The MEIC will allow nuclear scientists to map the spin and spatial structure of quarks and gluons in nucleons, to discover the collective effects of gluons in nuclei, and to understand the emergence of hadrons from quarks and gluons. The proposed electron-ion collider at Jefferson Lab will collide a highly polarized electron beam originating from the CEBAF recirculating superconducting radiofrequency (SRF) linear accelerator (linac) with highly polarized light-ion beams or unpolarized light- to heavy-ion beams from a new ion accelerator and storage complex. Since the very

Science Requirements and Conceptual Design for a Polarized Medium Energy Electron-Ion Collider at Jlab

International Nuclear Information System (INIS)

Abeyratne, S.; Accardi, A.; Ahmed, S.; Barber, D.; Bisognano, J.; Bogacz, A.; Castilla, A.; Chevtsov, P.; Corneliussen, S.; Deconinck, W.; Degtiarenko, P.; Delayen, J.; Derbenev, Ya.; DeSilva, S.; Douglas, D.; Dudnikov, V.; Ent, R.; Erdelyi, B.; Evtushenko, P.; Fujii, Yu; Filatov, Yury; Gaskell, D.; Geng, R.; Guzey, V.; Horn, T.; Hutton, A.; Hyde, C.; Johnson, R.; Kim, Y.; Klein, F.; Kondratenko, A.; Kondratenko, M.; Krafft, G.; Li, R.; Lin, F.; Manikonda, S.; Marhauser, F.; McKeown, R.; Morozov, V.; Dadel-Turonski, P.; Nissen, E.; Ostroumov, P.; Pivi, M.; Pilat, F.; Poelker, M.; Prokudin, A.; Rimmer, R.; Satogata, T.; Sayed, H.; Spata, M.; Sullivan, M.; Tennant, C.; Terzic, B.; Tiefenback, M.; Wang, H.; Wang, S.; Weiss, C.; Yunn, B.; Zhang, Y.

2012-01-01

Researchers have envisioned an electron-ion collider with ion species up to heavy ions, high polarization of electrons and light ions, and a well-matched center-of-mass energy range as an ideal gluon microscope to explore new frontiers of nuclear science. In its most recent Long Range Plan, the Nuclear Science Advisory Committee (NSAC) of the US Department of Energy and the National Science Foundation endorsed such a collider in the form of a 'half-recommendation.' As a response to this science need, Jefferson Lab and its user community have been engaged in feasibility studies of a medium energy polarized electron-ion collider (MEIC), cost-effectively utilizing Jefferson Lab's already existing Continuous Electron Beam Accelerator Facility (CEBAF). In close collaboration, this community of nuclear physicists and accelerator scientists has rigorously explored the science case and design concept for this envisioned grand instrument of science. An electron-ion collider embodies the vision of reaching the next frontier in Quantum Chromodynamics - understanding the behavior of hadrons as complex bound states of quarks and gluons. Whereas the 12 GeV Upgrade of CEBAF will map the valence-quark components of the nucleon and nuclear wave functions in detail, an electron-ion collider will determine the largely unknown role sea quarks play and for the first time study the glue that binds all atomic nuclei. The MEIC will allow nuclear scientists to map the spin and spatial structure of quarks and gluons in nucleons, to discover the collective effects of gluons in nuclei, and to understand the emergence of hadrons from quarks and gluons. The proposed electron-ion collider at Jefferson Lab will collide a highly polarized electron beam originating from the CEBAF recirculating superconducting radiofrequency (SRF) linear accelerator (linac) with highly polarized light-ion beams or unpolarized light- to heavy-ion beams from a new ion accelerator and storage complex. Since the very

Reactions induced by low energy electrons in cryogenic films

International Nuclear Information System (INIS)

Bass, A.D.; Sanche, L.

2003-01-01

We review recent research on reactions (including dissociation) initiated by low-energy electron bombardment of monolayer and multilayer molecular solids at cryogenic temperatures. With incident electrons of energies below 20 eV, dissociation is observed by the electron stimulated desorption (ESD) of anions from target films and is attributed to the processes of dissociative electron attachment (DEA) and to dipolar dissociation. It is shown that DEA to condensed molecules is sensitive to environmental factors such as the identity of co-adsorbed species and film morphology. The effects of image-charge induced polarization on cross-sections for DEA to CH3Cl are also discussed. Taking as examples, the electron-induced production of CO within multilayer films of methanol and acetone, it is shown that the detection of electronic excited states by high resolution electron energy loss spectroscopy can be used to monitor electron beam damage. In particular, the incident energy dependence of the CO indicates that below 19 eV, dissociation proceeds via the decay of transient negative ions (TNI) into electronically excited dissociative states. The electron induced dissociation of biomolecular targets is also considered, taking as examples the ribose analog tetrahydrofuran and DNA bases adenine and thymine, cytosine and guanine. The ESD of anions from such films also show dissociation via the formation of TNI. In multilayer molecular solids, fragment species resulting from dissociation, may react with neighboring molecules, as is demonstrated in anion ESD measurements from films containing O 2 and various hydrocarbon molecules. X-ray photoelectron spectroscopy measurements reported for electron irradiated monolayers of H 2 O and CF 4 on a Si - H passivated surface further show that DEA is an important initial step in the electron-induced chemisorption of fragment species

A frame work for heat generation/absorption and modified homogeneous–heterogeneous reaction in flow based on non-Darcy–Forchheimer medium

Directory of Open Access Journals (Sweden)

Tasawar Hayat

2018-04-01

Full Text Available The present work aims to report the consequences of Darcy–Forchheimer medium in flow of Cross fluid model toward a stretched surface. Flow in porous space is categorized by Darcy–Forchheimer medium. Further heat transfer characteristics are examined via thermal radiation and heat generation/absorption. Transformation procedure is used. The arising system of nonlinear ordinary differential equations is solved numerically by means of shooting method. The effects of different flow variables on velocity, temperature, concentration, skin friction, and heat transfer rate are discussed. The obtained outcomes show that velocity was enhanced with the increase in the Weissenberg number but decays with increase in the porosity parameter and Hartman number. Temperature field is boosted by thermal radiation and heat generation; however, it decays with the increase in the Prandtl number. Keywords: Cross Fluid, Heat Generation/Absorption, Homogeneous–Heterogeneous Reactions, Non-Darcy–Forchheimer Medium, Thermal Radiation

Progress on the design of the polarized Medium-energy Electron Ion Collider at JLAB

Energy Technology Data Exchange (ETDEWEB)

Lin, F.; Bogacz, A.; Brindza, P.; Camsonne, A.; Daly, E.; Derbenev, Ya. S.; Douglas, D.; Ent, R.; Gaskell, D.; Geng, R.; Grames, J.; Guo, J.; Harwood, L.; Hutton, A.; Jordan, K.; Kimber, A.; Krafft, G.; Li, R.; Michalski, T.; Morozov, V. S.; Nadel-Turonski, P.; /Jefferson Lab /Argonne /DESY /Moscow , Inst. Phys. Tech., Dolgoprydny /Dubna, JINR /Northern Illinois U. /Old Doominion U. /Novosibirsk, GOO Zaryad /SLAC /Texas A-M

2015-07-14

The Medium-energy Electron Ion Collider (MEIC) at JLab is designed to provide high luminosity and high polarization needed to reach new frontiers in the exploration of nuclear structure. The luminosity, exceeding 10³³ cm^-2s^-1 in a broad range of the center-of-mass (CM) energy and maximum luminosity above 10³⁴ cm^-2s^-1, is achieved by high-rate collisions of short small-emittance low-charge bunches made possible by high-energy electron cooling of the ion beam and synchrotron radiation damping of the electron beam. The polarization of light ion species (p, d, ³He) can be easily preserved and manipulated due to the unique figure-8 shape of the collider rings. A fully consistent set of parameters have been developed considering the balance of machine performance, required technical development and cost. This paper reports recent progress on the MEIC accelerator design including electron and ion complexes, integrated interaction region design, figure-8-ring-based electron and ion polarization schemes, RF/SRF systems and ERL-based high-energy electron cooling. Luminosity performance is also presented for the MEIC baseline design.

[Synthetic Studies of Bioactive Heterocyclic Natural Products and Fused Heterocyclic Compounds Based on the Thermal Electrocyclic or Azaelectocyclic Reaction of 6π-Electron or Aza-6π-electron Systems].

Science.gov (United States)

Hibino, Satoshi

2016-01-01

Since 1979, synthetic studies of bioactive heterocyclic natural products and condensed heteroaromatic compounds based on the thermal electrocyclic reaction of 6π-electron or aza-6π-electron systems incorporating the double bond of the principal aromatic or heteroaromatic ring have been conducted by our research group. In this review, five types of electrocyclic and azaelectrocyclic reaction are described: 1) the synthesis of the carbazole alkaloids hyellazole and 6-chlorohyellazole through the electrocyclic reaction of 2,3-bisalkenylindoles; 2) synthetic studies of the pyridocarbazole alkaloids ellipticine and olivacine through the electrocyclic reactions of the indole-2,3- and pyridine-3,4-quinodimethane intermediates; 3) synthetic studies of polysubstituted carbazole alkaloids through the allene-mediated electrocyclic reactions involving the indole 2,3-bond; 4) synthetic studies of fused pyridine rings through the azaelectrocyclic reaction of the 1-aza-6π-electron system using the oxime or oxime ether; and 5) synthetic studies of fused pyridine rings through the azaelectrocyclic reaction of the 2-aza-6π-electron system using a carbodiimide or isocyanate.

Risk of application of contrast medium in computed tomography

Energy Technology Data Exchange (ETDEWEB)

Wende, S.; Speck, U.

1981-06-01

The paper deals with the risk associated with the application of contrast medium in CT. The risk is to be seen in intolerance reactions, such as allergic or circulatory reactions and neurotoxic side-effects. In this paper the problems of renal failure caused by the injection of contrast medium are given special attention. Furthermore an iodine-induced hyperthyreosis might result. Especially the possible disturbance of the kidney function means that contrast medium should not be applied arbitrarily and that the examination should be done only by experienced staff. Furthermore the indication for the application of contrast medium in CT should be strictly qualified.

Duplex-assisted carotid artery stenting without administration of contrast medium for patients with chronic kidney disease or allergic reaction.

Science.gov (United States)

Mizowaki, Takashi; Fujita, Atsushi; Imahori, Taichiro; Uyama, Atsushi; Inoue, Satoshi; Kohta, Masaaki; Hamaguchi, Hirotoshi; Sasayama, Takashi; Hosoda, Kohkichi; Kohmura, Eiji

2016-07-01

We aimed to investigate the safety and feasibility of duplex-assisted carotid artery stenting (CAS) without administration of contrast medium for the prevention of adverse reactions. Fifteen patients (9 % of all CASs) with severe carotid stenosis (≥70 %) associated with chronic kidney disease (CKD) (stage ≥3) or allergy to contrast medium underwent duplex-assisted CAS without administration of contrast medium over 4 years. The procedural success rate and perioperative complication rates were compared between the duplex-assisted CAS (n = 15) and conventional CAS (n = 153) groups. The technical success rate was 100 % in both groups. Combined stroke or death rates during the post-procedural period did not differ significantly between the duplex-assisted CAS group (0/15, 0 %) and conventional CAS group (4/153, 2.6 %). None of the 14 patients with CKD in the duplex-assisted CAS group experienced further deterioration of renal function. The mean surface radiation dose of participants in the duplex-assisted CAS group (n = 13, 312 ± 131 mGy) was significantly lower than that of the conventional CAS group (n = 31, 1036 ± 571 mGy) (p duplex-assisted CAS group (156 ± 39.7 min) and the conventional CAS group (156 ± 37.4 min). Duplex-assisted CAS without administration of contrast medium could be an alternative option in selected patients deemed to be at high risk for renal failure from nephrotoxic contrast medium or who have an allergy to contrast medium.

Unconventional exo selectivity in thermal normal-electron-demand Diels-Alder reactions

Science.gov (United States)

Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng

2016-10-01

The Diels-Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels-Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction.

Tuning the two-dimensional electron liquid at oxide interfaces by buffer-layer-engineered redox reactions

DEFF Research Database (Denmark)

Chen, Yunzhong; Green, Robert J.; Sutarto, Ronny

2017-01-01

Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO3 (STO) achieved using polar La7/8Sr1/8MnO3 (LSMO) buffer layers to manipulate both...... polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant x-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how...... these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer...

An Improved Protocol for the Aldehyde Olefination Reaction Using (bmim ( as Reaction Medium

Directory of Open Access Journals (Sweden)

Vivek Srivastava

2013-01-01

Full Text Available [Ru(CODCl2]/CuCl2·2H2O/LiCl catalytic system works efficiently in ionic liquid media for aldehyde olefination reaction. It offers good yield and selectivity with the added advantage of 5 times recyclability for [Ru(CODCl2] /CuCl2·2H2O/LiCl catalytic system. We also successfully reduced the reaction time from 12 hours to 9 hours for the aldehyde olefination reaction.

Attainment of Electron Beam Suitable for Medium Energy Electron Cooling

International Nuclear Information System (INIS)

Seletskiy, Sergey M.; Rochester U.

2005-01-01

Electron cooling of charged particle beams is a well-established technique at electron energies of up to 300 keV. However, up to the present time the advance of electron cooling to the MeV-range energies has remained a purely theoretical possibility. The electron cooling project at Fermilab has recently demonstrated the first cooling of 8.9 GeV/c antiprotons in the Recycler ring, and therefore, has proved the validity of the idea of relativistic electron cooling. The Recycler Electron Cooler (REC) is the key component of the Tevatron Run II luminosity upgrade project. Its performance depends critically on the quality of electron beam. A stable electron beam of 4.3 MeV carrying 0.5 A of DC current is required. The beam suitable for the Recycler Electron Cooler must have an angular spread not exceeding 200 (micro)rad. The full-scale prototype of the REC was designed, built and tested at Fermilab in the Wideband laboratory to study the feasibility of attaining the high-quality electron beam. In this thesis I describe various aspects of development of the Fermilab electron cooling system, and the techniques used to obtain the electron beam suitable for the cooling process. In particular I emphasize those aspects of the work for which I was principally responsible. Chapter 1 is an introduction where I describe briefly the theory and the history of electron cooling, and derive the requirements to the quality of electron beam and requirements to the basic parameters of the Recycler Electron Cooler. Chapter 2 is devoted to the theoretical consideration of the motion of electrons in the cooling section, description of the cooling section and of the measurement of the magnetic fields. In Chapter 3 I consider different factors that increase the effective electron angle in the cooling section and suggest certain algorithms for the suppression of parasitic angles. Chapter 4 is devoted to the measurements of the energy of the electron beam. In the concluding Chapter 5 I review

The measurement of the total electron content applied to the observation of medium scale gravity wave

International Nuclear Information System (INIS)

Bertel, L.; Bertin, F.; Testud, J.

1976-01-01

The interpretation of the measurements of the integrated electron content in terms of gravity wave requires (1) a gravity wave model at thermospheric altitudes; (2) a gravity wave-ionization interaction model in the F-region of the ionosphere; and (3) a computing program for the resulting perturbation on the integrated electron content between the satellite and the earth station used. The gravity wave model considered in this paper takes into account the dissipative effects (viscosity, thermal conduction) which become very importanr above 250 km altitude and the effect of the base wind which is capable of affecting deeply the propagation of the waves of medium scale. Starting with this model, the domains of frequencies and the wavelength of atmospheric waves which may exist in the upper atmosphere are considered. The interaction of such waves and the ionization is examined. The theoretical results give information particularly on the selectivity of the ionospheric response to the wave passage. The deduced selectivity of the models appears to be smaller than that given by other authors who used simplified gravity wave models. The method for computing the perturbation of the of the integrated electron content introduced by the wave passage is given for a geostationary satellite. Computational results are presented for application to the case of medium scale gravity waves. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Wang, Changhua [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); College of Chemistry and Biology, Beihua University, Jilin 132013 (China); Zhang, Xintong, E-mail: xtzhang@nenu.edu.cn [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); Liu, Yichun [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China)

2015-12-15

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

The EPR paradox, the hydrated (solvated) electron, and the reactions of the hydrated electron (Preprint no. RC-02)

International Nuclear Information System (INIS)

Gopinathan, C.

1991-01-01

Einstein, Podolsky and Rosen pointed out in 1935 a serious flaw in the reasoning behind quantum mechanical modelling. It is shown in this work that this flaw applies to the interpretation of the hydrated electron and its reactions as well. (author). 3 refs

Risk of application of contrast medium in computed tomography

International Nuclear Information System (INIS)

Wende, S.; Speck, U.; Schering A.G., Berlin

1981-01-01

The paper deals with the risk associated with the application of contrast medium in CT. The risk is to be seen in intolerance reactions, such as allergic or circulatory reactions and neurotoxic side-effects. In this paper the problems of renal failure caused by the injection of contrast medium are given special attention. Furthermore an iodine-induced hyperthyreosis might result. Especially the possible disturbance of the kidney function means that contrast medium should not be applied arbitrarily and that the examination should be done only by experienced staff. Furthermore the indication for the application of contrast medium in CT should be strictly qualified. (orig.) [de

Attainment of Electron Beam Suitable for Medium Energy Electron Cooling

Energy Technology Data Exchange (ETDEWEB)

Seletskiy, Sergei M. [Univ. of Rochester, NY (United States)

2005-01-01

Electron cooling of charged particle beams is a well-established technique at electron energies of up to 300 keV. However, up to the present time the advance of electron cooling to the MeV-range energies has remained a purely theoretical possibility. The electron cooling project at Fermilab has recently demonstrated the ¯rst cooling of 8.9 GeV/c antiprotons in the Recycler ring, and therefore, has proved the validity of the idea of relativistic electron cool- ing. The Recycler Electron Cooler (REC) is the key component of the Teva- tron Run II luminosity upgrade project. Its performance depends critically on the quality of electron beam. A stable electron beam of 4.3 MeV car- rying 0.5 A of DC current is required. The beam suitable for the Recycler Electron Cooler must have an angular spread not exceeding 200 ¹rad. The full-scale prototype of the REC was designed, built and tested at Fermilab in the Wideband laboratory to study the feasibility of attaining the high-quality electron beam. In this thesis I describe various aspects of development of the Fermilab electron cooling system, and the techniques used to obtain the electron beam suitable for the cooling process. In particular I emphasize those aspects of the work for which I was principally responsible.

Probing the electronic structure of redox species and direct determination of intrinsic reorganization energies of electron transfer reactions

International Nuclear Information System (INIS)

Wang, Xue-Bin; Wang, Lai-Sheng

2000-01-01

An experimental technique capable of directly determining the intrinsic reorganization energies of bimolecular electron transfer reactions is described. Appropriate solution phase redox species are prepared in the gas phase using electrospray ionization and probed using photodetachment spectroscopy. Five metal complex anions involved in the Fe 2+ -Fe 3+ redox couple are investigated and the intramolecular reorganization energies are measured directly from spectral features due to removing the most loosely bound 3d electron from the Fe(II)-complexes. The photodetachment spectra also yield electronic structure information about the Fe 2+ -Fe 3+ redox couple and provide a common electronic structure origin for the reducing capability of the Fe(II)-complexes, the most common redox reagents. (c) 2000 American Institute of Physics

Analysis of transformations of the ultrafast electron transfer photoreaction mechanism in liquid solutions by the rate distribution approach.

Science.gov (United States)

Kuzmin, Michael G; Soboleva, Irina V

2014-05-01

Representation of the experimental reaction kinetics in the form of rate distribution is shown to be an effective method for the analysis of the mechanisms of these reactions and for comparisons of the kinetics with QC calculations, as well as with the experimental data on the medium mobility. The rate constant distribution function P(k) can be obtained directly from the experimental kinetics N(t) by an inverse Laplace transform. The application of this approach to kinetic data for several excited-state electron transfer reactions reveals the transformations of their rate control factors in the time domain of 1-1000 ps. In neat electron donating solvents two components are observed. The fastest component (k > 1 ps(-1)) was found to be controlled by the fluctuations of the overall electronic coupling matrix element, involving all the reactant molecules, located inside the interior of the solvent shell, rather than for specific pairs of reactant molecules. The slower component (1 > k > 0.1 ps(-1)) is controlled by the medium reorganization (longitudinal relaxation times, τL). A substantial contribution from the non-stationary diffusion controlled reaction is observed in diluted solutions ([Q] transformation of the rate control factors in the course of the reactions.

Self-Controlled Synthesis of Hyperbranched Polyetherketones From A3 + B2 Approach Via Different Solubilities of Monomers in the Reaction Medium (Preprint)

Science.gov (United States)

2006-10-01

higher yields than 1a and 2a after the similar work-up procedure, which involved Soxhlet extraction with water for 2 days and methanol for 2 days to get...the co-monomers. One such reaction medium, optimized PPA/P2O5 mixture, has been established for the electrophilic substitution reaction to yield high... Soxhlet -extracted with water for 2 days, methanol for 2 days, and finally dried under reduced pressure (0.05 mmHg) at 100°C for 150 h to give 3.30 g (76

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

NARCIS (Netherlands)

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

2002-01-01

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

Silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes.

Science.gov (United States)

Türkmen, Yunus E; Montavon, Timothy J; Kozmin, Sergey A; Rawal, Viresh H

2012-06-06

A highly effective silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes has been developed. The reactions provide ready access to a wide range of siloxy naphthalenes and anthracenes, which are formed in good to high yields, under mild reaction conditions, using low catalyst loadings.

Study of photo-activated electron transfer reactions in the first excited singlet state by picosecond and nanosecond laser spectroscopy

International Nuclear Information System (INIS)

Doizi, Denis

1983-01-01

Picosecond laser spectroscopy has been used to study two photo-activated electron transfer reactions: - a bimolecular electron transfer reaction between a sensitizer, DODCI, and an electron acceptor, methylviologen. The two radical ions created with an electron transfer efficiency γ ≅ 0.07 have been identified in picosecond and nanosecond laser absorption spectroscopy by adding selective solutes such as para-benzoquinone (an electron acceptor) or L(+) ascorbic acid (an electron donor). - an intramolecular electron transfer reaction in a triad molecule consisting of a tetra-aryl-porphyrin covalently linked to both a carotenoid and a quinone. The photoinduced charge separation occurs within 30 ps and leads, with a yield of 25 pc, to the formation of a zwitterion whose half-life is 2.5 μs. The experimental results obtained in these two studies show an effective decrease in the recombination rate of the two radical ions created in the encounter pair. (author) [fr

Electron capture rates in stars studied with heavy ion charge exchange reactions

Science.gov (United States)

Bertulani, C. A.

2018-01-01

Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean ~ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.

Late adverse reactions to intravascular iodinated contrast media

International Nuclear Information System (INIS)

Webb, Judith A.W.; Stacul, Fulvio; Thomsen, Henrik S.; Morcos, Sameh K.

2003-01-01

Late adverse reactions to intravascular iodinated contrast media are defined as reactions occurring 1 h to 1 week after contrast medium injection. They have received increasing interest over the past decade, but their prevalence remains uncertain and their pathophysiology is not fully understood. The Contrast Media Safety Committee of the European Society of Urogenital Radiology decided to review the literature and to issue guidelines. An extensive literature search was carried out and summarized in a report. Based on the available information, simple guidelines have been drawn up. The report and guidelines were discussed at the 8th European Symposium on Urogenital Radiology in Genoa. Late adverse reactions after intravascular iodinated contrast medium include symptoms such as nausea, vomiting, headache, itching, skin rash, musculoskeletal pain, and fever. A significant proportion of these reactions is unrelated to the contrast medium; however, allergy-like skin reactions are well-documented side effects of contrast media with an incidence of approximately 2%. Late reactions appear to be commoner after non-ionic dimers. The majority of late skin reactions after contrast medium exposure are probably T-cell-mediated allergic reactions. Patients at increased risk of late skin reactions are those with a history of previous contrast medium reaction and those on interleukin-2 treatment. Most skin reactions are self-limiting and resolve within a week. Management is symptomatic and similar to the management of other drug-induced skin reactions. (orig.)

Bibliographic survey of medium energy inclusive reaction data

International Nuclear Information System (INIS)

Arthur, E.D.; Madland, D.G.; McClellan, D.M.

1986-04-01

A bibliographic survey of inclusive reaction data (experimental and theoretical) for several projectile types having energies between 50 and 1000 MeV has been completed. Approximately one thousand references selected from this survey describe the current state of knowledge for particle-induced inclusive reaction data. The search covered data for the following projectiles: p, d, t, 3 He, 4 He, and lithium ions

Selected phytotoxins and organic extracts from endophytic fungus Edenia gomezpompae as light reaction of photosynthesis inhibitors.

Science.gov (United States)

Macías-Rubalcava, Martha Lydia; Ruiz-Velasco Sobrino, María Emma; Meléndez-González, Claudio; King-Díaz, Beatriz; Lotina-Hennsen, Blas

2014-09-05

In a search for natural herbicides, we investigated the action mechanism of the naphthoquinone spiroketals, isolated from the endophytic fungus Edenia gomezpompae: preussomerins EG1 (1) and EG4 (2), and palmarumycins CP17 (3), and CP2 (4) on the photosynthesis light reactions. The naphthoquinone spiroketals 1-4 inhibited the ATP synthesis in freshly lysed spinach thylakoids from water to MV, and they also inhibited the non-cyclic electron transport in the basal, phosphorylating and uncoupled conditions from water to MV. Therefore, they act as Hill reaction inhibitors. The results suggested that naphthoquinone spiroketals 1-4 have two interactions and inhibition site on the PSII electron transport chain. The first one involves the water splitting enzyme inhibition; and, the second on the acceptor site of PSII in a similar way that herbicide Diuron, studied by polaroghaphy and corroborated by fluorescence of the chlorophyll a of PSII. The culture medium and mycelium organic extracts from four morphological variants of E. gomezpompae were phytotoxic, and the culture medium extracts were more potent than mycelium extracts. They also act as Hill reaction inhibitors. Copyright © 2014 Elsevier B.V. All rights reserved.

