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

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)

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.

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 ...

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...

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

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.

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.

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

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.

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

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)

Synthesis of Al-5Ti-1B Refiner by Melt Reaction Method

OpenAIRE

LI He; CHAI Li-hua; MA Teng-fei; CHEN Zi-yong

2017-01-01

Al-5Ti-1B refiner was successfully prepared by melt reaction method. Through the thermodynamics calculation, the initial reaction temperature was determined. The influence of reaction temperature on microstructure and absorption rate of the alloy was investigated. The phase and microstructure of the alloy were observed by X-ray diffraction, scanning electron microscope and energy dispersive spectrometer. The Al-5Ti-1B refiner was extruded at high temperature to wire with the diameter of 9.5mm...

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

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

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.

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.

Application of CTOF method to detect secondly charged particle from 2 GeV electron

International Nuclear Information System (INIS)

Takahashi, Kazutoshi; Sanami, Toshiya; Ban, Syuichi; Lee, Hee-Seok; Sato, Tatsuhiko

2002-01-01

To design a shield and evaluate leakage radiation at high energy electron accelerators, the energy and angular data of secondary particle from the reaction of electrons with structural materials are required. Secondly neutron spectrum from structural materials has been measured by using electron accelerator in PAL (Pohang Accelerator Laboratory). In the neutron measurement, the electronics with Multi-hit TDC (MHTDC) was adopted to measure Time of Flight of every particles (TOFs) emitted from the reactions by each single electron bunch. The measurements are extended to secondly charged particles. For the charged particles measurement, the pulse height data for every particles are indispensable to distinguish charged particles by Δ E-E method. A new system which can measure pulse height for every particle is required instead of the MHTDC system. For this requirement, the method which can take output current from detectors was developed by using digital storage oscilloscope system is named ''Current Time of Flight method'' (CTOF). The CTOF method is able to measure pulse height and TOF for every particles produced by single electron bunch. Electrons are accelerated to 2.04 GeV and the repetition rate is 10 Hz. These electrons bombard thin disk samples of Cu 1mm, Al 4 mm and W 0.5 mm. Secondly charged particles, proton and deuteron, are produced in the samples by photonuclear reaction. Two dimensional of Δ E-E spectrum for each the samples measured by CTOF shows separation between proton and deuteron perfectly. Thus, proton and deuteron spectrum are obtained from this data. (M. Suetake)

A high-performance liquid chromatography-electronic circular dichroism online method for assessing the absolute enantiomeric excess and conversion ratio of asymmetric reactions

Science.gov (United States)

Zhang, Xiang; Wang, Mingchao; Li, Li; Yin, Dali

2017-03-01

Asymmetric reactions often need to be evaluated during the synthesis of chiral compounds. However, traditional evaluation methods require the isolation of the individual enantiomer, which is tedious and time-consuming. Thus, it is desirable to develop simple, practical online detection methods. We developed a method based on high-performance liquid chromatography-electronic circular dichroism (HPLC-ECD) that simultaneously analyzes the material conversion ratio and absolute optical purity of each enantiomer. In particular, only a reverse-phase C18 column instead of a chiral column is required in our method because the ECD measurement provides a g-factor that describes the ratio of each enantiomer in the mixtures. We used our method to analyze the asymmetric hydrosilylation of β-enamino esters, and we discussed the advantage, feasibility, and effectiveness of this new methodology.

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.

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)

Discussion of the Investigation Method on the Reaction Kinetics of Metallurgical Reaction Engineering

Science.gov (United States)

Du, Ruiling; Wu, Keng; Zhang, Jiazhi; Zhao, Yong

Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed, which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

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

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...

Trojan Horse Method: A tool to explore electron screening effect

Energy Technology Data Exchange (ETDEWEB)

Pizzone, R G; Spitaleri, C; Cherubini, S; Cognata, M La; Lamia, L; Romano, S; Sergi, M L [Laboratori Nazionali del Sud-INFN, Catania (Italy) and Dipartimento di Metodologie Fisiche e Chimiche per l' Ingegneria, Universita di Catania, Catania (Italy); Rolfs, C; Strieder, F [Ruhr Universitaet Bochum (Germany); Burjan, V; Kroha, V; Mrazek, J [Cyclotron Institute, Academy of Science, Rez (Czech Republic); Li, C; Wen, Q; Zhou, S [CIAE, Beijing (China); Tumino, A, E-mail: rgpizzone@lns.infn.i [Universita Kore, Erma (Italy)

2010-01-01

Owing the presence of the Coulomb barrier at astrophysically relevant energies, it is very difficult, or sometimes impossible to measure reaction rates for charged particle induced reactions. Moreover due to the presence of the electron screening effect in direct measurements, the relevant nuclear input for astrophysics, i.e. the bare nucleus S(E)-factor, can hardly be extracted. This is why different indirect techniques are being used along with direct measurements. The THM is an unique: indirect technique which allows one to measure reactions cross sections of astrophysical interest down the thermal energies typical of the different scenarios. The basic principle and a review of the main applications of the Trojan Horse Method are given. The applications aiming at the extraction of the bare S{sub b}(E) astrophysical factor and electron screening potentials U{sub e} for several two body processes are discussed.

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

How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?

Science.gov (United States)

Orenha, Renato Pereira; Santiago, Régis Tadeu; Haiduke, Roberto Luiz Andrade; Galembeck, Sérgio Emanuel

2017-05-05

Two treatments of relativistic effects, namely effective core potentials (ECP) and all-electron scalar relativistic effects (DKH2), are used to obtain geometries and chemical reaction energies for a series of ruthenium complexes in B3LYP/def2-TZVP calculations. Specifically, the reaction energies of reduction (A-F), isomerization (G-I), and Cl - negative trans influence in relation to NH 3 (J-L) are considered. The ECP and DKH2 approaches provided geometric parameters close to experimental data and the same ordering for energy changes of reactions A-L. From geometries optimized with ECP, the electronic energies are also determined by means of the same ECP and basis set combined with the computational methods: MP2, M06, BP86, and its derivatives, so as B2PLYP, LC-wPBE, and CCSD(T) (reference method). For reactions A-I, B2PLYP provides the best agreement with CCSD(T) results. Additionally, B3LYP gave the smallest error for the energies of reactions J-L. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

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.

Method for predicting enzyme-catalyzed reactions

Science.gov (United States)

Hlavacek, William S.; Unkefer, Clifford J.; Mu, Fangping; Unkefer, Pat J.

2013-03-19

The reactivity of given metabolites is assessed using selected empirical atomic properties in the potential reaction center. Metabolic reactions are represented as biotransformation rules. These rules are generalized from the patterns in reactions. These patterns are not unique to reactants but are widely distributed among metabolites. Using a metabolite database, potential substructures are identified in the metabolites for a given biotransformation. These substructures are divided into reactants or non-reactants, depending on whether they participate in the biotransformation or not. Each potential substructure is then modeled using descriptors of the topological and electronic properties of atoms in the potential reaction center; molecular properties can also be used. A Support Vector Machine (SVM) or classifier is trained to classify a potential reactant as a true or false reactant using these properties.

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.

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

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.

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

A Multilevel Adaptive Reaction-splitting Simulation Method for Stochastic Reaction Networks

KAUST Repository

Moraes, Alvaro; Tempone, Raul; Vilanova, Pedro

2016-01-01

In this work, we present a novel multilevel Monte Carlo method for kinetic simulation of stochastic reaction networks characterized by having simultaneously fast and slow reaction channels. To produce efficient simulations, our method adaptively classifies the reactions channels into fast and slow channels. To this end, we first introduce a state-dependent quantity named level of activity of a reaction channel. Then, we propose a low-cost heuristic that allows us to adaptively split the set of reaction channels into two subsets characterized by either a high or a low level of activity. Based on a time-splitting technique, the increments associated with high-activity channels are simulated using the tau-leap method, while those associated with low-activity channels are simulated using an exact method. This path simulation technique is amenable for coupled path generation and a corresponding multilevel Monte Carlo algorithm. To estimate expected values of observables of the system at a prescribed final time, our method bounds the global computational error to be below a prescribed tolerance, TOL, within a given confidence level. This goal is achieved with a computational complexity of order O(TOL-2), the same as with a pathwise-exact method, but with a smaller constant. We also present a novel low-cost control variate technique based on the stochastic time change representation by Kurtz, showing its performance on a numerical example. We present two numerical examples extracted from the literature that show how the reaction-splitting method obtains substantial gains with respect to the standard stochastic simulation algorithm and the multilevel Monte Carlo approach by Anderson and Higham. © 2016 Society for Industrial and Applied Mathematics.

A Multilevel Adaptive Reaction-splitting Simulation Method for Stochastic Reaction Networks

KAUST Repository

Moraes, Alvaro

2016-07-07

In this work, we present a novel multilevel Monte Carlo method for kinetic simulation of stochastic reaction networks characterized by having simultaneously fast and slow reaction channels. To produce efficient simulations, our method adaptively classifies the reactions channels into fast and slow channels. To this end, we first introduce a state-dependent quantity named level of activity of a reaction channel. Then, we propose a low-cost heuristic that allows us to adaptively split the set of reaction channels into two subsets characterized by either a high or a low level of activity. Based on a time-splitting technique, the increments associated with high-activity channels are simulated using the tau-leap method, while those associated with low-activity channels are simulated using an exact method. This path simulation technique is amenable for coupled path generation and a corresponding multilevel Monte Carlo algorithm. To estimate expected values of observables of the system at a prescribed final time, our method bounds the global computational error to be below a prescribed tolerance, TOL, within a given confidence level. This goal is achieved with a computational complexity of order O(TOL-2), the same as with a pathwise-exact method, but with a smaller constant. We also present a novel low-cost control variate technique based on the stochastic time change representation by Kurtz, showing its performance on a numerical example. We present two numerical examples extracted from the literature that show how the reaction-splitting method obtains substantial gains with respect to the standard stochastic simulation algorithm and the multilevel Monte Carlo approach by Anderson and Higham. © 2016 Society for Industrial and Applied Mathematics.

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

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...

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

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.

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.

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

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)

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

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

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

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.

Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

Science.gov (United States)

Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

2016-12-01

Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

Electron scattering and reactions from exotic nuclei

International Nuclear Information System (INIS)

Karataglidis, S.

2017-01-01

The SCRIT and FAIR/ELISe experiments are the first to attempt to measure directly electron scattering form factors from nuclei far from stability. This will give direct information for the (one-body) charge densities of those systems, about which there is little information available. The SCRIT experiment will be taking data for medium-mass exotic nuclei, while the electron-ion collider at ELISe, when constructed, will be able to measure form factors for a wide range of exotic nuclei, as available from the radioactive ion beams produced by the FAIR experiment. Other facilities are now being proposed, which will also consider electron scattering from exotic nuclei at higher energies, to study short-range correlations in exclusive reactions. This review will consider all available information concerning the current status (largely theoretical) of electron scattering from exotic nuclei and, where possible, complement such information with equivalent information concerning the neutron densities of those exotic systems, as obtained from intermediate energy proton scattering. The issue of long- and short-range correlations will be discussed, and whether extending such studies to the exotic sector will elicit new information. (orig.)

Electron scattering and reactions from exotic nuclei

Energy Technology Data Exchange (ETDEWEB)

Karataglidis, S. [University of Johannesburg, Department of Physics, Auckland Park (South Africa); University of Melbourne, School of Physics, Victoria (Australia)

2017-04-15

The SCRIT and FAIR/ELISe experiments are the first to attempt to measure directly electron scattering form factors from nuclei far from stability. This will give direct information for the (one-body) charge densities of those systems, about which there is little information available. The SCRIT experiment will be taking data for medium-mass exotic nuclei, while the electron-ion collider at ELISe, when constructed, will be able to measure form factors for a wide range of exotic nuclei, as available from the radioactive ion beams produced by the FAIR experiment. Other facilities are now being proposed, which will also consider electron scattering from exotic nuclei at higher energies, to study short-range correlations in exclusive reactions. This review will consider all available information concerning the current status (largely theoretical) of electron scattering from exotic nuclei and, where possible, complement such information with equivalent information concerning the neutron densities of those exotic systems, as obtained from intermediate energy proton scattering. The issue of long- and short-range correlations will be discussed, and whether extending such studies to the exotic sector will elicit new information. (orig.)

In honour of N. Yngve Öhrn: surveying proton cancer therapy reactions with Öhrn's electron nuclear dynamics method. Aqueous clusters radiolysis and DNA-base damage by proton collisions

Science.gov (United States)

Mclaurin, Patrick M.; Privett, Austin J.; Stopera, Christopher; Grimes, Thomas V.; Perera, Ajith; Morales, Jorge A.

2015-02-01

Proton cancer therapy (PCT) utilises high-energy H+ projectiles to cure cancer. PCT healing arises from its DNA damage in cancerous cells, which is mostly inflicted by the products from PCT water radiolysis reactions. While clinically established, a complete microscopic understanding of PCT remains elusive. To help in the microscopic elucidation of PCT, Professor Öhrn's simplest-level electron nuclear dynamics (SLEND) method is herein applied to H+ + (H2O)3-4 and H+ + DNA-bases at ELab = 1.0 keV. These are two types of computationally feasible prototypes to study water radiolysis reactions and H+-induced DNA damage, respectively. SLEND is a time-dependent, variational, non-adiabatic and direct-dynamics method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction. Additionally, our SLEND + effective-core-potential method is herein employed to simulate some computationally demanding PCT reactions. Due to these attributes, SLEND proves appropriate for the simulation of various types of PCT reactions accurately and feasibly. H+ + (H2O)3-4 simulations reveal two main processes: H+ projectile scattering and the simultaneous formation of H and OH fragments; the latter process is quantified through total integrals cross sections. H+ + DNA-base simulations reveal atoms and groups displacements, ring openings and base-to-proton electron transfers as predominant damage processes. The authors warmly dedicate this SLEND investigation in honour of Professor N. Yngve Öhrn on the occasion of his 80th birthday celebration during the 54th Sanibel Symposium in St. Simons' Island, Georgia, on February 16-21, 2014. Associate Professor Jorge A. Morales was a former chemistry PhD student under the mentorship of Professor Öhrn and Dr Ajith Perera took various quantum chemistry courses taught by Professor Öhrn during his chemistry PhD studies. Both Jorge and Ajith look back to those great times of their scientific formation under

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...

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.

Initial deposition and electron paramagnetic resonance defects characterization of TiO2 films prepared using successive ionic layer adsorption and reaction method

International Nuclear Information System (INIS)

Wu Yiyong; Shi Yaping; Xu Xianbin; Sun Chengyue

2012-01-01

Successive ionic layer adsorption and reaction (SILAR) technique was considered promisingly to deposit ultra thin titanium dioxide (TiO 2 ) films under ambient condition. In this paper, the growth process, structures and paramagnetic defects of the films were characterized by complementary techniques of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. The results indicate that on glass substrate the SILAR TiO 2 film nucleates in an island mode within the initial five deposition cycles but grows in a layer-by-layer mode afterwards. The growth rate was measured as 4.6 Å/cycle. In the as-deposited films, a kind of paramagnetic defects is detected at g (2.0029) and it can be attributed to oxygen vacancies. These as-received oxygen vacancies could be annealed out at 473 K. Ultraviolet irradiation on the as-deposited films can also decrease the density of the defects. The relative mechanisms on the phenomenon were discussed in this paper. - Highlights: ► TiO 2 films are deposited on glass at 25 °C by successive ionic layer adsorption and reaction method with a rate of 4.6 Å/cycle. ► The films nucleate in an island mode initially but grow in a layer mode afterwards. ► The SILAR TiO 2 films nucleation period is five cycles. ► Electron paramagnetic resonance spectroscopy shows that TiO 2 films paramagnetic defects are attributed to oxygen vacancies. ► They will decrease by anneal or ultraviolet radiation and form hydroxyl or superoxide radicals.

New methods in nuclear reaction theory

International Nuclear Information System (INIS)

Redish, E.F.

1979-01-01

Standard nuclear reaction methods are limited to treating problems that generalize two-body scattering. These are problems with only one continuous (vector) degree of freedom (CDOF). The difficulty in extending these methods to cases with two or more CDOFs is not just the additional numerical complexity: the mathematical problem is usually not well-posed. It is hard to guarantee that the proper boundary conditions (BCs) are satisfied. Since this is not generally known, the discussion is begun by considering the physics of this problem in the context of coupled-channel calculations. In practice, the difficulties are usually swept under the rug by the use of a highly developed phenomenology (or worse, by the failure to test a calculation for convergence). This approach limits the kind of reactions that can be handled to ones occurring on the surface of where a second CDOF can be treated perturbatively. In the past twenty years, the work of Faddeev, the quantum three-body problem has been solved. Many techniques (and codes) are now available for solving problems with two CDOFs. A method for using these techniques in the nuclear N-body problem is presented. A set of well-posed (connected kernal) equations for physical scattering operators is taken. Then it is shown how approximation schemes can be developed for a wide range of reaction mechanisms. The resulting general framework for a reaction theory can be applied to a number of nuclear problems. One result is a rigorous treatment of multistep transfer reactions with the possibility of systematically generating corrections. The application of the method to resonance reactions and knock-out is discussed. 12 figures

Wang-Landau Reaction Ensemble Method: Simulation of Weak Polyelectrolytes and General Acid-Base Reactions.