Radiolytic and electron-transfer reactions in supercritical CO2

International Nuclear Information System (INIS)

Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

2000-01-01

Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

Reaction of congo red in water after irradiation by pulsed intense relativistic electron beam

International Nuclear Information System (INIS)

Kikuchi, Takashi; Kondo, Hironobu; Sasaki, Toru; Harada, Nob.; Moriwaki, Hiroshi; Nakanishi, Hiromitsu; Imada, Go

2011-01-01

The reaction of congo red, a well-known toxic azo dye, occurred after irradiation by a pulsed intense relativistic electron beam (PIREB). An aquation of congo red was irradiated by PIREB (2 MeV, 0.36 kA, 140 ns). After PIREB irradiation, the solution was measured by electrospray ionization-mass spectrometry and liquid chromatography/mass spectrometry. It was found that congo red underwent a reaction (77% conversion after five shots of PIREB irradiation) and the hydroxylated compounds of the dye were observed as reaction products. (author)

Electron and photon-beam induced reactions of adsorbed disilane: Low-temperature thin-film growth

International Nuclear Information System (INIS)

Bozso, F.; Avouris, Ph.

1991-01-01

Electrons and photons of sufficient energy can cause fragmentation and desorption of adsorbed molecules or fragments of them, by inducing electronic excitations to dissociative states. The surface species after such excitations are mostly of highly reactive radical character, which readily react with the substrate and with other molecular or radical species in the adsorbed layer. This paper discusses the adsorption, thermal and electron/photon-beam induced reactions of disilane, oxygen and ammonia on Si(111)-7x7, and the electron/photon-induced growth of silicon, silicon dioxide and silicon nitride films at 100K

The exothermic reaction route of a self-heatable conductive ink for rapid processable printed electronics.

Science.gov (United States)

Shin, Dong-Youn; Han, Jin Wook; Chun, Sangki

2014-01-07

We report the exothermic reaction route and new capability of a self-heatable conductive ink (Ag2O and silver 2,2-dimethyloctanoate) in order to achieve both a low sintering temperature and electrical resistivity within a short sintering time for flexible printed electronics and display appliances. Unlike conventional conductive ink, which requires a costly external heating instrument for rapid sintering, self-heatable conductive ink by itself is capable of generating heat as high as 312 °C when its exothermic reaction is triggered at a temperature of 180 °C. This intensive exothermic reaction is found to result from the recursive reaction of the 2,2-dimethyloctanoate anion, which is thermally dissociated from silver 2,2-dimethyloctanoate, with silver oxide microparticles. Through this recursive reaction, a massive number of silver atoms are supplied from silver oxide microparticles, and the nucleation of silver atoms and the fusion of silver nanoparticles become the major source of heat. This exothermic reaction eventually realizes the electrical resistivity of self-heatable conductive ink as low as 27.5 μΩ cm within just 40 s by combining chemical annealing, which makes it suitable for the roll-to-roll printable electronics such as a flexible touch screen panel.

Dose distribution considerations of medium energy electron beams at extended source-to-surface distance

International Nuclear Information System (INIS)

Saw, Cheng B.; Ayyangar, Komanduri M.; Pawlicki, Todd; Korb, Leroy J.

1995-01-01

Purpose: To determine the effects of extended source-to-surface distance (SSD) on dose distributions for a range of medium energy electron beams and cone sizes. Methods and Materials: The depth-dose curves and isodose distributions of 6 MeV, 10 MeV, and 14 MeV electron beams from a dual photon and multielectron energies linear accelerator were studied. To examine the influence of cone size, the smallest and the largest cone sizes available were used. Measurements were carried out in a water phantom with the water surface set at three different SSDs from 101 to 116 cm. Results: In the region between the phantom surface and the depth of maximum dose, the depth-dose decreases as the SSD increases for all electron beam energies. The effects of extended SSD in the region beyond the depth of maximum dose are unobservable and, hence, considered minimal. Extended SSD effects are apparent for higher electron beam energy with small cone size causing the depth of maximum dose and the rapid dose fall-off region to shift deeper into the phantom. However, the change in the depth-dose curve is small. On the other hand, the rapid dose fall-off region is essentially unaltered when the large cone is used. The penumbra enlarges and electron beam flatness deteriorates with increasing SSD

Effect of the Reduction Temperature of PdAg Nanoparticles during the Polyol Process in the Ethanol Electrooxidation Reaction

OpenAIRE

Carrera-Cerritos, R.; Salazar-Hernandez, C.; Galindo-Esquivel, I. R.; Fuentes-Ramirez, R.

2018-01-01

This work reports the effect of reduction temperature during the synthesis of PdAg catalysts through the polyol process and their evaluation in the ethanol electrooxidation reaction (EOR). The characterization was performed using Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). The electrochemical evaluation for the ethanol electrooxidation reaction was implemented in alkaline medium using chronoamperometry (CA) and cyclic voltammetry (CV). An important effect of the reduct...

Linking the gaseous and the condensed phases of matter: The slow electron and its interactions

International Nuclear Information System (INIS)

Christophorou, L.G.

1993-01-01

The interfacing of the gaseous and the condensed phases of matter as effected by interphase and cluster studies on the behavior of key reactions involving slow electrons either as reacting initial particles or as products of the reactions themselves is discussed. Emphasis is placed on the measurement of both the cross sections and the energetics involved, although most of the available information to date is on the latter. The discussion is selectively focussed on electron scattering (especially the role of negative ion states in gases, clusters, and dense matter), ionization, electron attachment and photodetachment. The dominant role of the electric polarization of the medium is emphasized

Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

International Nuclear Information System (INIS)

Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

2014-01-01

Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

Pulse radiolysis investigation of the reaction of the electronic adduct of bovine serum albumin with oxygen. Polychromatic kinetics of the reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

The method of pulse radiolysis was used to investigate the reaction of the electronic adduct of bovine serum albumin with oxygen. It was suggested that the disappearance of the electronic adduct of the protein occurs in the course of its interaction with oxygen adsorbed on the globular protein molecule

Electron transfer reactions to probe the electrode/solution interface

Energy Technology Data Exchange (ETDEWEB)

Capitanio, F.; Guerrini, E.; Colombo, A.; Trasatti, S. [Milan Univ., Milan (Italy). Dept. of Physical Chemistry and Electrochemistry

2008-07-01

The reactions that occur at the interface between an electrode and an electrolyte were examined with particular reference to the interaction of different electrode surfaces with redox couples. A semi-integration or convolution technique was used to study the kinetics of electron transfer on different electrode materials with different hydrophilic behaviour, such as Boron-Doped-Diamond (BDD), Au and Pt. Standard reversible redox couples were also investigated, including (Fe3+/2+, Fe(CN)63-/4-, Ru(NH3)63+/2+, Co(NH3)63+/2+, Ir4+/3+, V4+/5+ and V3+/2+). The proposed method proved to be simple, straightforward and reliable since the obtained kinetic information was in good agreement with data in the literature. It was concluded that the kinetics of the electrode transfer reactions depend on the chemical nature of the redox couple and electrode material. The method should be further extended to irreversible couples and other electrode materials such as mixed oxide electrodes. 3 refs., 2 figs.

Facile Hydrogen Evolution Reaction on WO3Nanorods

Directory of Open Access Journals (Sweden)

Rajeswari Janarthanan

2007-01-01

Full Text Available AbstractTungsten trioxide nanorods have been generated by the thermal decomposition (450 °C of tetrabutylammonium decatungstate. The synthesized tungsten trioxide (WO3 nanorods have been characterized by XRD, Raman, SEM, TEM, HRTEM and cyclic voltammetry. High resolution transmission electron microscopy and X-ray diffraction analysis showed that the synthesized WO3nanorods are crystalline in nature with monoclinic structure. The electrochemical experiments showed that they constitute a better electrocatalytic system for hydrogen evolution reaction in acid medium compared to their bulk counterpart.

Formation of Anionic C, N-bearing Chains in the Interstellar Medium via Reactions of H- with HC x N for Odd-valued x from 1 to 7

Science.gov (United States)

Gianturco, F. A.; Satta, M.; Yurtsever, E.; Wester, R.

2017-11-01

We investigate the relative efficiencies of low-temperature chemical reactions in the interstellar medium with H- anion reacting in the gas phase with cyanopolyyne neutral molecules, leading to the formation of anionic {{{C}}}x{{{N}}}- linear chains of different lengths and of H2. All the reactions turn out to be without barriers, highly exothermic reactions that provide a chemical route to the formation of anionic chains of the same length. Some of the anions have been observed in the dark molecular clouds and in the diffuse interstellar envelopes. Quantum calculations are carried out for the corresponding reactive potential energy surfaces for all the odd-numbered members of the series (x = 1, 3, 5, 7). We employ the minimum energy paths to obtain the relevant transition state configurations and use the latter within the variational transition state model to obtain the chemical rates. The present results indicate that at typical temperatures around 100 K, a set of significantly larger rate values exists for x = 3 and x = 5, while the rate values are smaller for CN- and {{{C}}}7{{{N}}}-. At those temperatures, however, all the rates turn out to be larger than the estimates in the current literature for the radiative electron attachment (REA) rates, thus indicating the greater importance of the present chemical path with respect to REA processes at those temperatures. The physical reasons for our findings are discussed in detail and linked with the existing observational findings.

On the nature of organic and inorganic centers that bifurcate electrons, coupling exergonic and endergonic oxidation-reduction reactions.

Science.gov (United States)

Peters, John W; Beratan, David N; Schut, Gerrit J; Adams, Michael W W

2018-04-19

Bifurcating electrons to couple endergonic and exergonic electron-transfer reactions has been shown to have a key role in energy conserving redox enzymes. Bifurcating enzymes require a redox center that is capable of directing electron transport along two spatially separate pathways. Research into the nature of electron bifurcating sites indicates that one of the keys is the formation of a low potential oxidation state to satisfy the energetics required of the endergonic half reaction, indicating that any redox center (organic or inorganic) that can exist in multiple oxidation states with sufficiently separated redox potentials should be capable of electron bifurcation. In this Feature Article, we explore a paradigm for bifurcating electrons down independent high and low potential pathways, and describe redox cofactors that have been demonstrated or implicated in driving this unique biochemistry.

Direct observation and theory of trajectory-dependent electronic energy losses in medium-energy ion scattering.

Science.gov (United States)

Hentz, A; Parkinson, G S; Quinn, P D; Muñoz-Márquez, M A; Woodruff, D P; Grande, P L; Schiwietz, G; Bailey, P; Noakes, T C Q

2009-03-06

The energy spectrum associated with scattering of 100 keV H+ ions from the outermost few atomic layers of Cu(111) in different scattering geometries provides direct evidence of trajectory-dependent electronic energy loss. Theoretical simulations, combining standard Monte Carlo calculations of the elastic scattering trajectories with coupled-channel calculations to describe inner-shell ionization and excitation as a function of impact parameter, reproduce the effects well and provide a means for far more complete analysis of medium-energy ion scattering data.

Short- and medium-range order of atomic structure and electronic properties of arsenic salinide and sulphide amorphous films

International Nuclear Information System (INIS)

Sarsembinov, Sh.Sh.; Prikhodko, O.Yu.; Ryaguzov, A.P.; Maksimova, S.Ya.; Ushanov, V.Zh.

2004-01-01

Full text: The relationship between short- and medium-range order of atomic structure and electronic properties is the object of invariable attention of disordered matter physics. This problem is the most important for non-crystalline semiconductors, and specifically for chalcogenide glassy semiconductors (ChGS) films due to low co-ordination of atoms, which leads to lability of their structure. In this report we present results of atomic structure, electric, optical properties and carrier drift investigation in amorphous films of As 2 Se 3 and As 2 S 3 prepared by thermal evaporation in a vacuum (TE films) and by RF ion-plasma sputtering (RF films). These techniques strongly differing in the conditions of substance vaporization and condensation atoms on a substrate. The short- and medium-range order of the films atomic structure has been studied by X-ray diffraction analysis using the CuKα radiation (λ=1.5418 Angstrom) and by Raman spectroscopy. Raman spectra were measured at room temperature on Perkin-Elmer Spectrum GX Raman FT-IR Spectrometer (180 deg. backscattering). Vibrational modes were excited vertically polarized light of DPY Nd:YAG laser (1.064 μm). The radii of the first and second coordination spheres, number of the nearest neighbours of As and Se (S) atoms in the first coordination sphere, dimension of the medium-range order domain and 'quasi-period' in that region have been determined for the studied samples. The identification of the structural units in matrix of the film has been carried out, too. It is established that the films prepared by different methods have differences in the parameters of short- and medium range orders. It follows from the comparative analysis of Raman spectra that spectrum of RF films is significantly more complex than that of glass and TE films. The matrix of RF films contains, along with the structural units AsSe 3/2 (AsS 3/2 ) inherent in TE films and glass, other structural units with As and Se (S) excess. It may be

HELP: a model for evaluating the feasibility of using various chemical reaction systems as electronic lasers

Energy Technology Data Exchange (ETDEWEB)

Herbelin, J M; Cohen, N

1975-09-01

An analytical model for estimating the minimum requirements of a chemically pumped electronic laser is developed. From a knowledge of the basic spectroscopic and thermodynamic properties of a particular reaction, the model can quickly classify the system in accordance with the feasibility of generating stimulated emission at different possible wavelengths. Sample calculations of the reactions of barium atoms with nitrous oxide and nitrogen dioxide indicate that the model is sufficiently sensitive to distinguish between very similar systems and, therefore, should be useful in providing classification criteria in the search for a chemically pumped electronic laser.

Research project AUS-10370/CF: electron impact ionization and surface induced reactions of edge plasma constituents

International Nuclear Information System (INIS)

Maerk, T.D.

1999-01-01

In order to better understand elementary reactions which are taking place at the plasma edge of thermonuclear fusion devices, three areas of research were persuaded: I) Experimental studies about electron ionization of neutrals and ions and electron attachment to molecules, II) Theoretical studies about electron ionisation of neutrals and ions and III) Reactive interaction of molecular ions with surfaces

Synthesis of ultrafine alumina powders using egg white as complexing medium

International Nuclear Information System (INIS)

Salem, R.E.P.; Guilherme, K. A.; Chinelatto, A.S.A.; Chinelatto, A.L.

2011-01-01

Synthesis of alumina powders through chemical methods has been attracting much attention of researchers in the past few years, due to the ability to produce powders in nanometric scale with high degree of purity. In this work, there were synthesized alumina powders through a chemical route, using egg white as a complexing medium and aluminium nitrate as the source of Al 3+ cations. Egg white contains ovalbumin, a protein which acts effectively on the isolation of aluminium cations during the mixing process, enabling the formation of ultrafine alumina powders in a relatively economic and environmentally friendly way. The powders obtained by calcinations of the precursor resin were characterized by X-ray diffraction, specific surface area measurements, infrared spectroscopy and scanning electron microscopy. It was observed that the egg white, present at the reaction medium, allowed obtaining transition alumina powders, with high degree of purity. (author)

Determination of the molecular structure via the medium energy electrons (500 eV-1,5 KeV) Ar, N2, Co e HCl

International Nuclear Information System (INIS)

Nogueira, J.C.

1977-01-01

Elastic Differential and Total Differential Cross Sections are measured for electron collision in medium-energy range (500 eV - 1,5 KeV) with argon, nitrogen, carbon monoxide and hydrogen chloride, all in their electronic ground state. Theoretical calculation for the Elastic Differential Cross Sections by atoms were done employing Hartree-Fock-Clementy wave function, and making use of Partial Wave and WKBJ Methods. Exchange effect is included in the case of argon. Independent Atom Model, Half Molecule Model and a new model, the Ionic Model were utilized for the molecular calculations. The Ionic Model is suggested for the interaction between HCl and electrons. Inelastic Differential Cross Section were also computed, making use of the First Born Approximation and Hartree-Fock-Clementi wave function. It is also demonstrated, for the first time, that medium energy electrons (500 eV - 1,5 Kev) can be used to determine molecular structure parameters, in gas phase [pt

Influence of multiple scattering of a relativistic electron in a periodic layered medium on coherent X-ray radiation

Energy Technology Data Exchange (ETDEWEB)

Blazhevich, S. V.; Kos’kova, T. V.; Noskov, A. V., E-mail: noskovbupk@mail.ru [Belgorod State National Research University (Russian Federation)

2016-01-15

A dynamic theory of coherent X-ray radiation generated in a periodic layered medium by a relativistic electron multiply scattered by target atoms has been developed. The expressions describing the spectral–angular characteristics of parametric X-ray radiation and diffracted transition radiation are derived. Numerical calculations based on the derived expressions have been performed.

Charge separation in photoinitiated electron transfer reactions induced by a polyelectrolyte

International Nuclear Information System (INIS)

Meyerstein, D.; Rabani, J.; Matheson, M.S.; Meisel, D.

1978-01-01

When uncharged molecules quench the luminescence of Ru(bpy) 3 /sup 2+*/ by electron transfer to the quencher, the addition of poly(vinyl sulfate) (PVS) may, through its potential field, affect the rate of quenching, enhance the net separated charge yield, and slow the back reaction of the separated photoredox products. In all such cases that we have studied the quenching rate in the presence of PVS was reduced to about 60% of the rate measured in the absence of PVS. For two neutral species, iron(III) nitrilotriacetate (FeNTA) and cobalt(III) acetylacetonate (Co(acac) 3 ), photoreduction of the quencher was observed, and the redox yield escaping geminate recombination was substantially increased by added PVS. In the case of FeNTA the rate of the bulk back reaction was not changed appreciably by the presence of PVS owing to the rapid neutralization of Fe(NTA) - by protonation. For Co(acac) 3 the rate of the bulk back reaction was decreased by several orders of magnitude and the back reaction was shown to occur via the enolate form of the ligand which is released to the bulk solution. 4 figures, 4 tables

Kinetics and mechanisms of photoinduced electron-transfer reaction of zinc myoglobin

International Nuclear Information System (INIS)

Tsukahara, Keiichi; Asami, Satoko; Okada, Mihoko; Sakurai, Takeshi.

1994-01-01

Photoinduced electron transfer (ET) between zinc myoglobin (ZnPPMb) and a variety of quenchers, such as hexacyanoferrate(III)([Fe(CN) 6 ] 3- ) and hexaammineruthenium(III)(Ru(NH 3 ) 6 ] 3+ ions, cationic viologens, copper(II) protein (stellacyanin), and metmyoglobins, has been studied in aqueous degassed solutions. The excited triplet state of ZnPPMb( * ZnPPMb) was quenched by [Fe(CN) 6 ] 3- in a self-associated complex. Both quenching rate constant and formation constant of the self-associated complex decrease with increasing ionic strengths. The thermal backward ET reaction for this system was not observed; it is most likely that the backward ET step is much faster than the quenching reaction. All of the cationic quenchers examined in this work did not form a self-associated complex with * ZnPPMb, and the intermolecular quenching occurred. The thermal backward ET reaction was observed for these cationic quenchers. Not only photoinduced ET but also thermal backward ET reactions were insensitive to the driving force of the reactions, suggesting that the reactions are controlled by conformational changes in ZnPPMb. The quenching rate constants increase with increasing ionic strength for the cationic quenchers. The effects of poly-L-lysine hydrochloride, sodium poly-L-glutamate, and sodium cyclo-hexaphosphate were also examined. The active site of the * ZnPPMb toward both anionic and cationic quenchers is assumed to be the positively charged site near the heme pocket. (author)

Heterogeneous reactions and aerosol formation in flue gas cleaning by electron beam

International Nuclear Information System (INIS)

Baumann, W.; Jordan, S.; Leichsenring, C.H.; Maetzing, H.; Paur, H.R.; Schikarski, W.

1990-08-01

The electron beam dry scrubbing process is a simultaneous method for the removal of SO 2 and NO x from flue gas. By electron irradiation radicals (OH, O 2 H, O) are formed from the main flue gas components which oxidize NO x and SO 2 into the acids HNO 3 and H 2 SO 4 . These are then neutralized by the injection of NH 3 . A submicron aerosol consisting of ammonium salts is formed which is filtered from the offgas. The main pathways of the gas phase chemistry and product formation have been elucidated by experimental and theoretical studies. Back reactions which occur in the gas and the particle phase limit the energy efficiency of the process. By recirculation of irradiated gas into the reaction vessel (multiple irradiation) a significant improvement of removal yields was obtained. This enhancement of the energy efficiency requires the removal of products between the irradiation steps. Studies show that the material balance is complete. Deficits in the N and S balance of the process are due to the additional formation of molecular nitrogen and the deposition of ammonium sulfate in the ducts. Aerosol formation participates only with 30% in the material balance. The remaining 70% of the product are formed by surface reactions in the filter cake (40%) and in the ducts (30%). (orig.) With 38 figs., 29 tabs [de

An Investigation of Electronic Structure and Aromaticity in Medium-Sized Nanoclusters of Gold-Doped Germanium

Directory of Open Access Journals (Sweden)

Xiao-Jun Li

2012-01-01

Full Text Available The electronic property and aromaticity of endohedrally doped and clusters are investigated using the density-functional theory (DFT within the hybrid B3LYP method. The calculated results reveal that the two clusters have high thermodynamic stability reflected by reaction energy. At the same time, it could be hoped that their high stability may arise from the closed-shell spherical aromaticity with eight -electrons satisfying the counting rule with . A popular nucleus-independent chemical shifts (NICSs calculation on basis of magnetic shieldings is also performed to confirm the aromaticity of the three-dimensional nanoclusters with largely negative NICS values. In addition, the electronic features and chemical bonding of the two clusters are analyzed with the help of the density of states (DOS and electron localization function (ELF, and the majority of Ge–Ge bonds on the cage show more covalent characters.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-08-26

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

Chemical reaction effect on MHD free convective surface over a moving vertical plate through porous medium

Directory of Open Access Journals (Sweden)

R.S. Tripathy

2015-09-01

Full Text Available An attempt has been made to study the heat and mass transfer effect in a boundary layer flow of an electrically conducting viscous fluid subject to transverse magnetic field past over a moving vertical plate through porous medium in the presence of heat source and chemical reaction. The governing non-linear partial differential equations have been transformed into a two-point boundary value problem using similarity variables and then solved numerically by fourth order Runge–Kutta fourth order method with shooting technique. Graphical results are discussed for non-dimensional velocity, temperature and concentration profiles while numerical values of the skin friction, Nusselt number and Sherwood number are presented in tabular form for various values of parameters controlling the flow system.

Studies of transfer reactions of photosensitized electrons involving complexes of transition metals in view of solar energy storage

International Nuclear Information System (INIS)

Takakubo, Masaaki

1984-01-01

This research thesis addresses electron transfer reactions occurring during photosynthesis, for example, photosensitized reaction in which chlorophyll is the sensitizer. More specifically, the author studied experimentally electron photo-transfers with type D sensitizers (riboflavin, phenoxazine and porphyrin), and various complexes of transition metals. After a presentation of these experiments, the author describes the photosensitisation process (photo-physics of riboflavin, oxygen deactivation, sensitized photo-oxidation and photo-reduction). The theoretical aspect of electron transfer is then addressed: generalities, deactivation of the riboflavin triplet, initial efficiency of electron transfer. Experimental results on three basic processes (non-radiative deactivation, energy transfer, electron transfer) are interpreted in a unified way by using the non-radiative transfer theory. Some applications are described: photo-electrochemical batteries, photo-oxidation and photo-reduction of the cobalt ion

Effects of ion and electron screening on thermonuclear reaction rates

International Nuclear Information System (INIS)

Brady, L.R. Jr.

1977-01-01

The effects of screening by ions and electrons on thermonuclear reaction rates in stellar plasmas are considered. The enhancement of the reaction rate ranges from negligible to extremely large (on the order of 10 26 or greater). In order to calculate these effects, the potential about a given reacting nucleus is determined. First, Boltzmann-Vlasov and Poisson-Boltzmann equations are solved to yield a Yukawa potential. A suitable approximation to this potential is integrated in the action integral to give the barrier penetration. The screened reaction rate is then found by the saddle-point method. In developing a general formalism to calculate the screened reaction rate and the screening factor, effects due to the finite size of the nucleus are considered and found to be negligible. An expression for the screening factor for resonant reaction rates is also derived. A different and relatively simple approach, based on work of Stewart and Pyatt (1966), is used to find the barrier penetration from the action integral in two approximations: a modified Coulomb potential and a constant-shift potential. Screening factors are calculated for carbon burning at T 6 = 100 and T 6 = 400 for a wide range of densities and also for several examples in late stellar evolution. These screening factors are, for the most part, greater than those given by most others by a few percent at low density to 4 or more orders of magnitude at T 6 = 100 and rho = 10 10 g/cm 3 . Near the edge of the crystalline lattice region, however, they are significantly lower than those of some others. The increase in reaction rates for carbon burning indicates that carbon ignition may occur at lower densities than previously thought and may affect the density at which a supernova shock may occur

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

Energy Technology Data Exchange (ETDEWEB)

Mallouk, T.E.

1993-01-01

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

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

Energy Technology Data Exchange (ETDEWEB)

Tully, John C. [Yale Univ., New Haven, CT (United States)

2017-06-10

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

FOLD-EM: automated fold recognition in medium- and low-resolution (4-15 Å) electron density maps.

Science.gov (United States)

Saha, Mitul; Morais, Marc C

2012-12-15

Owing to the size and complexity of large multi-component biological assemblies, the most tractable approach to determining their atomic structure is often to fit high-resolution radiographic or nuclear magnetic resonance structures of isolated components into lower resolution electron density maps of the larger assembly obtained using cryo-electron microscopy (cryo-EM). This hybrid approach to structure determination requires that an atomic resolution structure of each component, or a suitable homolog, is available. If neither is available, then the amount of structural information regarding that component is limited by the resolution of the cryo-EM map. However, even if a suitable homolog cannot be identified using sequence analysis, a search for structural homologs should still be performed because structural homology often persists throughout evolution even when sequence homology is undetectable, As macromolecules can often be described as a collection of independently folded domains, one way of searching for structural homologs would be to systematically fit representative domain structures from a protein domain database into the medium/low resolution cryo-EM map and return the best fits. Taken together, the best fitting non-overlapping structures would constitute a 'mosaic' backbone model of the assembly that could aid map interpretation and illuminate biological function. Using the computational principles of the Scale-Invariant Feature Transform (SIFT), we have developed FOLD-EM-a computational tool that can identify folded macromolecular domains in medium to low resolution (4-15 Å) electron density maps and return a model of the constituent polypeptides in a fully automated fashion. As a by-product, FOLD-EM can also do flexible multi-domain fitting that may provide insight into conformational changes that occur in macromolecular assemblies.

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

Science.gov (United States)

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

2015-01-01

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

Stopping power and energy loss cross section of a point charge penetrating through a dense medium of bound electrons

International Nuclear Information System (INIS)

Belkacem, A.; Sigmund, P.; Odense Univ.

1989-01-01

We have derived the dielectric function ε(k,ω) in the Lindhard approximation for a medium consisting of electrons individually bound by harmonic forces. The dielectric function is expressible in terms of a hypergeometric series and approaches well-known results in the limits of negligible binding, large momentum transfer, and long wavelength, respectively. The stopping power of a moving point charge scales very well with the shifted resonance frequency α 0 = (ω O 2 + ω P 2 ) 1/2 (ω O = oscillator frequency; ω P = plasma frequency) that follows from classical dispersion theory. The results differ noticeably from free-electron behavior even at rather high electron density. The discrete excitation levels of an isolated harmonic oscillator are increasingly shifted and broadened with increasing electron density. 15 refs., 2 figs

Vector mesons in reactions with colliding electron-positron beams

International Nuclear Information System (INIS)

Rekalo, M.P.; Gakh, G.I.

1980-01-01

Polarization phenomena in the processes of vector meson production in reactions with colliding electron-positron beams e + e - → V+X, where V is a vector meson, X is a nondetected set of particles are investigated. For the one-photon mechanism of the process, where V and X are hadrons, the mutually unambiguous correspondence between the structural functions is found. The dependence of the e + e - → VX differential cross section upon the electron and positron polarizations is calculated using the virtual photon density matrix in the helicity basis. This formalism permits to take explicitly into account the P-invariance consequences for the angular distribution of the V-meson decay products. For the processes e + e - → πA 1 , and e + e - → rho + rho - the structural functions are calculated in terms of the corresponding electromagnetic form factors. It is noted that six functions out ten real structural functions describing the e + e - → VX reaction can be determined by means of investigation of the angular distribution of the V-meson decay products which is produced in collisions of unpolarized leptons. To study the collision of polarized leptons one more structural function can be determined. The formation of the X system with definite values of parity and spin is characterized by seven structural functions, five of which can be found while studying the angular distribution of the V-meson decay products produced in e + e - collisions with unpolarized (polarized) particles. If the spin of the X state is 1, in experiments with polarized beams all structural functions can be determined while investigating the angular distribution of the V-meson decay products

Functional LH1 antenna complexes influence electron transfer in bacterial photosynthetic reaction centers

NARCIS (Netherlands)

Visschers, R.W.; Vulto, S.I.E.; Jones, M.R.; van Grondelle, R.; Kraayenhof, R.

1999-01-01

The effect of the light harvesting 1 (LH1) antenna complex on the driving force for light-driven electron transfer in the Rhodobacter sphaeroides reaction center has been examined. Equilibrium redox titrations show that the presence of the LH1 antenna complex influences the free energy change for

Functional LH1 antenna complexes influence electron transfer in bacterial photosynthetic reaction centers.

NARCIS (Netherlands)

Visschers, R.W.; Vulto, S.I.E.; Jones, M.R.; van Grondelle, R.; Kraayenhof, R.

1999-01-01

The effect of the light harvesting 1 (LH1) antenna complex on the driving force for light-driven electron transfer in the Rhodobacter sphaeroides reaction center has been examined. Equilibrium redox titrations show that the presence of the LH1 antenna complex influences the free energy change for

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

Science.gov (United States)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

Polymeric reaction of polymer-monomer system for pressure sensitive adhesives by low energy electron beam

International Nuclear Information System (INIS)

Takiguchi, R.; Uryu, T.

1985-01-01

Application of low-energy electron beam to non-solvent type pressure sensitive adhesives is investigated. The adhesive properties such as peel strength and holding time (dead-load strength) were closely related to the reaction of acrylate polymer-monomer systems. The reaction behavior is elucidated by combining the measurement of gel fraction, infrared spectrum of gel, and the molecular weight distribution detected by gel permeation chromatography. It was important for the production of pressure sensitive adhesives by electron beam that the adhesive with high peel strength and long holding time is composed of a proper combination of three factors, that is, about 35% gel fraction, 25% monomer units in gel, and 15% graft efficiency by irradiating the polymer-monomer system containing low molecular weight poly (butyl acrylate). (author)

Analytical electron microscopy examination of solid reaction products in long-term test of SRL 200 waste glasses

International Nuclear Information System (INIS)

Buck, E.C.; Fortner, J.A.; Bates, J.K.; Feng, X.; Dietz, N.L.; Bradley, C.R.; Tani, B.S.

1993-01-01

Alteration phases, found on the leached surfaces and present as colloids in the leachates of 200-based frit (fully active and simulated) nuclear waste glass, reacted under static test conditions, at a surface area to leachate volume ratio of 20,000 m -1 for 15 days to 728 days, have been examined by analytical electron microscopy. The compositions of the secondary phases were determined using x-ray energy dispersive spectroscopy and electron energy loss spectroscopy, and structural analysis was accomplished by electron diffraction. Long-term samples of simulated glass, which had undergone an acceleration of reaction after 182 days, possessed a number of silicate secondary phases, including; smectite (iron silicate and potassium iron alumina-silicate, weeksite (uranium silicate), zeolite (calcium potassium alumino-silicate), tobermorite (calcium silicate), and a pure silica phase. However, uranium silicates and smectite have also been observed in tests, which have not undergone the acceleration of reaction, in both the leachate and leached layer, suggesting that these phases are not responsible for the acceleration of reaction

Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics : Effect of Franck-Condon States

NARCIS (Netherlands)

Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K.

2017-01-01

Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches

Mechanisms before Reactions: A Mechanistic Approach to the Organic Chemistry Curriculum Based on Patterns of Electron Flow

Science.gov (United States)

Flynn, Alison B.; Ogilvie, William W.

2015-01-01

A significant redesign of the introductory organic chemistry curriculum at the authors' institution is described. There are two aspects that differ greatly from a typical functional group approach. First, organic reaction mechanisms and the electron-pushing formalism are taught before students have learned a single reaction. The conservation of…

Current state and prospects of industrial application of electron beam irradiation

International Nuclear Information System (INIS)

Washio, Masakazu

2000-01-01

This paper reviewed the low energy, medium energy, and high energy accelerators used for the industrial application of electron beams. Next, it described the absorption of electron beam energy, distribution of the absorbed dose of electron beams in a substance, and the basis of electron beam reaction. Furthermore, as the industrial application examples of electron beams, it briefly described about the reforming and curing of polymers, irradiation effect of inorganic material (characteristic control of semiconductors), and sterilization. Regarding curing, as examples using mainly low energy electron beams (300 keV or below), this paper briefly explained the manufacture of thermosensitive recording materials, electron beam cured silicone for release papers, tunnel metal interior finishing board, high gloss - high smooth paper. Finally, it looked at latest trends and prospects of electron beam generators. (A.O.)

Low energy electron-initiated ion-molecule reactions of ribose analogues

International Nuclear Information System (INIS)

Mozejko, P.

2003-01-01

Recent experiments in which plasmid DNA samples were bombarded with low energy ( 2 O, DNA bases, and sugar-phosphate backbone analogues. To this end, the cyclic molecule tetrahydrofuran, and its derivatives, provide useful models for the sugar-like molecules contained in the backbone of DNA. In addition to LEE induced dissociation by processes such as dissociative electron attachment (DEA), molecules may be damaged by ions and neutral species of non-thermal energies created by LEE in the surrounding environment. In this contribution, we investigate with electron stimulated desorption techniques, LEE damage to films of desoxy-ribose analogues in the presence of various molecular coadsorbates, that simulate changes in local molecular environment. In one type of experiments tetrahydrofuran is deposited onto multilayer O2. A desorbed signal of OH - indicates ion-molecule reactions of the type O - + C 4 H 8 O -> OH - + C 4 H 7 O, where the O - was formed initially by DEA to O 2 . Further electron stimulated desorption measurements for tetrahydrofuran and derivatives adsorbed on H 2 O, Kr, N 2 O and CH 3 OH will be presented and discussed

Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth.

Science.gov (United States)

Sutter, Eli A; Sutter, Peter W

2014-12-03

In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e(-)aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e(-)aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e(-)aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e(-)aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution.

Experimental Evidence of Radiation Reaction in the Collision of a High-Intensity Laser Pulse with a Laser-Wakefield Accelerated Electron Beam

Science.gov (United States)

Cole, J. M.; Behm, K. T.; Gerstmayr, E.; Blackburn, T. G.; Wood, J. C.; Baird, C. D.; Duff, M. J.; Harvey, C.; Ilderton, A.; Joglekar, A. S.; Krushelnick, K.; Kuschel, S.; Marklund, M.; McKenna, P.; Murphy, C. D.; Poder, K.; Ridgers, C. P.; Samarin, G. M.; Sarri, G.; Symes, D. R.; Thomas, A. G. R.; Warwick, J.; Zepf, M.; Najmudin, Z.; Mangles, S. P. D.

2018-02-01

The dynamics of energetic particles in strong electromagnetic fields can be heavily influenced by the energy loss arising from the emission of radiation during acceleration, known as radiation reaction. When interacting with a high-energy electron beam, today's lasers are sufficiently intense to explore the transition between the classical and quantum radiation reaction regimes. We present evidence of radiation reaction in the collision of an ultrarelativistic electron beam generated by laser-wakefield acceleration (ɛ >500 MeV ) with an intense laser pulse (a0>10 ). We measure an energy loss in the postcollision electron spectrum that is correlated with the detected signal of hard photons (γ rays), consistent with a quantum description of radiation reaction. The generated γ rays have the highest energies yet reported from an all-optical inverse Compton scattering scheme, with critical energy ɛcrit>30 MeV .

The ribose and glycine Maillard reaction in the interstellar medium ...

Indian Academy of Sciences (India)

WINTEC

mechanics are briefly addressed in this work. Keywords. Density functional computational study; ribose; glycine; Maillard reaction; gaseous phase .... following the total mass balance of the reaction. Thus, ..... Jalbout A F Origin Life Evol. Biosph ...

Kinetics of Oxidation of 3-Benzoylpropionic Acid by N-Bromoacetamide in Aqueous Acetic Acid Medium

Directory of Open Access Journals (Sweden)

N. A. Mohamed Farook

2011-01-01

Full Text Available The kinetics of oxidation of 3-benzoylpropionic acid (KA with N-bromoacetamide (NBA have been studied potentiometrically in 50:50 (v/v aqueous acetic acid medium at 298 K The reaction was first order each with respect to [KA], [NBA] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of acetamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. A mechanism consistent with observed results have been proposed and the related rate law was deduced.

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

DEFF Research Database (Denmark)

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

2013-01-01

The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer...

Contributions of electron microscopy to the understanding of reactions on compound semiconductor surfaces

International Nuclear Information System (INIS)

Sands, T.

1986-01-01

Reacted films on compound semiconductor substrates present challenging materials characterization problems which often require the application of transmission electron microscopy (TEM) techniques. In this paper, both the problem - solving potential of the TEM techniques and the limits imposed by preparation of thin film/compound semiconductor TEM specimens are discussed. Studies of the Ni/GaAs, CuCl/aq)/CdS and Pd/GaAs reactions exemplify the role of TEM in identifying and determining the spatial distribution of interface - stabilized polymorphs and new ternary phases (e.g. tetragonal Cu/sub 2/S, Ni/sub 3/GaAs and Pd/sub x/GaAs). These examples also serve to clarify the relationship between TEM and complementary analysis techniques such as Rutherford backscattering spectrometry, Auger electron spectroscopy and glancing-angle x-ray diffraction. In particular, it is argued that a combination of (1) high-spatial-resolution information obtained by TEM and (2) an indication of the ''average'' behavior provided by data from a complementary characterization technique provide the minimum quality and quantity of data necessary to understand most reactions on compound semiconductor substrates

Use of carbon dioxide as a reaction medium in the thermo-chemical process for the enhanced generation of syngas and tuning adsorption ability of biochar

International Nuclear Information System (INIS)

Cho, Dong-Wan; Kwon, Eilhann E.; Song, Hocheol

2016-01-01

Highlights: • Utilizing CO_2 as a reaction medium in thermo-chemical conversion of aquatic biomass. • Enhanced generation of syngas in the presence of CO_2. • Considerable reduction of pyrolytic oil in CO_2-assisted pyrolysis. • Generation of biochar with high surface area and more porous structure by CO_2. - Abstract: This study mechanistically investigated the influences of CO_2 on syngas (H_2 and CO) production during thermo-chemical conversion of red seaweed, and further explored the possible utility of the produced biochar as a medium for adsorption of inorganic/organic contaminants in aqueous phase. In order to elucidate the key roles of CO_2 in the thermo-chemical process, the composition analysis of syngas and the qualitative analysis of pyrolytic oil were conducted and compared with those in pyrolysis in N_2 condition. Pyrolysis of red seaweed in the presence of CO_2 led to the enhanced generation of syngas at the entire experimental temperatures. For example, the ratio of CO to H_2 in the presence of CO_2 at 620 °C was enhanced by ∼400%, as compared to the case in N_2. This enhanced generation of syngas resulted in significant pyrolytic oil reduction by ∼70% at 620 °C via the unknown reactions between VOCs and CO_2. In addition, biochar generated in the CO_2 environment exhibited comparatively higher surface area (61 m"2 g"−"1) and more porous structure. The morphological modification induced by CO_2 provided the favorable condition for removal of methylene blue from the aqueous phase. Thus, this study experimentally demonstrated that exploiting CO_2 as a reaction medium would provide an attractive option for the enhanced generation of syngas and the tuned adsorption capability of biochar.

Using Ring Strain to Control 4π-Electrocyclization Reactions: Torquoselectivity in Ring Closing of Medium-Ring Dienes and Ring Opening of Bicyclic Cyclobutenes.

Science.gov (United States)

Boon, Byron A; Green, Aaron G; Liu, Peng; Houk, K N; Merlic, Craig A

2017-05-05

Syntheses of strained cyclic dienes were accomplished via palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generate strained (E,E)-1,3-dienes that undergo spontaneous 4π-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by the strain in the medium-ring (E,E)-1,3-diene intermediate. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. DFT calculations verified the thermodynamic versus kinetic control of the reactions, and kinetic studies are in excellent agreement with the calculated energy changes. An extension of the tandem coupling/4π-electrocyclization pathway was demonstrated by a palladium(II)-catalyzed oxidative homocoupling/8π-electrocyclization cascade.

Spin dynamics and zero-field splitting constants of the triplet exciplex generated by photoinduced electron transfer reaction between erythrosin B and duroquinone

OpenAIRE

Tachikawa, Takashi; Kobori, Yasuhiro; Akiyama, Kimio; Katsuki, Akio; Steiner, Ulrich; Tero-Kubota, Shozo

2002-01-01

The spin dynamics of the duroquinone anion radical generated by photoinduced electron transfer reactions from triplet erythrosin B to duroquinone has been studied by using transient absorption and pulsed FT-EPR spectroscopy. Triplet exciplex formation as the reaction intermediate is verified by the observation of spin orbit coupling induced electron spin polarization. The kinetic parameters for exciplex formation and the intrinsic enhancement factors of electron spin polarization are determin...

Electrons in water radiolysis

International Nuclear Information System (INIS)

Laverne, J.A.; Pimblott, S.M.

2006-01-01

The hydrated electron is the main reducing species produced in the radiolysis of water. Many studies have examined its reactivity using pulsed radiolysis techniques and competition kinetics. Data bases list hundreds of rate coefficients for reaction of the hydrated electron with substances ranging from inorganic ions like nitrate to biopolymers like DNA. Although the chemistry of the hydrated electron is often examined, its mechanism of formation and variation in yield are considerable less known, especially under extreme conditions such as in high temperature water or with heavy ion radiolysis. This work will examine various aspects of the radiation chemistry of the hydrated electron beginning with the generation of secondary electrons in primary energy loss events during the passage of ionizing radiation to the radiolytic yields of the hydrated electron produced by different types of radiation. Ion radiation is a 'white light source.' Energy losses range from the minimum excitation energy of the medium up to the kinematic maximum determined by the collision parameters. However, certain energy loss events are more probable than others. The dipole oscillator strength distributions of media essentially give the probability of energy loss events in collisions with no momentum transfer. Dipole oscillator distributions have been constructed from experimental data for a wide variety of materials including all the phases of water. Calculations using cross sections based on dipole oscillator distributions show that the most probable energy loss event in water is only about 20 eV with an average value closer to 60 eV. The preponderance of energy loss events of less than 100 eV means that many low energy electrons are formed by the passage of a single ion. Low energy electrons have short mean free paths and they remain in the vicinity of the primary energy loss events. The spatial distribution of these low energy electrons defines the radial track structure of the incident

Experimental Evidence of Radiation Reaction in the Collision of a High-Intensity Laser Pulse with a Laser-Wakefield Accelerated Electron Beam

Directory of Open Access Journals (Sweden)

J. M. Cole

2018-02-01

Full Text Available The dynamics of energetic particles in strong electromagnetic fields can be heavily influenced by the energy loss arising from the emission of radiation during acceleration, known as radiation reaction. When interacting with a high-energy electron beam, today’s lasers are sufficiently intense to explore the transition between the classical and quantum radiation reaction regimes. We present evidence of radiation reaction in the collision of an ultrarelativistic electron beam generated by laser-wakefield acceleration (ϵ>500  MeV with an intense laser pulse (a_{0}>10. We measure an energy loss in the postcollision electron spectrum that is correlated with the detected signal of hard photons (γ rays, consistent with a quantum description of radiation reaction. The generated γ rays have the highest energies yet reported from an all-optical inverse Compton scattering scheme, with critical energy ϵ_{crit}>30  MeV.

The role of the excited electronic states in the C++H2O reaction

International Nuclear Information System (INIS)

Flores, Jesus R.; Gonzalez, Adan B.

2008-01-01

The electronic excited states of the [COH 2 ] + system have been studied in order to establish their role in the dynamics of the C + +H 2 O→[COH] + +H reaction, which is a prototypical ion-molecule reaction. The most relevant minima and saddle points of the lowest excited state have been determined and energy profiles for the lowest excited doublet and quartet electronic states have been computed along the fragmentation and isomerization coordinates. Also, nonadiabatic coupling strengths between the ground and the first excited state have been computed where they can be large. Our analysis suggests that the first excited state could play an important role in the generation of the formyl isomer, which has been detected in crossed beam experiments [D. M. Sonnenfroh et al., J. Chem. Phys. 83, 3985 (1985)], but could not be explained in quasiclassical trajectory computations [Y. Ishikawa et al., Chem. Phys. Lett. 370, 490 (2003); J. R. Flores, J. Chem. Phys. 125, 164309 (2006)

Characterization of the free energy dependence of an interprotein electron transfer reaction by variation of pH and site-directed mutagenesis.

Science.gov (United States)

Dow, Brian A; Davidson, Victor L

2015-10-01

The interprotein electron transfer (ET) reactions of the cupredoxin amicyanin, which mediates ET from the tryptophan tryptophylquinone (TTQ) cofactor of methylamine dehydrogenase to cytochrome c-551i have been extensively studied. However, it was not possible to perform certain key experiments in that native system. This study examines the ET reaction from reduced amicyanin to an alternative electron acceptor, the diheme protein MauG. It was possible to vary the ΔG° for this ET reaction by simply changing pH to determine the dependence of kET on ΔG°. A P94A mutation of amicyanin significantly altered its oxidation-reduction midpoint potential value. It was not possible to study the ET from reduced P94A amicyanin to cytochrome c-551i in the native system because that reaction was kinetically coupled. However, the reaction from reduced P94A amicyanin to MauG was a true ET reaction and it was possible to determine values of reorganization energy (λ) and electronic coupling for the reactions of this variant as well as native amicyanin. Comparison of the λ values associated with the ET reactions between amicyanin and the TTQ of methylamine dehydrogenase, the diheme center of MauG and the single heme of cytochrome c-551i, provides insight into the factors that dictate the λ values for the respective reactions. These results demonstrate how study of ET reactions with alternative redox partner proteins can complement and enhance our understanding of the reactions with the natural redox partners, and further our understanding of mechanisms of protein ET reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

Theory of photon and electron induced reactions: Progress report, July 1, 1988--June 30, 1989

International Nuclear Information System (INIS)

Onley, D.S.; Wright, L.E.

1989-03-01

During the first twenty months of our new grant from the Department of Energy we have made considerable progress or have completed our studies on the following aspects of the general investigation of electron and photon induced reactions: photo- and electro-production of mesons; the radiation tail accompanying elastic electron scattering and pair production; and studies involving the relativistic shell model. We will report on each of these developments in the following sections

Theory of photon and electron induced reactions: Progress report, July 1, 1986-June 30, 1987

International Nuclear Information System (INIS)

Onley, D.S.; Wright, L.E.

1988-07-01

During the third year of our three-year contract from the Department of Energy, we have made considerable progress or have completed our studies on the following aspects of the general investigation of electron and photon induced reactions; photo- and electro-production of mesons; the radiation tail accompanying elastic electron scattering and pair production; studies involving relativistic shell model; and electrofission coincidence angular distributions. We will report on each of these developments in this paper

Kinetic Studies on the Selective Oxidation of Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis

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K. Bijudas

2014-07-01

Full Text Available Kinetic studies on the oxidation of benzyl alcohol and substituted benzyl alcohols in benzene as the reaction medium have been studied by using potassium dichromate under phase transfer catalysis (PTC. The phase transfer catalysts (PT catalysts used were tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB.  Benzyl alcohols were selectively oxidised to corresponding benzaldehydes in good yield (above 90%.  The order of reactivity among the studied benzyl alcohols is p - OCH3 > p - CH3 > - H > p - Cl.  Plots of log k2 versus Hammett's substituent constant (s has been found to be curve shaped and this suggests that there should be a continuous change in transition state with changes in substituent present in the substrate from electron donating to electron withdrawing. A suitable mechanism has been suggested in which the rate determining step involves both C - H bond cleavage and C - O bond formations in concerted manner. © 2014 BCREC UNDIP. All rights reserved.Received: 16th March 2014; Revised: 18th May 2014; Accepted: 18th May 2014[How to Cite: Bijudas, K., Bashpa, P., Nair, T.D.R. (2014. Kinetic Studies on the Selective Oxidation of Benzyl Alcohol and Substituted Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-147. (doi:10.9767/bcrec.9.2.6476.142-147][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6476.142-147] 

Electron beam induced emission from carbon plasmas

International Nuclear Information System (INIS)

Whetstone, S.; Kammash, T.

1989-01-01

Plasma use as a lasing medium has many potential advantages over conventional techniques including increased power levels and greater wavelength ranges. The basic concept is to heat and then rapidly cool a plasma forcing inversion through bottleneck creation between the recombination reaction populating a given energy level and the subsequent decay processes. Much effort has been devoted to plasmas heated by lasers and pinch devices. The authors are concerned here with electron beam heated plasmas focusing on the CIV 5g-4f transition occurring at 2530 Angstroms. These studies were initiated to provide theoretical support for experiments being performed at the University of Michigan using the Michigan Electron Long-Pulse Beam Accelerator (MELBA)

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

Energy Technology Data Exchange (ETDEWEB)

Cames, B

1997-12-31

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media ({<=} 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 {<=} E {<=} 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

A medium energy neutron deep penetration experiment

International Nuclear Information System (INIS)

Amian, W.; Cloth, P.; Druecke, V.; Filges, D.; Paul, N.; Schaal, H.

1986-11-01

A deep penetration experiment conducted at the Los Alamos WNR facility's Spallation Neutron Target is compared with calculations using intra-nuclear-cascade and S N -transport codes installed at KFA-IRE. In the experiment medium energy reactions induced by neutrons between 15 MeV and about 150 MeV inside a quasi infinite slab of iron have been measured using copper foil monitors. Details of the experimental procedure and the theoretical methods are described. A comparison of absolute reaction rates for both experimentally and theoretically derived reactions is given. The present knowledge of the corresponding monitor reaction cross sections is discussed. (orig.)

Reactions of the hydrated electron with pyrene in lipid bilayer vesicles

International Nuclear Information System (INIS)

Schnecke, W.; Graetzel, M.; Henglein, A.

1977-01-01

Pyrene and some pyrene derivatives were solubilized in bilayer vesicles of lecithin and the rates of lecithin and the rates of reaction with the hydrated electron investigated. The concentration of the vesicles was 1.3 x 10 -7 M, that of pyrene 10 -6 - 10 -4 M. The rate constant decreases with increasing pyrene concentration. The effect is explained by the highly inhomogeneous distribution of pyrene molecules in the solutions. Only those pyrene molicules are reactive that reside close to the outer surface of the vesicles. The anions of pyrene formed disappear in a second order process. It is concluded that the anions are rapidly detached from their vesicular carriers and react with each other in the aqueous phase. Fluorescence, light scattering and electron microscopic investigations were also carried out to obtain information about the properties of the vesicles used. (orig.) [de

Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

Directory of Open Access Journals (Sweden)

Pégot Bruce

2006-09-01

Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

Development of time-resolved electron momentum spectroscopy. Toward real-time imaging of frontier electrons in molecular reactions

International Nuclear Information System (INIS)

Yamazaki, M.; Takahashi, M.

2016-01-01

This report will introduce a new experimental technique to readers, which we would like to propose towards advances in the field of molecular reaction dynamics. It is time-resolved electron momentum spectroscopy and aims to take in momentum space snapshots of the rapid change of molecular orbitals, which is the driving force behind any structural changes occurring in transient molecules. Following a description of the working principle of the technique, some preliminary result will be presented in order to illustrate the current performance of the apparatus. (author)

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

International Nuclear Information System (INIS)

Geraldes, Adriana Napoleão; Furtunato da Silva, Dionisio; Pino, Eddy Segura; Martins da Silva, Júlio César; Brambilla de Souza, Rodrigo Fernando; Hammer, Peter; Spinacé, Estevam Vitório; Neto, Almir Oliveira; Linardi, Marcelo; Coelho dos Santos, Mauro

2013-01-01

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd:Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3–5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd:Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 90 °C, and the best performance of 44 mW cm −2 in 2.0 mol L −1 ethanol was obtained at 85 °C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support

Role of Electronic Structure In Ion Band State Theory of Low Energy Nuclear Reactions

Science.gov (United States)

Chubb, Scott

2004-03-01

The Nuts and Bolts of our Ion Band State (IBS) theory of low energy nuclear reactions (LENR's) in palladium-deuteride (PdD) and palladium-hydride (PdH) are the electrons that hold together or tear apart the bonds (or lack of bonds) between deuterons (d's) or protons (p's) and the host material. In PdDx and PdH_x, this bonding is strongly correlated with loading: in ambient loading conditions (x< 0. 6), the bonding in hibits IBS occupation. As x arrow 1, slight increases and decreases in loading can lead to vibrations (which have conventionally been thought to occur from phonons) that can induce potential losses or increases of p/d. Naive assumptions about phonons fail to include these losses and increases. These effects can occur because neither H or D has core electrons and because in either PdD or PdH, the electrons near the Fermi Energy have negligible overlap with the nucleus of either D or H. I use these ideas to develop a formal justification, based on a generalization of conventional band theory (Scott Chubb, "Semi-Classical Conduction of Charged and Neutral Particles in Finite Lattices," 2004 March Meeting."), for the idea that occupation of IBS's can occur and that this can lead to nuclear reactions.