Science.gov (United States)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-02-14

We present a novel method for the study of weak polyelectrolytes and general acid-base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang-Landau sampling method. Deprotonation and protonation reactions are simulated explicitly with the help of the reaction ensemble method, while the accurate sampling of the corresponding phase space is achieved by the Wang-Landau approach. The combination of both techniques provides a sufficient statistical accuracy such that meaningful estimates for the density of states and the partition sum can be obtained. With regard to these estimates, several thermodynamic observables like the heat capacity or reaction free energies can be calculated. We demonstrate that the computation times for the calculation of titration curves with a high statistical accuracy can be significantly decreased when compared to the original reaction ensemble method. The applicability of our approach is validated by the study of weak polyelectrolytes and their thermodynamic properties.

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

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.

Improving electronic structure methods to predict nano-optoelectronics and nano-catalyst functions.

Energy Technology Data Exchange (ETDEWEB)

Nielsen, Ida Marie B.; Marzari, Nicola (Massachusetts Institute of Technology); Shelnutt, John Allen; Kulik, Heather J. (Massachusetts Institute of Technology); Medforth, Craig John (University of New Mexico, Albuquerque, NM); Leung, Kevin

2009-10-01

This report focuses on quantum chemistry and ab initio molecular dynamics (AIMD) calculations applied to elucidate the mechanism of the multi-step, 2-electron, electrochemical reduction of the green house gas molecule carbon dioxide (CO{sub 2}) to carbon monoxide (CO) in aqueous media. When combined with H{sub 2} gas to form synthesis ('syn') gas, CO becomes a key precursor to methane, methanol, and other useful hydrocarbon products. To elucidate the mechanism of this reaction, we apply computational electrochemistry which is a fledgling, important area of basic science critical to energy storage. This report highlights several approaches, including the calculation of redox potentials, the explicit depiction of liquid water environments using AIMD, and free energy methods. While costly, these pioneering calculations reveal the key role of hydration- and protonation-stabilization of reaction intermediates, and may inform the design of CO{sub 2}-capture materials as well as its electrochemical reduction. In the course of this work, we have also dealt with the challenges of identifying and applying electronic structure methods which are sufficiently accurate to deal with transition metal ion complex-based catalyst. Such electronic structure methods are also pertinent to the accurate modeling of actinide materials and therefore to nuclear energy research. Our multi-pronged effort towards achieving this titular goal of the LDRD is discussed.

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)

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

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

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.

Methods for measurement of electron emission yield under low energy electron-irradiation by collector method and Kelvin probe method

Energy Technology Data Exchange (ETDEWEB)

Tondu, Thomas; Belhaj, Mohamed; Inguimbert, Virginie [Onera, DESP, 2 Avenue Edouard Belin, 31400 Toulouse (France); Onera, DESP, 2 Avenue Edouard Belin, 31400 Toulouse, France and Fondation STAE, 4 allee Emile Monso, BP 84234-31432, Toulouse Cedex 4 (France); Onera, DESP, 2 Avenue Edouard Belin, 31400 Toulouse (France)

2010-09-15

Secondary electron emission yield of gold under electron impact at normal incidence below 50 eV was investigated by the classical collector method and by the Kelvin probe method. The authors show that biasing a collector to ensure secondary electron collection while keeping the target grounded can lead to primary electron beam perturbations. Thus reliable secondary electron emission yield at low primary electron energy cannot be obtained with a biased collector. The authors present two collector-free methods based on current measurement and on electron pulse surface potential buildup (Kelvin probe method). These methods are consistent, but at very low energy, measurements become sensitive to the earth magnetic field (below 10 eV). For gold, the authors can extrapolate total emission yield at 0 eV to 0.5, while a total electron emission yield of 1 is obtained at 40{+-}1 eV.

Methods for measurement of electron emission yield under low energy electron-irradiation by collector method and Kelvin probe method

International Nuclear Information System (INIS)

Tondu, Thomas; Belhaj, Mohamed; Inguimbert, Virginie

2010-01-01

Secondary electron emission yield of gold under electron impact at normal incidence below 50 eV was investigated by the classical collector method and by the Kelvin probe method. The authors show that biasing a collector to ensure secondary electron collection while keeping the target grounded can lead to primary electron beam perturbations. Thus reliable secondary electron emission yield at low primary electron energy cannot be obtained with a biased collector. The authors present two collector-free methods based on current measurement and on electron pulse surface potential buildup (Kelvin probe method). These methods are consistent, but at very low energy, measurements become sensitive to the earth magnetic field (below 10 eV). For gold, the authors can extrapolate total emission yield at 0 eV to 0.5, while a total electron emission yield of 1 is obtained at 40±1 eV.

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.)

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.

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

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

Kinematical coincidence method in transfer reactions

Energy Technology Data Exchange (ETDEWEB)

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

2013-07-01

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

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.

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

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.

Method for local temperature measurement in a nanoreactor for in situ high-resolution electron microscopy.

Science.gov (United States)

Vendelbo, S B; Kooyman, P J; Creemer, J F; Morana, B; Mele, L; Dona, P; Nelissen, B J; Helveg, S

2013-10-01

In situ high-resolution transmission electron microscopy (TEM) of solids under reactive gas conditions can be facilitated by microelectromechanical system devices called nanoreactors. These nanoreactors are windowed cells containing nanoliter volumes of gas at ambient pressures and elevated temperatures. However, due to the high spatial confinement of the reaction environment, traditional methods for measuring process parameters, such as the local temperature, are difficult to apply. To address this issue, we devise an electron energy loss spectroscopy (EELS) method that probes the local temperature of the reaction volume under inspection by the electron beam. The local gas density, as measured using quantitative EELS, is combined with the inherent relation between gas density and temperature, as described by the ideal gas law, to obtain the local temperature. Using this method we determined the temperature gradient in a nanoreactor in situ, while the average, global temperature was monitored by a traditional measurement of the electrical resistivity of the heater. The local gas temperatures had a maximum of 56 °C deviation from the global heater values under the applied conditions. The local temperatures, obtained with the proposed method, are in good agreement with predictions from an analytical model. Copyright © 2013 Elsevier B.V. All rights reserved.

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)

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

(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)

Development and Application of Ligand-Exchange Reaction Method ...

African Journals Online (AJOL)

Purpose: This paper presents an improved kinetic-spectrophotometric procedure for determining clonazepam (CZP) in pharmaceutical formulations and human serum. Methods: The method is based on ligand-exchange reaction. The reaction was followed spectrophotometrically by measuring the rate of change of ...

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

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.)

Initial deposition and electron paramagnetic resonance defects characterization of TiO{sub 2} films prepared using successive ionic layer adsorption and reaction method

Energy Technology Data Exchange (ETDEWEB)

Wu Yiyong, E-mail: wuyiyong2001@yahoo.com.cn [National Key Laboratory of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, P.O. 432, Nan gang District, Harbin, 150080 (China); Shi Yaping [National Key Laboratory of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, P.O. 432, Nan gang District, Harbin, 150080 (China); Harbin University of Commerce, P.O. 493, Song bei District, Harbin, 150028 (China); Xu Xianbin; Sun Chengyue [National Key Laboratory of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, P.O. 432, Nan gang District, Harbin, 150080 (China)

2012-06-01

Successive ionic layer adsorption and reaction (SILAR) technique was considered promisingly to deposit ultra thin titanium dioxide (TiO{sub 2}) films under ambient condition. In this paper, the growth process, structures and paramagnetic defects of the films were characterized by complementary techniques of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. The results indicate that on glass substrate the SILAR TiO{sub 2} film nucleates in an island mode within the initial five deposition cycles but grows in a layer-by-layer mode afterwards. The growth rate was measured as 4.6 A/cycle. In the as-deposited films, a kind of paramagnetic defects is detected at g (2.0029) and it can be attributed to oxygen vacancies. These as-received oxygen vacancies could be annealed out at 473 K. Ultraviolet irradiation on the as-deposited films can also decrease the density of the defects. The relative mechanisms on the phenomenon were discussed in this paper. - Highlights: Black-Right-Pointing-Pointer TiO{sub 2} films are deposited on glass at 25 Degree-Sign C by successive ionic layer adsorption and reaction method with a rate of 4.6 A/cycle. Black-Right-Pointing-Pointer The films nucleate in an island mode initially but grow in a layer mode afterwards. Black-Right-Pointing-Pointer The SILAR TiO{sub 2} films nucleation period is five cycles. Black-Right-Pointing-Pointer Electron paramagnetic resonance spectroscopy shows that TiO{sub 2} films paramagnetic defects are attributed to oxygen vacancies. Black-Right-Pointing-Pointer They will decrease by anneal or ultraviolet radiation and form hydroxyl or superoxide radicals.

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

A method of simulating and visualizing nuclear reactions

International Nuclear Information System (INIS)

Atwood, C.H.; Paul, K.M.

1994-01-01

Teaching nuclear reactions to students is difficult because the mechanisms are complex and directly visualizing them is impossible. As a teaching tool, the authors have developed a method of simulating nuclear reactions using colliding water droplets. Videotaping of the collisions, taken with a high shutter speed camera and run frame-by-frame, shows details of the collisions that are analogous to nuclear reactions. The method for colliding the water drops and videotaping the collisions are shown

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

[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.

A dielectric method for measuring early and late reactions in irradiated human skin

International Nuclear Information System (INIS)

Nuutinen, J.; Lahtinen, T.; Turunen, M.; Alanen, E.; Tenhunen, M.; Usenius, T.; Kolle, R.

1998-01-01

Background and purpose: To measure the dielectric constant of irradiated human skin in order to test the feasibility of the dielectric measurements in the quantitation of acute and late radiation reactions. Materials and methods: The dielectric constant of irradiated breast skin was measured at an electromagnetic frequency of 300 MHz in 21 patients during postmastectomy radiotherapy. The measurements were performed with an open-ended coaxial line reflection method. The irradiation technique consisted of an anterior photon field to the lymph nodes and a matched electron field to the chest wall using conventional fractionation of five fractions/week to 50 Gy. Fourteen out of the 21 patients were remeasured 2 years later and the skin was palpated for subcutaneous fibrosis. Results: At 5 weeks the dielectric constant had decreased by 31 and 39% for the investigated skin sites of the photon and electron fields, respectively. There was a statistically significant inverse correlation between the mean dielectric constant and the clinical score of erythema. An unexpected finding was a decrease of the dielectric constant of the contralateral healthy skin during radiotherapy. Two years later a statistically significant positive correlation was found between the dielectric constant at the irradiated skin sites and the clinical score of subcutaneous fibrosis. Conclusions: Dielectric measurements non-invasively yield quantitative information concerning radiation-induced skin reactions. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

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.

Synthesis of Al-5Ti-1B Refiner by Melt Reaction Method

Directory of Open Access Journals (Sweden)

LI He

2017-02-01

Full Text Available Al-5Ti-1B refiner was successfully prepared by melt reaction method. Through the thermodynamics calculation, the initial reaction temperature was determined. The influence of reaction temperature on microstructure and absorption rate of the alloy was investigated. The phase and microstructure of the alloy were observed by X-ray diffraction, scanning electron microscope and energy dispersive spectrometer. The Al-5Ti-1B refiner was extruded at high temperature to wire with the diameter of 9.5mm, and then the refinement experiment was carried out on pure aluminium. The results indicate that the refiner consists of TiB2, TiAl3 and α-Al, and the microstructure prepared at 850℃ is the optimum and the absorption rate of Ti and B matches the best. The TiAl3 and TiB2 phases distribute homogeneously in the matrix after extrusion. When adding 0.2%(mass fraction of Al-5Ti-1B refiner, the grain size of pure aluminium reduces from 3.99mm to 0.45mm.

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.

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.

Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

International Nuclear Information System (INIS)

Araujo, Rafael B.; Almeida, J. de S; Ferreira da Silva, A.; Ahuja, Rajeev

2015-01-01

The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO 4 and FePO 4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO 4 and FePO 4 . However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system

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...

Nonperturbative quantum simulation of time-resolved nonlinear spectra: Methodology and application to electron transfer reactions in the condensed phase

International Nuclear Information System (INIS)

Wang Haobin; Thoss, Michael

2008-01-01

A quantum dynamical method is presented to accurately simulate time-resolved nonlinear spectra for complex molecular systems. The method combines the nonpertubative approach to describe nonlinear optical signals with the multilayer multiconfiguration time-dependent Hartree theory to calculate the laser-induced polarization for the overall field-matter system. A specific nonlinear optical signal is obtained by Fourier decomposition of the overall polarization. The performance of the method is demonstrated by applications to photoinduced ultrafast electron transfer reactions in mixed-valence compounds and at dye-semiconductor interfaces

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.

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

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

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

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

Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

International Nuclear Information System (INIS)

Coker, D.F.

2003-01-01

Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

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.

31 CFR 203.10 - Electronic payment methods.

Science.gov (United States)

2010-07-01

... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false Electronic payment methods. 203.10... TAX AND LOAN PROGRAM Electronic Federal Tax Payments § 203.10 Electronic payment methods. (a) General. Electronic payment methods for Federal tax payments available under this subpart include ACH debit entries...

Fragment molecular orbital study on electron tunneling mechanisms in bacterial photosynthetic reaction center.

Science.gov (United States)

Kitoh-Nishioka, Hirotaka; Ando, Koji

2012-11-01

The tunneling mechanisms of electron transfers (ETs) in photosynthetic reaction center of Blastochloris viridis are studied by the ab initio fragment molecular orbital (FMO) method combined with the generalized Mulliken-Hush (GMH) and the bridge Green function (GF) calculations of the electronic coupling T(DA) and the tunneling current method for the ET pathway analysis at the fragment-based resolution. For the ET from batctriopheophytin (H(L)) to menaquinone (MQ), a major tunneling current through Trp M250 and a minor back flow via Ala M215, Ala M216, and His M217 are quantified. For the ET from MQ to ubiquinone, the major tunneling pathway via the nonheme Fe(2+) and His L190 is identified as well as minor pathway via His M217 and small back flows involving His L230, Glu M232, and His M264. At the given molecular structure from X-ray experiment, the spin state of the Fe(2+) ion, its replacement by Zn(2+), or its removal are found to affect the T(DA) value by factors within 2.2. The calculated T(DA) values, together with experimentally estimated values of the driving force and the reorganization energy, give the ET rates in reasonable agreement with experiments.

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

The Trojan Horse method for nuclear astrophysics: Recent results on resonance reactions

Energy Technology Data Exchange (ETDEWEB)

Cognata, M. La; Pizzone, R. G. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania (Italy); Spitaleri, C.; Cherubini, S.; Romano, S. [Dipartimento di Fisica e Astronomia, Università di Catania, Catania, Italy and Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania (Italy); Gulino, M.; Tumino, A. [Kore University, Enna, Italy and Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania (Italy); Lamia, L. [Dipartimento di Fisica e Astronomia, Università di Catania, Catania (Italy)

2014-05-09

Nuclear astrophysics aims to measure nuclear-reaction cross sections of astrophysical interest to be included into models to study stellar evolution and nucleosynthesis. Low energies, < 1 MeV or even < 10 keV, are requested for this is the window where these processes are more effective. Two effects have prevented to achieve a satisfactory knowledge of the relevant nuclear processes, namely, the Coulomb barrier exponentially suppressing the cross section and the presence of atomic electrons. These difficulties have triggered theoretical and experimental investigations to extend our knowledge down to astrophysical energies. For instance, indirect techniques such as the Trojan Horse Method have been devised yielding new cutting-edge results. In particular, I will focus on the application of this indirect method to resonance reactions. Resonances might dramatically enhance the astrophysical S(E)-factor so, when they occur right at astrophysical energies, their measurement is crucial to pin down the astrophysical scenario. Unknown or unpredicted resonances might introduce large systematic errors in nucleosynthesis models. These considerations apply to low-energy resonances and to sub-threshold resonances as well, as they may produce sizable modifications of the S-factor due to, for instance, destructive interference with another resonance.

The Trojan Horse method for nuclear astrophysics: Recent results on resonance reactions

International Nuclear Information System (INIS)

Cognata, M. La; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Romano, S.; Gulino, M.; Tumino, A.; Lamia, L.

2014-01-01

Nuclear astrophysics aims to measure nuclear-reaction cross sections of astrophysical interest to be included into models to study stellar evolution and nucleosynthesis. Low energies, < 1 MeV or even < 10 keV, are requested for this is the window where these processes are more effective. Two effects have prevented to achieve a satisfactory knowledge of the relevant nuclear processes, namely, the Coulomb barrier exponentially suppressing the cross section and the presence of atomic electrons. These difficulties have triggered theoretical and experimental investigations to extend our knowledge down to astrophysical energies. For instance, indirect techniques such as the Trojan Horse Method have been devised yielding new cutting-edge results. In particular, I will focus on the application of this indirect method to resonance reactions. Resonances might dramatically enhance the astrophysical S(E)-factor so, when they occur right at astrophysical energies, their measurement is crucial to pin down the astrophysical scenario. Unknown or unpredicted resonances might introduce large systematic errors in nucleosynthesis models. These considerations apply to low-energy resonances and to sub-threshold resonances as well, as they may produce sizable modifications of the S-factor due to, for instance, destructive interference with another resonance

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)

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.