Analysis of mechanism of complex chemical reaction taking radiation chemical purification of gases from impurities as an example

International Nuclear Information System (INIS)

Gerasimov, G.Ya.; Makarov, V.N.

1997-01-01

Algorithm of selecting optimal mechanism of complex chemical reaction, enabling to reduce the number of its stages, is suggested. Main steps of constructing the kinetic model of the medium are considered, taking the radiation chemical purification (using fast electron radiation) of gases (N 2 , CO 2 , O 2 and others) from impurities as an example. 17 refs., 3 figs., 2 tabs

An in-situ chemical reaction deposition of nanosized wurtzite CdS thin films

International Nuclear Information System (INIS)

Chu Juan; Jin Zhengguo; Cai Shu; Yang Jingxia; Hong Zhanglian

2012-01-01

Nanocrystalline CdS thin films were deposited on glass substrates by an ammonia-free in-situ chemical reaction synthesis technique using cadmium cationic precursor solid films as reaction source and sodium sulfide based solutions as anionic reaction medium. Effects of ethanolamine addition to the cadmium cationic precursor solid films, deposition cycle numbers and annealing treatments in Ar atmosphere on structure, morphology, chemical composition and optical properties of the resultant films were investigated by X-ray diffraction, field emission scanning electron microscope, energy dispersive X-ray analysis and UV–Vis spectra measurements. The results show that CdS thin films deposited by the in-situ chemical reaction synthesis have wurtzite structure with (002) plane preferential orientation and crystallite size is in the range of 16 nm–19 nm. The growth of film thickness is almost constant with deposition cycle numbers and about 96 nm per cycle.

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

International Nuclear Information System (INIS)

Shin, Kwang Min; Watt, Richard K.; Watt, Gerald D.; Choi, Sang H.; Kim, Hyug-Han; Kim, Sun I.; Kim, Seon Jeong

2010-01-01

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

Electron transport effects in ion induced electron emission

Energy Technology Data Exchange (ETDEWEB)

Dubus, A. [Universite Libre de Bruxelles, Service de Metrologie Nucleaire (CP 165/84), 50 av. FD Roosevelt, B-1050 Brussels (Belgium)]. E-mail: adubus@ulb.ac.be; Pauly, N. [Universite Libre de Bruxelles, Service de Metrologie Nucleaire (CP 165/84), 50 av. FD Roosevelt, B-1050 Brussels (Belgium); Roesler, M. [Karl-Pokern-Str. 12, D-12587 Berlin (Germany)

2007-03-15

Ion induced electron emission (IIEE) is usually described as a three-step process, i.e. electron excitation by the incident projectile, electron transport (and multiplication) and electron escape through the potential barrier at the surface. In many cases, the first step of the process has been carefully described. The second step of the process, i.e. electron transport and multiplication, has often been treated in a very rough way, a simple decreasing exponential law being sometimes used. It is precisely the aim of the present work to show the importance of a correct description of electron transport and multiplication in a theoretical calculation of IIEE. A short overview of the electron transport models developed for IIEE is given in this work. The so-called 'Infinite medium slowing-down model' often used in recent works is evaluated by means of Monte Carlo simulations. In particular, the importance of considering correctly the semi-infinite character of the medium and the boundary condition at the vacuum-medium interface is discussed. Quantities like the electron escape depth are also briefly discussed. This evaluation has been performed in the particular case of protons (25keV

Pulsed laser-assisted focused electron-beam-induced etching of titanium with XeF2: enhanced reaction rate and precursor transport.

Science.gov (United States)

Noh, J H; Fowlkes, J D; Timilsina, R; Stanford, M G; Lewis, B B; Rack, P D

2015-02-25

In order to enhance the etch rate of electron-beam-induced etching, we introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. The evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. The increased etch rate is attributed to photothermally enhanced Ti-F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

Topological Aspects of Chemical Reactivity. Destiny of Electron Pairs in Allowed and Forbidden Pericyclic Reactions.

Czech Academy of Sciences Publication Activity Database

Ponec, Robert

2017-01-01

Roč. 30, č. 12 (2017), č. článku e3706. ISSN 0894-3230 Institutional support: RVO:67985858 Keywords : curved arrow formalism * electron reorganization * pericyclic reactions Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 1.336, year: 2016

Shape nuclei and nuclear reactions

International Nuclear Information System (INIS)

Yushkov, A.V.

1975-01-01

Experimental methods for obtaining the nucleus shape parameters are reviewed throughout the period of 1955-1975. Spatial properties of a nucleus, which can be directly or indirectly measured, are determined. They include: parameters of nucleus localization in space; parameters characterizing the nucleus nonsphericity; parameters of the nucleus nonaxiality. Dimensional parameters of a nucleus, namely, radius R and surface ΔR are derived from electron scattering. The deformation sign is indirectly obtained in the experiments. Parameters of the nucleus shape, namely, the sign and magnitude of nuclear deformation are derived from the mean energy proton scattering by a coupled channels method. The only direct way of deriving the nucleus surface deformation signs is the method of the Blaire phase shift. Results on scattering of electrons, protons, and α-particles on light and medium nuclei are reported. Data on the nucleus shape can be also obtained from reactions with heavy ions. A difference between strong absorptions of incident particles of high and average energy by a nucleus is noted. Numerous diagrams illustrate experimental and theoretical results

The dependence of the electronic coupling on energy gap and bridge conformation - Towards prediction of the distance dependence of electron transfer reactions

International Nuclear Information System (INIS)

Eng, Mattias P.; Albinsson, Bo

2009-01-01

The attenuation factor, β, for the distance dependence of electron exchange reactions is a sensitive function of the donor-bridge energy gap and bridge conformation. In this work the electronic coupling for electron and triplet excitation energy transfer has been investigated for five commonly used repeating bridge structures. The investigated bridge structures are OF (oligo fluorene), OP (oligo phenylene), OPE (oligo p-phenyleneethynylene), OPV (oligo phenylenevinylene), and OTP (oligo thiophene). Firstly, the impact of the donor-bridge energy gap was investigated by performing calculations with a variety of donors appended onto bridges that were kept in a planar conformation. This resulted in, to our knowledge, the first presented sets of bridge specific parameters to be inserted into the commonly used McConnell model. Secondly, since at experimental conditions large conformational flexibility is expected, a previously developed model that takes conformational disorder of the bridge into account has been applied to the investigated systems [M.P. Eng, T. Ljungdahl, J. Martensson, B. Albinsson, J. Phys. Chem. B 110 (2006) 6483]. This model is based on Boltzmann averaging and has been shown to describe the temperature dependence of the attenuation factor through OPE-bridges. Together, the parameters describing the donor-bridge energy gap dependence, for planar bridge structures, and the Boltzmann averaging procedure, describing the impact of rotational disorder, have the potential to a priori predict attenuation factors for electron and excitation energy transfer reactions through bridged donor-acceptor systems

Electron flux during pericyclic reactions in the tunneling limit: Quantum simulation for cyclooctatetraene

International Nuclear Information System (INIS)

Hege, Hans-Christian; Manz, Joern; Marquardt, Falko; Paulus, Beate; Schild, Axel

2010-01-01

Graphical abstract: In the limit of coherent tunneling, double bond shifting (DBS) of cyclooctatetraene from a reactant (R) to a product (P) is associated with pericyclic electron fluxes from double to single bonds, corresponding to a pincer-motion-type set of arrows in the Lewis structures, each representing a transfer of 0.19 electrons. - Abstract: Pericyclic rearrangement of cyclooctatetraene proceeds from equivalent sets of two reactants to two products. In the ideal limit of coherent tunneling, these reactants and products may tunnel to each other by ring inversions and by double bond shifting (DBS). We derive simple cosinusoidal or sinusoidal time evolutions of the bond-to-bond electron fluxes and yields during DBS, for the tunneling scenario. These overall yields and fluxes may be decomposed into various contributions for electrons in so called pericyclic, other valence, and core orbitals. Pericyclic orbitals are defined as the subset of valence orbitals which describe the changes of Lewis structures during the pericyclic reaction. The quantum dynamical results are compared with the traditional scheme of fluxes of electrons in pericyclic orbitals, as provided by arrows in Lewis structures.

Electrochemical Reduction of Oxygen on Anthraquinone/Carbon Nanotubes Nanohybrid Modified Glassy Carbon Electrode in Neutral Medium

Directory of Open Access Journals (Sweden)

Zheng Gong

2013-01-01

Full Text Available The electrochemical behaviors of monohydroxy-anthraquinone/multiwall carbon nanotubes (MHAQ/MWCNTs nanohybrid modified glassy carbon (MHAQ/MWCNTs/GC electrodes in neutral medium were investigated; also reported was their application in the electrocatalysis of oxygen reduction reaction (ORR. The resulting MHAQ/MWCNTs nanohybrid was characterized by scanning electron microscope (SEM and transmission electron microscope (TEM. It was found that the ORR at the MHAQ/MWCNTs/GC electrode occurs irreversibly at a potential about 214 mV less negative than at a bare GC electrode in pH 7.0 buffer solution. Cyclic voltammetric and rotating disk electrode (RDE techniques indicated that the MHAQ/MWCNTs nanohybrid has high electrocatalytic activity for the two-electron reduction of oxygen in the studied potential range. The kinetic parameters of ORR at the MHAQ/MWCNTs nanohybrid modified GC electrode were also determined by RDE and EIS techniques.

On the usage of electron beam as a tool to produce radioactive isotopes in photonuclear reactions

International Nuclear Information System (INIS)

Bunatyan, G.G.; Nikolenko, V.G.; Popov, A.B.

2009-01-01

We treat the Bremsstrahlung, induced by initial electron beam in converter, and the production of a desirable radioisotope due to the photonuclear reaction caused by this Bremsstrahlung. By way of illustration, the yield of a number of some, the most applicable in practice, radioisotopes is evaluated. The acquired findings persuade us that usage of modern electron accelerators offers a practicable way to produce the radioisotopes needful nowadays for various valuable applications in the nuclear medicine

Electron spin interactions in chemistry and biology fundamentals, methods, reactions mechanisms, magnetic phenomena, structure investigation

CERN Document Server

Likhtenshtein, Gertz

2016-01-01

This book presents the versatile and pivotal role of electron spin interactions in nature. It provides the background, methodologies and tools for basic areas related to spin interactions, such as spin chemistry and biology, electron transfer, light energy conversion, photochemistry, radical reactions, magneto-chemistry and magneto-biology. The book also includes an overview of designing advanced magnetic materials, optical and spintronic devices and photo catalysts. This monograph appeals to scientists and graduate students working in the areas related to spin interactions physics, biophysics, chemistry and chemical engineering.

The inverse electron demand Diels-Alder click reaction in radiochemistry.

Science.gov (United States)

Reiner, Thomas; Zeglis, Brian M

2014-04-01

The inverse electron-demand Diels-Alder (IEDDA) cycloaddition between 1,2,4,5-tetrazines and strained alkene dienophiles is an emergent variety of catalyst-free 'click' chemistry that has the potential to have a transformational impact on the synthesis and development of radiopharmaceuticals. The ligation is selective, rapid, high-yielding, clean, and bioorthogonal and, since its advent in 2008, has been employed in a wide variety of chemical settings. In radiochemistry, the reaction has proven particularly useful with (18)  F and has already been utilized to create a number of (18)  F-labeled agents, including the PARP1-targeting small molecule (18)  F-AZD2281, the αv β3 integrin-targeting peptide (18)  F-RGD, and the GLP-1-targeting peptide (18)  F-exendin. The inherent flexibility of the ligation has also been applied to the construction of radiometal-based probes, specifically the development of a modular strategy for the synthesis of radioimmunoconjugates that effectively eliminates variability in the construction of these agents. Further, the exceptional speed and biorthogonality of the reaction have made it especially promising in the realm of in vivo pretargeted imaging and therapy, and pretargeted imaging strategies based on the isotopes (111) In, (18)  F, and (64) Cu have already proven capable of producing images with high tumor contrast and low levels of uptake in background, nontarget organs. Ultimately, the characteristics of inverse electron-demand Diels-Alder click chemistry make it almost uniquely well-suited for radiochemistry, and although the field is young, this ligation has the potential to make a tremendous impact on the synthesis, development, and study of novel radiopharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.

Nuclear structure studies by the scattering of medium-energy electrons. Progress report, September 1, 1984-August 31, 1985

International Nuclear Information System (INIS)

Peterson, G.A.; Hicks, R.S.

1985-09-01

The University of Massachusetts Medium Energy Nuclear Physics Group reports the status of its experimental and theoretical programs. An overview of projects in elastic and quasi-elastic electron scattering which have been completed in the past year is given. Projects which have been designed and which will soon be started are described as well. Descriptions of the theoretical models for nucleon-nucleon interactions, nuclear structure, electromagnetic interactions, and weak interactions are given as well. Listings of the literature of the group are given

Neutron induced reactions II: (n,x) reactions on medium and heavy nuclei

International Nuclear Information System (INIS)

Cindro, N.

1976-01-01

Recent interest in (n,x) reactions in the MeV and above range of energies is concentrated on two main subjects: the mechanism of nucleon emission (precompound in particular) and the possible role of clustering in the emission of complex particles. Hence the first two sections of this paper will be devoted to these two subjects. In the last section some other subjects that have recently emerged in the field are discussed

Direct characterization of phase transformations and morphologies in moving reaction zones in Al/Ni nanolaminates using dynamic transmission electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Kim, J.S., E-mail: judy.kim@materials.ox.ac.uk [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); LaGrange, T.; Reed, B.W. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Knepper, R.; Weihs, T.P. [Department of Materials Science and Engineering, Johns Hopkins University, 3400 N. Charles St., Baltimore, MD 21218 (United States); Browning, N.D. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); Campbell, G.H. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States)

2011-05-15

Highlights: > Fast phase transformations are examined in Al/Ni reactive nanolaminates. > Results visible only by dynamic transmission electron microscopy at ns resolution. > NiAl forms under 15 ns after reaction front in all three stoichiometries studied. > DTEM imaging reveals a transient cellular morphology in nonequiatomic films. - Abstract: Phase transformations and transient morphologies are examined as exothermic formation reactions self-propagate across Al/Ni nanolaminate films. The rapid evolution of these phases and sub-micrometer morphological features requires nanoscale temporal and spatial resolution that is not available with traditional in situ electron microscopy. This work uses dynamic transmission electron microscopy to identify intermetallic products and phase morphologies, as exothermic formation reactions self-propagate in nanolaminate films grown with 3:2, 2:3 and 1:1 Al/Ni atomic ratios. Single-shot diffraction patterns with 15 ns temporal resolution reveal that the NiAl intermetallic forms within {approx}15 ns of the reaction front's arrival in all three types of films and is the only intermetallic phase to form, as the reactions self-propagate and quench very rapidly. Time-resolved imaging reveals a transient cellular morphology in the Al-rich and Ni-rich foils, but not in the equiatomic films. The cellular features in the Al-rich and Ni-rich films are attributed to a cooling trajectory through a two-phase field of liquid + NiAl.

In-medium effects around the Fermi energy

Directory of Open Access Journals (Sweden)

Lopez O.

2015-01-01

Full Text Available We study nuclear stopping in central collisions for heavy-ion induced reactions in the Fermi energy domain (15-100 AMeV. Using the large dataset provided by the 4π array INDRA, we determine that stopping can be directly related to the transport properties in the nuclear medium. By looking specifically at protons, we present a comprehensive body of experimental results concerning the mean free path, the nucleon-nucleon cross-section and in-medium effects in nuclear matter.

The Role of Low-Energy Electrons in Astrochemistry: A Tale of Two Molecules

Science.gov (United States)

Arumainayagam, Chris; Cambell, Jyoti; Leon Sanche, Michael Boyer, and Petra Swiderek.

2016-06-01

In the interstellar medium, UV photolysis of ice mantles encasing dust grains is thought to be the mechanism that drives the synthesis of “complex” molecules. The source of this reaction-initiating UV light is assumed to be local because externally-sourced UV radiation cannot pass through the ice-containing dark, dense molecular clouds. Externally sourced cosmic rays (Emax ~ 1020 eV), in addition to producing UV light within these clouds, also produce large numbers of low-energy (≤ 20 eV) secondary electrons. The goal of our studies is to understand the low-energy electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices. Using electron stimulated desorption (ESD), post-irradiation temperature-programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS), we have investigated the radiolysis initiated by electrons in condensed methanol and ammonia at ~ 90 K under ultrahigh vacuum (1×10-9 Torr) conditions. We have identified fifteen low-energy (≤ 20 eV) electron-induced methanol radiolysis products, many of which have been previously identified as being formed by methanol UV photolysis in the interstellar medium. We have also found evidence for the electron-induced formation from ammonia of hydrazine (N2H4), diazene (N2H2), cyclotriazane/triazene (N3H3) and triazane (N3H5). We have investigated the reaction yields’ dependence on film thickness, irradiation time, incident current, electron energy, and metal substrate. These results provide a basis from which we can begin to understand the mechanisms by which methanol and ammonia can form more complex species in cosmic ices. Studies such as ours may ultimately help us better understand the initial stages of the genesis of life.

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

Directory of Open Access Journals (Sweden)

Ding-Shyue Yang

2016-05-01

Full Text Available Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V−V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions.

Late adverse reactions to intravascular iodine based contrast media

DEFF Research Database (Denmark)

Bellin, Marie-France; Stacul, Fulvio; Webb, Judith A W

2011-01-01

DEFINITION: Late adverse reactions (LAR) to contrast media (CM) are defined as reactions occurring 1 h to 1 week after exposure. NEED FOR REVIEW: In view of more prospective studies of LAR and new data about their pathophysiology, the Contrast Medium Safety Committee (CMSC) of the European Society...... or delayed reading intradermal). The main risk factors for LAR are a previous reaction to contrast medium, a history of allergy, and interleukin-2 treatment. Most skin reactions are mild or moderate and self-limiting. MANAGEMENT: Management is symptomatic and similar to the management of other drug......-induced skin reactions. To reduce the risk of repeat reactions avoidance of the relevant CM and any cross-reacting agents identified by skin testing is recommended....

Efficient analysis of mode profiles in elliptical microcavity using dynamic-thermal electron-quantum medium FDTD method.

Science.gov (United States)

Khoo, E H; Ahmed, I; Goh, R S M; Lee, K H; Hung, T G G; Li, E P

2013-03-11

The dynamic-thermal electron-quantum medium finite-difference time-domain (DTEQM-FDTD) method is used for efficient analysis of mode profile in elliptical microcavity. The resonance peak of the elliptical microcavity is studied by varying the length ratio. It is observed that at some length ratios, cavity mode is excited instead of whispering gallery mode. This depicts that mode profiles are length ratio dependent. Through the implementation of the DTEQM-FDTD on graphic processing unit (GPU), the simulation time is reduced by 300 times as compared to the CPU. This leads to an efficient optimization approach to design microcavity lasers for wide range of applications in photonic integrated circuits.

Spectroscopic research of Lambda hypernuclei up to medium-heavy mass region with the (e,e'K⁺) reaction

Energy Technology Data Exchange (ETDEWEB)

Gogami, Toshiyuki [Tohoku Univ., Sendai (Japan)

2014-06-01

In 2009 (August-November), the E05-115 experiment was carried out at JLab to investigate L hypernuclei in the wide mass region up to A = 52 ($7\\atop{Λ}$He, $10\\atop{Λ}$Be, $12\\atop{Λ}$B and $52\\atop{Λ}$V) with the (e,e'K⁺) reaction. This is the first attempt to investigate a medium heavy L hypernucleus with the (e,e'K⁺) reaction. Experimentally, it is difficult to measure heavier L hypernuclei as background rates of particles which originate from electromagnetic processes are roughly in proportion to Z2 (Z: target proton number) in the (e,e'K⁺) experiment. To perform the experiment, many experimental techniques have been developed and introduced such as optimization of the electron spectrometer configuration (tilt method), clean kaon identification, particle tracking under high multiplicity environment, precise energy scale calibration and so on. In the present thesis, experimental results of the elementary process of p(e,e'K⁺)L, L hypernuclei of $7\\atop{Λ}$He, $10\\atop{Λ}$Be, $12\\atop{Λ}$B and $52\\atop{Λ}$V are shown. Elementary processes of the electroproduction of L and Σ⁰, p(e,e'K⁺)L, Σ⁰ were used for the absolute energy scale calibration of our spectrometer systems. A careful Monte Carlo simulation shows that the binding energy can be obtained with a systematic error of 0.11 MeV with our energy scale calibration method. A study of the elementary process of L is important to understand L hypernuclei as it is essential for theoretical calculations of L hypernuclei. The differential cross section of the p(e,e'K⁺)L reaction at the small K⁺ scattering angle (theta-CM/gamma-K approx. 15.5°), the small Q² (approx 0.01 [GeV/c]²) and the total energy of W = 1.92 GeV, where no experimental data exists was obtained to be 235 ± 13$+28\\atop{-24}$ nb/sr. The ground state (1/2⁺) binding energy

Proton-gamma coincidence experiment on medium mass nuclei at 400MeV and study of reaction mechanisms

International Nuclear Information System (INIS)

Baldit, Alain.

1981-01-01

Previous γ ray production experiments produced by proton on nuclei show important cross sections for residual nuclei corresponding to a four nucleon (2p + 2n) removal. With our (p - γ) coincidence experiment the forward emitted proton reflects the primary interaction and the γ spectra characterizes the final state of the reaction. Protons are detected with a magnetic spectrometer and γ rays are selected with a Ge(Li) diode. Angular and momentum analysis of scattered protons demonstrate a primary quasi free process on nucleons. No indication of knock out reactions on clusters has been seen. The residual nuclei are mainly produced by evaporation processes. A theoretical calculation involving intranuclear cascades and evaporation processes has been performed. The nucleus model is based upon a Fermi gas and nuclear density agrees with diffusion electron experiments. Residual nuclei far from target are well described with a such model. Residual nuclei near the target are sensitive to the nuclear structure [fr

Kinetics and Mechanism of Oxidation of Isoleucine by N-Bromophthalimide in Aqueous Perchloric Acid Medium

Directory of Open Access Journals (Sweden)

N. M. I. Alhaji

2011-01-01

Full Text Available The kinetics of oxidation of isoleucine with N-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.

Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

International Nuclear Information System (INIS)

Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

2014-01-01

Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications

Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

Energy Technology Data Exchange (ETDEWEB)

Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Ma, Lichun; Qi, Meiwei; Yu, Jiali [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

2014-10-15

Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications.

Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

Science.gov (United States)

Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

2017-09-01

The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Luo, Langli; Liu, Bin; Song, Shidong; Xu, Wu; Zhang, Ji-Guang; Wang, Chongmin

2017-03-27

The capacity, Coulombic efficiency, rate, and cyclability of a Li-O2 battery critically depend on the electrode reaction mechanism and the structure/morphology of the reaction product as well as their spatial and temporal evolution1-8, which are all further complicated by the choice of different electrolyte. For the case of aprotic cell, the discharge product, Li2O2, is formed through solution and surface mechanisms9,10, but little is known on the formation mechanism of the perplexing morphology of the reaction product11-15. For the case of Li-O2 battery using solid electrolyte, neither electrode reaction mechanism nor the nature of the reaction production is known. Herein, we reveal the full cycle reaction pathway for Li-O2 batteries and its correlation with the nature of the reaction product. Using an aberration-corrected environmental TEM under oxygen environment, we captured, for the first time, the morphology and phase evolution on the carbon nanotube (CNT) cathode of a working solid-state Li-O2 nano-battery16 and directly correlated these features with electrochemical reaction. We found that the oxygen reduction reaction on CNTs initially produces LiO2, which subsequently evolves to Li2O2 and O2 through disproportionation reaction. Surprisingly it is just the releasing of O2 that inflates the particles to a hollow structure with a Li2O outer surface layer and Li2O2 inner-shell, demonstrating that, in general, accommodation of the released O2 coupled with the Li+ ion diffusion and electron transport paths across both spatial and temporal scales critically governs the morphology of the discharging/charging product in Li-O2 system. We anticipate that the direct observation of Li-O2 reaction mechanisms and their correlation with the morphology of the reaction product set foundation for quantitative understanding/modeling of the electrochemical processes in the Li-O2 system, enabling rational design of both solid-state and aprotic Li-O2 batteries.

Heat sink design considerations in medium power electronic applications with long power cycles

CERN Document Server

AUTHOR|(SzGeCERN)744611; Papastergiou, Konstantinos; Thiringer, Torbjörn; Bongiorno, Massimo

2015-01-01

The aim of this work is to investigate the impact of the heat sink thickness and material, as well as, of the convection coefficient of the water cooling system on the power-electronics module thermal stressing. The heat extraction capability of different thicknesses is tested. It is concluded that the thickest heat sink results in marginally lower temperature variation at the junction level compared to the second thickest one. In the thickest heat sink case, the linear dependence of the thermal resistance on the thickness counteracts the benefit of the increased thermal capacitance. The increase in the cooling medium flow rate, which corresponds to an increase in the convection coefficient between the heat sink bottom surface and the water, can be avoided by increasing the thickness of the heat sink. In this way, the energy consumption of the cooling system is reduced. The increase in the flow rate drastically reduces the thermal stressing in the thinnest heat sink case. The increase of the heat sink thickne...

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

Science.gov (United States)

Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

2016-05-01

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

One-electron redox reactions of water-soluble vitamins. IV. Thiamin (vitamin B1), biotin, and pantothenic acid

International Nuclear Information System (INIS)

Moorthy, P.N.; Hayon, E.