Distorted wave method in reactions with composite particles

International Nuclear Information System (INIS)

Zelenskaya, N.S.; Teplov, I.B.

1980-01-01

The work deals with the distorbed wave method with a finite radius of interaction (DWBAFR) as applied to quantitative analysis of direct nuclear reactions with composite particles (including heavy ions) considering the reaction mechanisms other than the cluster stripping mechanism, in particular the exchange processes. The accurate equations of the distorbed-wave method in the three-body problem and the general formula dor calculating differential cross-sections of arbitrary binary reactions by DWBAFR are presented. Accurate and approximate methods allowing for finite interaction radius are discussed. Two main versions of exact account of recoil effects: separation of variables in wave functions of relative motion of particles and in interaction potentials and separation of variables in distorted waves are analysed. Given is a characteristic of the known calculated programs approximately and exactly taking account of recoil effects for direct and exchange processes [ru

Investigation of Evaluation method of chemical runaway reaction

International Nuclear Information System (INIS)

Sato, Yoshihiko; Sasaya, Shinji; Kurakata, Koichiro; Nojiri, Ichiro

2002-02-01

Safety study 'Study of evaluation of abnormal occurrence for chemical substances in the nuclear fuel facilities' will be carried out from 2001 to 2005. In this study, the prediction of thermal hazards of chemical substances will be investigated and prepared. The hazard prediction method of chemical substances will be constructed from these results. Therefore, the hazard prediction methods applied in the chemical engineering in which the chemical substances with the hazard of fire and explosion were often treated were investigated. CHETAH (The ASTM Computer Program for Chemical Thermodynamic and Energy Release Evaluation) developed by ASTM (American Society for Testing and Materials) and TSS (Thermal Safety Software) developed by CISP (ChemInform St. Petersburg) were introduced and the fire and explosion hazards of chemical substances and reactions in the reprocessing process were evaluated. From these evaluated results, CHETAH could almost estimate the heat of reaction at 10% accuracy. It was supposed that CHETAH was useful as a screening for the hazards of fire and explosion of the new chemical substances and so on. TSS could calculate the reaction rate and the reaction behavior from the data measured by the various calorimeters rapidly. It was supposed that TSS was useful as an evaluation method for the hazards of fire and explosion of the new chemical reactions and so on. (author)

Quantum dynamics through a wave packet method to study electron-hydrogen and atom-dihydrogen collisions; Dynamique quantique par une methode de paquets d'ondes. Etude des collisions electron-hydrogene et atome-dihydrogene

Energy Technology Data Exchange (ETDEWEB)

Mouret, L

2002-11-01

The thesis concerns the development and implementation of numerical methods for solving the time-dependent Schroedinger equation. We first considered the case of electron-hydrogen scattering. The originality of our method is the use of a non-uniform radial grid defined by a Schwarz interpolation based on a Coulomb reference function. This grid allows many hydrogen bound states and associated matrix elements of various operators to be reproduced to machine accuracy. The wave function is propagated in time using a Split-Operator method. The efficiency of our method allows the wave function to be propagated out to large distances for all partial waves. We obtain excitation and ionization cross sections in excellent agreement with the best experimental and theoretical data. We subsequently adapted the method and the program package to study reactive atom-dihydrogen scattering. The wave packet is described using product Jacobi coordinates on a regular grid of radial coordinates combined with a basis of Legendre polynomials for the angular part (partial wave S). The wave function is analysed using a time-to-energy Fourier transform, which provides results over the energy range covered by the initial wave packet in one calculation. The method was first tested on the quasi-direct (F,H2) reaction and then applied to the indirect (C(1D),H2)reaction. The state-to-state reaction probabilities are in good agreement with those obtained by a time-independent approach. In particular, the strongly resonant structure of the (C(1D),H2) reaction probabilities is well reproduced. (author)

Recent results on solvation dynamics of electron and spur reactions of solvated electron in polar solvents studied by femtosecond laser spectroscopy and picosecond pulse radiolysis

International Nuclear Information System (INIS)

Mostafavi, M.

2006-01-01

Here, we report several studies done recently at ELYSE laboratory on the solvation dynamics of electron and on the kinetics of solvated electron in the spur reactions, performed by femtosecond laser spectroscopy and picosecond pulse radiolysis, respectively. Solvated electrons have been produced in polyol (1,2-Etanediol, 1,2-Propanediol and 1,3-Propanediol) by two-photon ionization of the solvent with 263 nm femtosecond laser pulses at room temperature. The two-photon absorption coefficient of these solvents at 263 nm has been determined. The dynamics of electron solvation in polyols has been studied by pump-probe transient absorption spectroscopy. So, time resolved absorption spectra ranging from 430 to 720 nm have been measured (Figure 1). A blue shift of the spectra is observed for the first tens of picoseconds. Using Bayesian data analysis method, the observed solvation dynamics are reconstructed with different models: stepwise mechanisms, continuous relaxation models or combinations of stepwise and continuous relaxation. That analysis clearly indicates that it is not obvious to select a unique model to describe the solvation dynamics of electron in diols. We showed that several models are able to reproduce correctly the data: a two-step model, a heterogeneous or bi-exponential continuous relaxation model and even a hybrid model with a stepwise transition and homogeneous continuous relaxation. Nevertheless, the best fits are given by the continuous spectral relaxation models. The fact that the time-evolution of the absorption spectrum of the solvated electron in diols can be accurately described by the temperature dependent absorption spectrum of the ground state solvated electron suggests that the spectral blue shift is mostly caused by the continuous relaxation of the electron trapped in a large distribution of solvent cages. Similar trends on electron solvation dynamics are observed in the cases of 1,2-ethanediol, 1,3-propanediol and 1,2 propanediol

Quantum dynamics of fast chemical reactions

Energy Technology Data Exchange (ETDEWEB)

Light, J.C. [Univ. of Chicago, IL (United States)

1993-12-01

The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

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.

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

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.

Quantum dynamics through a wave packet method to study electron-hydrogen and atom-dihydrogen collisions; Dynamique quantique par une methode de paquets d'ondes. Etude des collisions electron-hydrogene et atome-dihydrogene

Energy Technology Data Exchange (ETDEWEB)

Mouret, L

2002-11-01

The thesis concerns the development and implementation of numerical methods for solving the time-dependent Schroedinger equation. We first considered the case of electron-hydrogen scattering. The originality of our method is the use of a non-uniform radial grid defined by a Schwarz interpolation based on a Coulomb reference function. This grid allows many hydrogen bound states and associated matrix elements of various operators to be reproduced to machine accuracy. The wave function is propagated in time using a Split-Operator method. The efficiency of our method allows the wave function to be propagated out to large distances for all partial waves. We obtain excitation and ionization cross sections in excellent agreement with the best experimental and theoretical data. We subsequently adapted the method and the program package to study reactive atom-dihydrogen scattering. The wave packet is described using product Jacobi coordinates on a regular grid of radial coordinates combined with a basis of Legendre polynomials for the angular part (partial wave S). The wave function is analysed using a time-to-energy Fourier transform, which provides results over the energy range covered by the initial wave packet in one calculation. The method was first tested on the quasi-direct (F,H2) reaction and then applied to the indirect (C(1D),H2)reaction. The state-to-state reaction probabilities are in good agreement with those obtained by a time-independent approach. In particular, the strongly resonant structure of the (C(1D),H2) reaction probabilities is well reproduced. (author)

Redox reaction studies by nanosecond pulse radiolysis

International Nuclear Information System (INIS)

Moorthy, P.N.

1979-01-01

Free radicals are formed as intermediates in many chemical and biochemical reactions. An important type of reaction which they can undergo is a one electron or redox process. The direction and rate of such electron transfer reactions is governed by the relative redox potentials of the participating species. Because of the generally short lived nature of free radicals, evaluation of their redox potentials poses a number of problems. Two techniques are described for the experimental determination of the redox potentials of short lived species generated by either a nanosecond electron pulse or laser flash. In the first method, redox titration of the short lived species with stable molecules of known redox potential is carried out, employing the technique of fast kinetic spectrophotometry. Conversely, by the same method it is also possible to evaluate the one electron redox potentials of stable molecules by redox titration with free radicals of known redox potential produced as above. In the second method, electrochemical reduction or oxidation of the short lived species at an appropriate electrode (generally a mercury drop) is carried out at different fixed potentials, and the redox potential evaluated from the current-potential curves (polarograms). Full description of the experimental set up and theoretical considerations for interpretation of the raw data are given. The relative merits of the two methods and their practical applicability are discussed. (auth.)

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

The determination methods of the velocity constant for electrochemical reactions; Les methodes de determination de la constante de vitesse des reactions electrochimiques

Energy Technology Data Exchange (ETDEWEB)

Molina, R

1963-07-01

In a brief introduction are recalled the fundamental mechanisms of the electrochemical reaction and the definition of the intrinsic velocity constant of a such reaction. By the nature of the different parameters which enter in this definition are due some experimental problems which are examined. Then are given the principles of the measurement methods of the velocity constant. These methods are developed with the mathematical expression of the different rates of the mass transfer to an electrode. In each case are given the experimental limits of use of the methods and the size order of the velocity constant that can be reached. A list of fundamental works to be consulted conclude this work. (O.M.) [French] Dans une breve introduction sont rappeles les mecanismes fondamentaux de la reaction electrochimique et la definition de la constante de vitesse intrinseque d'une telle reaction. De la nature des differents parametres qui entrent dans celle definition, decoulent un certain nombre de problemes experimentaux qui sont passes en revue. On donne ensuite les principes des methodes de mesure de la constante de vitesse. L'exposition de ces methodes est developpee a l'aide de l'expression mathematique des differents regimes de transfert de masse a une electrode. On s'attache dans chaque cas, a donner les limitations experimentales d'utilisation des methodes et l'ordre de grandeur de la constante de vitesse qu'elles permettent d'atteindre. Une liste des ouvrages fondamentaux a consulter conclut ce travail. (auteur)

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)

Trojan Horse Method for neutrons-induced reaction studies

Science.gov (United States)

Gulino, M.; Asfin Collaboration

2017-09-01

Neutron-induced reactions play an important role in nuclear astrophysics in several scenario, such as primordial Big Bang Nucleosynthesis, Inhomogeneous Big Bang Nucleosynthesis, heavy-element production during the weak component of the s-process, explosive stellar nucleosynthesis. To overcome the experimental problems arising from the production of a neutron beam, the possibility to use the Trojan Horse Method to study neutron-induced reactions has been investigated. The application is of particular interest for reactions involving radioactive nuclei having short lifetime.

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.

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

Solution-phase parallel synthesis of aryloxyimino amides via a novel multicomponent reaction among aromatic (Z)-chlorooximes, isocyanides, and electron-deficient phenols.

Science.gov (United States)

Mercalli, Valentina; Giustiniano, Mariateresa; Del Grosso, Erika; Varese, Monica; Cassese, Hilde; Massarotti, Alberto; Novellino, Ettore; Tron, Gian Cesare

2014-11-10

A library of 41 aryloxyimino amides was prepared via solution phase parallel synthesis by extending the multicomponent reaction of (Z)-chlorooximes and isocyanides to the use of electron-deficient phenols. The resulting aryloxyiminoamide derivatives can be used as intermediates for the synthesis of benzo[d]isoxazole-3-carboxamides, dramatically reducing the number of synthetic steps required by other methods reported in literature.

Use of nonlocal helium microplasma for gas impurities detection by the collisional electron spectroscopy method

Energy Technology Data Exchange (ETDEWEB)

Kudryavtsev, Anatoly A., E-mail: akud@ak2138.spb.edu [St. Petersburg State University, 7-9 Universitetskaya nab., 199034 St. Petersburg (Russian Federation); Stefanova, Margarita S.; Pramatarov, Petko M. [Institute of Solid State Physics, Bulgarian Academy of Sciences, 72 Tzarigradsko Chaussee blvd., 1784 Sofia (Bulgaria)

2015-10-15

The collisional electron spectroscopy (CES) method, which lays the ground for a new field for analytical detection of gas impurities at high pressures, has been verified. The CES method enables the identification of gas impurities in the collisional mode of electron movement, where the advantages of nonlocal formation of the electron energy distribution function (EEDF) are fulfilled. Important features of dc negative glow microplasma and probe method for plasma diagnostics are applied. A new microplasma gas analyzer design is proposed. Admixtures of 0.2% Ar, 0.6% Kr, 0.1% N{sub 2}, and 0.05% CO{sub 2} are used as examples of atomic and molecular impurities to prove the possibility for detecting and identifying their presence in high pressure He plasma (50–250 Torr). The identification of the particles under analysis is made from the measurements of the high energy part of the EEDF, where maxima appear, resulting from the characteristic electrons released in Penning reactions of He metastable atoms with impurity particles. Considerable progress in the development of a novel miniature gas analyzer for chemical sensing in gas phase environments has been made.

Nucleophilic Fluorination Reactions in Novel Reaction Media for 18F-Fluorine Labeling Method

International Nuclear Information System (INIS)

Kim, Dong Wook; Jeong, Hwan Jeong; Lim, Seok Tae; Sohn, Myung Hee

2009-01-01

Noninvasive imaging of molecular and biological processes in living subjects with positron emission tomography (PET) provides exciting opportunities to monitor metabolism and detect diseases in humans. Measuring these processes with PET requires the preparation of specific molecular imaging probes labeled with 18F-fluorine. In this review we describe recent methods and novel trends for the introduction of 18 F-fluorine into molecules which in turn are intended to serve as imaging agents for PET study. Nucleophilic 18 F-fluorination of some halo- and mesyloxyalkanes to the corresponding 18 F-fluoroalkanes with 18 F-fluoride obtained from an 18 O(p,n) 18 F reaction, using novel reaction media system such as an ionic liquidor tert-alcohol, has been studied as a new method for 18 F-fluorine labeling. Ionic liquid method is rapid and particularly convenient because 18 F-fluoride in H 2 O can be added directly to the reaction media, obviating the careful drying that is typically required for currently used radiofluorination methods. The nonpolar protic tert-alcohol enhances the nucleophilicity of the fluoride ion dramatically in the absence of any kind of catalyst, greatly increasing the rate of the nucleophilic fluorination and reducing formation of byproducts compared with conventional methods using dipolar aprotic solvents. The great efficacy of this method is a particular advantage in labeling radiopharmaceuticals with 18 F-fluorine for PET imaging, and it is illustrated by the synthesis of 18 F-fluoride radiolabeled molecular imaging probes, such as 18 F-FDG, 18 F-FLT, 18 F-FP-CIT, and 18 F-FMISO, in high yield and purity and in shorter times compared to conventional syntheses

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

New method to measure the carbamoylating activity of nitrosoureas by electron paramagnetic resonance spectroscopy.

Science.gov (United States)

Gadzheva, V; Ichimori, K; Raikov, Z; Nakazawa, H

1997-08-01

A new method for measuring the carbamoylating activity of nitrosoureas and isocyanates using electron paramagnetic resonance (EPR) spectroscopy is described. The extent and time course of carbamoylation reaction of chloroethyl isocyanate and a series of 9 nitrosoureas toward amino group of 4-amino-2,2,6,6-tetramethyl-piperidine-1-oxyl were examined with both the EPR method and the HPLC method which has been proposed by Brubaker et al. [Biochem. Pharmacol. 35:2359 (1986)]. Spin-labeled nitrosoureas we synthesized are included in this study since they have less toxicity or more efficiency than commercially available drug in some cases. The concentration of carbamoylated product was easily determined with the EPR spectra. There is a very high correlation (r = 0.982, t = 2.58, N = 10, p nitrosoureas showed lower carbamoylating activity than non-labeled analogues. The carbamoylating activity for these nitrosourea depended on the reactivity of isocyanate intermediate and almost independent of their half life. This rapid and simple EPR method is suitable for the detailed investigation of the rate and extent of carbamoylation reaction.

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

Treatment of liquid separated from sludge by the method using electron beam and ozone in combination

International Nuclear Information System (INIS)

Hosono, Masakazu; Arai, Hidehiko; Aizawa, Masaki; Shimooka, Toshio; Shimizu, Ken; Sugiyama, Masashi.

1995-01-01

Since the liquid separated from sludge in the dehydration or concentration process of sewer sludge contains considerable amount of organic compositions that are hard to be decomposed by microorganisms, it has become difficult to be treated by conventional activated sludge process. In the case of discharging the separated liquid into closed water areas, the higher quality treatment is required. The method of using electron beam irradiation and ozone oxidation in combination for cleaning the liquid separated from sludge was examined, therefore, the results are reported. The water quality of the sample from the sludge treatment plant in A City is shown. The method of bio-pretreatment, the treatment method by using electron beam and ozone in combination, and the method of analyzing the water quality are described. The effect of the treatment by activated sludge process, as the effect of the treatment by the combined use of electron beam and ozone, the change of COD and TOC, the change of chromaticity, the change of gel chromatogram, and the reaction mechanism are reported. In this paper, only the basic concept on the model plant for applying the method of the combined use of electron beam and ozone to the treatment of the liquid separated from sludge is discussed. (K.I.)

Two-step nuclear reactions: The Surrogate Method, the Trojan Horse Method and their common foundations

Energy Technology Data Exchange (ETDEWEB)

Hussein, Mahir S. [DCTA, Instituto Tecnologico de Aeronautica, Sao Jose dos Campos, SP (Brazil); Universidade de Sao Paulo, Instituto de Estudos Avancados, C. P. 72012, Sao Paulo, SP (Brazil); Universidade de Sao Paulo, Instituto de Fisica, C. P. 66318, Sao Paulo, SP (Brazil)

2017-05-15

In this Letter I argue that the Surrogate Method, used to extract the fast neutron capture cross section on actinide target nuclei, which has important practical application for the next generation of breeder reactors, and the Trojan Horse Method employed to extract reactions of importance to nuclear astrophysics, have a common foundation, the Inclusive Non-Elastic Breakup (INEB) Theory. Whereas the Surrogate Method relies on the premise that the extracted neutron cross section in a (d, p) reaction is predominantly a compound-nucleus one, the Trojan Horse Method assumes a predominantly direct process for the secondary reaction induced by the surrogate fragment. In general, both methods contain both direct and compound contributions, and I show how these seemingly distinct methods are in fact the same but at different energies and different kinematic regions. The unifying theory is the rather well developed INEB theory. (orig.)

Two-step nuclear reactions: The Surrogate Method, the Trojan Horse Method and their common foundations

International Nuclear Information System (INIS)

Hussein, Mahir S.

2017-01-01

In this Letter I argue that the Surrogate Method, used to extract the fast neutron capture cross section on actinide target nuclei, which has important practical application for the next generation of breeder reactors, and the Trojan Horse Method employed to extract reactions of importance to nuclear astrophysics, have a common foundation, the Inclusive Non-Elastic Breakup (INEB) Theory. Whereas the Surrogate Method relies on the premise that the extracted neutron cross section in a (d, p) reaction is predominantly a compound-nucleus one, the Trojan Horse Method assumes a predominantly direct process for the secondary reaction induced by the surrogate fragment. In general, both methods contain both direct and compound contributions, and I show how these seemingly distinct methods are in fact the same but at different energies and different kinematic regions. The unifying theory is the rather well developed INEB theory. (orig.)

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

The effect of B_2O_3 flux on growth NLBCO superconductor by solid state reaction and wet-mixing methods

International Nuclear Information System (INIS)

Suharta, W. G.; Wendri, N.; Ratini, N.; Suarbawa, K. N.

2016-01-01

The synthesis of B_2O_3 flux substituted NLBCO superconductor NdBa_1_._7_5La_0_._2_5Cu_3O_7_-_∂ has been done using solid state reaction and wet-mixing methods in order to obtain homogeneous crystals and single phase. From DTA/TGA characteritations showed the synthesis process by wet-mixing requires a lower temperature than the solid state reaction in growing the superconductor NdBa_1_._7_5La_0_._2_5Cu_3O_7_-_∂. Therefore, in this research NdBa_1_._7_5La_0_._2_5Cu_3O_7_-_∂ sample calcinated at 650°C for wet-mixing method and 820°C for solid state reaction methods. The all samples was sintered at 950°C for ten hours. Crystallinity of the sample was confirmed using X-ray techniques and generally obtained sharp peaks that indicates the sample already well crystallized. Search match analyses for diffraction data gave weight fractions of impurity phase of the solid state reaction method higher than wet-mixing method. In this research showed decreasing the price of the lattice parameter about 1% with the addition of B_2O_3 flux for the both synthesis process and 2% of wet mixing process for all samples. Characterization using scanning electron microscopy (SEM) showed the distribution of crystal zise for wet-mixing method more homogeneous than solid state reaction method, with he grain size of samples is around 150–250 nm. The results of vibrating sample magnetometer (VSM) showed the paramagnetic properties for all samples.

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).

Substrate-Directed Catalytic Selective Chemical Reactions.

Science.gov (United States)

Sawano, Takahiro; Yamamoto, Hisashi

2018-05-04

The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

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)

Selected methods of electron-and ion-diagnostics in tokamak scrape-off-layer

Directory of Open Access Journals (Sweden)

Sadowski Marek J.

2015-06-01

Full Text Available This invited paper considers reasons why exact measurements of fast electron and ion losses in tokamaks, and particularly i n a scrape-off-layer and near a divertor region, are necessary in order to master nuclear fusion energy production. Attention is also paid to direct measurements of escaping fusion products from D-D and D-T reactions, and in particular of fast alphas which might be used for plasma heating. The second part describes the generation of so-called runaway and ripple-born electrons which might induce high energy losses and cause severe damages of internal walls in fusion facilities. Advantages and disadvantages of different diagnostic methods applied for studies of such fast electrons are discussed. Particular attention is paid to development of a direct measuring technique based on the Cherenkov effect which might be induced by fast electrons in appropriate radiators. There are presented various versions of Cherenkov-type probes which have been developed by the NCBJ team and applied in different tokamak experiments. The third part is devoted to direct measurements of fast ions (including those produced by the nuclear fusion reactions which can escape from a high-temperature plasma region. Investigation of fast fusion-produced protons from tokamak discharges is reported. New ion probes, which were developed by the NCBJ team, are also presented. For the first time there is given a detailed description of an ion pinhole camera, which enables irradiation of several nuclear track detectors during a single tokamak discharge, and a miniature Thomson-type mass-spectrometer, which can be used for ion measurements at plasma borders.

Reaction kinetics, reaction products and compressive strength of ternary activators activated slag designed by Taguchi method

NARCIS (Netherlands)

Yuan, B.; Yu, Q.L.; Brouwers, H.J.H.

2015-01-01

This study investigates the reaction kinetics, the reaction products and the compressive strength of slag activated by ternary activators, namely waterglass, sodium hydroxide and sodium carbonate. Nine mixtures are designed by the Taguchi method considering the factors of sodium carbonate content

Method for Selection of Solvents for Promotion of Organic Reactions

DEFF Research Database (Denmark)

Gani, Rafiqul; Jiménez-González, Concepción; Constable, David J.C.

2005-01-01

is to produce, for a given reaction, a short list of chemicals that could be considered as potential solvents, to evaluate their performance in the reacting system, and, based on this, to rank them according to a scoring system. Several examples of application are given to illustrate the main features and steps......A method to select appropriate green solvents for the promotion of a class of organic reactions has been developed. The method combines knowledge from industrial practice and physical insights with computer-aided property estimation tools for selection/design of solvents. In particular, it employs...... estimates of thermodynamic properties to generate a knowledge base of reaction, solvent and environment related properties that directly or indirectly influence the rate and/or conversion of a given reaction. Solvents are selected using a rules-based procedure where the estimated reaction-solvent properties...

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…

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

Contribution to an effective design method for stationary reaction-diffusion patterns

International Nuclear Information System (INIS)

Szalai, István; Horváth, Judit; De Kepper, Patrick

2015-01-01

The British mathematician Alan Turing predicted, in his seminal 1952 publication, that stationary reaction-diffusion patterns could spontaneously develop in reacting chemical or biochemical solutions. The first two clear experimental demonstrations of such a phenomenon were not made before the early 1990s when the design of new chemical oscillatory reactions and appropriate open spatial chemical reactors had been invented. Yet, the number of pattern producing reactions had not grown until 2009 when we developed an operational design method, which takes into account the feeding conditions and other specificities of real open spatial reactors. Since then, on the basis of this method, five additional reactions were shown to produce stationary reaction-diffusion patterns. To gain a clearer view on where our methodical approach on the patterning capacity of a reaction stands, numerical studies in conditions that mimic true open spatial reactors were made. In these numerical experiments, we explored the patterning capacity of Rabai's model for pH driven Landolt type reactions as a function of experimentally attainable parameters that control the main time and length scales. Because of the straightforward reversible binding of protons to carboxylate carrying polymer chains, this class of reaction is at the base of the chemistry leading to most of the stationary reaction-diffusion patterns presently observed. We compare our model predictions with experimental observations and comment on agreements and differences

Contribution to an effective design method for stationary reaction-diffusion patterns

Energy Technology Data Exchange (ETDEWEB)

Szalai, István; Horváth, Judit [Laboratory of Nonlinear Chemical Dynamics, Institute of Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary); De Kepper, Patrick [Centre de Recherche Paul Pascal, CNRS, University of Bordeaux, 115, Avenue Schweitzer, F-33600 Pessac (France)

2015-06-15

The British mathematician Alan Turing predicted, in his seminal 1952 publication, that stationary reaction-diffusion patterns could spontaneously develop in reacting chemical or biochemical solutions. The first two clear experimental demonstrations of such a phenomenon were not made before the early 1990s when the design of new chemical oscillatory reactions and appropriate open spatial chemical reactors had been invented. Yet, the number of pattern producing reactions had not grown until 2009 when we developed an operational design method, which takes into account the feeding conditions and other specificities of real open spatial reactors. Since then, on the basis of this method, five additional reactions were shown to produce stationary reaction-diffusion patterns. To gain a clearer view on where our methodical approach on the patterning capacity of a reaction stands, numerical studies in conditions that mimic true open spatial reactors were made. In these numerical experiments, we explored the patterning capacity of Rabai's model for pH driven Landolt type reactions as a function of experimentally attainable parameters that control the main time and length scales. Because of the straightforward reversible binding of protons to carboxylate carrying polymer chains, this class of reaction is at the base of the chemistry leading to most of the stationary reaction-diffusion patterns presently observed. We compare our model predictions with experimental observations and comment on agreements and differences.

A multilevel adaptive reaction-splitting method for SRNs

KAUST Repository

Moraes, Alvaro; Tempone, Raul; Vilanova, Pedro

2016-01-01

In [5], we present a novel multilevel Monte Carlo method for kinetic simulation of stochastic reaction networks (SRNs) specifically designed for systems in which the set of reaction channels can be adaptively partitioned into two subsets characterized by either high or low activity. To estimate expected values of observables of the system, our method bounds the global computational error to be below a prescribed tolerance, TOL, within a given confidence level. This is achieved with a computational complexity of order O(TOL-2). We also present a novel control variate technique which may dramatically reduce the variance of the coarsest level at a negligible computational cost.

A multilevel adaptive reaction-splitting method for SRNs

KAUST Repository

Moraes, Alvaro

2016-01-06

In [5], we present a novel multilevel Monte Carlo method for kinetic simulation of stochastic reaction networks (SRNs) specifically designed for systems in which the set of reaction channels can be adaptively partitioned into two subsets characterized by either high or low activity. To estimate expected values of observables of the system, our method bounds the global computational error to be below a prescribed tolerance, TOL, within a given confidence level. This is achieved with a computational complexity of order O(TOL-2). We also present a novel control variate technique which may dramatically reduce the variance of the coarsest level at a negligible computational cost.

A multilevel adaptive reaction-splitting method for SRNs

KAUST Repository

Moraes, Alvaro

2015-01-07

In this work, we present a novel multilevel Monte Carlo method for kinetic simulation of stochastic reaction networks specifically designed for systems in which the set of reaction channels can be adaptively partitioned into two subsets characterized by either “high” or “low” activity. To estimate expected values of observables of the system, our method bounds the global computational error to be below a prescribed tolerance, within a given confidence level. This is achieved with a computational complexity of order O (TOL-2).We also present a novel control variate technique which may dramatically reduce the variance of the coarsest level at a negligible computational cost. Our numerical examples show substantial gains with respect to the standard Stochastic Simulation Algorithm (SSA) by Gillespie and also our previous hybrid Chernoff tau-leap method.

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.

A method for measuring light ion reaction cross-sections

International Nuclear Information System (INIS)

Carlson, R.F.; Ingemarsson, A.; Lantz, M.; Arendse, G.J.; Auce, A.; Cox, A.J.; Foertsch, S.V.; Jacobs, N.M.; Johansson, R.; Nyberg, J.; Peavy, J.; Renberg, P.-U.; Sundberg, O.; Stander, J.A.; Steyn, G.F.; Tibell, G.; Zorro, R.

2005-01-01

An experimental procedure for measuring reaction cross-sections of light ions in the energy range 20-50 MeV/nucleon, using a modified attenuation technique, is described. The detection method incorporates a forward detector that simultaneously measures the reaction cross-sections for five different sizes of the solid angle in steps from 99.1% to 99.8% of the total solid angle. The final reaction cross-section values are obtained by extrapolation to the full solid angle

A method for measuring light ion reaction cross sections

International Nuclear Information System (INIS)

Carlson, R.F.; Ingemarsson, A.; Lantz, M.

2005-03-01

An experimental procedure for measuring reaction cross sections of light ions in the energy range 20-50 MeV/nucleon, using a modified attenuation technique, is described. The detection method incorporates a forward detector that simultaneously measures the reaction cross sections for five different sizes of the solid angles in steps from 99.1 to 99.8% of the total solid angle. The final reaction cross section values are obtained by extrapolation to the full solid angle

Mitoxantrone removal by electrochemical method: A comparison of homogenous and heterogenous catalytic reactions

Directory of Open Access Journals (Sweden)

Abbas Jafarizad

2017-08-01

Full Text Available Background: Mitoxantrone (MXT is a drug for cancer therapy and a hazardous pharmaceutical to the environment which must be removed from contaminated waste streams. In this work, the removal of MXT by the electro-Fenton process over heterogeneous and homogenous catalysts is reported. Methods: The effects of the operational conditions (reaction medium pH, catalyst concentration and utilized current intensity were studied. The applied electrodes were carbon cloth (CC without any processing (homogenous process, graphene oxide (GO coated carbon cloth (GO/CC (homogenous process and Fe3O4@GO nanocomposite coated carbon cloth (Fe3O4@GO/CC (heterogeneous process. The characteristic properties of the electrodes were determined by atomic force microscopy (AFM, field emission scanning electron microscopy (FE-SEM and cathode polarization. MXT concentrations were determined by using ultraviolet-visible (UV-Vis spectrophotometer. Results: In a homogenous reaction, the high concentration of Fe catalyst (>0.2 mM decreased the MXT degradation rate. The results showed that the Fe3O4@GO/CC electrode included the most contact surface. The optimum operational conditions were pH 3.0 and current intensity of 450 mA which resulted in the highest removal efficiency (96.9% over Fe3O4@GO/CC electrode in the heterogeneous process compared with the other two electrodes in a homogenous process. The kinetics of the MXT degradation was obtained as a pseudo-first order reaction. Conclusion: The results confirmed the high potential of the developed method to purify contaminated wastewaters by MXT.

Short-baseline electron antineutrino disappearance study by using neutrino sources from {sup 13}C + {sup 9}Be reaction

Energy Technology Data Exchange (ETDEWEB)

Shin, Jae Won; Cheoun, Myung-Ki [Department of Physics and Origin of Matter and Evolution of Galaxies (OMEG) Institute, Soongsil University, Seoul 156-743 (Korea, Republic of); Kajino, Toshitaka [Division of Theoretical Astronomy, National Astronomical Observatory of Japan, Mitaka, Tokyo 181-8588 (Japan); Hayakawa, Takehito, E-mail: shine8199@skku.edu, E-mail: cheoun@ssu.ac.kr, E-mail: kajino@nao.ac.jp, E-mail: hayakawa.takehito@qst.go.jp [Quantum Beam Science Directorate (QUBS), Japan Atomic Energy Agency (JAEA), 2-4 Shirane, Shirakata, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan)

2017-04-01

To investigate the existence of sterile neutrino, we propose a new neutrino production method using {sup 13}C beams and a {sup 9}Be target for short-baseline electron antineutrino (ν-bar {sub e} ) disappearance study. The production of secondary unstable isotopes which can emit neutrinos from the {sup 13}C + {sup 9}Be reaction is calculated with three different nucleus-nucleus (AA) reaction models. Different isotope yields are obtained using these models, but the results of the neutrino flux are found to have unanimous similarities. This feature gives an opportunity to study neutrino oscillation through shape analysis. In this work, expected neutrino flux and event rates are discussed in detail through intensive simulation of the light ion collision reaction and the neutrino flux from the beta decay of unstable isotopes followed by this collision. Together with the reactor and accelerator anomalies, the present proposed ν-bar {sub e} source is shown to be a practically alternative test of the existence of the Δ m {sup 2} ∼ 1 eV{sup 2} scale sterile neutrino.

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 .

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

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...