1977-01-01

The technique of pulse radiolysis and kinetic absorption spectrophotometry was used to study the one-electron reduction of thiamin, thiazole, 4-aminopyrimidine, biotin, and pantothenic acid in aqueous solution. The acetone ketyl radical and e/sub aq/ - were used as the one-electron reducing agents. The reaction rate constants of e/sub aq/ - and (CH 3 ) 2 COH with these compounds were determined at different pH values, taking into account the dissociation constants of the substrates. The transient optical absorption spectra of the intermediates produced, their extinction coefficients, decay kinetics, and ionization constants were determined. One-electron reduction of the thiazolium ring of thiamin is suggested, based on the formation of dihydrothiamin as a final product. Other assignments for these radicals are suggested and discussed. The reaction of OH radicals with biotin and pantothenic acid leads, primarily, to H atom abstraction at various sites in the molecule. The formation and ionization of the -C(OH)CONH- radical from pantothenic acid, pK/sub a/ = 6.0 +- 0.3, is proposed

A theoretical quantum chemical study of alanine formation in interstellar medium

Science.gov (United States)

Shivani; Pandey, Parmanad; Misra, Alka; Tandon, Poonam

2017-08-01

The interstellar medium, the vast space between the stars, is a rich reservoir of molecular material ranging from simple diatomic molecules to more complex, astrobiologically important molecules such as amino acids, nucleobases, and other organic species. Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low temperature chemistry. An attempt has been made to explore the possibility of formation of complex organic molecules in interstellar medium, through detected interstellar molecules like CH3CN and HCOOH. The gas phase reactions are theoretically studied using quantum chemical techniques. We used the density functional theory (DFT) at the B3LYP/6-311G( d, p) level. The reaction energies, potential barrier and optimized structures of all the geometries, involved in the reaction path, has been discussed. We report the potential energy surfaces for the reactions considered in this work.

Density functional theory studies on electronic properties of thiophene s oxides as aromatic dienophiles for reactivity prediction in diels-alder reactions

International Nuclear Information System (INIS)

Banjo, S.

2013-01-01

The reactivity of thiophene S-oxides was discussed with special emphasis on the use of thiophene S-oxides as dienophiles in Diels-Alder type reactions. The omega values obtained for thiophene S-oxide (TO) with electron-donating group (-CH/sub 3/) increased the nucleophilicity power whereas substitution with electron-withdrawing groups (such as -NO/sub 2/ and -CO/sub 2/CH/sub 2/CH/sub 3/) increased the electrophilicity power, indicating an increase of reactivity towards a nucleophiles. The higher the value of delta omega the more favourable the D-A process, therefore apart from (4+2) addition reactions of these TO as diene with the typical dienophiles like 1,2-dicyanoethene and 1,2-dicyanoethene, it could be possible for TO with strong electron withdrawing substituents to serve as dienophile, e.g. heterocycles Ie and If. Also, from the value of delta omega heterocycle 1d could involve in (4+2) addition reactions with heterocyles 1e and If. (author)

Palladium-catalyzed coupling reactions

CERN Document Server

Molnár, Árpád

2013-01-01

This handbook and ready reference brings together all significant issues of practical importance for interested readers in one single volume. While covering homogeneous and heterogeneous catalysis, the text is unique in focusing on such important aspects as using different reaction media, microwave techniques or catalyst recycling. It also provides a comprehensive treatment of modern-day coupling reactions and emphasizes those topics that show potential for future development, such as continuous flow systems, water as a reaction medium, and catalyst immobilization, among others. With i

Theoretical study on pp → pnπ+ reaction at medium energies

International Nuclear Information System (INIS)

Ouyang, Zhen; Xie, Jujun; Zou, Bingsong; Xu, Hushan

2009-01-01

The pp → pnπ + reaction is a channel with the largest total cross section for pp collision in COSY/CSR energy region. In this work, we investigate individual contributions from various N* and Δ* resonances with mass up to about 2 GeV for the pp → pnπ + reaction. We extend a resonance model, which can reproduce the observed total cross section quite well, to give theoretical predictions of various differential cross sections for the present reaction at T p = 2.88 GeV. It could serve as a reference for identifying new physics in the future experiments at HIRFL-CSR. (author)

Effects of different reaction mediums on ring opening polymerization ...

African Journals Online (AJOL)

This work examined the effects of reaction conditions on ring opening ... of this study was to observe molecular weight distribution, conversion rates, and thermal ... M monomer and 0.56 M solvent), 10 mg lipase were used in the experiments.

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

Science.gov (United States)

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

Slavov, Chavdar Lyubomirov

2009-07-09

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

E-commerce in small and medium companies in the Republic of Croatia

Directory of Open Access Journals (Sweden)

Heri Bezić

2009-12-01

Full Text Available Fast progress of information-communication technology, distribution of computer networks and wider usage of Internet are basis for the new industrial revolution. Therefore, e-commerce presents new possibility of gathering competitive advantages on the world market, especially for small and medium companies. In order to determine the current stage of electronic readiness and electronic intensity of using the e-commerce in small and medium companies in Croatia, there was a research carried through micro, small and medium companies on national level. Although the acceptance of Internet technologies and implementation of e-commerce ensures to small and medium companies to compete on the world market with large companies and to have efective infuence on their growth and development, the research showed that Croatian micro, small and medium companies, despite of their high level of electronic readiness and implementation of modern information-communication technologies, are not favorable in their usage in everyday business. It is necessary to figure out the universal model to remove barriers for implementation and acceptance of e-commerce.

Electrochemical oxidation of loop diuretic furosemide in aqueous acid medium and its analytical application

Directory of Open Access Journals (Sweden)

Shikandar D. Bukkitgar

2016-12-01

Full Text Available An investigation of oxidative–reductive mechanisms of pharmaceutically important molecules gives us information about the metabolic fact of targeted drug. As compared to recent ongoing, time-consuming and costly techniques, there is an urgent needing for development of a sensitive technique, which can help easy understanding of these pathways. Therefore, in the present work, an effective, low-cost and time-saving technique to investigate the reaction mechanism of furosemide in aqueous acid medium is attempted. Furosemide undergoes two-proton and two-electron transfer reaction. The product obtained was analysed by UV spectra. It was found that the chemical oxidation and electrochemical oxidation of furosemide follows two different pathways. In addition, an effective technique has been developed to determine furosemide in its trace level. Good recoveries and low detection limit accomplished the magnitude of the proposed method. The proposed method was adopted for furosemide determination in human urine and pharmaceutical samples.

Electronic dissipation processes during chemical reactions on surfaces

CERN Document Server

Stella, Kevin

2012-01-01

Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

Bio-orthogonal Fluorescent Labelling of Biopolymers through Inverse-Electron-Demand Diels-Alder Reactions.

Science.gov (United States)

Kozma, Eszter; Demeter, Orsolya; Kele, Péter

2017-03-16

Bio-orthogonal labelling schemes based on inverse-electron-demand Diels-Alder (IEDDA) cycloaddition have attracted much attention in chemical biology recently. The appealing features of this reaction, such as the fast reaction kinetics, fully bio-orthogonal nature and high selectivity, have helped chemical biologists gain deeper understanding of biochemical processes at the molecular level. Listing the components and discussing the possibilities and limitations of these reagents, we provide a recent snapshot of the field of IEDDA-based biomolecular manipulation with special focus on fluorescent modulation approaches through the use of bio-orthogonalized building blocks. At the end, we discuss challenges that need to be addressed for further developments in order to overcome recent limitations and to enable researchers to answer biomolecular questions in more detail. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

High content of pyridinic- and pyrrolic-nitrogen-modified carbon nanotubes derived from blood biomass for the electrocatalysis of oxygen reduction reaction in alkaline medium

International Nuclear Information System (INIS)

Zheng, Jie; Guo, Chaozhong; Chen, Chunyan; Fan, Mingzhi; Gong, Jianping; Zhang, Yanfang; Zhao, Tianxin; Sun, Yuelin; Xu, Xiaofan; Li, Mengmeng; Wang, Ran; Luo, Zhongli; Chen, Changguo

2015-01-01

Graphical abstract: Display Omitted -- Highlights: •An ORR electrocatalyst was fabricated from blood biomass and carbon nanotube. •The N-CNT catalyst exhibits good ORR activity, methanol resistance and stability. •The pyrolysis process produces high contents of pyridinic and pyrrolic N species. •The pyridinic-N group may play more important role in the active sites for ORR. -- Abstract: Here we present a facile synthetic route to design nitrogen-doped nanostructured carbon-based electrocatalyst for oxygen reduction reaction (ORR) by the copyrolysis of blood biomass from pig and carbon nanotubes (CNTs) at high temperatures. The nitrogen-doped CNTs obtained at 800 °C not only results in excellent ORR activity with four-electron transfer selectivity in alkaline medium, but also exhibits superior methanol-tolerant property and long-term stability. It is confirmed that high-temperature pyrolysis processes can facilitate to produce higher contents of pyridinic- and pyrrolic-N binding groups in electrocatalysts, contributing to the enhancement of ORR performance in terms of onset potential, half-wave potential, and limited current density. We also propose that the planar-N configuration may be the active site that is responsible for the improved ORR electrocatalytic performance. The straight-forward and cheap synthesis of the active and stable electrocatalyst makes it a promising candidate for electrochemical power sources such as fuel cells or metal-air batteries

A new pathway for transmembrane electron transfer in photosynthetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

NARCIS (Netherlands)

van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

1997-01-01

It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

A new pathway for transmembrane electron transfer in photosyntetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

NARCIS (Netherlands)

van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

1997-01-01

It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

In-medium scaling law and electron scattering from high-spin states in 208Pb

International Nuclear Information System (INIS)

Arias de Saavedra, F.; Lallena, A.M.

1994-01-01

The effects of the environment modifications in the structure of the low-lying high-spin states of 208 Pb are studied by analyzing how the in-medium scaling law works on the excitation energies, wave functions, and electron scattering form factors corresponding to these states. It is shown that the consideration of f π * in addition to the effective ρ-meson mass does not affect too much most of the states analyzed. However, some of them appear to be extremely sensitive to its inclusion in the residual nucleon-nucleon interaction. As a result, a value of m ρ * /m ρ ∼f π * /f π ∼0.91 gives a good description of the (e,e') form factors of these particular states without any quenching factor. This value is in agreement with the one found for 48 Ca in a similar analysis performed in a previous work

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

Science.gov (United States)

Liechty, Derek S.

2014-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites

CSIR Research Space (South Africa)

Mamuru, SA

2010-05-01

Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...

Heat and mass transfer effects on MHD viscoelastic fluid over a stretching sheet through porous medium in presence of chemical reaction

Directory of Open Access Journals (Sweden)

Manoj Kumar Nayak

2016-03-01

Full Text Available An attempt has been made to study the heat and mass transfer effects in a boundary layer flow through porous medium of an electrically conducting viscoelastic fluid subject to transverse magnetic field in the presence of heat source/sink and chemical reaction. It has been considered the effects of radiation, viscous and Joule dissipations and internal heat generation/absorption. Closed form solutions for the boundary layer equations of viscoelastic, second-grade and Walters׳ B′ fluid models are obtained. The method of solution involves similarity transformation. The transformed equations of thermal and mass transport are solved by applying Kummer׳s function. The solutions of temperature field for both prescribed surface temperature (PST as well as prescribed surface heat flux (PHF are obtained. It is important to remark that the interaction of magnetic field is found to be counterproductive in enhancing velocity and concentration distribution whereas the presence of chemical reaction as well as porous matrix with moderate values of magnetic parameter reduces the temperature and concentration fields at all points of flow domain.

Low-Energy Nuclear Reactions Resulting as Picometer Interactions with Similarity to K-Shell Electron Capture

Science.gov (United States)

Hora, H.; Miley, G. H.; Li, X. Z.; Kelly, J. C.; Osman, F.

2006-02-01

Since the appeal by Brian Josephson at the meeting of the Nobel Laureates July 2004, it seems to be indicated to summarize the following serious, reproducible and confirmed observations on reactions of protons or deuterons incorporated in host metals such as palladium. Some reflections to Rutherford's discovery of nuclear physics, the Cockroft-Oliphant discovery of anomalous low-energy fusion reactions and the chemist Hahn's discovery of fission had to be included. Using gaseous atmosphere or discharges between palladium targets, rather significant results were seen e.g. from the "life after death" heat production of such high values per host atom that only nuclear reactions can be involved. This supports the earlier evaluation of neutron generation in fully reversible experiments with gas discharges hinting that a reasonable screening effect - preferably in the swimming electron layer - may lead to reactions at nuclear distances d of picometers with reaction probability times U of about megaseconds similar to the K-shell capture radioactivity. Further electrolytic experiments led to low-energy nuclear reactions (LENR) where the involvement of pollution could be excluded from the appearance of very seldom rare earth elements. A basically new theory for DD cross-sections is used to confirm the picometer-megasecond reactions of cold fusion. Other theoretical aspects are given from measured heavy element distributions similar to the standard abundance distribution, SAD, in the Universe with consequences on endothermic heavy nuclei generation, magic numbers and to quark-gluon plasmas.

Low-energy nuclear reactions resulting as parametric interactions with similarity to K-shell electron capture

International Nuclear Information System (INIS)

Hora, H.; Miley, G.H.; Li, X.Z.; Kelly, J.C.; Osman, F.

2006-01-01

Since the appeal by Brian Josephson at the meeting of the Nobel Laureates July 2004, it seems to be indicated to summarize the following serious, reproducible and confirmed observations on reactions of protons of deuterons incorporated in host metals such as palladium. Some reflections to Rutherford's discovery of nuclear physics, the Cockcroft Oliphant discovery of anomalous low-energy fusion reactions and the chemist Hahn's discovery of fission had to be included. Using gaseous atmosphere or discharges between palladium targets, rather significant results were seen e.g. from the 'life after death' heat production of such high values per host atom that only nuclear reactions can be involved. This supports the earlier evaluation of neutron generation in fully reversible experiments with gas discharges hinting that a reasonable screening effect - preferably in the swimming electron layer - may lead to reactions at nuclear distances d of pico-meters with reaction probability times U of about mega-seconds similar to the K-shell capture radioactivity. Further electrolytic experiments led to low-energy nuclear reactions (LENR) where the involvement of pollution could be excluded from the appearance of very seldom rare earth elements. A basically new theory for DD cross-sections is used to confirm the pico-meter- mega-second reactions of cold fusion. Other theoretical aspects are given from measured heavy element distributions similar to the standard abundance distribution, SAD, in the Universe with consequences on endothermic heavy nuclei generation, magic numbers and to quark-gluon plasmas. (authors)

Mechanistic Investigation of Oxidation of Phenylpropanolamine with N-Bromobenzenesulfonamide in Alkaline Medium: A Kinetic Approach

Directory of Open Access Journals (Sweden)

Ningegowda Prasad

2008-01-01

Full Text Available The kinetics of oxidation of phenylpropanolamine (PPA with sodium N-bromobenzenesulfonamide or bromamine-B (BAB has been investigated in alkaline medium at 308 K. The oxidation reaction obeys the rate law, – d[BAB]/dt = k [BAB] [PPA]x [OH-], where x is less than unity. The variation of ionic strength of the medium, addition of the reduction product, benzenesulfonamide, and chloride ion had no pronounced effect on the reaction rate. Decrease of dielectric permittivity of the medium by increasing the CH3CN content increased the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated from the Arrhenius plot. The stiochiometry of the reaction was found to be 1:1, and the oxidation product of phenylpropanolamine was identified as benzaldehyde and ethylideneamine. The rate decreased in D2O medium and the normal isotope effect k' (H2O / k' (D2O is 2.18. Proton inventory studies have been made in H2O - D2O mixtures. Formation and decomposition constant of BAB-PPA complexes in the reaction scheme have been determined. The conjugate acid, C6H5SO2NHBr is assumed to be the reactive species. The proposed mechanism and the derived rate law are consistent with the observed experimental results.

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

Energy Technology Data Exchange (ETDEWEB)

Dixon, David Adams [The University of Alabama

2013-07-02

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

A Harmonic Kicker Scheme for the Circulator Cooler Ring in the Proposed Medium Energy Electron-Ion Collider

Energy Technology Data Exchange (ETDEWEB)

Nissen, Edward W.; Hutton, Andrew M.; Kimber, Andrew J.

2013-06-01

The current electron cooler design for the proposed Medium Energy Electron-Ion collider (MEIC) at Jefferson Lab utilizes a circulator ring for reuse of the cooling electron bunch up to 100 times to cool the ion beams. This cooler requires a fast kicker system for injecting and extracting individual bunches in the circulator ring. Such a kicker must work at a high repetition rate, up to 7.5 to 75 MHz depending on the number of turns in the recirculator ring. It also must have a very short rise and fall time (of order of 1 ns) such that it will kick an individual bunch without disturbing the others in the ring. Both requirements are orders of magnitude beyond the present state-of-the-art as well as the goals of other on-going kicker R&D programs such as that for the ILC damping rings. In this paper we report a scheme of creating this fast, high repetition rate kicker by combining RF waveforms at multiple frequencies to create a kicker waveform that will, for example, kick every eleventh bunch while leaving the other ten unperturbed. We also present a possible implementation of this scheme as well as discuss its limitations.

5,5'-Dithiobis-(2-nitrobenzoic acid) as a probe for a non-essential cysteine residue at the medium chain acyl-coenzyme A dehydrogenase binding site of the human 'electron transferring flavoprotein' (ETF).

Science.gov (United States)

Parker, A; Engel, P C

1999-01-01

Human 'electron transferring flavoprotein' (ETF) was inactivated by the thiol-specific reagent 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB). The kinetic profile showed the reaction followed pseudo-first-order kinetics during the initial phase of inactivation. Monitoring the release of 5-thio-2-nitrobenzoate (TNB) showed that modification of 1 cysteine residue was responsible for the loss of activity. The inactivation of ETF by DTNB could be reversed upon incubation with thiol-containing reagents. The loss of activity was prevented by the inclusion of medium chain acyl-CoA dehydrogenase (MCAD) and octanoyl-CoA. Cyanolysis of the DTNB modified-ETF with KCN led to the release of TNB accompanied presumably by the formation of the thio-cyano enzyme and with almost full recovery of activity. Conservation studies and the lack of 100% inactivation, however, suggested that this cysteine residue is not essential for the interaction with MCAD.

Effect of Acidity of a Medium on Riboflavin Photodestruction

Science.gov (United States)

Astanov, S. Kh.; Turdiev, M.; Sharipov, M. Z.; Kurtaliev, É. N.; Nizomov, N. N.

2016-03-01

Effect of acidity of a medium on the spectroscopic characteristics of riboflavin aqueous solutions is investigated by the method of fluorescent and absorption spectroscopy. Significant deformation of the electronic spectra of riboflavin aqueous solutions irradiated with unfiltered light of a PRK-2 lamp is observed. It is established that riboflavin photostability in an acid medium is about twice as much as the photostability in a neutral medium, which is caused by the formation of a protonated species.

Base-catalyzed tandem Michael/dehydro-Diels-Alder reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes: a facile entry to angularly fused polycycles.

Science.gov (United States)

Zhang, Mingrui; Zhang, Junliang

2014-01-07

Angularly fused carbocyclic frameworks and their heteroatom-substituted analogues exist in many natural products that display a broad and interesting range of biological activities. Preparation of polycyclic products by cycloaddition reactions have been the long-standing hot topic in the synthetic community. Dehydro-Diels-Alder (DDA) reactions are one class of dehydropericyclic reactions that are derived conceptually by systematic removal of hydrogen atom pairs. A base-promoted tandem Michael addition and DDA reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes was realized in which a DDA reaction takes place between the arylalkynes and electron-deficient tetrasubstituted olefin. The control experiments support the stepwise anionic reaction pathway rather than the concerted reaction pathway. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process and apparatus for reacting laser radiation with a reactive medium

International Nuclear Information System (INIS)

Vanderleeden, J.C.

1980-01-01

The invention is based on the concept of irradiating the reaction medium with laser radiation in a reaction zone bounded by two longitudinally spaced reflecting surfaces, the beam of laser radiation being reflected back and forth between the surfaces which are contoured in such a way that the radiation flux density profile at substantially all transverse cross sections of the reaction zone is matched to the transverse distribution profile, that is the transverse distribution of the availability of a reactive species in the medium. A necessary condition for achieving this is that the beam be successively reflected between the surfaces along successive paths of progressively changing cross-sectional area intersected by respective, contiguous, non-overlapping areas of these surfaces. This process may be applied in particular to the selective laser-induced decomposition of HDCO to yield HD and CO

Photo-Induced Electron-Exchange Reactions Exhibiting Chain Characteristics; Echanges d'Electrons Photoinduits Presentant les Caracteristiques d'une Reaction en Chaine; Vyzvannye fotonami reaktsii ehlektronnogo obmena, proyavlyayushchie kharakteristiki tsepochki; Intercambio de Electrones Fotoinducido del Tipo de Cadena

Energy Technology Data Exchange (ETDEWEB)

Stranks, D. R.; Yandell, J. R. [University of Adelaide, Adelaide (Australia)

1965-10-15

The absorption of light of an appropriate wavelength can markedly accelerate the rate of a two-electron exchange reaction. Charge-transfer absorption generates an intermediate oxidation state which is responsible for propagating a chain reaction between the two stable oxidation states. The general kinetic equations for exchange systems involving chain propagation and either linear or quadratic termination are derived. It is shown that the dependence of the observed quantum yield on reactant concentrations and the absorbed light intensity is more complex than has been hitherto assumed. In principle, a kinetic investigation of such an exchange system should evaluate the primary quantum yield for the initial charge-transfer absorption process, the rates of electron transfer between each of the two stable oxidation states and the intermediate state, and the rate of disproportionation of the intermediate oxidation state. These general considerations are illustrated with the results of an experimental study of the thallium(I)- thallium(III) system. Selective charge-transfer absorption at 2537 A by the Tl{sup 3+}. OH{sup -} ion-pair is used to generate Tl{sup II}. The ensuing exchange reaction with Tl{sup +} exhibits marked induction periods and is sensitive to micromolar concentrations of oxidants and reductants. At millimolar concentrations of Tl{sup +} and Tl{sup 3+}, the observed quantum yields are directly proportional to the Tl{sup +} and Tl{sup 3+} concentrations. At higher concentrations, the quantum yields level oui to ''plateau'' values which range from 6 to 30, depending on the absorbed light intensity. The plateau quantum yield is a direct measure of the relative rates of the propagation reactions Tl{sup +} + Tl{sup 2+} -> Tl{sup 2+} + T1+ and Tl{sup 2+} + Tl{sup 3+} -> Tl{sup 3+} + Tl{sup 2+} compared to the termination reaction 2 Tl{sup 2+} -> Tl{sup +} + Tl{sup 3+}. This disproportionation reaction is consistent with a light intensity exponent of 0. 50

The suppression of radiation reaction and laser field depletion in laser-electron beam interaction

Science.gov (United States)

Ong, J. F.; Moritaka, T.; Takabe, H.

2018-03-01

The effects of radiation reaction (RR) have been studied extensively by using the interaction of ultraintense lasers with a counter-propagating relativistic electron. At the laser intensity at the order of 1023 W/cm2, the effects of RR are significant in a few laser periods for a relativistic electron. However, a laser at such intensity is tightly focused and the laser energy is usually assumed to be fixed. Then, the signal of RR and energy conservation cannot be guaranteed. To assess the effects of RR in a tightly focused laser pulse and the evolution of the laser energy, we simulated this interaction with a beam of 109 electrons by means of a Particle-In-Cell method. We observe that the effects of RR are suppressed due to the ponderomotive force and accompanied by a non-negligible amount of laser field energy reduction. This is because the ponderomotive force prevents the electrons from approaching the center of the laser pulse and leads to an interaction at the weaker field region. At the same time, the laser energy is absorbed through ponderomotive acceleration. Thus, the kinetic energy of the electron beam has to be carefully selected such that the effects of RR become obvious.

Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory.

Science.gov (United States)

Bylaska, Eric J; Glaesemann, Kurt R; Felmy, Andrew R; Vasiliu, Monica; Dixon, David A; Tratnyek, Paul G

2010-11-25

Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH− of 1,2,3-trichloropropane. The thermochemical properties ΔH(f)°(298.15 K), S°(298.15 K, 1 bar), and ΔG(S)(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3−CHCl−CH2Cl, CH2Cl−CH2−CH2Cl, C•H2−CHCl−CH2Cl, CH2Cl−C•H−CH2Cl, CH2═CCl−CH2Cl, cis-CHCl═CH−CH2Cl, trans-CHCl═CH−CH2Cl, CH2═CH−CH2Cl, CH2Cl−CHCl−CH2OH, CH2Cl−CHOH−CH2Cl, CH2═CCl−CH2OH, CH2═COH−CH2Cl, cis-CHOH═CH−CH2Cl, trans-CHOH═CH−CH2Cl, CH(═O)−CH2−CH2Cl, and CH3−C(═O)−CH2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔG(rxn)° ≈ −32 kcal/mol), followed closely by reductive dechlorination (ΔG(rxn)° ≈ −27 kcal/mol), dehydrochlorination (ΔG(rxn)° ≈ −27 kcal/mol), and nucleophilic substitution by OH− (ΔG(rxn)° ≈ −25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H2−CHCl−CH2Cl and the CH2Cl−C•H−CH2Cl species, was not favorable in the standard state (ΔG(rxn)° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

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

DEFF Research Database (Denmark)

Ulstrup, Jens

1999-01-01

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

Saponification reaction system: a detailed mass transfer coefficient determination.

Science.gov (United States)

Pečar, Darja; Goršek, Andreja

2015-01-01

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

Final Report Theoretical Studies of Surface Reactions on Metals and Electronic Materials

Energy Technology Data Exchange (ETDEWEB)

Jerry L. Whitten

2012-04-23

This proposal describes the proposed renewal of a theoretical research program on the structure and reactivity of molecules adsorbed on transition metal surfaces. A new direction of the work extends investigations to interfaces between solid surfaces, adsorbates and aqueous solutions and includes fundamental work on photoinduced electron transport into chemisorbed species and into solution. The goal is to discover practical ways to reduce water to hydrogen and oxygen using radiation comparable to that available in the solar spectrum. The work relates to two broad subject areas: photocatalytic processes and production of hydrogen from water. The objective is to obtain high quality solutions of the electronic structure of adsorbate-metal-surface-solution systems so as to allow activation barriers to be calculated and reaction mechanisms to be determined. An ab initio embedding formalism provides a route to the required accuracy. New theoretical methods developed during the previous grant period will be implemented in order to solve the large systems involved in this work. Included is the formulation of a correlation operator that is used to treat localized electron distributions such as ionic or regionally localized distributions. The correlation operator which is expressed as a two-particle projector is used in conjunction with configuration interaction.