Resonance strength measurement at astrophysical energies: The {sup 17}O(p,α){sup 14}N reaction studied via Trojan Horse Method

Energy Technology Data Exchange (ETDEWEB)

Sergi, M. L., E-mail: sergi@lns.infn.it; La Cognata, M.; Pizzone, R. G. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Spitaleri, C. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Dipartimento di Fisica e Astronomia, Università degli studi di Catania, Catania (Italy); Lamia, L.; Rapisarda, G. G. [Dipartimento di Fisica e Astronomia, Università degli studi di Catania, Catania (Italy); Mukhamedzhanov, A. [Cyclotron Institute, Texas A& M University, College Station, Texas 77843 (United States); Irgaziev, B. [GIK Institute of Engineering Sciences and Technology, Topi, Districti Swabi, Khyber Pakhtunkhwa (Pakistan); Tang, X. D.; Wiescher, M. [Department of Physics, Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame 46556, Indiana (United States); Mrazek, J.; Kroha, V. [Nuclear Physics Institute of ASCR, Rez (Czech Republic)

2015-10-15

In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on {sup 17}O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

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

Exchange Reactions. Proceedings of the Symposium on Exchange Reactions

International Nuclear Information System (INIS)

1965-01-01

The mechanisms and kinetics of chemical reactions are of great interest to chemists. The study of exchange reactions in particular helps to shed light on the dynamics of chemical change, providing an insight into the structures and the reactivities of the chemical species involved. The main theme of this meeting was the subject of oxidation-reduction reactions in which the net result is the transfer of one or more electrons between the different oxidation states of the same element. Other studies reported included the transfer of protons, atoms, complex ligands or organic radicals between molecules. Heterogeneous exchange, which is of importance in many cases of catalytic action, was also considered. For a long time isotopic tracers have formed the most convenient means of studying exchange reactions and today a considerable amount of work continues to be done with their aid. Consequently, several papers presented at this Symposium reported on work carried out by purely radiochemical tracer methods. In recognition, however, of the important role which nuclear magnetic resonance and electron spin resonance play in this field, in particular in the study of fast reactions, a number of reports on investigations in which these techniques had been used was included in the programme. By kind invitation of the United States Government the Symposium on Exchange Reactions was held from 31 May to 4 June at the Brookhaven National Laboratory, Upton, Long Island, N.Y., USA. It was attended by 46 participants from nine countries and one inter-governmental organization. The publication of these Proceedings makes the contents of the papers and the discussion available to a wider audience

Neutron-induced cross sections of actinides via the surrogate-reaction method

Directory of Open Access Journals (Sweden)

Ducasse Q.

2013-12-01

Full Text Available The surrogate-reaction method is an indirect way of determining cross sections for reactions that proceed through a compound nucleus. This technique may enable neutron-induced cross sections to be extracted for short-lived nuclei that otherwise cannot be measured. However, the validity of the surrogate method has to be investigated. In particular, the absence of a compound nucleus formation and the Jπ dependence of the decay probabilities may question the method. In this work we study the reactions 238U(d,p239U, 238U(3He,t238Np, 238U(3He,4He237U as surrogates for neutron-induced reactions on 238U, 237Np and 236U, respectively, for which good quality data exist. The experimental set-up enabled the measurement of fission and gamma-decay probabilities. The first results are hereby presented.

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

Drafting method of electricity and electron design

International Nuclear Information System (INIS)

Gungbon, Junchun

1989-11-01

This book concentrates on drafting of electricity and electron design. It deals with The meaning of electricity and electron drafting JIS standard regulation the types of drafting and line and letter, basics drafting with projection drafting method, plan projection and development elevation, Drafting method of shop drawing, practical method of design and drafting, Design and drafting of technic and illustration, Connection diagram, Drafting of wiring diagram for light and illumination, Drafting of development connection diagram for sequence control, Drafting of logic circuit sign of flow chart and manual, drafting for a electron circuit diagram and Drawing of PC board.

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)

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.

A simultaneous electron energy and dosimeter calibration method for an electron beam irradiator

International Nuclear Information System (INIS)

Tanaka, R.; Sunaga, H.; Kojima, T.

1991-01-01

In radiation processing using electron accelerators, the reproducibility of absorbed dose in the product depends not only on the variation of beam current and conveyor speed, but also on variations of other accelerator parameters. This requires routine monitoring of the beam current and the scan width, and also requires periodical calibration of routine dosimeters usually in the shape of film, electron energy, and other radiation field parameters. The electron energy calibration is important especially for food processing. The dose calibration method using partial absorption calorimeters provides only information about absorbed dose. Measurement of average electron current density provides basic information about the radiation field formed by the beam scanning and scattering at the beam window, though it does not allow direct dose calibration. The total absorption calorimeter with a thick absorber allows dose and dosimeter calibration, if the depth profile of relative dose in a reference absorber is given experimentally. It also allows accurate calibration of the average electron energy at the surface of the calorimeter core, if electron fluence received by the calorimeter is measured at the same time. This means that both electron energy and dosimeters can be simultaneously calibrated by irradiation of a combined system including the calorimeter, the detector of the electron current density meter, and a thick reference absorber for depth profile measurement of relative dose. We have developed a simple and multifunctional system using the combined calibration method for 5 MeV electron beams. The paper describes a simultaneous calibration method for electron energy and film dosimeters, and describes the electron current density meter, the total absorption calorimeter, and the characteristics of this method. (author). 13 refs, 7 figs, 3 tabs

Applying some methods to process the data coming from the nuclear reactions

International Nuclear Information System (INIS)

Suleymanov, M.K.; Abdinov, O.B.; Belashev, B.Z.

2010-01-01

Full text : The methods of a posterior increasing the resolution of the spectral lines are offered to process the data coming from the nuclear reactions. The methods have applied to process the data coming from the nuclear reactions at high energies. They give possibilities to get more detail information on a structure of the spectra of particles emitted in the nuclear reactions. The nuclear reactions are main source of the information on the structure and physics of the atomic nuclei. Usually the spectrums of the fragments of the reactions are complex ones. Apparently it is not simple to extract the necessary for investigation information. In the talk we discuss the methods of a posterior increasing the resolution of the spectral lines. The methods could be useful to process the complex data coming from the nuclear reactions. We consider the Fourier transformation method and maximum entropy one. The complex structures were identified by the method. One can see that at lest two selected points are indicated by the method. Recent we presented a talk where we shown that the results of the analyzing the structure of the pseudorapidity spectra of charged relativistic particles with ≥ 0.7 measured in Au+Em and Pb+Em at AGS and SPS energies using the Fourier transformation method and maximum entropy one. The dependences of these spectra on the number of fast target protons were studied. These distribution shown visually some plateau and shoulder that was at least three selected points on the distributions. The plateaus become wider in PbEm reactions. The existing of plateau is necessary for the parton models. The maximum entropy method could confirm the existing of the plateau and the shoulder on the distributions. The figure shows the results of applying the maximum entropy method. One can see that the method indicates several clean selected points. Some of them same with observed visually ones. We would like to note that the Fourier transformation method could not

Solvent engineering and other reaction design methods for favouring enzyme-catalysed synthesis

DEFF Research Database (Denmark)

Zeuner, Birgitte

. However, both FAEs catalysed the feruloylation and/or sinapoylation of solvent cation C2OHMIm+, thus underlining the broad acceptor specificity of FAEs and their potential for future solvent reactions. An engineered sialidase from Trypanosoma rangeli, Tr6, catalyses trans-sialylation but the yield......This thesis investigates different methods for improving reaction yields of enzyme-catalysed synthesis reactions. These methods include the use of non-conventional media such as ionic liquids (ILs) and organic solvents as main solvents or as co-solvents as well as the use of more classical reaction...... design methods, i.e. enzyme immobilization and the use of an enzymatic membrane reactor. Two different enzyme classes, namely feruloyl esterases (FAEs) and sialidases are employed. Using sinapoylation of glycerol as a model reaction it was shown that both the IL anion nature and the FAE structure were...

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.

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

N-body methods in the theory of nuclear reactions

International Nuclear Information System (INIS)

Bencze, Gy.

1980-08-01

The traditional method of applying two-body methods for the study of nuclear reactions is briefly reviewed. The recent developments in the N particle scattering theory are described in detail. The application of the methods in the study of effective two and few-body problems is also considered. (P.L.)

Reaction kinetics for preparation of silica film with Stoeber method

International Nuclear Information System (INIS)

Shang Mengying; Jiang Xiaodong; Liu Miao; Luo Xuan; Tang Yongjian; Cao Linhong

2013-01-01

A new formula was proposed to investigate the relationship between reaction time and tetraethylorthosilicate (TEOS) conversion rate for preparation of silica sol with Stöber method, by studying the reaction kinetics of TEOS hydrolytic process. An appropriate conversion rate was then determined and used to calculate the theoretical optimal reaction time. Meanwhile, silica sols were prepared by sol-gel process using TEOS as precursor and ammonia as catalyst. It was found that the reaction time decreases with an increasing amount of ammonia and water. The values of experimental optimal reaction time were obtained, and agree with the theoretical results (the errors are within 5%), which shows good applicability of our formula. (authors)

Ab initio study on electron excitation and electron transfer in tryptophan-tyrosine system

International Nuclear Information System (INIS)

Tong Jing; Li Xiangyuan

2002-01-01

In this article, ab initio calculation has been performed to evaluate the transition energy of electronic excitation in tryptophan and tyrosine by using semiempirical molecular orbital method AM1 and complete active space self-consistent field method. The solvent effect has been considered by means of the conductor-like screening model. After geometric optimizations of isolated tryptophan and tyrosine, and their corresponding radicals and cations, reaction heat of these electron transfer reactions have been obtained by the means of complete active space self-consistent field method. The transition energies from the ground state, respectively, to the lowest excited state and to the lowest triplet state of these two amino acids are also calculated and compared with the experimentally observed values. The ionization potential and electron affinity are also calculated for tryptophan and tyrosine employing Koopmans' theorem and ab initio calculation. Compared with the experimental measurements, the theoretical results are found satisfactory. Theoretical results give good explanations on the experimental phenomena that N 3 · can preferably oxide the side chain of tryptophan residue and then the electron transfer from tyrosine residue to tryptophan residue follows in peptides involving tryptophan and tyrosine

Neutron-induced cross sections of actinides via the surrogate-reaction method

Directory of Open Access Journals (Sweden)

Tveten G. M.

2013-03-01

Full Text Available The surrogate-reaction method is an indirect way of determining cross sections for reactions that proceed through a compound nucleus. This technique may enable neutron-induced cross sections to be extracted for short-lived nuclei that otherwise cannot be measured. However, the validity of the surrogate method for extracting capture cross sections has to be investigated. In this work we study the reactions 238U(d,p239U, 238U(3He,t238Np, 238U(3He,4He237U as surrogates for neutroninduced reactions on 238U, 237Np and 236U, respectively, for which good quality data exist. The experimental set-up enabled the measurement of fission and gamma-decay probabilities. First results are presented and discussed.

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

Thermonuclear reaction generation method and device

International Nuclear Information System (INIS)

Imazaki, Kazuo

1998-01-01

The present invention provides a method of and a device for causing thermonuclear reaction capable of obtaining extremely high profits (about 1000 times), capable of forming a target which is strong against instability upon implosion as a problem of an inertia process and capable of realizing utilization of nuclear fusion. Namely, elementary particles such as pion, muon and K particles are deposited a portion or some portion of thermonuclear fuel materials by using high energy ions and highly brilliant γ rays generated from a high energy accelerator. The thermonuclear fuel materials are compressed to high density. The nuclear fusion reaction is promoted to ignite and burn thermonuclear fuels. A portion of nuclear fuels is ignited selectively by the means. High profits can be obtained. Since there is no need to attain implosion rate required for self ignition of nuclear fuels, a target of low aspect ratio can be used. (I.S.)

Method of operating a thermal engine powered by a chemical reaction

Science.gov (United States)

Ross, J.; Escher, C.

1988-06-07

The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction. 7 figs.

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.

Discussion of the experimental methods of the estimation of the reaction impact parameter

International Nuclear Information System (INIS)

Muryn, B.; Dziunikowska, K.; Eskreys, A.; Coghen, T.

1978-01-01

Two methods of determination of the reaction impact parameter, the one proposed by Webber and other by Henyey and Pumplin, are compared and discussed. It is shown that the lower limits of the impact parameter bsub(L) obtained by means of these methods are comparable and are always very low (approximately < 0.5 fm). On the example of the Henyey - Pumplin method it is argued that the experimentally obtained values bsub(L) may be very unreliable estimates of the reaction impact parameter and that any comparison of different reactions or reactions channels may be meaningless. (author)

Statistical methods of spin assignment in compound nuclear reactions

International Nuclear Information System (INIS)

Mach, H.; Johns, M.W.

1984-01-01

Spin assignment to nuclear levels can be obtained from standard in-beam gamma-ray spectroscopy techniques and in the case of compound nuclear reactions can be complemented by statistical methods. These are based on a correlation pattern between level spin and gamma-ray intensities feeding low-lying levels. Three types of intensity and level spin correlations are found suitable for spin assignment: shapes of the excitation functions, ratio of intensity at two beam energies or populated in two different reactions, and feeding distributions. Various empirical attempts are examined and the range of applicability of these methods as well as the limitations associated with them are given. 12 references

Statistical methods of spin assignment in compound nuclear reactions

International Nuclear Information System (INIS)

Mach, H.; Johns, M.W.

1985-01-01

Spin assignment to nuclear levels can be obtained from standard in-beam gamma-ray spectroscopy techniques and in the case of compound nuclear reactions can be complemented by statistical methods. These are based on a correlation pattern between level spin and gamma-ray intensities feeding low-lying levels. Three types of intensity and level spin correlations are found suitable for spin assignment: shapes of the excitation functions, ratio of intensity at two beam energies or populated in two different reactions, and feeding distributions. Various empirical attempts are examined and the range of applicability of these methods as well as the limitations associated with them are given

Effect of reaction time on structural, morphology and optical properties of ZnO nanoflakes prepared by chemical bath deposition method

Energy Technology Data Exchange (ETDEWEB)

Molefe, F.V.; Koao, L.F., E-mail: koaolf@qwa.ufs.ac.za; Dolo, J.J.; Dejene, B.F.

2014-04-15

ZnO nanoflakes have been successfully synthesized by the chemical bath deposition (CBD) method for different reaction times. X-ray diffraction (XRD) results confirm the initial formation of the cubic ZnO structure. However, increasing the reaction time resulted into the emergence of the well-known hexagonal wurtzite structure of ZnO. Scanning electron microscopy images showed the presence of agglomerated nanoflakes. The morphology was found not to depend on synthesis time. UV–vis spectra showed a partially increase in the percentage reflectance and the absorption edges red shifted to the higher wavelength with an increase in synthesis time. The highest band gap energy was obtained for ZnO synthesized for 1 min, with its estimated band gap energy of 3.91±0.08 eV. The estimated band gap decreased with an increase in the reaction time. The photoluminescent intensity of the emission peak at 473 nm decreased with an increase in reaction time.

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

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.

Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

2016-02-28

Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

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.

A method for carrying out radiolysis and chemical reactions by means of the radiations resulting from a thermonuclear reaction

International Nuclear Information System (INIS)

Gomberg, H.J.

1974-01-01

The invention relates to the use of the radiations resulting from thermonuclear reactions. It deals with a method comprising a combination of thermo-chemical and radiolytic reactions for treating a molecule having a high absorption rate, by the radiations of a thermonuclear reaction. This is applicable to the dissociation of water into oxygen and hydrogen [fr

The effect of B{sub 2}O{sub 3} flux on growth NLBCO superconductor by solid state reaction and wet-mixing methods

Energy Technology Data Exchange (ETDEWEB)

Suharta, W. G., E-mail: wgsuharta@gmail.com; Wendri, N.; Ratini, N.; Suarbawa, K. N. [Departement of Physics Faculty of Mathematics and Natural Science Udayana University Bali Indonesia (Indonesia)

2016-03-11

The synthesis of B{sub 2}O{sub 3} flux substituted NLBCO superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} has been done using solid state reaction and wet-mixing methods in order to obtain homogeneous crystals and single phase. From DTA/TGA characteritations showed the synthesis process by wet-mixing requires a lower temperature than the solid state reaction in growing the superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂}. Therefore, in this research NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} sample calcinated at 650°C for wet-mixing method and 820°C for solid state reaction methods. The all samples was sintered at 950°C for ten hours. Crystallinity of the sample was confirmed using X-ray techniques and generally obtained sharp peaks that indicates the sample already well crystallized. Search match analyses for diffraction data gave weight fractions of impurity phase of the solid state reaction method higher than wet-mixing method. In this research showed decreasing the price of the lattice parameter about 1% with the addition of B{sub 2}O{sub 3} flux for the both synthesis process and 2% of wet mixing process for all samples. Characterization using scanning electron microscopy (SEM) showed the distribution of crystal zise for wet-mixing method more homogeneous than solid state reaction method, with he grain size of samples is around 150–250 nm. The results of vibrating sample magnetometer (VSM) showed the paramagnetic properties for all samples.

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.

The synthesis method for design of electron flow sources

Science.gov (United States)

Alexahin, Yu I.; Molodozhenzev, A. Yu

1997-01-01

The synthesis method to design a relativistic magnetically - focused beam source is described in this paper. It allows to find a shape of electrodes necessary to produce laminar space charge flows. Electron guns with shielded cathodes designed with this method were analyzed using the EGUN code. The obtained results have shown the coincidence of the synthesis and analysis calculations [1]. This method of electron gun calculation may be applied for immersed electron flows - of interest for the EBIS electron gun design.