Ignition Features of Plasma-Beam Discharge in Gas-Discharge Electron Gun Operation

Directory of Open Access Journals (Sweden)

Valery A. Tutyk

2013-01-01

Full Text Available The current paper presents the results of experimental researches to determine the mode features of plasma-beam discharge (PBD generation by an electron beam injected by a low-vacuum gasdischarge electron gun (LGEG with the cold cathode and hollow anode on the basis of the high-voltage glow discharge and in the range of helium pressure of P ? 10 ÷ 130 Pa. The PBD boundaries and their dependences on parameters of an electron beam are found. The influence of PBD on parameters of low-vacuum gas-discharge electron gun is revealed. It causes an avalanche increase of electron beam current and burning of plasma-beam discharge in the whole space of the vacuum chamber volume and generation of electromagnetic radiation is revealed. Achieved results will be used for implementation of various vacuum technologies in the medium of reaction gas and generated electromagnetic radiation.

Low-energy nuclear reactions resulting as parametric interactions with similarity to K-shell electron capture

Energy Technology Data Exchange (ETDEWEB)

Hora, H. [University of New South Wales, Sydney 2052 (Australia); Miley, G.H. [Fusion Studies Laboratory, University of Illinois, Urbana, lL 61801 (United States); Li, X.Z. [Physics Department, Tsinghua University, Beijing 100084 (China); Kelly, J.C. [School of Physics, Sydney University, Sydney 2006 (Australia); Osman, F. [University of Western Sydney, Penrith-Soutti, NSW 1791 (Australia)

2006-07-01

Since the appeal by Brian Josephson at the meeting of the Nobel Laureates July 2004, it seems to be indicated to summarize the following serious, reproducible and confirmed observations on reactions of protons of deuterons incorporated in host metals such as palladium. Some reflections to Rutherford's discovery of nuclear physics, the Cockcroft Oliphant discovery of anomalous low-energy fusion reactions and the chemist Hahn's discovery of fission had to be included. Using gaseous atmosphere or discharges between palladium targets, rather significant results were seen e.g. from the 'life after death' heat production of such high values per host atom that only nuclear reactions can be involved. This supports the earlier evaluation of neutron generation in fully reversible experiments with gas discharges hinting that a reasonable screening effect - preferably in the swimming electron layer - may lead to reactions at nuclear distances d of pico-meters with reaction probability times U of about mega-seconds similar to the K-shell capture radioactivity. Further electrolytic experiments led to low-energy nuclear reactions (LENR) where the involvement of pollution could be excluded from the appearance of very seldom rare earth elements. A basically new theory for DD cross-sections is used to confirm the pico-meter- mega-second reactions of cold fusion. Other theoretical aspects are given from measured heavy element distributions similar to the standard abundance distribution, SAD, in the Universe with consequences on endothermic heavy nuclei generation, magic numbers and to quark-gluon plasmas. (authors)

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

Science.gov (United States)

Liechty, Derek S.

2013-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

Calibration for medium resolution off-axis electron holography using a flexible dual-lens imaging system in a JEOL ARM 200F microscope.

Science.gov (United States)

Cantu-Valle, Jesus; Ruiz-Zepeda, Francisco; Mendoza-Santoyo, Fernando; Jose-Yacaman, Miguel; Ponce, Arturo

2014-12-01

In this work the calibration of a medium resolution off-axis electron holography using a dual-lens imaging system in a JEOL ARM 200F is shown. The objective dual-lens configuration allows adjusting the field of view from 35nm to 2.5μm. Subsequently, the parameters used in phase shift reconstruction were calibrated considering biprism voltage versus fringe spacing (σ) and versus fringe width (W). The reliability of the transmission electron microscope performance using these parameters was achieved using gold nanoparticles of known size and adjusting the excitation voltage of the lenses. Copyright © 2014 Elsevier B.V. All rights reserved.

Selected specific rates of reactions of transients from water in aqueous solution. Hydrated electron, supplemental data. [Reactions with transients from water, with inorganic solutes, and with solutes

Energy Technology Data Exchange (ETDEWEB)

Ross, A.B.

1975-06-01

A compilation of rates of reactions of hydrated electrons with other transients and with organic and inorganic solutes in aqueous solution appeared in NSRDS-NBS 43, and covered the literature up to early 1971. This supplement includes additional rates which have been published through July 1973.

Calibration for medium resolution off-axis electron holography using a flexible dual-lens imaging system in a JEOL ARM 200F microscope

International Nuclear Information System (INIS)

Cantu-Valle, Jesus; Ruiz-Zepeda, Francisco; Mendoza-Santoyo, Fernando; Jose-Yacaman, Miguel; Ponce, Arturo

2014-01-01

In this work the calibration of a medium resolution off-axis electron holography using a dual-lens imaging system in a JEOL ARM 200F is shown. The objective dual-lens configuration allows adjusting the field of view from 35 nm to 2.5 μm. Subsequently, the parameters used in phase shift reconstruction were calibrated considering biprism voltage versus fringe spacing (σ) and versus fringe width (W). The reliability of the transmission electron microscope performance using these parameters was achieved using gold nanoparticles of known size and adjusting the excitation voltage of the lenses. - Highlights: • We presented the off-axis electron holography calibration in dual-lens mode of a JEOL ARM 200F. • We provide optimal conditions for a wide field of views varying the objective lens excitation. • The calibration was made using Au-nanoparticles controlling fringe width, spacing and contrast. • Application of electron holography to nanoparticles is also shown

Pre-equilibrium emission of nucleons from reactions induced by medium-energy heavy ions

International Nuclear Information System (INIS)

Korolija, M.; Holuh, E.; Cindro, N.; Hilscher, D.

1984-01-01

Recent data on fast-nucleon emission in heavy-ion-induced reactions are analysed successfully in terms of pre-equilibrium models; it is shown that the relevant parameters of those models preserve the physical meaning they have in light-ion-induced reactions. The initial exciton number obtained from a Griffin-plot analysis and the initial number of degrees of freedom, which is the relevant parameter of the modified HMB model, appear to be approximately equal for a given reaction at a given energy. It is inferred that, for heavy-ion reactions, the determination of such a parameter is substantially dominated by the centre-of-mass energy per nucleon above the Coulomb barrier, in contrast with the results of nucleon-induced reactions

Activation-energy for the reaction h+oh--]eaq- - kinetic determination of the enthalpy and entropy of solvation of the hydrated electron

DEFF Research Database (Denmark)

Hickle, B.; Sehested, Knud

1985-01-01

The reaction between atomic hydrogen and hydroxide ion in aqueous solutions H + OH- - eaq- + H20 has been studied by pulse radiolysis. The rate constant was measured at pH 11.7 and 12 by following the growth of the hydrated electron absorption at 600 nm. The activation energy of the reaction has...

Understanding the electron-stimulated surface reactions of organometallic complexes to enable design of precursors for electron beam-induced deposition

Energy Technology Data Exchange (ETDEWEB)

Spencer, Julie A.; Rosenberg, Samantha G.; Barclay, Michael; Fairbrother, D. Howard [Johns Hopkins University, Department of Chemistry, Baltimore, MD (United States); Wu, Yung-Chien; McElwee-White, Lisa [University of Florida, Department of Chemistry, Gainesville, FL (United States)

2014-12-15

Standard practice in electron beam-induced deposition (EBID) is to use precursors designed for thermal processes, such as chemical vapor deposition (CVD). However, organometallic precursors that yield pure metal deposits in CVD often create EBID deposits with high levels of organic contamination. This contamination negatively impacts the deposit's properties (e.g., by increasing resistivity or decreasing catalytic activity) and severely limits the range of potential applications for metal-containing EBID nanostructures. To provide the information needed for the rational design of precursors specifically for EBID, we have employed an ultra-high vacuum (UHV) surface science approach to identify the elementary reactions of organometallic precursors during EBID. These UHV studies have demonstrated that the initial electron-induced deposition of the surface-bound organometallic precursors proceeds through desorption of one or more of the ligands present in the parent compound. In specific cases, this deposition step has been shown to proceed via dissociative electron attachment, involving low-energy secondary electrons generated by the interaction of the primary beam with the substrate. Electron beam processing of the surface-bound species produced in the initial deposition event usually causes decomposition of the residual ligands, creating nonvolatile fragments. This process is believed to be responsible for a significant fraction of the organic contaminants typically observed in EBID nanostructures. A few ligands (e.g., halogens) can, however, desorb during electron beam processing while other ligands (e.g., PF{sub 3}, CO) can thermally desorb if elevated substrate temperatures are used during deposition. Using these general guidelines for reactivity, we propose some design strategies for EBID precursors. The ultimate goal is to minimize organic contamination and thus overcome the key bottleneck for fabrication of relatively pure EBID nanostructures. (orig.)

Hadron photoproduction at medium energy

International Nuclear Information System (INIS)

Dainton, J.B.

1985-04-01

Results from measurements of multibody photoproduction at medium incident photon energy (2.8 to 4.8 GeV) are presented and discussed. Particular emphasis is placed on topics which are not well understood and which therefore motivate experiments with the upgraded electron accelerator and storage ring ELSA at the University of Bonn, FR Germany. (author)

Spectroscopic and mechanistic investigations into oxidation of aspartame by diperiodatocuprate(III in aqueous alkaline medium

Directory of Open Access Journals (Sweden)

Jayant I. Gowda

2015-12-01

Full Text Available The oxidation of aspartame (ASP by diperiodatocuprate(III (DPC in aqueous alkaline medium at 298 K and a constant ionic strength of 0.30 mol dm−3 was studied spectrophotometrically. The reaction between aspartame and diperiodatocuprate(III in alkaline medium exhibits 1:6 stoichiometry in the reaction. The order of the reaction with respect to [diperiodatocuprate(III] was unity, while the apparent order with respect to [aspartame] was less than unity over the concentration range studied. The rate of the reaction increased with increase in [OH−] whereas the rate decreased with increase in [$ {\\text{IO}}^-_4 $]. Increasing the ionic strength of the medium increased the rate. The main products were identified by FT-IR, NMR, and LC-MS spectral studies. The probable mechanism was proposed. The activation parameters with respect to slow step of the mechanism were computed and discussed. Thermodynamic quantities were also calculated. Kinetic studies suggest that [Cu(H2IO6(H2O2] is the reactive species of Cu(III.

Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods

KAUST Repository

Minenkov, Yury; Wang, Heng; Wang, Zhandong; Sarathy, Mani; Cavallo, Luigi

2017-01-01

Computational electronic structure calculations are routinely undertaken to predict thermodynamic properties of the various species. However, the application of highly accurate wave function theory methods, such as the “gold standard” coupled cluster approach including single, double and partly triple excitations in perturbative fashion, CCSD(T), to large molecules is limited due to high computational cost. In this work, the promising domain based local pair natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 accurate formation enthalpies of medium-size molecules (few dozens heavy atoms) important for bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. As for comparison, 8 density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T-PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 (Mean unsigned error (MUE)/ Mean Signed Error (MSE)=9.1/6.0 kcal/mol) and B3LYP (MUE/MSE=13.5/-13.3 kcal/mol). An influence of an empirical dispersion correction term on these functionals performance is not homogenous: B3LYP performance is improved (B3LYP-D3 (MUE/MSE=6.0/0.8 kcal/mol)) meanwhile PBE0 performance is worse (PBE0-D3 (MUE/MSE=14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE=3.8/-2.0 kcal/mol) and M06-2X (MUE/MSE=3.5/3.0 kcal/mol), and recently developed ωB97X-D3 (MUE/MSE=3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE=2.2/1.3 kcal/mol) methods provided significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from some double hybrid methods (B2PLYP-D3 (MUE/MSE=4.7/2.0 kcal/mol), PWPB95-D3 (MUE/MSE=4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE=4.1/-3.0 kcal/mol) and B2T-PLYP-D (MUE/MSE=3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in

Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods

KAUST Repository

Minenkov, Yury

2017-06-21

Computational electronic structure calculations are routinely undertaken to predict thermodynamic properties of the various species. However, the application of highly accurate wave function theory methods, such as the “gold standard” coupled cluster approach including single, double and partly triple excitations in perturbative fashion, CCSD(T), to large molecules is limited due to high computational cost. In this work, the promising domain based local pair natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 accurate formation enthalpies of medium-size molecules (few dozens heavy atoms) important for bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. As for comparison, 8 density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T-PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 (Mean unsigned error (MUE)/ Mean Signed Error (MSE)=9.1/6.0 kcal/mol) and B3LYP (MUE/MSE=13.5/-13.3 kcal/mol). An influence of an empirical dispersion correction term on these functionals performance is not homogenous: B3LYP performance is improved (B3LYP-D3 (MUE/MSE=6.0/0.8 kcal/mol)) meanwhile PBE0 performance is worse (PBE0-D3 (MUE/MSE=14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE=3.8/-2.0 kcal/mol) and M06-2X (MUE/MSE=3.5/3.0 kcal/mol), and recently developed ωB97X-D3 (MUE/MSE=3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE=2.2/1.3 kcal/mol) methods provided significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from some double hybrid methods (B2PLYP-D3 (MUE/MSE=4.7/2.0 kcal/mol), PWPB95-D3 (MUE/MSE=4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE=4.1/-3.0 kcal/mol) and B2T-PLYP-D (MUE/MSE=3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in

Pulse radiolytic study of the reaction OH + O3 in aqueous medium

International Nuclear Information System (INIS)

Sehested, K.; Holcman, J.; Bjergbakke, E.; Hart, E.J.

1984-01-01

In slightly alkaline solution the ozonide radical ion, O 3 - , forms as a product of the hydroxyl radical reaction with ozone. For each O 3 - formed, two O 3 molecules are consumed. In acid solution the product of this reaction is the perhydroxyl radical, HO 2 , formed from one O 3 molecule. Our results are consistent with the gas-phase reaction where the products are HO 2 and O 2 . A rate constant of (1.1 +/- 0.2) x 10 8 dm 3 mol -1 s -1 is found for the reaction OH + O 3 → HO 2 + O 2 . This rate constant was obtained by three systems, by buildup of O 3 - in basic solutions, by competition of the OH radical with the carbonate ion, and directly by O 3 consumption in acid solution. The rate constant for the reaction of HO 2 with O 3 is very low, 4 dm 3 mol -1 s -1 . At pH greater than or equal to 1, HO 2 reacts with O 3 preferentially in its dissociated form, O 2 - . No spectroscopic evidence has been found for the HO 3 and HO 4 free-radical intermediates. 24 references, 4 figures, 2 tables

Redox reactions of neptunium in tributyl phosphate-dodecane mixtures

International Nuclear Information System (INIS)

Wehrey, F.

1989-01-01

In relation with the reprocessing of irradiated fuels, disproportionation and oxidation by nitric acid of pentavalent neptunium in tributyl phosphate-dodecane mixtures have been studied. The experimental part of this work is based on spectrophotometric measurements. The disproportionation of pentavalent neptunium in organic perchloric medium is a second order reaction with respect to neptunium V. The reaction rate is strongly influenced by the perchloric acid concentration and has a higher value than in an aqueous medium. The reverse reaction in nitric media is a first order with respect to tetravalent and hexavalent ions. The reaction rate is a function of the reverse of the square of the nitric acid concentration. The energy of activation is the same than in aqueous medium. The oxidation rate of pentavalent neptunium by nitric acid is increased by nitrous acid. When no nitrous acid is added to the mixture, the reaction revealed to be autocatalytic, possesses an induction period. When nitrous and nitric acids are in excess to neptunium the reaction is first order with respect to neptunium. The reaction rate depends on the concentration of nitric acid and is a linear function of the concentration of nitrous acid. In tributyl phosphate dodecane mixtures the reaction occurs spontaneously. It is not the case in aqueous media. The values of thermodynamical and kinetical constants determined in this work could be used in a modelization of the behavior of neptunium in the reprocessing of irradiated fuels, which has to eliminate this element among its tasks [fr

Switching power converters medium and high power

CERN Document Server

Neacsu, Dorin O

2013-01-01

An examination of all of the multidisciplinary aspects of medium- and high-power converter systems, including basic power electronics, digital control and hardware, sensors, analog preprocessing of signals, protection devices and fault management, and pulse-width-modulation (PWM) algorithms, Switching Power Converters: Medium and High Power, Second Edition discusses the actual use of industrial technology and its related subassemblies and components, covering facets of implementation otherwise overlooked by theoretical textbooks. The updated Second Edition contains many new figures, as well as

Correlations and polarization in electronic and atomic collisions and (e,2e) reactions

International Nuclear Information System (INIS)

Teubner, P.J.O.; Weigold, E.

1992-01-01

This volume contains the invited papers presented at the Sixth International Symposium on Correlations and Polarization in Electronic and Atomic collisions and (e,2e) Reactions held at Flinders University, Adelaide, Australia from 18-21 July, 1991. This symposium was a satellite meeting to the XVII International Conference on the Physics of Electronic and Atomic Collisions (ICPEAC) held in Brisbane, Australia. It follows a tradition of satellite meetings on (e,2e) collisions and on correlation and polarization in electronic and atomic collisions held in association with previous ICPEACs. The subject matter of this symposium covered that of the previous meeting at Hoboken, USA (1989) on correlation and polarization phenomena as well as that of the previous meeting at the University of Maryland (1989) on (e,2e) collisions. In addition it extended the scope to include some discussion of (e,3e), (γ,eγ) and (γ,2γ) coincidence measurements. The discussion of the current rapid advances in coincidence experiments, correlations and polarization measurements and related theoretical developments brought together 100 scientist from many countries with broad interdisciplinary backgrounds. The symposium stressed the common threads weaving through all these areas of research. (Author)

Non-stationary filtration mode during chemical reactions with the gas phase

Science.gov (United States)

Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

2015-04-01

An experimental and numerical study of filtration accompanied by chemical reactions between displacing fluid and solid skeleton is considered. Glass balls (400-500 μm in diameter) were placed in 1 cm gap between two glass sheets and were used as model porous medium. The baking soda was added to the glass balls. The 70% solution of acetic acid was used as the displacer. The modeling porous medium was saturated with a mineral oil, and then 70% solution of colored acetic acid was pumped through the medium. The glass balls and a mineral oil have a similar refractive index, so the model porous medium was optically transparent. During the filtration, the gas phase was generated by the chemical reactions between the baking soda and acetic acid, and time-dependent displacement of the chemical reaction front was observed. The front of the chemical reaction was associated with the most intensive gas separation. The front moved, stopped, and then moved again to the area where it had been already. We called this process a secondary oxidation wave. To describe this effect, we added to the balance equations a term associated with the formation and disappearance of phases due to chemical reactions. The equations were supplemented by Darcy's law for multiphase filtration. Nonstationarity front propagation of the chemical reaction in the numerical experiment was observed at Damköhler numbers greater than 100. The mathematical modelling was agreed well with the experimental results.

In situ synthesis of TiB2-TiC particulates locally reinforced medium carbon steel-matrix composites via the SHS reaction of Ni-Ti-B4C system during casting

International Nuclear Information System (INIS)

Wang, H.Y.; Huang, L.; Jiang, Q.C.

2005-01-01

The fabrication of medium carbon steel-matrix composites locally reinforced with in situ TiB 2 -TiC particulates using self-propagating high-temperature synthesis (SHS) reaction of Ni-Ti-B 4 C system during casting was investigated. X-ray diffraction (XRD) results reveal that the exotherm of 1042 deg. C initiated by heat release of the solid state reaction in the differential thermal analysis (DTA) curve is an incomplete reaction in Ni-Ti-B 4 C system. As-cast microstructures of the in situ processed composites reveal a relatively uniform distribution of TiB 2 -TiC particulates in the locally reinforced regions. Furthermore, the particulate size and micro-porosity in the locally reinforced regions are significantly decreased with the increasing of the Ni content in the preforms. For a Ni content of 30 and 40 wt.%, near fully dense composites locally reinforced with in situ TiB 2 and TiC particulates can be fabricated. Although most of fine TiB 2 and TiC particulates which form by the reaction-precipitation mechanism during SHS reaction are present in the locally reinforced region, some large particulates which form by the nucleation-growth mechanism during solidification are entrapped inside the Fe-rich region located in the reinforcing region or inside the matrix region nearby the interface between matrix and reinforcing region. The hardness of the reinforcing region in the composite is significantly higher than that of the unreinforced medium carbon steel. Furthermore, the hardness values of the composites synthesized from 30 to 40 wt.% Ni-Ti-B 4 C systems are higher than those of the composites synthesized from 10 to 20 wt.% Ni-Ti-B 4 C systems

Vanadocene reactions with hydroxy acids

International Nuclear Information System (INIS)

Latyaeva, V.N.; Lineva, A.N.; Zimina, S.V.; Ehllert, O.G.; Arsen'eva, T.I.

1984-01-01

To prepare a series of vanadium cyclopentadienylcarboxylates soluble in water, the vanadocene reactions with lactic, γ-oxybutyric-, salicylic,- gallic-, orotic-, and acetylsalicylic acids have been studied. To determine the influence of cyclopentadienyl groups, bound with a vanadium atom, on the physiological activity of the complexes formed, vanadium halides are made to react with lactic acid. Only the vanadocene reaction with orotic acid was conducted in an aqueous medium, other interactions were realized in the diethyl ether, toluene, T, H, P medium. The interaction of vanadocene and vanadium halides with lactic-, salicylic-, acetylsalicylic- and gallic acids was found to lead to the formation of water-soluble vanadium complexes of Cp 2 , VOCOR or CpV (OCOR) 2 type. The data on the produced compounds yield, their IR spectra, decomposition temperatures, solubility, effective magnetic moments are presented

Spectral studies of intermediate species formed in one-electron reactions of bovine liver catalase at room and low temperatures. A comparison with peroxidase reactions

International Nuclear Information System (INIS)

Metodiewa, D.; Dunford, H.B.

1992-01-01

The reactions of native bovine catalase with superoxide and solvated electrons have been investigated using three different methods for generating these reducing substrates: γ-radiolysis of oxygenated or deaerated buffer solutions in the presence of an OH radical scavenger; either xanthine or acetaldehyde with xanthine oxidase; and low-temperature (77 K) γ-radiolysis of buffered ethylene glycol/water solutions with subsequent annealing of samples at 183 K. (Author)

A study on the secondary electrons in a clinical electron beam

International Nuclear Information System (INIS)

Krithivas, G.; Rao, S.N.

1989-01-01

The central axis dose of a 12 MeV clinical electron beam is investigated in terms of an axial component due to primary electrons in the central ray and a lateral component due to secondary electrons originating from multiple scattering of electrons in the off-axis rays. To this effect secondary electron fluence measurements in a polystyrene medium irradiated with a collimated beam are made with a sensitive diode detector. This leads to a construction of secondary electron depth-dose profiles for beam sizes of diameters ranging from 1.7 to 17.4 cm. The results indicate that the lateral electrons account for 25% of the dose in the therapeutic region. For these electrons, the depth of dose maximum is correlated with diffusion depth and maximum lateral excursion in the medium. Dose component due to backscatter electrons at depths is also investigated using a thin-window parallel-plate ion chamber. The role of lateral and backscatter electrons in characterising central axis per cent depth-dose is discussed. (author)

Predicting the Rate Constant of Electron Tunneling Reactions at the CdSe-TiO2 Interface.

Science.gov (United States)

Hines, Douglas A; Forrest, Ryan P; Corcelli, Steven A; Kamat, Prashant V

2015-06-18

Current interest in quantum dot solar cells (QDSCs) motivates an understanding of the electron transfer dynamics at the quantum dot (QD)-metal oxide (MO) interface. Employing transient absorption spectroscopy, we have monitored the electron transfer rate (ket) at this interface as a function of the bridge molecules that link QDs to TiO2. Using mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 16-mercaptohexadecanoic acid, we observe an exponential attenuation of ket with increasing linker length, and attribute this to the tunneling of the electron through the insulating linker molecule. We model the electron transfer reaction using both rectangular and trapezoidal barrier models that have been discussed in the literature. The one-electron reduction potential (equivalent to the lowest unoccupied molecular orbital) of each molecule as determined by cyclic voltammetry (CV) was used to estimate the effective barrier height presented by each ligand at the CdSe-TiO2 interface. The electron transfer rate (ket) calculated for each CdSe-ligand-TiO2 interface using both models showed the results in agreement with the experimentally determined trend. This demonstrates that electron transfer between CdSe and TiO2 can be viewed as electron tunneling through a layer of linking molecules and provides a useful method for predicting electron transfer rate constants.

Medium energy probes and nuclear structure

International Nuclear Information System (INIS)

Ginocchio, J.N.

1984-01-01

In this paper we explore two topics. The first topic is the marriage of medium energy reaction theory with the interacting boson model of nuclei in such a way that the multiple scattering is summed to all orders. The second topic is an exactly solvable potential model which gives realistic shell model eigenfunctions which can be used to calculate static and transition nuclear densities. (orig./HSI)

Two-pion production in photon-induced reactions

Indian Academy of Sciences (India)

photoproduction from nuclei is also used to investigate the in-medium modification of meson–meson interactions. ... the observation of an in-medium modification of the vector meson masses can pro- vide a unique .... similar behavior is found in (γ,π+π0) reactions, shown in the right panel of figure 3. Additionally, the peak in ...

Fluence of dielectric constant (D), (H/sup +/) and (SO/sub 4/sup -2/) on the rate of redox reaction between tris (2,2-bipyridine) iron (II) and ceric sulphate in aqueous sulphuric acid medium

International Nuclear Information System (INIS)

Khattak, R.; Naqvi, I.I.; Farrukh, M.A.

2007-01-01

Kinetic of the redox reaction between tris (2,2-bipyridine)iron(II) cation and ceric sulphate has been studied in aqueous sulphuric acid medium. Different methods were employed for the determination of order of reaction. The order of reaction is found to be first with respect to reductant however retarding effect of increasing initial concentration of oxidant is found. Influence of (H/sup +/), (SO/sub 4/sup 2-) and dielectric constant (D) on the rate of redox reaction has also been studied. Increase in (H/sup +/) and dielectric constant of the medium retard the rate while enhancement of the (SO/sub 4/sup 2-/) accelerates the rate first and then the reaction goes towards retardation. Effects of (H/sup +/) and (SO/sub 4/sup 2-/) were studied by using acetic acid-sodium acetate buffer for the first one and varying ionic concentrations of the salt sodium sulphate for the latter one, whereas dielectric constant was varied by using 0%, 10% and 20% ethanol-water mixtures. Results of effects of each one of the factors i.e., H/sup +/, SO/sub 4/sup 2-/ and dielectric constant (D) have been compared and on the basis of these factors, (Ce(SO/sub 4/ )/sub 3/)/sup 2-/ is suggested to be the active species of cerium(IV). However a rate law consistent with the observed kinetic data has also been derived supporting the proposed mechanism. (author)

Computational Approach to Electron Charge Transfer Reactions

DEFF Research Database (Denmark)

Jónsson, Elvar Örn

-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

International Nuclear Information System (INIS)

Feng Yongjun; He Ting; Alonso-Vante, Nicolas

2009-01-01

We investigated the effect of CoSe 2 /C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H 2 O 2 production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe 2 nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H 2 O 2 production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe 2 loading on the disk electrode. H 2 O 2 production also decreased with increasing catalytic site density, a phenomenon related to the CoSe 2 loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe 2 /C nanoparticles at 22 μg cm -2 , we determined that the transfer process involves about 3.5 electrons.