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

produire Tl{sup II}, les auteurs ont utilise une absorption selective avec transfert de charges a 2537 A au moyen de la paire d'ions Tl{sup 3+}. OH{sup -}. L'echange avec Tl{sup +} qui s'ensuit presente des periodes d'induction bien marquees; il est sensible aux concentrations micromolaires en oxydants et en reducteurs. Pour des concentrations millimolaires en Tl{sup +} et Tl{sup 3+} , les rendements quantiques observes sont directement proportionnels ie ces concentrations. Pour de plus fortes concentrations, la courbe des valeurs du rendement quantique presente un plateau dont le niveau se situe entre 6 et 30, selon l'intensite de la lumiere absorbee, La valeur de plateau du rendement quantique constitue une mesure directe des vitesses relatives des reactions de propagation Tl{sup +} + Tl{sup 2+} -> Tl{sup 2+} + T1+ and Tl{sup 2+} + Tl{sup 3+} -> Tl{sup 3+} + Tl{sup 2+} comparees ie la reaction de terminaison 2 Tl{sup 2+} -> Tl{sup +} + Tl{sup 3+}. Cette reaction de dismutation est compatible avec un exposant de 0,50 pour l'intensite de la lumiere, que l'on peut observer dans des solutions rigoureusement pures des corps en reaction. Toutefois, dans les solutions contenant des concentrations micromolaires d'impuretes, cet exposant peut aller jusqu'a 0,70 en raison de l'importance de la reaction de balayage Tl{sup 2}+ + S ->Tl{sup +} (or Tl{sup 3+}) + S'. Jusqu'a present, la courte duree de vie de Tl{sup 2+} (qui se mesure probablement millisecondes) n'a pas permis de mesurer la vitesse de la reaction de dismutation de Tl{sup 2+} par les methodes des secteurs en rotation. Les auteurs discutent les vitesses relatives de ces echanges par transfert d'electrons en invoquant des theories fondees sur l'effet tunnel. Ils montrent que le rendement quantique primaire observe pour la reaction Tl{sup 3+}. OH{sup -} + hv -> Tl{sup 2+} + OH est compatible avec la theorie de Noyes sur la diffusion de radicaux gemines. (author) [Spanish] La absorcion de luz de una longitud de onda

Direct determination of enthalpies of solid phase reactions by immersion method; Determination directe des enthalpies de reaction en phase solide par une methode de plongee

Energy Technology Data Exchange (ETDEWEB)

Roux, A; Richard, M; Eyraud, L; Stevanovic, M; Elston, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1967-07-01

It is not generally possible to measure the enthalpy change corresponding to solid phase reactions using the dynamic differential thermal analysis method because these reactions are usually too slow at the temperature of operation of present equipment. A ballistic differential thermal analysis apparatus has been developed which is based on an immersion-compensation method; it overcomes the difficulties previously encountered. This apparatus has been used after calibration for determining the enthalpies of formation of calcium and cadmium titanates. and also the Wigner energies of BeO, MgO and Al{sub 2}O{sub 3} samples irradiated at variable dose at a temperature of under 100 deg. C. (authors) [French] Il n'est generalement pas possible de mesurer la variation d'enthalpie correspondant aux reactions en phase solide par la methode d'analyse thermique differentielle dynamique. En effet, ces reactions sont le plus souvent trop lentes aux temperatures d'utilisation des dispositifs actuels. Un appareil d'analyse thermique differentielle balistique, base sur une methode de plongee avec compensation, a ete mis au point et permet de surmonter les difficultes precedentes. Apres etalonnages, cet appareil a ete utilise pour la determination des enthalpies de formation du titanate de calcium et du titanate de cadmium ainsi que pour celle des energies Wigner emmagasinees dans des echantillons de BeO, MgO et Al{sub 2}O{sub 3} irradies a une temperature inferieure a 100 deg. C et a differentes doses. (auteurs)

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-03-02

This is the final technical report for a project carried out at Tulane University of New Orleans that describes the development of light induced (solar) reactions geared toward decomposing water into its component elements : hydrogen and oxygen. Much of the work involved optimizing systems for absorbing visible light and undergoing light promoted reactions to generate very strong reducing agents that are capable of reacting with water to produce hydrogen. Additional portions of the research were collaborative efforts to put the strong reducing agents to work in reaction with hydrogen generation catalysts prepared elsewhere. Time resolved laser spectroscopic methods were used to evaluate the light induced reactions and characterize very reactive intermediate substances formed during the reactions.

Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

OpenAIRE

Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

2018-01-01

The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

Efficient electronic structure methods applied to metal nanoparticles

DEFF Research Database (Denmark)

Larsen, Ask Hjorth

of efficient approaches to density functional theory and the application of these methods to metal nanoparticles. We describe the formalism and implementation of localized atom-centered basis sets within the projector augmented wave method. Basis sets allow for a dramatic increase in performance compared....... The basis set method is used to study the electronic effects for the contiguous range of clusters up to several hundred atoms. The s-electrons hybridize to form electronic shells consistent with the jellium model, leading to electronic magic numbers for clusters with full shells. Large electronic gaps...... and jumps in Fermi level near magic numbers can lead to alkali-like or halogen-like behaviour when main-group atoms adsorb onto gold clusters. A non-self-consistent NewnsAnderson model is used to more closely study the chemisorption of main-group atoms on magic-number Au clusters. The behaviour at magic...

Electron emission from transfer ionization reaction in 30 keV amu‑1 He 2+ on Ar collision

Science.gov (United States)

Amaya-Tapia, A.; Antillón, A.; Estrada, C. D.

2018-06-01

A model is presented that describes the transfer ionization process in H{e}2++Ar collision at a projectile energy of 30 keV amu‑1. It is based on a semiclassical independent-particle close-coupling method that yields a reasonable agreement between calculated and experimental values of the total single-ionization and single-capture cross sections. It is found that the transfer ionization reaction is predominantly carried out through simultaneous capture and ionization, rather than by sequential processes. The transfer-ionization differential cross section in energy that is obtained satisfactorily reproduces the global behavior of the experimental data. Additionally, the probabilities of capture and ionization as function of the impact parameter for H{e}2++A{r}+ and H{e}++A{r}+ collisions are calculated, as far as we know, for the first time. The results suggest that the model captures essential elements that describe the two-electron transfer ionization process and could be applied to systems and processes of two electrons.

The determination methods of the velocity constant for electrochemical reactions

International Nuclear Information System (INIS)

Molina, R.

1963-01-01

In a brief introduction are recalled the fundamental mechanisms of the electrochemical reaction and the definition of the intrinsic velocity constant of a such reaction. By the nature of the different parameters which enter in this definition are due some experimental problems which are examined. Then are given the principles of the measurement methods of the velocity constant. These methods are developed with the mathematical expression of the different rates of the mass transfer to an electrode. In each case are given the experimental limits of use of the methods and the size order of the velocity constant that can be reached. A list of fundamental works to be consulted conclude this work. (O.M.) [fr

Application of the Trojan Horse Method to study neutron induced reactions: the 17O(n, α14C reaction

Directory of Open Access Journals (Sweden)

Gulino M.

2014-03-01

Full Text Available The reaction 17O(n, α14C was studied using virtual neutrons coming from the quasi-free deuteron break-up in the three body reaction 17O+d → α+14C+p. This technique, called virtual neutron method, extends the Trojan Horse method to neutron-induced reactions allowing to study the reaction cross section avoiding the suppression effects coming from the penetrability of the centrifugal barrier. For incident neutron energies from thermal up to a few hundred keV, direct experiments have shown the population of two out of three expected excited states at energies 8213 keV and 8282 keV and the influence of the sub-threshold level at 8038 keV. In the present experiment the 18O excited state at E* = 8.125 MeV, missing in the direct measurement, is observed. The angular distributions of the populated resonances have been measured for the first time. The results unambiguously indicate the ability of the method to overcome the centrifugal barrier suppression effect and to pick out the contribution of the bare nuclear interaction.

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.

14 CFR 1260.69 - Electronic funds transfer payment methods.

Science.gov (United States)

2010-01-01

... Government by electronic funds transfer through the Treasury Fedline Payment System (FEDLINE) or the... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS General Special Conditions § 1260.69 Electronic funds transfer payment methods...

Reaction mechanisms for enhancing carbon dioxide mineral sequestration

Science.gov (United States)

Jarvis, Karalee Ann

Increasing global temperature resulting from the increased release of carbon dioxide into the atmosphere is one of the greatest problems facing society. Nevertheless, coal plants remain the largest source of electrical energy and carbon dioxide gas. For this reason, researchers are searching for methods to reduce carbon dioxide emissions into the atmosphere from the combustion of coal. Mineral sequestration of carbon dioxide reacted in electrolyte solutions at 185°C and 2200 psi with olivine (magnesium silicate) has been shown to produce environmentally benign carbonates. However, to make this method feasible for industrial applications, the reaction rate needs to be increased. Two methods were employed to increase the rate of mineral sequestration: reactant composition and concentration were altered independently in various runs. The products were analyzed with complete combustion for total carbon content. Crystalline phases in the product were analyzed with Debye-Scherrer X-ray powder diffraction. To understand the reaction mechanism, single crystals of San Carlos Olivine were reacted in two solutions: (0.64 M NaHCO3/1 M NaCl) and (5.5 M KHCO3) and analyzed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and fluctuation electron microscopy (FEM) to study the surface morphology, atomic crystalline structure, composition and amorphous structure. From solution chemistry studies, it was found that increasing the activity of the bicarbonate ion increased the conversion rate of carbon dioxide to magnesite. The fastest conversion, 60% conversion in one hour, occurred in a solution of 5.5 M KHCO3. The reaction product particles, magnesium carbonate, significantly increased in both number density and size on the coupon when the bicarbonate ion activity was increased. During some experiments reaction vessel corrosion also altered the mineral sequestration mechanism. Nickel ions from vessel

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.

Variational methods in electron-atom scattering theory

CERN Document Server

Nesbet, Robert K

1980-01-01

The investigation of scattering phenomena is a major theme of modern physics. A scattered particle provides a dynamical probe of the target system. The practical problem of interest here is the scattering of a low­ energy electron by an N-electron atom. It has been difficult in this area of study to achieve theoretical results that are even qualitatively correct, yet quantitative accuracy is often needed as an adjunct to experiment. The present book describes a quantitative theoretical method, or class of methods, that has been applied effectively to this problem. Quantum mechanical theory relevant to the scattering of an electron by an N-electron atom, which may gain or lose energy in the process, is summarized in Chapter 1. The variational theory itself is presented in Chapter 2, both as currently used and in forms that may facilitate future applications. The theory of multichannel resonance and threshold effects, which provide a rich structure to observed electron-atom scattering data, is presented in Cha...

System for cooling hybrid vehicle electronics, method for cooling hybrid vehicle electronics

Science.gov (United States)

France, David M.; Yu, Wenhua; Singh, Dileep; Zhao, Weihuan

2017-11-21

The invention provides a single radiator cooling system for use in hybrid electric vehicles, the system comprising a surface in thermal communication with electronics, and subcooled boiling fluid contacting the surface. The invention also provides a single radiator method for simultaneously cooling electronics and an internal combustion engine in a hybrid electric vehicle, the method comprising separating a coolant fluid into a first portion and a second portion; directing the first portion to the electronics and the second portion to the internal combustion engine for a time sufficient to maintain the temperature of the electronics at or below 175.degree. C.; combining the first and second portion to reestablish the coolant fluid; and treating the reestablished coolant fluid to the single radiator for a time sufficient to decrease the temperature of the reestablished coolant fluid to the temperature it had before separation.

Method for coating a resinous coating material. [electron beam irradiation

Energy Technology Data Exchange (ETDEWEB)

Ino, T; Fujioka, S; Mibae, J; Takahashi, M

1968-07-13

The strength, flexibility and durability of a vinyl chloride resin, acryl resin and the like are improved. This method of application comprises the steps of applying and thereafter radically curing a mixture composed of a polymer (II) having double bond(s) on its side chain and an ethylenic unsaturated monomer, said polymer (II) being obtained by the reaction between an unsaturated carboxylic acid or anhydride represented by the formula XCH = CHY (X = (CH/sub 2/)sub(n)COOH, where 0 <= n <= 2, Y = COOR/sub 1/ or R/sub 2/(R/sub 1/ and R/sub 2/ are hydrogen or an alkyl group having from 1 to 10 atoms of carbon)) and the acrylic copolymer (I), containing a hydroxyl group, obtained by copolymerization of 10 to 50% by weight of at least one selected from the group of beta-hydroxy alkyl acrylate, beta-hydroxy alkyl methacrylate, N-methylol acrylamide and N-methylol methacryl amide with at least one selected from the group of acrylic ester, methacrylic ester and stylene. The copolymer (I) can be obtained by the usual radical polymerization such as bulk polymerization, solution polymerization, suspension polymerization or the like. The polymer (II) is dissolved in the ethylenic unsaturated monomer and radically cured with radical polymerization catalysts or electron beams, etc. The energy range of the electron beams may be 0.1 to 3 MeV. Any type of electron accelerator may be used.

Final-photon polarization in the scattering of photons by high-energy electrons

International Nuclear Information System (INIS)

Choi, J.; Choi, S.Y.; Ie, S.H.; Song, H.S.; Good, R.H. Jr.

1987-01-01

A general method for calculating the polarization of the outgoing photon beam in any reaction is presented. As an example the method is applied to the high-energy photon beam produced in Compton scattering of a laser beam by a high-energy electron beam. The Stokes parameters of the outgoing photon beam, relative to a unit vector normal to the photon momentum and including their dependence on the polarization of incident photon and electron beams, are obtained explicitly. It is expected that this method will be useful, both in photon production reactions and in the subsequent high-energy photon reactions

Method for calculating the characteristics of nuclear reactions with composite particle

International Nuclear Information System (INIS)

Zelenskaya, N.S.

1978-01-01

The purpose of the lectures is to attempt to give a brief review of the present status of the theory of nuclear reactions involving composite particles (heavy ions, 6 Li, 7 Li, and 9 Be ions, α-particles). In order to analyze such reactions, one should employ and ''exact'' method of distorted waves with a finite radius of interaction. Since the zero radius approximation is valid only at low momentum transfer, its rejection immediately includes all possible transferred momenta and consequently, the reaction mechanisms different from the usual cluster stripping we shall discuss a sufficiently general formalism of the distorted waves method, which does not use additional assumptions about the smaliness of the region of interaction between particles and about the possible reaction mechanisms. We shall also discuss all physical simplifications introduced in specific particular codes and the ranges of their applicability will be established. (author)

Large-scale photochemical reactions of nanocrystalline suspensions: a promising green chemistry method.

Science.gov (United States)

Veerman, Marcel; Resendiz, Marino J E; Garcia-Garibay, Miguel A

2006-06-08

Photochemical reactions in the solid state can be scaled up from a few milligrams to 10 grams by using colloidal suspensions of a photoactive molecular crystal prepared by the solvent shift method. Pure products are recovered by filtration, and the use of H(2)O as a suspension medium makes this method a very attractive one from a green chemistry perspective. Using the photodecarbonylation of dicumyl ketone (DCK) as a test system, we show that reaction efficiencies in colloidal suspensions rival those observed in solution. [reaction: see text

A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

Science.gov (United States)

Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

2018-03-01

Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.

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

Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method

International Nuclear Information System (INIS)

Franco, A.; Pessoni, H.V.S.; Soares, M.P.

2014-01-01

Nanoparticulate powders of Eu-doped ZnO with 1.0, 1.5, 2.0 and 3.0 at% Eu were synthesized by combustion reaction method using zinc nitrate, europium nitrate and urea as fuel without subsequent heat treatments. X-ray diffraction patterns (XRD) of all samples showed broad peaks consistent with the ZnO wurtzite structure. The absence of extra reflections in the diffraction patterns ensures the phase purity, except for x=0.03 that exhibits small reflection corresponding to Eu 2 O 3 phase. The average crystallite size determined from the most prominent (1 0 1) peak of the diffraction using Scherrer's equation was in good agreement with those determined by transmission electron microscopy (TEM); being ∼26 nm. The magnetic properties measurements were performed using a vibrating sample magnetometer (VSM) in magnetic fields up to 2.0 kOe at room temperature. The hysteresis loops, typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure can exist in the Eu-doped ZnO wurtzite structure at room temperature. The room temperature ferromagnetism behavior increases with the Eu 3+ doping concentration. All samples exhibited the same Curie temperature (T C ) around ∼726 K, except for x=0.01; T C ∼643 K. High resolution transmission electron microscopy (HRTEM) images revealed defects/strain in the lattice and grain boundaries of Eu-doped ZnO nanoparticulate powders. The origin of room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders was discussed in terms of these defects, which increase with the Eu 3+ doping concentration. - Highlights: • Room-temperature ferromagnetism. • Structural and magnetic properties of nanoparticulate powders of Zn 1−x Eu x O. • Combustion reaction method

A Reliable Method for the Evaluation of the Anaphylactoid Reaction Caused by Injectable Drugs

Directory of Open Access Journals (Sweden)

Fang Wang

2016-10-01

Full Text Available Adverse reactions of injectable drugs usually occur at first administration and are closely associated with the dosage and speed of injection. This phenomenon is correlated with the anaphylactoid reaction. However, up to now, study methods based on antigen detection have still not gained wide acceptance and single physiological indicators cannot be utilized to differentiate anaphylactoid reactions from allergic reactions and inflammatory reactions. In this study, a reliable method for the evaluation of anaphylactoid reactions caused by injectable drugs was established by using multiple physiological indicators. We used compound 48/80, ovalbumin and endotoxin as the sensitization agents to induce anaphylactoid, allergic and inflammatory reactions. Different experimental animals (guinea pig and nude rat and different modes of administration (intramuscular, intravenous and intraperitoneal injection and different times (15 min, 30 min and 60 min were evaluated to optimize the study protocol. The results showed that the optimal way to achieve sensitization involved treating guinea pigs with the different agents by intravenous injection for 30 min. Further, seven related humoral factors including 5-HT, SC5b-9, Bb, C4d, IL-6, C3a and histamine were detected by HPLC analysis and ELISA assay to determine their expression level. The results showed that five of them, including 5-HT, SC5b-9, Bb, C4d and IL-6, displayed significant differences between anaphylactoid, allergic and inflammatory reactions, which indicated that their combination could be used to distinguish these three reactions. Then different injectable drugs were used to verify this method and the results showed that the chosen indicators exhibited good correlation with the anaphylactoid reaction which indicated that the established method was both practical and reliable. Our research provides a feasible method for the diagnosis of the serious adverse reactions caused by injectable drugs which

Electron microscopy methods in studies of cultural heritage sites

Science.gov (United States)

Vasiliev, A. L.; Kovalchuk, M. V.; Yatsishina, E. B.