The Role of Low-Energy (less than 20 eV) Electrons in Astrochemistry: A Tale of Two Molecules

Science.gov (United States)

Arumainayagam, Chris

2016-07-01

In the interstellar medium, UV photolysis of ice mantles encasing dust grains is thought to be the mechanism that drives the synthesis of "complex" molecules. The source of this reaction-initiating UV light is assumed to be local because externally-sourced UV radiation cannot pass through the ice-containing dark, dense molecular clouds. Externally sourced cosmic rays (E_{max} ˜10^{20} eV), in addition to producing UV light within these clouds, also produce large numbers of low-energy (≤ 20 eV) secondary electrons. The goal of our studies is to understand the low-energy electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices. Using electron stimulated desorption (ESD), post-irradiation temperature-programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS), we have investigated the radiolysis initiated by electrons in condensed methanol and ammonia at ˜90K under ultrahigh vacuum (1 × 10^{-9} Torr) conditions. We have identified fifteen low-energy electron-induced methanol radiolysis products, many of which have been previously identified as being formed by methanol UV photolysis in the interstellar medium. We have also found evidence for the electron-induced formation from ammonia of hydrazine (N_2 H_4), diazene (N_2 H_2), cyclotriazane/triazene (N_3 H_3) and triazane (N_3 H_5). We have investigated the reaction yields' dependence on film thickness, irradiation time, incident current, electron energy, and metal substrate. These results provide a basis from which we can begin to understand the mechanisms by which methanol and ammonia can form more complex species in cosmic ices. Studies such as ours may ultimately help us better understand the initial stages of the genesis of life.

Characterization of alternate reductant binding and electron transfer in the dopamine β-monooxygenase reaction

International Nuclear Information System (INIS)

Stewart, L.C.; Klinman, J.P.

1987-01-01

The steady-state limiting kinetic parameters V/sub max/, V/K/sub DA/, and V/K/sub O 2 /, together with deuterium isotope effects on these parameters, have been determined for the dopamine β-monooxygenase (DβM) reaction in the presence of structurally distinct reductants. The results show the one-electron reductant ferrocyanide to be nearly as kinetically competent as the presumed in vivo reductant ascrobate. Further, a reductant system of ferricyanide plus substrate dopamine yields steady-state kinetic parameters and isotope effects very similar to those measured solely in the presence of ferrocyanide, indicating a role for catecholamine in the rapid recycling of oxidized ferrocyanide. Use of substrate dopamine as the sole reductant is found to lead to a highly unusual kinetic independence of oxygen concentration, as well as significantly reduced values of V/sub max/ and V/K/sub DA/, and the authors conclude that dopamine reduces enzymic copper in a rate-limiting step that is 40-fold slower than with ascorbate. The near-identical kinetic parameters measured in the presence of either ascorbate or ferrocyanide, together with markedly reduced rates with dopamine, are interpreted in terms of a binding site for reductant that is physically distinct from the substrate binding site. This view is supported by molecular modeling, which reveals ascorbate and ferrocyanide to possess an unexpected similarity in potential sites for interaction with enzymic residues. With regard to electron flux, identical values of V/K/sub O 2 / have been measured with [2,2- 2 H 2 ]dopamine as substrate both in the presence and in the absence of added ascorbate. This key result unambiguously rules out an entry of electrons to enzyme forms leading from the enzyme-dopamine complex to enzyme-bound product and, hence, reaction mechanisms involving a reductive activation of the putative Cu(II)-OOH prior to substrate hydroxylation

Heterogeneously Catalysed Aldol Reactions in Supercritical Carbon Dioxide as Innovative and Non-Flammable Reaction Medium

DEFF Research Database (Denmark)

Musko, Nikolai; Grunwaldt, Jan-Dierk

2011-01-01

Aldol reactions of several aldehydes have been investigated over acidic and basic catalysts in supercritical carbon dioxide at 180 bar and 100 °C. Both acidic (Amberlyst-15, tungstosilicic acid (TSA) on SiO2 and MCM-41) and basic (hydrotalcite) materials showed interesting performance in this pre...

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

Science.gov (United States)

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

2014-05-19

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

Calculation of the energetics of chemical reactions

Energy Technology Data Exchange (ETDEWEB)

Dunning, T.H. Jr.; Harding, L.B.; Shepard, R.L.; Harrison, R.J.

1988-01-01

To calculate the energetics of chemical reactions we must solve the electronic Schroedinger equation for the molecular conformations of importance for the reactive encounter. Substantial changes occur in the electronic structure of a molecular system as the reaction progresses from reactants through the transition state to products. To describe these changes, our approach includes the following three elements: the use of multiconfiguration self-consistent field wave functions to provide a consistent zero-order description of the electronic structure of the reactants, transition state, and products; the use of configuration interaction techniques to describe electron correlation effects needed to provide quantitative predictions of the reaction energetics; and the use of large, optimized basis sets to provide the flexibility needed to describe the variations in the electronic distributions. With this approach we are able to study reactions involving as many as 5--6 atoms with errors of just a few kcal/mol in the predicted reaction energetics. Predictions to chemical accuracy, i.e., to 1 kcal/mol or less, are not yet feasible, although continuing improvements in both the theoretical methodology and computer technology suggest that this will soon be possible, at least for reactions involving small polyatomic species. 4 figs.

Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce3+ phosphor

International Nuclear Information System (INIS)

Kumar, Vinay; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.; Mishra, Varun

2010-01-01

The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce 3+ nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm 2 . XPS was used to study the chemical composition of the CaS:Ce 3+ nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO 4 layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO 4 layer on the surface.

B-side charge separation in bacterial photosynthetic reaction centers: nanosecond time scale electron transfer from HB- to QB.

Science.gov (United States)

Kirmaier, Christine; Laible, Philip D; Hanson, Deborah K; Holten, Dewey

2003-02-25

We report time-resolved optical measurements of the primary electron transfer reactions in Rhodobacter capsulatus reaction centers (RCs) having four mutations: Phe(L181) --> Tyr, Tyr(M208) --> Phe, Leu(M212) --> His, and Trp(M250) --> Val (denoted YFHV). Following direct excitation of the bacteriochlorophyll dimer (P) to its lowest excited singlet state P, electron transfer to the B-side bacteriopheophytin (H(B)) gives P(+)H(B)(-) in approximately 30% yield. When the secondary quinone (Q(B)) site is fully occupied, P(+)H(B)(-) decays with a time constant estimated to be in the range of 1.5-3 ns. In the presence of excess terbutryn, a competitive inhibitor of Q(B) binding, the observed lifetime of P(+)H(B)(-) is noticeably longer and is estimated to be in the range of 4-8 ns. On the basis of these values, the rate constant for P(+)H(B)(-) --> P(+)Q(B)(-) electron transfer is calculated to be between approximately (2 ns)(-)(1) and approximately (12 ns)(-)(1), making it at least an order of magnitude smaller than the rate constant of approximately (200 ps)(-)(1) for electron transfer between the corresponding A-side cofactors (P(+)H(A)(-) --> P(+)Q(A)(-)). Structural and energetic factors associated with electron transfer to Q(B) compared to Q(A) are discussed. Comparison of the P(+)H(B)(-) lifetimes in the presence and absence of terbutryn indicates that the ultimate (i.e., quantum) yield of P(+)Q(B)(-) formation relative to P is 10-25% in the YFHV RC.

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.

Oxidoreduction reactions involving the electrostatic and the covalent complex of cytochrome c and plastocyanin: Importance of the protein rearrangement for the intracomplex electron-transfer reaction

International Nuclear Information System (INIS)

Peerey, L.M.; Kostic, N.M.

1989-01-01

Horse heart cytochrome c and French bean plastocyanin are cross-linked one-to-one by a carbodiimide in the same general orientation in which they associate electrostatically. The reduction potentials of the Fe and Cu atoms in the covalent diprotein complex are respectively 245 and 385 mV vs NHE; the EPR spectra of the two metals are not perturbed by cross-linking. For isomers of the covalent diprotein complex, which probably differ slightly from one another in the manner of cross-linking, are separated efficiently by cation-exchange chromatography. Stopped-flow spectrophotometric experiments with the covalent diprotein complex show that the presence of plastocyanin somewhat inhibits oxidation of ferrocytochrome c by [Fe(CN) 6 ] 3- and somewhat promotes oxidation of this protein by [Fe(C 5 H 5 ) 2 ] + . These changes in reactivity are explained in terms of electrostatic and steric effects. Pulse-radiolysis experiments with the electrostatic diprotein complex yield association constants of ≥5 x 10 6 and 1 x 10 5 M -1 at ionic strengths of 1 and 40 mM, respectively, and the rate constant of 1.05 x 10 3 s -1 , regardless of the ionic strength, for the intracomplex electron-transfer reaction. Analogous pulse-radiolysis experiments with each of the four isomers of the covalent diprotein complex, at ionic strengths of both 2 and 200 mM, show an absence of the intracomplex electron-transfer reaction. A rearrangement of the proteins for this reaction seems to be possible (or unnecessary) in the electrostatic complex but impossible in the covalent complex

Effect of Water Clustering on the Activity of Candida antarctica Lipase B in Organic Medium

DEFF Research Database (Denmark)

Banik, Sindrila Dutta; Nordblad, Mathias; Woodley, John M.

2017-01-01

The effect of initial water activity of MTBE (methyl tert-butyl ether) medium on CALB (Candida antarctica lipase B) catalyzed esterification reaction is investigated using experimental methods and classical molecular dynamics (MD) simulations. The experimental kinetic studies show that the initial...... reaction rate of CALB-catalyzed esterification reaction between butyric acid and ethanol decreases with increasing initial water activity of the medium. The highest rate of esterification is observed at the lowest water activity studied. MD simulations were performed to gain a molecular insight...... on the effect of initial water activity on the rate of CALB-catalyzed reaction. Our results show that hydration has an insignificant effect on the structure and flexibility of CALB. Rather, it appears that water molecules bind to certain regions ("hot spots") on the CALB surface and form clusters. The size...

Reaction of LiD with water vapor: thermogravimetric and scanning electron microscopy studies

International Nuclear Information System (INIS)

Balooch, M; Dinh, L N; LeMay, J D

2000-01-01

The kinetics of hydroxide film growth on LiD have been studied by the thermogravimetric method in nitrogen saturated with water vapor and by scanning electron microscopy (SEM) of samples that have been exposed to air with 50% relative humidity. The reaction probability is estimated to be 4 x 10 -7 for LiD exposed to ambient air with 50% relative humidity, suggesting that the diffusion through the hydroxide film is not the limiting step on the overall process at high moisture levels. The rate of growth is drastically reduced when the temperature is increased to 60 C

Electron reactions in model liquids and biological systems

International Nuclear Information System (INIS)

Bakale, G.; Gregg, E.C.

1982-01-01

Progress is reported in the following studies: (1) Field-dependent electron attachment; (2) Dependence of electron attachment rate on electron-acceptor dipole moment; (3) Electron attachment in i-octane/TMS mixtures; (4) Electron attachment/detachment equilibria; (5) Electron attachment to reversed micelles; (6) Electron attachment to chemical carcinogens; (7) Radiation-induced bacterial mutagenesis; and (8) Bacterial mutagenicity of nitrobenzene derivatives. 14 references

Aerosol simulation including chemical and nuclear reactions

International Nuclear Information System (INIS)

Marwil, E.S.; Lemmon, E.C.

1985-01-01

The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs

Microwave-Assisted Organic Synthesis Using Benign Reaction Medium and Reagents

Science.gov (United States)

Account of chemical reactions expedited by microwave (MW) exposure of neat reactants for the rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermediates via enamines or using hypervalent iodine reagents will be described that can be adapted for ...

The bimolecular reaction of radiolysis product of hydrated electron at temperature up to 473K; Reaksi bimolekular antar produk radiolisis elektron terhidrasi pada temperatur hingga 473K

Energy Technology Data Exchange (ETDEWEB)

Sunaryo, G R [Reactor Safety Technology Research Centre, National Atomic Energy Agency, Serpong (Indonesia)

1996-06-01

Rate constant from the bimolecular reaction of hydrated electron was determined by using radiolysis method. The methanol solution with concentration of 5 x 10{sup -2} dm{sup 3} mol{sup -1} was used as a scavenger of H and OH radicals. The pH was kept by adding the buffer solution of 1.0 x 10{sup -3} dm{sup 3} mol{sup -1} Na{sub 2}HPO{sub 4} + 1.0 x 10{sup 4} dm{sup 3} mol{sup -1} NaH{sub 2}PO{sub 4}. The irradiation was done by using the electron beam which come from linear accelerator 28 MeV with pulse width 10ns and dose of 80 Gy per pulse. The absorbance of hydrated electron was observed at wavelength of 824 nm. By using the kinetic equation the rate reaction constants were obtained. The bimolecular reaction of hydrated electron increase with temperature up to 423K. The activation energy was 19.3 kJ mol{sup -1} and the 2 k (298K) was 1.1 x 10{sup 10} dm{sup 3} mol{sup -1}. Then this bimolecular reaction decrease at temperature higher than 423K and the rate reaction constant at 473K almost similar with that at 298K. (author)

Scattering of polarized electrons from polarized targets: Coincidence reactions and prescriptions for polarized half-off-shell single-nucleon cross sections

International Nuclear Information System (INIS)

Caballero, J.A.; Massachusetts Inst. of Tech., Cambridge, MA; Donnelly, T.W.; Massachusetts Inst. of Tech., Cambridge, MA; Poulis, G.I.; Massachusetts Inst. of Tech., Cambridge, MA

1993-01-01

Coincidence reactions of the type vector A( vector e, e'N)B involving the scattering of polarized electrons from polarized targets are discussed within the context of the plane-wave impulse approximation. Prescriptions are developed for polarized half-off single-nucleon cross sections; the different prescriptions are compared for typical quasi-free kinematics. Illustrative results are presented for coincidence polarized electron scattering from typical polarized nuclei. (orig.)

Interfacial reaction in SiC_f/Ti-6Al-4V composite by using transmission electron microscopy

International Nuclear Information System (INIS)

Huang, Bin; Li, Maohua; Chen, Yanxia; Luo, Xian; Yang, Yanqing

2015-01-01

The interfacial reactions of continuous SiC fiber reinforced Ti-6Al-4V matrix composite (SiC_f/Ti-6Al-4V composite) and continuous SiC fiber coated by C reinforced Ti-6Al-4V matrix composite (SiC_f/C/Ti-6Al-4V composite) were investigated by using micro-beam electron diffraction (MBED) and energy disperse spectroscopy (EDS) on transmission electron microscopy (TEM). The sequence of the interfacial reactions in the as-processed and exposed at 900°C for 50h SiC_f/Ti-6Al-4V composites can be described as SiC||TiC||Ti_5Si_3 + TiC||Ti-6Al-4V and SiC||TiC||Ti_5Si_3||TiC||Ti_5Si_3||TiC||Ti_5Si_3||Ti-6Al-4V, respectively. Additionally, both in as-processed and exposed composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. For the SiC_f/C/Ti-6Al-4V composite exposed at 900 °C for 50 h, the sequence of the interfacial reaction can be described as SiC||C||TiC_F||TiC_C||Ti-6Al-4V before C coating is completely consumed by interfacial reaction. When interfacial reaction consumes C coating completely, the sequence of the interfacial reaction can be described as SiC||TiC||Ti_5Si_3||TiC||Ti-6Al-4V. Furthermore, in SiC_f/C/Ti-6Al-4V composite, C coating can absolutely prevent Si diffusion from SiC fiber to matrix. Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed. - Highlights: • We obtained the sequence of the interfacial reactions in the as-processed and exposed at 900 °C for 50 h SiC_f/Ti-6Al-4 V composites as well as in the SiC_f/C/Ti-6Al-4 V composite exposed at 900 °C for 50 h. • We verified that both in as-processed and exposed SiC_f/Ti-6Al-4 V composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. • Carbon coating can absolutely prevent silicon diffusion from SiC fiber to matrix. • Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed.

Towards preparative peroxygenase-catalyzed oxyfunctionalization reactions in organic media

NARCIS (Netherlands)

Fernandez Fueyo, E.; Ni, Y.; Gomez Baraibar, A.; Alcalde, Miguel; van Langen, L.M.; Hollmann, F.

2016-01-01

The peroxygenase from Agrocybe aegerita (AaeUPO) has been evaluated for stereoselective oxyfunctionalization chemistry under non-aqueous reaction conditions. The stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol was performed in neat substrate as reaction medium together with

Electron transfer reactions in microporous solids

Energy Technology Data Exchange (ETDEWEB)

Mallouk, T.E.

1993-01-01

Basic thrust the research program involves use of microporous solids (zeolites, clays, layered and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. Purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H[sub 2] and I[sub 3][sup [minus

Coupled processes of fluid flow, solute transport, and geochemical reactions in reactive barriers

Energy Technology Data Exchange (ETDEWEB)

Kim, Jeongkon; Schwartz, Franklin W.; Xu, Tianfu; Choi, Heechul, and Kim, In S.

2004-01-02

A complex pattern of coupling between fluid flow and mass transport develops when heterogeneous reactions occur. For instance, dissolution and precipitation reactions can change a porous medium's physical properties, such as pore geometry and thus permeability. These changes influence fluid flow, which in turn impacts the composition of dissolved constituents and the solid phases, and the rate and direction of advective transport. Two-dimensional modeling studies using TOUGHREACT were conducted to investigate the coupling between flow and transport developed as a consequence of differences in density, dissolution precipitation, and medium heterogeneity. The model includes equilibrium reactions for aqueous species, kinetic reactions between the solid phases and aqueous constituents, and full coupling of porosity and permeability changes resulting from precipitation and dissolution reactions in porous media. In addition, a new permeability relationship is implemented in TOUGHREACT to examine the effects of geochemical reactions and density difference on plume migration in porous media. Generally, the evolutions in the concentrations of the aqueous phase are intimately related to the reaction-front dynamics. Plugging of the medium contributed to significant transients in patterns of flow and mass transport.

Electron transfer in proteins

DEFF Research Database (Denmark)

Farver, O; Pecht, I

1991-01-01

Electron migration between and within proteins is one of the most prevalent forms of biological energy conversion processes. Electron transfer reactions take place between active centers such as transition metal ions or organic cofactors over considerable distances at fast rates and with remarkable...... specificity. The electron transfer is attained through weak electronic interaction between the active sites, so that considerable research efforts are centered on resolving the factors that control the rates of long-distance electron transfer reactions in proteins. These factors include (in addition......-containing proteins. These proteins serve almost exclusively in electron transfer reactions, and as it turns out, their metal coordination sites are endowed with properties uniquely optimized for their function....

Students’ attitudes to lecturers' English in English-medium higher education in Denmark

DEFF Research Database (Denmark)

Jensen, Christian; Denver, Louise; Mees, Inger M.

2013-01-01

This study examines the evaluative reactions of university students to their non-native lecturers’ English skills in English-medium instruction, i.e. when English is used as a lingua franca in an academic context. In particular, we examine the relationship between perceptions of English language ....... This effect should be addressed when universities use student ratings to evaluate teaching in English-medium content courses.......This study examines the evaluative reactions of university students to their non-native lecturers’ English skills in English-medium instruction, i.e. when English is used as a lingua franca in an academic context. In particular, we examine the relationship between perceptions of English language...... proficiency and perceptions of general lecturing competence (defined here as knowledge of subject and teaching skills). Statistical analyses of 1,700 student responses to 31 non-native English-speaking lecturers at a major business school in Denmark revealed that the students’ perceptions of the lecturers...

Detailed Monte Carlo simulation of electron elastic scattering

International Nuclear Information System (INIS)

Chakarova, R.

1994-04-01

A detailed Monte Carlo model is described which simulates the transport of electrons penetrating a medium without energy loss. The trajectory of each electron is constructed as a series of successive interaction events - elastic or inelastic scattering. Differential elastic scattering cross sections, elastic and inelastic mean free paths are used to describe the interaction process. It is presumed that the cross sections data are available and the Monte Carlo algorithm does not include their evaluation. Electrons suffering successive elastic collisions are followed until they escape from the medium or (if the absorption is negligible) their path length exceeds a certain value. The inelastic events are thus treated as absorption. The medium geometry is a layered infinite slab. The electron source could be an incident electron beam or electrons created inside the material. The objective is to obtain the angular distribution, the path length and depth distribution and the collision number distribution of electrons emitted through the surface of the medium. The model is applied successfully to electrons with energy between 0.4 and 20 keV reflected from semi-infinite homogeneous materials with different scattering properties. 16 refs, 9 figs

Spur Reaction Model of Positronium Formation

DEFF Research Database (Denmark)

Mogensen, O. E.

1974-01-01

A new model of positronium (Ps) formation is proposed. Positronium is assumed to be formed by a reaction between a positron and an electron in the positron spur. Ps formation must compete with electron‐ion recombination and electron or positron reactions with solvent molecules and scavenger...

The radiation amplification effect in the scattering of a quasi-classical electron by an ion in an electromagnetic field of medium intensity

International Nuclear Information System (INIS)

Freiv, A V; Roshchupkin, S P

2008-01-01

The possibility of amplification of electromagnetic radiation is theoretically studied in the scattering of a quasi-classical electron by an ion in a field of linearly polarized waves of medium intensity. An expression for the total cross-section (the gain coefficient) for the wide interval of values of the adiabaticity parameter is obtained. It is shown that the wave amplification takes place in the range of values of adiabaticity parameter greater than 2 and can be sufficiently large

Evaluation of RBE of thermal neutron capture reaction

International Nuclear Information System (INIS)

Fukuda, Hiroshi; Matsuzawa, Taiju; Kobayashi, Toru; Kanda, Keiji.

1985-01-01

B16 melanoma cells were grown in a flask (Falcon 3031). When the cells reached the latter stage of logarithmic phase, B-boric acid (92 % concentrated 10 B) was added to the flask until 5 μg/ml medium was attained (Medium I). The other medium did not contain 10 B (Medium II). After both media were exposed to thermal neutrons, survival curves were obtained from the colony method and the absorbed dose of the cells were obtained from the mathematical models. Survival curves from the colony method had no shoulders, showing that Do was 0.95 x 10 12 n/cm 2 in Medium I and 3.2 x 10 12 n/cm 2 in Medium II. Do calculated by mathematical models was 0.507 Gy in Medium I and 0.604 Gy in Medium II. REB of thermal neutrons was 3.04 in Medium I and 2.55 in Medium II. REB of 10 B (n, α) 7 Li reaction was 3.30. (Namekawa, K.)

Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

International Nuclear Information System (INIS)

Gupta, R.

1990-01-01

The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H + . A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given. (Author)

Temperature dependence of the rate constant for reactions of hydrated electrons with H, OH and H2O2

DEFF Research Database (Denmark)

Christensen, H.; Sehested, K.; Løgager, T.

1994-01-01

The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H2O2 has been determined. The reaction with H atoms, studied in the temperature range 20-250-degrees-C gives k(20-degrees-C) = 2.4 x 10(10) M-1 s-1 and the activation energy E......-1 and E(A) = 15.6 kJ mol-1 (3.7 kcal mol-1) measured from 5-150-degrees-C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction......(A) = 14.0 kJ mol-1 (3.3 kcal mol-1). For reaction with OH radicals the corresponding values are, k(20-degrees-C) = 3.1 x 10(10) M-1 s-1 and E(A) = 14.7 kJ mol-1 (3.5 kcal mol-1) determined in the temperature range 5-175-degrees-C. For reaction with H2O2 the values are, k(20-degrees-C) = 1.2 x 10(10) M-1 s...

Properties of the nuclear medium

International Nuclear Information System (INIS)

Baldo, M; Burgio, G F

2012-01-01

linking the physics of exotic nuclei and the astrophysics of neutron stars is particularly stressed. Finally, we discuss the thermal properties of the nuclear medium, in particular the liquid–gas phase transition and its connection with the phenomenology on heavy ion reactions and the cooling evolution of neutron stars. The presentation has been taken for non-specialists and possibly for non-nuclear physicists.

Language of Mechanisms: Exam Analysis Reveals Students' Strengths, Strategies, and Errors When Using the Electron-Pushing Formalism (Curved Arrows) in New Reactions

Science.gov (United States)

Flynn, Alison B.; Featherstone, Ryan B.

2017-01-01

This study investigated students' successes, strategies, and common errors in their answers to questions that involved the electron-pushing (curved arrow) formalism (EPF), part of organic chemistry's language. We analyzed students' answers to two question types on midterms and final exams: (1) draw the electron-pushing arrows of a reaction step,…

Protein sequences and redox titrations indicate that the electron acceptors in reaction centers from heliobacteria are similar to Photosystem I

Science.gov (United States)

Trost, J. T.; Brune, D. C.; Blankenship, R. E.

1992-01-01

Photosynthetic reaction centers isolated from Heliobacillus mobilis exhibit a single major protein on SDS-PAGE of 47 000 Mr. Attempts to sequence the reaction center polypeptide indicated that the N-terminus is blocked. After enzymatic and chemical cleavage, four peptide fragments were sequenced from the Heliobacillus mobilis apoprotein. Only one of these sequences showed significant specific similarity to any of the protein and deduced protein sequences in the GenBank data base. This fragment is identical with 56% of the residues, including both cysteines, found in highly conserved region that is proposed to bind iron-sulfur center Fx in the Photosystem I reaction center peptide that is the psaB gene product. The similarity to the psaA gene product in this region is 48%. Redox titrations of laser-flash-induced photobleaching with millisecond decay kinetics on isolated reaction centers from Heliobacterium gestii indicate a midpoint potential of -414 mV with n = 2 titration behavior. In membranes, the behavior is intermediate between n = 1 and n = 2, and the apparent midpoint potential is -444 mV. This is compared to the behavior in Photosystem I, where the intermediate electron acceptor A1, thought to be a phylloquinone molecule, has been proposed to undergo a double reduction at low redox potentials in the presence of viologen redox mediators. These results strongly suggest that the acceptor side electron transfer system in reaction centers from heliobacteria is indeed analogous to that found in Photosystem I. The sequence similarities indicate that the divergence of the heliobacteria from the Photosystem I line occurred before the gene duplication and subsequent divergence that lead to the heterodimeric protein core of the Photosystem I reaction center.