2016-11-01

The history of the development and application of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray microanalysis (EDXMA) in studies of cultural heritage sites is considered. In fact, investigations based on these methods began when electron microscopes became a commercial product. Currently, these methods, being developed and improved, help solve many historical enigmas. To date, electron microscopy combined with microanalysis makes it possible to investigate any object, from parchment and wooden articles to pigments, tools, and objects of art. Studies by these methods have revealed that some articles were made by ancient masters using ancient "nanotechnologies"; hence, their comprehensive analysis calls for the latest achievements in the corresponding instrumental methods and sample preparation techniques.

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)

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

Intramolecular and Transannular Diels-Alder Reactions

DEFF Research Database (Denmark)

Tanner, David Ackland; Ascic, Erhad

2014-01-01

Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

A Novel Computational Method to Reduce Leaky Reaction in DNA Strand Displacement

Directory of Open Access Journals (Sweden)

Xin Li

2015-01-01

Full Text Available DNA strand displacement technique is widely used in DNA programming, DNA biosensors, and gene analysis. In DNA strand displacement, leaky reactions can cause DNA signals decay and detecting DNA signals fails. The mostly used method to avoid leakage is cleaning up after upstream leaky reactions, and it remains a challenge to develop reliable DNA strand displacement technique with low leakage. In this work, we address the challenge by experimentally evaluating the basic factors, including reaction time, ratio of reactants, and ion concentration to the leakage in DNA strand displacement. Specifically, fluorescent probes and a hairpin structure reporting DNA strand are designed to detect the output of DNA strand displacement, and thus can evaluate the leakage of DNA strand displacement reactions with different reaction time, ratios of reactants, and ion concentrations. From the obtained data, mathematical models for evaluating leakage are achieved by curve derivation. As a result, it is obtained that long time incubation, high concentration of fuel strand, and inappropriate amount of ion concentration can weaken leaky reactions. This contributes to a method to set proper reaction conditions to reduce leakage in DNA strand displacement.

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.

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.

Methods for forming complex oxidation reaction products including superconducting articles

International Nuclear Information System (INIS)

Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

1992-01-01

This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

Electron microscopy methods in studies of cultural heritage sites

Energy Technology Data Exchange (ETDEWEB)

Vasiliev, A. L., E-mail: a.vasiliev56@gmail.com; Kovalchuk, M. V.; Yatsishina, E. B. [National Research Centre “Kurchatov Institute” (Russian Federation)

2016-11-15

The history of the development and application of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray microanalysis (EDXMA) in studies of cultural heritage sites is considered. In fact, investigations based on these methods began when electron microscopes became a commercial product. Currently, these methods, being developed and improved, help solve many historical enigmas. To date, electron microscopy combined with microanalysis makes it possible to investigate any object, from parchment and wooden articles to pigments, tools, and objects of art. Studies by these methods have revealed that some articles were made by ancient masters using ancient “nanotechnologies”; hence, their comprehensive analysis calls for the latest achievements in the corresponding instrumental methods and sample preparation techniques.

Electron microscopy methods in studies of cultural heritage sites

International Nuclear Information System (INIS)

Vasiliev, A. L.; Kovalchuk, M. V.; Yatsishina, E. B.

2016-01-01

The history of the development and application of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray microanalysis (EDXMA) in studies of cultural heritage sites is considered. In fact, investigations based on these methods began when electron microscopes became a commercial product. Currently, these methods, being developed and improved, help solve many historical enigmas. To date, electron microscopy combined with microanalysis makes it possible to investigate any object, from parchment and wooden articles to pigments, tools, and objects of art. Studies by these methods have revealed that some articles were made by ancient masters using ancient “nanotechnologies”; hence, their comprehensive analysis calls for the latest achievements in the corresponding instrumental methods and sample preparation techniques.

Computational methods of electron/photon transport

International Nuclear Information System (INIS)

Mack, J.M.

1983-01-01

A review of computational methods simulating the non-plasma transport of electrons and their attendant cascades is presented. Remarks are mainly restricted to linearized formalisms at electron energies above 1 keV. The effectiveness of various metods is discussed including moments, point-kernel, invariant imbedding, discrete-ordinates, and Monte Carlo. Future research directions and the potential impact on various aspects of science and engineering are indicated

Observing the motion of electrons in atoms and molecules

International Nuclear Information System (INIS)

McCarthy, I.E.; Weigold, E.

1981-07-01

The dynamic electronic structure of atoms and molecules can be directly observed by means of the (e,2e) reaction, which measures the distribution of energies and momenta of two electrons in coincidence after a knockout reaction initiated by an electron beam of known momentum incident on a molecular gas target. The molecular state for each event is identified by the electron separation energy. The recoil momentum for each event is known from the difference of measured initial and final momenta. It has been verified that values of this momentum are equal under suitable conditions to the momentum of the electron in the target immediately before knockout. Thus the spherically-averaged electron momentum distribution for each molecular orbital is measured. This is directly related to molecular orbitals calculated by the methods of quantum chemistry. Properties of different types of molecules obtained by this method are discussed

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

Method of fabricating a cooled electronic system

Science.gov (United States)

Chainer, Timothy J; Gaynes, Michael A; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Schmidt, Roger R; Schultz, Mark D; Simco, Daniel P; Steinke, Mark E

2014-02-11

A method of fabricating a liquid-cooled electronic system is provided which includes an electronic assembly having an electronics card and a socket with a latch at one end. The latch facilitates securing of the card within the socket. The method includes providing a liquid-cooled cold rail at the one end of the socket, and a thermal spreader to couple the electronics card to the cold rail. The thermal spreader includes first and second thermal transfer plates coupled to first and second surfaces on opposite sides of the card, and thermally conductive extensions extending from end edges of the plates, which couple the respective transfer plates to the liquid-cooled cold rail. The extensions are disposed to the sides of the latch, and the card is securable within or removable from the socket using the latch without removing the cold rail or the thermal spreader.

An electron moiré method for a common SEM

Institute of Scientific and Technical Information of China (English)

Y.M.Xing; S.Kishimoto; Y.R.Zhao

2006-01-01

In the electron moiré method,a high-frequency grating is used to measure microscopic deformation,which promises significant potential applications for the method in the microscopic analysis of materials.However,a special beam scanning control device is required to produce a grating and generate a moiré fringe pattern for the scanning electron microscope (SEM).Because only a few SEMs used in the material science studies are equipped with this device,the use of the electron moiré method is limited.In this study,an electron moiré method for a common SEM without the beam control device is presented.A grating based on a multi-scanning concept is fabricated in any observing mode.A real-time moiré pattern can also be generated in the SEM or an optical filtering system.Without the beam control device being a prerequisite,the electron moiré method can be more widely used.The experimental results from three different types of SEMS show that high quality gratings with uniform lines and less pitch error can be fabricated by this method,and moiré patterns can also be correctly generated.

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...

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)

Method and apparatus for controlling gas evolution from chemical reactions

Science.gov (United States)

Skorpik, James R.; Dodson, Michael G.

1999-01-01

The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846.

Cascading pressure reactor and method for solar-thermochemical reactions

Science.gov (United States)

Ermanoski, Ivan

2017-11-14

Reactors and methods for solar thermochemical reactions are disclosed. The reactors and methods include a cascade of reduction chambers at successively lower pressures that leads to over an order of magnitude pressure decrease compared to a single-chambered design. The resulting efficiency gains are substantial, and represent an important step toward practical and efficient solar fuel production on a large scale.

Method for conducting exothermic reactions

Science.gov (United States)

Smith, L. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-01-05

A liquid phase process for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Application of the singularity subtraction method for (d,p) reactions on light nuclei

International Nuclear Information System (INIS)

Borbely, I.

1974-01-01

It is shown that the method of subtraction the nearest singularity can be used successfully for data processing of (d,p) reactions. The data on the nuclear structure, thus obtained, can then be used for a more efficient study of the reaction mechanism with the use of traditional methods

Methods of Analysis of Electronic Money in Banks

Directory of Open Access Journals (Sweden)

Melnychenko Oleksandr V.

2014-03-01

Full Text Available The article identifies methods of analysis of electronic money, formalises its instruments and offers an integral indicator, which should be calculated by issuing banks and those banks, which carry out operations with electronic money, issued by other banks. Calculation of the integral indicator would allow complex assessment of activity of the studied bank with electronic money and would allow comparison of parameters of different banks by the aggregate of indicators for the study of the electronic money market, its level of development, etc. The article presents methods which envisage economic analysis of electronic money in banks by the following directions: solvency and liquidity, efficiency of electronic money issue, business activity of the bank and social responsibility. Moreover, the proposed indicators by each of the directions are offered to be taken into account when building integral indicators, with the help of which banks are studied: business activity, profitability, solvency, liquidity and so on.

Survey of electronic payment methods and systems

NARCIS (Netherlands)

Havinga, Paul J.M.; Smit, Gerardus Johannes Maria; Helme, A.; Verbraeck, A.

1996-01-01

In this paper an overview of electronic payment methods and systems is given. This survey is done as part of the Moby Dick project. Electronic payment systems can be grouped into three broad classes: traditional money transactions, digital currency and creditdebit payments. Such payment systems have

Development of an environmental high-voltage electron microscope for reaction science.

Science.gov (United States)

Tanaka, Nobuo; Usukura, Jiro; Kusunoki, Michiko; Saito, Yahachi; Sasaki, Katuhiro; Tanji, Takayoshi; Muto, Shunsuke; Arai, Shigeo

2013-02-01

Environmental transmission electron microscopy and ultra-high resolution electron microscopic observation using aberration correctors have recently emerged as topics of great interest. The former method is an extension of the so-called in situ electron microscopy that has been performed since the 1970s. Current research in this area has been focusing on dynamic observation with atomic resolution under gaseous atmospheres and in liquids. Since 2007, Nagoya University has been developing a new 1-MV high voltage (scanning) transmission electron microscope that can be used to observe nanomaterials under conditions that include the presence of gases, liquids and illuminating lights, and it can be also used to perform mechanical operations to nanometre-sized areas as well as electron tomography and elemental analysis by electron energy loss spectroscopy. The new instrument has been used to image and analyse various types of samples including biological ones.

First-principles method for electron-phonon coupling and electron mobility

DEFF Research Database (Denmark)

Gunst, Tue; Markussen, Troels; Stokbro, Kurt

2016-01-01

We present density functional theory calculations of the phonon-limited mobility in n-type monolayer graphene, silicene, and MoS2. The material properties, including the electron-phonon interaction, are calculated from first principles. We provide a detailed description of the normalized full......-band relaxation time approximation for the linearized Boltzmann transport equation (BTE) that includes inelastic scattering processes. The bulk electron-phonon coupling is evaluated by a supercell method. The method employed is fully numerical and does therefore not require a semianalytic treatment of part...... of the problem and, importantly, it keeps the anisotropy information stored in the coupling as well as the band structure. In addition, we perform calculations of the low-field mobility and its dependence on carrier density and temperature to obtain a better understanding of transport in graphene, silicene...

Electron self-exchange in hemoglobins revealed by deutero-hemin substitution.

Science.gov (United States)

Athwal, Navjot Singh; Alagurajan, Jagannathan; Sturms, Ryan; Fulton, D Bruce; Andreotti, Amy H; Hargrove, Mark S

2015-09-01

Hemoglobins (phytoglobins) from rice plants (nsHb1) and from the cyanobacterium Synechocystis (PCC 6803) (SynHb) can reduce hydroxylamine with two electrons to form ammonium. The reaction requires intermolecular electron transfer between protein molecules, and rapid electron self-exchange might play a role in distinguishing these hemoglobins from others with slower reaction rates, such as myoglobin. A relatively rapid electron self-exchange rate constant has been measured for SynHb by NMR, but the rate constant for myoglobin is equivocal and a value for nsHb1 has not yet been measured. Here we report electron self-exchange rate constants for nsHb1 and Mb as a test of their role in hydroxylamine reduction. These proteins are not suitable for analysis by NMR ZZ exchange, so a method was developed that uses cross-reactions between each hemoglobin and its deutero-hemin substituted counterpart. The resulting electron transfer is between identical proteins with low driving forces and thus closely approximates true electron self-exchange. The reactions can be monitored spectrally due to the distinct spectra of the prosthetic groups, and from this electron self-exchange rate constants of 880 (SynHb), 2900 (nsHb1), and 0.05M(-1) s(-1) (Mb) have been measured for each hemoglobin. Calculations of cross-reactions using these values accurately predict hydroxylamine reduction rates for each protein, suggesting that electron self-exchange plays an important role in the reaction. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

EDM 1.0: electron direct methods.

Science.gov (United States)

Kilaas, R; Marks, L D; Own, C S

2005-02-01

A computer program designed to provide a number of quantitative analysis tools for high-resolution imaging and electron diffraction data is described. The program includes basic image manipulation, both real space and reciprocal space image processing, Wiener-filtering, symmetry averaging, methods for quantification of electron diffraction patterns and two-dimensional direct methods. The program consists of a number of sub-programs written in a combination of C++, C and Fortran. It can be downloaded either as GNU source code or as binaries and has been compiled and verified on a wide range of platforms, both Unix based and PC's. Elements of the design philosophy as well as future possible extensions are described.

Simulation of weak polyelectrolytes: a comparison between the constant pH and the reaction ensemble method

Science.gov (United States)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-03-01

The reaction ensemble and the constant pH method are well-known chemical equilibrium approaches to simulate protonation and deprotonation reactions in classical molecular dynamics and Monte Carlo simulations. In this article, we demonstrate the similarity between both methods under certain conditions. We perform molecular dynamics simulations of a weak polyelectrolyte in order to compare the titration curves obtained by both approaches. Our findings reveal a good agreement between the methods when the reaction ensemble is used to sweep the reaction constant. Pronounced differences between the reaction ensemble and the constant pH method can be observed for stronger acids and bases in terms of adaptive pH values. These deviations are due to the presence of explicit protons in the reaction ensemble method which induce a screening of electrostatic interactions between the charged titrable groups of the polyelectrolyte. The outcomes of our simulation hint to a better applicability of the reaction ensemble method for systems in confined geometries and titrable groups in polyelectrolytes with different pKa values.

Photoinduced electron transfer in singly labeled thiouredopyrenetrisulfonate azurin derivatives

DEFF Research Database (Denmark)

Borovok, N; Kotlyar, A B; Pecht, I

1999-01-01

efficiency. TUPS derivatives of azurin, singly labeled at specific lysine residues, were prepared and purified to homogeneity by ion exchange HPLC. Transient absorption spectroscopy was used to directly monitor the rates of the electron transfer reaction from the photoexcited triplet state of TUPS to Cu......A novel method for the initiation of intramolecular electron transfer reactions in azurin is reported. The method is based on laser photoexcitation of covalently attached thiouredopyrenetrisulfonate (TUPS), the reaction that generates the low potential triplet state of the dye with high quantum......(II) and the back reaction from Cu(I) to the oxidized dye. For all singly labeled derivatives, the rate constants of copper ion reduction were one or two orders of magnitude larger than for its reoxidation, consistent with the larger thermodynamic driving force for the former process. Using 3-D coordinates...