Generation of 300 MeV Quasi-Monochromatic Electron Beams from Laser Wakefield and Initiation of Photonuclear Reactions

Science.gov (United States)

Maksimchuk, A.; Beene, J. R.

2005-10-01

In the interaction of 30 fs, 40 TW Ti:sapphire Hercules laser at the University of Michigan, which is focused to the intensity of 10^19 W/cm^2 onto a supersonic He gas jet with electron density close to the resonant density, we observed quasi-monoenergetic electron beams with energy up to 300 MeV and angular divergence of about 10 mrad. The results on characterization of relativistic electron beam in terms of energy spread, its charge, divergence and pointing stability will be presented. 2D PIC simulations performed for the parameters close to the experimental conditions show the evolution of the laser pulse in plasma, electron injection, and the specifics of electron acceleration observed in experiments. Resulted relativistic electron beams have been used to perform gamma-neutron activation of ^12C and ^63Cu and photo-fission of ^238U. We demonstrated that approximately 10^6 reaction per shot has been produced in each case. This work was supported by the NSF through the Physics Frontier Center FOCUS. JRB, DRS, DWS, and CRV acknowledge support by the DOE under contract DE-AC05-00OR22725 with UT-Battelle, LLC.

Effect of the Reduction Temperature of PdAg Nanoparticles during the Polyol Process in the Ethanol Electrooxidation Reaction

Directory of Open Access Journals (Sweden)

R. Carrera-Cerritos

2018-01-01

Full Text Available This work reports the effect of reduction temperature during the synthesis of PdAg catalysts through the polyol process and their evaluation in the ethanol electrooxidation reaction (EOR. The characterization was performed using Transmission Electron Microscopy (TEM and X-Ray Diffraction (XRD. The electrochemical evaluation for the ethanol electrooxidation reaction was implemented in alkaline medium using chronoamperometry (CA and cyclic voltammetry (CV. An important effect of the reduction temperature on electroactivity and catalytic stability was observed: both the maximum current density and the catalytic stability were higher in the catalyst synthesized at the highest temperature (135°C. This performance was associated with the extent of the interaction between Pd and Ag which was measured in terms of the structural expansion of Pd.

Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

Directory of Open Access Journals (Sweden)

Y. I. Hassan

2012-01-01

Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

Numerical analysis for Darcy-Forchheimer flow in presence of homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Muhammad Ijaz Khan

Full Text Available A mathematical study is presented to investigate the influences of homogeneous and heterogeneous reactions in local similar flow caused by stretching sheet with a non-linear velocity and variable thickness. Porous medium effects are characterized by using Darcy-Forchheimer porous-media. A simple isothermal model of homogeneous-heterogeneous reactions is used. The multiphysical boundary value problem is dictated by ten thermophysical parameters: ratio of mass diffusion coefficients, Prandtl number, local inertia coefficient parameter, inverse Darcy number, shape parameter, surface thickness parameter, Hartman number, Homogeneous heat reaction, strength of homogeneous-heterogeneous reactions and Schmidt number. Resulting systems are computed by Runge-Kutta-Fehlberg method. Different shapes of velocity are noticed for n > 1 and n < 1. Keywords: Homogeneous-heterogeneous reactions, Non Darcy porous medium, Variable sheet thickness, Homogeneous heat reaction with stoichiometric coefficient, Runge-Kutta-Fehlberg method

Verification of Radicals Formation in Ethanol-Water Mixture Based Solution Plasma and Their Relation to the Rate of Reaction.

Science.gov (United States)

Sudare, Tomohito; Ueno, Tomonaga; Watthanaphanit, Anyarat; Saito, Nagahiro

2015-12-03

Our previous research demonstrated that using ethanol-water mixture as a liquid medium for the synthesis of gold nanoparticles by the solution plasma process (SPP) could lead to an increment of the reaction rate of ∼35.2 times faster than that in pure water. This drastic change was observed when a small amount of ethanol, that is, at an ethanol mole fraction (χethanol) of 0.089, was added in the system. After this composition, the reaction rate decreased continuously. To better understand what happens in the ethanol-water mixture-based SPP, in this study, effect of the ethanol content on the radical formation in the system was verified. We focused on detecting the magnetic resonance of electronic spins using electron spin resonance spectroscopy to determine the type and quantity of the generated radicals at each χethanol. Results indicated that ethanol radicals were generated in the ethanol-water mixtures and exhibited maximum quantity at the xethanol of 0.089. Relationship between the ethanol radical yield and the rate of reaction, along with possible mechanism responsible for the observed phenomenon, is discussed in this paper.

Adverse reactions to iotroxate at intravenous cholangiography

International Nuclear Information System (INIS)

Nilsson, U.

1987-01-01

The number and type of adverse reactions to meglumine iotroxate at intravenous infusion cholangiography, performed one day prior to elective cholecystectomy, were recorded in a prospective investigation of 196 asymptomatic, anicteric patients. One hundred ml (50 mg I/ml) of contrast medium was infused over a period of 30 minutes. Only 2 minor (1%) and no severe or fatal reactions were noted. A review of the literature on the use of iotroxate in 2492 patients, including those in the present investigation, revealed a complication rate of 3.5% (3.0% minor, 0.3% moderate and 0.2% severe reactions) at infusion of iotroxate (5.0-8.0 g I) over a period of 30 to 120 minutes. This compared favourably with the 5% complication rate (4% minor, 0.5% moderate and 0.5% severe reactions) at infusion of iodoxamate and the 9% complication rate (5% minor, 1% moderate and 3% severe reactions) at infusion of ioglycamide. Irrespective of the contrast agent used, the frequency of adverse reactions at infusion was found to be 3 times lower than when equal amounts (5.0-5.6 g I) of the same medium were injected. It is concluded that, at present, infusion of iotroxate in an amount which approximates to the transportation maximum of the liver is the least toxic way of performing intravenous cholangiography with an optimum filling of the bile ducts. (orig.)

Use of Both Anode and Cathode Reactions in Wastewater Treatment

Science.gov (United States)

Brillas, Enric; Sirés, Ignasi; Cabot, Pere LluíS.

Here, we describe the fundamentals, laboratory experiments, and environmental applications of indirect electrooxidation methods based on H2O2 electrogeneration such as electro-Fenton, photoelectro-Fenton and peroxicoagulation for the treatment of acidic wastewaters containing toxic and recalcitrant organics. These methods are electrochemical advanced oxidation processes that can be used in divided and undivided electrolytic cells in which pollutants are oxidized by hydroxyl radical (•OH) produced from anode and/or cathode reactions. H2O2 is generated from the two-electron reduction of O2 at reticulated vitreous carbon, graphite, carbon-felt, and O2-diffusion cathodes. The most usual method is electro-Fenton where Fe2 + added to the wastewater reacts with electrogenerated H2O2 to yield •OH and Fe3 + from Fenton's reaction. An advantage of this technique is that Fe2 + is continuously regenerated from cathodic reduction of Fe3 +. The characteristics of different electro-Fenton systems where pollutants are simultaneously destroyed by •OH formed in the medium from Fenton's reaction and at the anode surface from water oxidation are explained. The effect of the anode [Pt or boron-doped diamond (BDD)] and cathode (carbon-felt or O2-diffusion) on the degradation rate of persistent industrial by-products, herbicides, pharmaceuticals, dyes, etc. is examined. Initial pollutants react much more rapidly with •OH formed in the medium and their degradation sequences are discussed from aromatic intermediates and finally short aliphatic acids are detected. The synergetic positive catalytic effect of Cu2 + on the electro-Fenton process is evidenced. The photoelectro-Fenton method involves the irradiation of the wastewater with UVA light that rapidly photodecomposes complexes of Fe3 + with final carboxylic acids enhancing total decontamination. The peroxicoagulation method uses a sacrificial Fe anode that is continuously oxidized to Fe2 + and organics are either mineralized

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

International Nuclear Information System (INIS)

Fernandez, Esther; Larsson, Jonas T.; McLean, Kirsty J.; Munro, Andrew W.; Gorton, Lo; Wachenfeldt, Claes von; Ferapontova, Elena E.

2013-01-01

The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer reactions of trHb-Bs were electrochemically studied in solution and at graphite electrodes. Spectrophotometrical potentiometric titration and direct electrochemical measurements gave a heme iron redox potential of −103 ± 4 mV and −108 ± 2 mV vs. NHE, at pH 7, respectively. The redox potential of the heme in trHb-Bs shifted −59 mV per pH unit at pH higher than 7, consistently with a 1e − /1 H + – transfer reaction. The heterogeneous rate constant k s for a quasi-reversible 1e − – 1H + – transfer reaction between graphite and trHb-Bs was 10.1 ± 2.3 s −1 . Upon reversible cyanide binding the k s doubled, while the redox potential of heme shifted 21 mV negatively, presumably reflecting changes in redox activity and in vivo signaling functions of trHb-Bs associated with ligand binding. Bioelectrocatalytic reduction of O 2 catalyzed by trHb-Bs was one of the most efficient hitherto reported for Hbs, with an apparent catalytic rate constant, k cat , of 56 ± 6 s −1 . The results obtained are of particular interest for applications of trHb in environmental biosensing and toxicity screening

Dosimetry for combustion flue gas treatment with electron beam

Energy Technology Data Exchange (ETDEWEB)

Mehta, K.; Bułka, S.; Sun, Y. [Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

2011-07-01

The electron beam treatment of flue gas is one of the new technologies. There are several reasons for carrying out dosimetry at various phases of the project as understanding the process and optimizing the equipment, for process control and for troubleshooting in case of malfunction etc. The main challenge in measuring dose for flue gas applications is that the medium being irradiated is gaseous. Two general approaches for dose measurements are: adding/placing some dosimeters in the reaction vessel (gas) and using the components of the gas itself as a dosimeter. Various techniques and methods have been tried which are discussed in this paper. (author)

Imaging the electron transfer reaction of Ne2+ with Ar using position-sensitive coincidence spectroscopy

International Nuclear Information System (INIS)

Harper, Sarah M; Hu Wanping; Price, Stephen D

2002-01-01

A new experiment, employing position-sensitive detection coupled with time-of-flight mass spectrometry, has been used to investigate the single-electron transfer reaction between Ne 2+ and Ar by detecting the resulting pairs of singly charged ions in coincidence. The experimental technique allows the determination of the individual velocity vectors of the ionic products, in the centre-of-mass frame, for each reactive event detected. The experiments show that forward scattering dominates the reactivity, although a bimodal angular distribution is apparent. In addition, the spectra show that at laboratory frame collision energies from 4-14 eV the reactivity is dominated by Ne 2+ (2p 4 , 3 P) accepting an electron from an argon atom to form the ground state of Ne + together with an Ar + ion in an excited electronic level, predominantly arising from the Ar + (3s 2 3p 4 3d) configuration. The form of this reactivity, and the differences between the reactivity observed in these experiments and those performed at higher collision energies, are well reproduced by Landau-Zener theory

The intriguing enhancement of chloroperoxidase mediated one-electron oxidations by azide, a known active-site ligand

International Nuclear Information System (INIS)

Andrew, Daniel; Hager, Lowell; Manoj, Kelath Murali

2011-01-01

Highlights: ► Azide is a well known heme–enzyme active site ligand and inhibitor. ► Herein, azide is reported to enhance a set of heme–enzyme mediated reactions. ► This effect is disconnected from native enzyme–azide binding. ► Azide could enhance heme–enzyme reactions via a newly proposed mechanism. ► Azide contained in reagents could impact reaction outcomes in redox biochemistry. -- Abstract: Azide is a well-known inhibitor of heme–enzymes. Herein, we report the counter-intuitive observation that at some concentration regimes, incorporation of azide in the reaction medium enhances chloroperoxidase (CPO, a heme–enzyme) mediated one-electron abstractions from several substrates. A diffusible azidyl radical based mechanism is proposed for explaining the phenomenon. Further, it is projected that the finding could have significant impact on routine in situ or in vitro biochemistry studies involving heme–enzyme systems and azide.

Electron screening in molecular fusion reactions

International Nuclear Information System (INIS)

Shoppa, T.D.

1996-01-01

Recent laboratory experiments have measured fusion cross sections at center-of-mass energies low enough for the effects of atomic and molecular electrons to be important. To extract the cross section for bare nuclei from these data (as required for astrophysical applications), it is necessary to understand these screening effects. We study electron screening effects in the low-energy collisions of Z=1 nuclei with hydrogen molecules. Our model is based on a dynamical evolution of the electron wave functions within the TDHF scheme, while the motion of the nuclei is treated classically. We find that at the currently accessible energies the screening effects depend strongly on the molecular orientation. The screening is found to be larger for molecular targets than for atomic targets, due to the reflection symmetry in the latter. The results agree fairly well with data measured for deuteron collisions on molecular deuterium and tritium targets. (orig.)

Molecular electronics of a single photosystem I reaction center: Studies with scanning tunneling microscopy and spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Lee, I.; Lee, J.W.; Warmack, R.J.; Allison, D.P.; Greenbaum, E. [Oak Ridge National Lab., TN (United States)

1995-03-14

Thylakoids and photosystem I (PSI) reaction centers were imaged by scanning tunneling microscopy. The thylakoids were isolated from spinach chloroplasts, and PSI reaction centers were extracted from thylakoid membranes. Because thylakoids are relatively thick nonconductors, they were sputter-coated with Pd/Au before imaging. PSI photosynthetic centers and chemically platinized PSI were investigated without sputter-coating. They were mounted on flat gold substrates that had been treated with mercaptoacetic acid to help bind the proteins. With tunneling spectroscopy, the PSI centers displayed a semiconductor-like response with a band gap of 1.8 eV. Lightly platinized (platinized for 1 hr) centers displayed diode-like conduction that resulted in dramatic contrast changes between images taken with opposite bias voltages. The electronic properties of this system were stable under long-term storage. 42 refs., 7 figs.

Trapped electron decay by the thermally-assisted tunnelling to electron acceptors in glassy matrices. A computer simulation study

International Nuclear Information System (INIS)

Feret, B.; Bartczak, W.M.; Kroh, J.

1991-01-01

The Redi-Hopefield quantum mechanical model of the thermally-assisted electron transfer has been applied to simulate the decay of trapped electrons by tunnelling to electron acceptor molecules added to the glassy matrix. It was assumed that the electron energy levels in donors and acceptors are statistically distributed and the electron excess energy after transfer is dissipated in the medium by the electron-phonon coupling. The electron decay curves were obtained by the method of computer simulation. It was found that for a given medium there exists a certain preferred value of the electronic excess energy which can be effectively converted into the matrix vibrations. If the mismatch of the electron states on the donor and acceptor coincides with the ''resonance'' energy the overall kinetics of electron transfer is accelerated. (author)

Hydroxylamine derivative in Purex process. Part 8. The kinetics and mechanism of the redox reaction of N-methylhydroxylamine and vanadium(V)

International Nuclear Information System (INIS)

Anyun Zhang; Shaanxi Normal Univ., Xi'an; Kai Li; Jingxin Hu

2004-01-01

The kinetic properties of the oxidation-reduction reaction between N-methylhydroxylamine (NMHAN) and vanadium(V) in nitric acid medium has been studied by spectrophotometry at 23.1 deg C. The rate equation of the redox reaction was determined as -d[V(V)]/dt = k[V(V)] [NMHAN] by investigating the influence of concentration of NMHAN, acidity, ionic strength and the ratio of initial concentration of V(V) to NMHAN on the reaction. The rate constant of the reaction k = 0.818 ± 0.051 (mol/l) -1 x s -1 at the ionic strength of 1.00 mol/l. The activation energy of the redox reaction was calculated to be 39.6 kJ/mol. A possibly radical mechanism of the redox reaction between NMHAN and V(V) has been suggested on the basis of electron spin resonance (ESR) spectra of nitroxyl radical, i.e., CH 3 NHO. It is helpful to understand and make the redox mechanism of NMHAN and Np(VI) clear in the reprocessing process of nuclear spent fuel. (author)

Isolated photosystem I reaction centers on a functionalized gated high electron mobility transistor.

Science.gov (United States)

Eliza, Sazia A; Lee, Ida; Tulip, Fahmida S; Mostafa, Salwa; Greenbaum, Elias; Ericson, M Nance; Islam, Syed K

2011-09-01

In oxygenic plants, photons are captured with high quantum efficiency by two specialized reaction centers (RC) called Photosystem I (PS I) and Photosystem II (PS II). The captured photon triggers rapid charge separation and the photon energy is converted into an electrostatic potential across the nanometer-scale (~6 nm) reaction centers. The exogenous photovoltages from a single PS I RC have been previously measured using the technique of Kelvin force probe microscopy (KFM). However, biomolecular photovoltaic applications require two-terminal devices. This paper presents for the first time, a micro-device for detection and characterization of isolated PS I RCs. The device is based on an AlGaN/GaN high electron mobility transistor (HEMT) structure. AlGaN/GaN HEMTs show high current throughputs and greater sensitivity to surface charges compared to other field-effect devices. PS I complexes immobilized on the floating gate of AlGaN/GaN HEMTs resulted in significant changes in the device characteristics under illumination. An analytical model has been developed to estimate the RCs of a major orientation on the functionalized gate surface of the HEMTs. © 2011 IEEE

Isolated Photosystem I Reaction Centers on a Functionalized Gated High Electron Mobility Transistor

Energy Technology Data Exchange (ETDEWEB)

Eliza, Sazia A. [University of Tennessee, Knoxville (UTK); Lee, Ida [ORNL; Tulip, Fahmida S [ORNL; Islam, Syed K [University of Tennessee, Knoxville (UTK); Mostafa, Salwa [University of Tennessee, Knoxville (UTK); Greenbaum, Elias [ORNL; Ericson, Milton Nance [ORNL

2011-01-01

In oxygenic plants, photons are captured with high quantum efficiency by two specialized reaction centers (RC) called Photosystem I (PS I) and Photosystem II (PS II). The captured photon triggers rapid charge separation and the photon energy is converted into an electrostatic potential across the nanometer-scale nm reaction centers. The exogenous photovoltages from a single PS I RC have been previously measured using the technique of Kelvin force probe microscopy (KFM). However, biomolecular photovoltaic applications require two-terminal devices. This paper presents for the first time, a micro-device for detection and characterization of isolated PS I RCs. The device is based on an AlGaN/GaN high electron mobility transistor (HEMT) structure. AlGaN/GaN HEMTs show high current throughputs and greater sensitivity to surface charges compared to other field-effect devices. PS I complexes immobilized on the floating gate of AlGaN/GaN HEMTs resulted in significant changes in the device characteristics under illumination. An analytical model has been developed to estimate the RCs of a major orientation on the functionalized gate surface of the HEMTs.

Polarization effects in the reaction of charm baryon production on colliding electron-positron beams

International Nuclear Information System (INIS)

Rekalo, M.P.; Korzh, A.P.; Barannik, V.P.

1980-01-01

To calculate energy and angular distributions of various decay products of charm baAyons, which are prodUced in reactions on colliding e + e - beams, it is necessary to know the differential cross sections of the e + e - → C+anti C process which correspond to different polarized states of produced C and anti C (C - charm baryon). These differential cross sections are calculated for a single-photon mechanism with respect to the contribution of the anapole and electric dipole form factors of C-baryon. Polarizations of colliding electron-positron beams are taken into account in a full volume

Prevention of adverse reactions to intravascular contrast media

International Nuclear Information System (INIS)

Soyer, P.; Levesque, M.

1990-01-01

The exact mechanisms of adverse reactions to contrast media are still imperfectly known. However, these reactions may be classified as idiosyncratic. Non-idiosyncratic reactions can be prevented by using new, non-ionic contrast agents. Idiosyncratic reactions can be prevented by specific premedication. Patients with a history of idiosyncratic reaction may benefit from corticosteroids and antihistamines administered prophylactically. Patients who seem to be more likely than others to react to contrast media must be premedicated, the risk of reaction being identified and evaluated by questioning. It has recently been suggested that all patients about to receive an intravascular injection of contrast medium should also be premedicated [fr

Nuclear reactions of medium and heavy target nuclei with high-energy projectiles

International Nuclear Information System (INIS)

Kozma, P.; Damdinsuren, C.

1988-01-01

The cross sections of a number of target fragmentation products formed in nuclear reactions of 3.65 AGeV 12 C-ions and 3.65 GeV protons with 197 Au have been measured. The measurements have been done by direct counting of irradiated targets with Ge(Li) gamma-spectrometers. Comparison between these and other data has been used to test the hypotheses of factorization and limiting fragmentation. The total cross section for residue production in both reactions indicates that target residues are formed mainly in central collisions

Late adverse reactions to intravascular iodine based contrast media

DEFF Research Database (Denmark)

Bellin, Marie-France; Stacul, Fulvio; Webb, Judith A W

2011-01-01

DEFINITION: Late adverse reactions (LAR) to contrast media (CM) are defined as reactions occurring 1 h to 1 week after exposure. NEED FOR REVIEW: In view of more prospective studies of LAR and new data about their pathophysiology, the Contrast Medium Safety Committee (CMSC) of the European Societ...

Mechanism of redox reactions induced by light and electron pulse in solutions of mixed ligand iron(II) complex cyanides

International Nuclear Information System (INIS)

Horvath, A.; Szoeke, J.; Wojnarovits, L.

1991-01-01

Redox reactions induced by light and electron pulse have been studied in aqueous solutions of mixed ligand iron(II) complex cyanides. The short lived intermediates have been identified by time resolved specroscopy, the results of detailed kinetic analysis have been discussed. (author) 6 refs.; 3 figs.; 2 tabs

Onset of Convection in the Presence of a Precipitation Reaction in a Porous Medium: A Comparison of Linear Stability and Numerical Approaches

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Parama Ghoshal

2017-12-01

Full Text Available Reactive convection in a porous medium has received recent interest in the context of the geological storage of carbon dioxide in saline formations. We study theoretically and numerically the gravitational instability of a diffusive boundary layer in the presence of a first-order precipitation reaction. We compare the predictions from normal mode, linear stability analysis, and nonlinear numerical simulations, and discuss the relative deviations. The application of our findings to the storage of carbon dioxide in a siliciclastic aquifer shows that while the reactive-diffusive layer can become unstable within a timescale of 1 to 1.5 months after the injection of carbon dioxide, it can take almost 10 months for sufficiently vigorous convection to produce a considerable increase in the dissolution flux of carbon dioxide.

Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

International Nuclear Information System (INIS)

Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

2015-01-01

Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

High-harmonic generation in a dense medium

International Nuclear Information System (INIS)

Strelkov, V.V.; Platonenko, V.T.; Becker, A.

2005-01-01

The high-harmonic generation in a plasma or gas under conditions when the single-atom response is affected by neighboring ions or atoms of the medium is studied theoretically. We solve numerically the three-dimensional Schroedinger equation for a single-electron atom in the combined fields of the neighboring particles and the laser, and average the results over different random positions of the particles using the Monte Carlo method. Harmonic spectra are calculated for different medium densities and laser intensities. We observe a change of the harmonic properties due to a random variation of the harmonic phase induced by the field of the medium, when the medium density exceeds a certain transition density. The transition density is found to depend on the harmonic order, but it is almost independent of the fundamental intensity. It also differs for the two (shorter and longer) quantum paths. The latter effect leads for ionic densities in the transition regime to a narrowing of the harmonic lines and a shortening of the attosecond pulses generated using a group of harmonics

Velocity and thermal slip effects on MHD third order blood flow in an irregular channel though a porous medium with homogeneous/ heterogeneous reactions

Science.gov (United States)

Gnaneswara Reddy, M.

2017-09-01

This communication presents the transportation of third order hydromagnetic fluid with thermal radiation by peristalsis through an irregular channel configuration filled a porous medium under the low Reynolds number and large wavelength approximations. Joule heating, Hall current and homogeneous-heterogeneous reactions effects are considered in the energy and species equations. The Second-order velocity and energy slip restrictions are invoked. Final dimensionless governing transport equations along the boundary restrictions are resolved numerically with the help of NDsolve in Mathematica package. Impact of involved sundry parameters on the non-dimensional axial velocity, fluid temperature and concentration characteristics have been analyzed via plots and tables. It is manifest that an increasing porosity parameter leads to maximum velocity in the core part of the channel. Fluid velocity boosts near the walls of the channel where as the reverse effect in the central part of the channel for higher values of first order slip. Larger values of thermal radiation parameter R reduce the fluid temperature field. Also, an increase in heterogeneous reaction parameter Ks magnifies the concentration profile. The present study has the crucial application of thermal therapy in biomedical engineering.

Photoreactivity of ZnO nanoparticles in visible light: Effect of surface states on electron transfer reaction

International Nuclear Information System (INIS)

Baruah, Sunandan; Dutta, Joydeep; Sinha, Sudarson Sekhar; Ghosh, Barnali; Pal, Samir Kumar; Raychaudhuri, A. K.

2009-01-01

Wide band gap metal oxide semiconductors such as zinc oxide (ZnO) show visible band photolysis that has been employed, among others, to degrade harmful organic contaminants into harmless mineral acids. Metal oxides show enhanced photocatalytic activity with the increase in electronic defects in the crystallites. By introducing defects into the crystal lattice of ZnO nanoparticles, we observe a redshift in the optical absorption shifting from the ultraviolet region to the visible region (400-700 nm), which is due to the creation of intermediate defect states that inhibit the electron hole recombination process. The defects were introduced by fast nucleation and growth of the nanoparticles by rapid heating using microwave irradiation and subsequent quenching during the precipitation reaction. To elucidate the nature of the photodegradation process, picosecond resolved time correlated single photon count (TCSPC) spectroscopy was carried out to record the electronic transitions resulting from the de-excitation of the electrons to their stable states. Photodegradation and TCSPC studies showed that defect engineered ZnO nanoparticles obtained through fast crystallization during growth lead to a faster initial degradation rate of methylene blue as compared to the conventionally synthesized nanoparticles

Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

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N. A. Mohamed Farook