Flexible barrier film, method of forming same, and organic electronic device including same

Science.gov (United States)

Blizzard, John; Tonge, James Steven; Weidner, William Kenneth

2013-03-26

A flexible barrier film has a thickness of from greater than zero to less than 5,000 nanometers and a water vapor transmission rate of no more than 1.times.10.sup.-2 g/m.sup.2/day at 22.degree. C. and 47% relative humidity. The flexible barrier film is formed from a composition, which comprises a multi-functional acrylate. The composition further comprises the reaction product of an alkoxy-functional organometallic compound and an alkoxy-functional organosilicon compound. A method of forming the flexible barrier film includes the steps of disposing the composition on a substrate and curing the composition to form the flexible barrier film. The flexible barrier film may be utilized in organic electronic devices.

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.

A novel method to quantify the activity of alcohol acetyltransferase Using a SnO2-based sensor of electronic nose.

Science.gov (United States)

Hu, Zhongqiu; Li, Xiaojing; Wang, Huxuan; Niu, Chen; Yuan, Yahong; Yue, Tianli

2016-07-15

Alcohol acetyltransferase (AATFase) extensively catalyzes the reactions of alcohols to acetic esters in microorganisms and plants. In this work, a novel method has been proposed to quantify the activity of AATFase using a SnO2-based sensor of electronic nose, which was determined on the basis of its higher sensitivity to the reducing alcohol than the oxidizing ester. The maximum value of the first-derivative of the signals from the SnO2-based sensor was therein found to be an eigenvalue of isoamyl alcohol concentration. Quadratic polynomial regression perfectly fitted the correlation between the eigenvalue and the isoamyl alcohol concentration. The method was used to determine the AATFase activity in this type of reaction by calculating the conversion rate of isoamyl alcohol. The proposed method has been successfully applied to determine the AATFase activity of a cider yeast strain. Compared with GC-MS, the method shows promises with ideal recovery and low cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ground-State Electronic Structure of RC-LH1 and LH2 Pigment Assemblies of Purple Bacteria via the EBF-MO Method.

Science.gov (United States)

Shrestha, Kushal; Jakubikova, Elena

2015-08-20

Light-harvesting antennas are protein-pigment complexes that play a crucial role in natural photosynthesis. The antenna complexes absorb light and transfer energy to photosynthetic reaction centers where charge separation occurs. This work focuses on computational studies of the electronic structure of the pigment networks of light-harvesting complex I (LH1), LH1 with the reaction center (RC-LH1), and light-harvesting complex II (LH2) found in purple bacteria. As the pigment networks of LH1, RC-LH1, and LH2 contain thousands of atoms, conventional density functional theory (DFT) and ab initio calculations of these systems are not computationally feasible. Therefore, we utilize DFT in conjunction with the energy-based fragmentation with molecular orbitals method and a semiempirical approach employing the extended Hückel model Hamiltonian to determine the electronic properties of these pigment assemblies. Our calculations provide a deeper understanding of the electronic structure of natural light-harvesting complexes, especially their pigment networks, which could assist in rational design of artificial photosynthetic devices.

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

The Suzuki-Miyaura Cross-Coupling Reaction of Halogenated Aminopyrazoles: Method Development, Scope, and Mechanism of Dehalogenation Side Reaction.

Science.gov (United States)

Jedinák, Lukáš; Zátopková, Renáta; Zemánková, Hana; Šustková, Alena; Cankař, Petr

2017-01-06

The efficient Suzuki-Miyaura cross-coupling reaction of halogenated aminopyrazoles and their amides or ureas with a range of aryl, heteroaryl, and styryl boronic acids or esters has been developed. The method allowed incorporation of problematic substrates: aminopyrazoles bearing protected or unprotected pyrazole NH, as well as the free amino or N-amide group. Direct comparison of the chloro, bromo, and iodopyrazoles in the Suzuki-Miyaura reaction revealed that Br and Cl derivatives were superior to iodopyrazoles, as a result of reduced propensity to dehalogenation. Moreover, the mechanism and factors affecting the undesired dehalogenation side reaction were revealed.

Chemical methods and techniques to monitor early Maillard reaction in milk products; A review.

Science.gov (United States)

Aalaei, Kataneh; Rayner, Marilyn; Sjöholm, Ingegerd

2018-01-23

Maillard reaction is an extensively studied, yet unresolved chemical reaction that occurs as a result of application of the heat and during the storage of foods. The formation of advanced glycation end products (AGEs) has been the focus of several investigations recently. These molecules which are formed at the advanced stage of the Maillard reaction, are suspected to be involved in autoimmune diseases in humans. Therefore, understanding to which extent this reaction occurs in foods, is of vital significance. Because of their composition, milk products are ideal media for this reaction, especially when application of heat and prolonged storage are considered. Thus, in this work several chemical approaches to monitor this reaction in an early stage are reviewed. This is mostly done regarding available lysine blockage which takes place in the very beginning of the reaction. The most popular methods and their applications to various products are reviewed. The methods including their modifications are described in detail and their findings are discussed. The present paper provides an insight into the history of the most frequently-used methods and provides an overview on the indicators of the Maillard reaction in the early stage with its focus on milk products and especially milk powders.

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...

New method of ionization energy calculation for two-electron ions

International Nuclear Information System (INIS)

Ershov, D.K.

1997-01-01

A new method for calculation of the ionization energy of two-electron ions is proposed. The method is based on the calculation of the energy of second electron interaction with the field of an one-electron ion the potential of which is well known

Neutron-induced cross sections of short-lived nuclei via the surrogate reaction method

Directory of Open Access Journals (Sweden)

Morel P.

2011-10-01

Full Text Available The measurement of neutron-induced cross sections of short-lived nuclei is extremely difficult due to the radioactivity of the samples. The surrogate reaction method is an indirect way of determining cross sections for nuclear reactions that proceed through a compound nucleus. This method presents the advantage that the target material can be stable or less radioactive than the material required for a neutron-induced measurement. We have successfully used the surrogate reaction method to extract neutron-induced fission cross sections of various short-lived actinides. In this work, we investigate whether this technique can be used to determine neutron-induced capture cross sections in the rare-earth region.

Neutron-induced cross sections of short-lived nuclei via the surrogate reaction method

Directory of Open Access Journals (Sweden)

Tassan-Got L.

2012-02-01

Full Text Available The measurement of neutron-induced cross sections of short-lived nuclei is extremely difficult due to the radioactivity of the samples. The surrogate reaction method is an indirect way of determining cross sections for nuclear reactions that proceed through a compound nucleus. This method presents the advantage that the target material can be stable or less radioactive than the material required for a neutron-induced measurement. We have successfully used the surrogate reaction method to extract neutron-induced fission cross sections of various short-lived actinides. In this work, we investigate whether this technique can be used to determine neutron-induced capture cross sections in the rare-earth region.

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.

Method of identification of unbranched chain reaction with cross termination of chain

International Nuclear Information System (INIS)

Poluehktov, V.A.; Begishev, I.R.

1977-01-01

Gas-phase chlorination of unsymmetrical difluoroethane initiated by gamma quanta of Co 60 has been studied. At decreased temperatures the only hydrogen is replaced by a chlorine atom. Over a wide range of ratios of the initial reagents, the reaction occurs with a chain rupture. An analysis of the kinetics of such a reaction provides a method for identification of an unbranched chain reaction with a cross-rupture of the chain

Size and composition tunable Ag-Au alloy nanoparticles by replacement reactions

International Nuclear Information System (INIS)

Zhang Qingbo; Lee, J Y; Yang Jun; Boothroyd, Chris; Zhang Jixuan

2007-01-01

Ag-Au alloy nanoparticles with tunable size and composition were prepared by a replacement reaction between Ag nanoparticles and HAuCl 4 at elevated temperatures. The formation of homogeneous alloy nanoparticles was confirmed by selected-area energy-dispersive x-ray spectroscopy (SAEDX), UV-visible absorption spectroscopy, high resolution transmission electron microscopy (HRTEM) and electron diffraction. This method leverages upon the rapid interdiffusion of Ag and Au atoms in the reduced dimension of a nanoparticle, elevated temperatures and the large number of vacancy defects created in the replacement reaction. This method of preparation has several notable advantages: (1) independent tuning of the size and composition of alloy nanoparticles; (2) production of alloy nanoparticles in high concentrations; (3) general utility in the synthesis of alloy nanoparticles that cannot be obtained by the co-reduction method

A Practical Quantum Mechanics Molecular Mechanics Method for the Dynamical Study of Reactions in Biomolecules.

Science.gov (United States)

Mendieta-Moreno, Jesús I; Marcos-Alcalde, Iñigo; Trabada, Daniel G; Gómez-Puertas, Paulino; Ortega, José; Mendieta, Jesús

2015-01-01

Quantum mechanics/molecular mechanics (QM/MM) methods are excellent tools for the modeling of biomolecular reactions. Recently, we have implemented a new QM/MM method (Fireball/Amber), which combines an efficient density functional theory method (Fireball) and a well-recognized molecular dynamics package (Amber), offering an excellent balance between accuracy and sampling capabilities. Here, we present a detailed explanation of the Fireball method and Fireball/Amber implementation. We also discuss how this tool can be used to analyze reactions in biomolecules using steered molecular dynamics simulations. The potential of this approach is shown by the analysis of a reaction catalyzed by the enzyme triose-phosphate isomerase (TIM). The conformational space and energetic landscape for this reaction are analyzed without a priori assumptions about the protonation states of the different residues during the reaction. The results offer a detailed description of the reaction and reveal some new features of the catalytic mechanism. In particular, we find a new reaction mechanism that is characterized by the intramolecular proton transfer from O1 to O2 and the simultaneous proton transfer from Glu 165 to C2. Copyright © 2015 Elsevier Inc. 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.

Neutron-induced capture cross sections via the surrogate reaction method

International Nuclear Information System (INIS)

Boutoux, G.; Jurado, B.; Aiche, M.; Barreau, G.; Capellan, N.; Companis, I.; Czajkowski, S.; Dassie, D.; Haas, B.; Mathieu, L.; Meot, V.; Bail, A.; Bauge, E.; Daugas, J. M.; Faul, T.; Gaudefroy, L.; Morel, P.; Pillet, N.; Roig, O.; Romain, P.; Taieb, J.; Theroine, C.; Burke, J.T.; Companis, I.; Derkx, X.; Gunsing, F.; Matea, I.; Tassan-Got, L.; Porquet, M.G.; Serot, O.

2011-01-01

The surrogate reaction method is an indirect way of determining cross sections for nuclear reactions that proceed through a compound nucleus. This technique enables neutron-induced cross sections to be extracted for nuclear reactions on short-lived unstable nuclei that otherwise can not be measured. This technique has been successfully applied to determine the neutron-induced fission cross sections of several short-lived nuclei. In this work, we investigate whether this powerful technique can also be used to determine of neutron-induced capture cross sections. For this purpose we use the surrogate reaction 174 Yb( 3 He, pγ) 176 Lu to infer the well known 175 Lu(n, γ) cross section and compare the results with the directly measured neutron-induced data. This surrogate experiment has been performed in March 2010. The experimental technique used and the first preliminary results will be presented. (authors)

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.)

States of the electron in hydrocarbon liquids

International Nuclear Information System (INIS)

Mozumder, A.

2005-01-01

Some features of the stationary and dynamic states of the electron are critically examined. Outline of a quantum mechanical description of electron thermalization is attempted qualitatively. The effects of both the mean free path and the reaction inefficiency on electron-ion geminate escape probability are investigated by a recently developed Metropolis method. The trapped state is interpreted in terms of Anderson localization, yielding an approximate number of molecules interacting with the trapped electron

Site-Specific Protein Labeling Utilizing Lipoic Acid Ligase (LplA) and Bioorthogonal Inverse Electron Demand Diels-Alder Reaction.

Science.gov (United States)

Baalmann, Mathis; Best, Marcel; Wombacher, Richard

2018-01-01

Here, we describe a two-step protocol for selective protein labeling based on enzyme-mediated peptide labeling utilizing lipoic acid ligase (LplA) and bioorthogonal chemistry. The method can be applied to purified proteins, protein in cell lysates, as well as living cells. In a first step a W37V mutant of the lipoic acid ligase (LplA W37V ) from Escherichia coli is utilized to ligate a synthetic chemical handle site-specifically to a lysine residue in a 13 amino acid peptide motif-a short sequence that can be genetically expressed as a fusion with any protein of interest. In a second step, a molecular probe can be attached to the chemical handle in a bioorthogonal Diels-Alder reaction with inverse electron demand (DA inv ). This method is a complementary approach to protein labeling using genetic code expansion and circumvents larger protein tags while maintaining label specificity, providing experimental flexibility and straightforwardness.

Time-Dependent Close-Coupling Methods for Electron-Atom/Molecule Scattering

International Nuclear Information System (INIS)

Colgan, James

2014-01-01

The time-dependent close-coupling (TDCC) method centers on an accurate representation of the interaction between two outgoing electrons moving in the presence of a Coulomb field. It has been extensively applied to many problems of electrons, photons, and ions scattering from light atomic targets. Theoretical Description: The TDCC method centers on a solution of the time-dependent Schrödinger equation for two interacting electrons. The advantages of a time-dependent approach are two-fold; one treats the electron-electron interaction essentially in an exact manner (within numerical accuracy) and a time-dependent approach avoids the difficult boundary condition encountered when two free electrons move in a Coulomb field (the classic three-body Coulomb problem). The TDCC method has been applied to many fundamental atomic collision processes, including photon-, electron- and ion-impact ionization of light atoms. For application to electron-impact ionization of atomic systems, one decomposes the two-electron wavefunction in a partial wave expansion and represents the subsequent two-electron radial wavefunctions on a numerical lattice. The number of partial waves required to converge the ionization process depends on the energy of the incoming electron wavepacket and on the ionization threshold of the target atom or ion.

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

Science.gov (United States)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

Energy Technology Data Exchange (ETDEWEB)

Larsson, L G; Moeller, E; Purohit, S N

1966-03-15

The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

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)

Quantum theory of exchange reactions: Use of nonorthogonal bases and coordinates

International Nuclear Information System (INIS)

Stechel, E.B.; Schmalz, T.G.; Light, J.C.

1979-01-01

A general approach to quantum scattering theory of exchange reactions utilizing nonorthogonal (''over-complete'') basis sets and nonorthogonal coordinates is presented. The method is shown to resolve many of the formal and practical difficulties attending earlier theories. Although the inspiration came from the early and accurate work on the collinear H+H 2 reaction by Diestler possible applications include electron transfer processes as well as chemical exchange reactions. The mathematics is formulated in detail and the solution is presented in terms of the R-matrix propagation method preserving all the symmetries of the physical process, i.e., conservation of flux and microscopic reversibility

An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

DEFF Research Database (Denmark)

Schneider, E.; Hagen, A.; Grunwaldt, J.-D.

2004-01-01

A new method for modifying zeolites with zinc is proposed. The solid state redox reaction between metallic zinc and ZSM-5 zeolites with different Si/Al ratios was investigated by temperature programmed hydrogen evolution (TPHE), X-ray absorption near edge structure (XANES) and diffuse reflectance...... infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...... should be located at the same sites as in catalysts prepared by conventional methods. Combination of XANES and catalytic activity point to zinc being mainly present in tetrahedral geometry under reaction conditions....

The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

International Nuclear Information System (INIS)

Tumino, A.; Gulino, M.; Spitaleri, C.; Cherubini, S.; Romano, S.; Cognata, M. La; Pizzone, R. G.; Rapisarda, G. G.; Lamia, L.

2014-01-01

The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally

The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

Energy Technology Data Exchange (ETDEWEB)

Tumino, A.; Gulino, M. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania, Italy and Università degli Studi di Enna Kore, Enna (Italy); Spitaleri, C.; Cherubini, S.; Romano, S. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania, Italy and Dipartimento di Fisica e Astronomia, Università di Catania, Catania (Italy); Cognata, M. La; Pizzone, R. G.; Rapisarda, G. G. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania (Italy); Lamia, L. [Dipartimento di Fisica e Astronomia, Università di Catania, Catania (Italy)

2014-05-09

The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally.

Development and Application of Kinetic Spectrophotometric Method ...

African Journals Online (AJOL)

ISSN: 1596-5996 (print); 1596-9827 (electronic) ... Methods: The method is based on oxidation reaction of MNZ by hydrogen peroxide ... optimum operating conditions for reagent concentrations and temperature were ... 1-yl) ethanol] is an amebicide, antiprotozoal and .... The dependence of reaction rate on concentration of.

Method for controlling low-energy high current density electron beams

International Nuclear Information System (INIS)

Lee, J.N.; Oswald, R.B. Jr.

1977-01-01

A method and an apparatus for controlling the angle of incidence of low-energy, high current density electron beams are disclosed. The apparatus includes a current generating diode arrangement with a mesh anode for producing a drifting electron beam. An auxiliary grounded screen electrode is placed between the anode and a target for controlling the average angle of incidence of electrons in the drifting electron beam. According to the method of the present invention, movement of the auxiliary screen electrode relative to the target and the anode permits reliable and reproducible adjustment of the average angle of incidence of the electrons in low energy, high current density relativistic electron beams

Study of the Reaction Rate of Gold Nanotube Synthesis from Sacrificial Silver Nanorods through the Galvanic Replacement Method

Directory of Open Access Journals (Sweden)

Sunil Kwon

2010-01-01

Full Text Available An investigation was carried out about the gold nanotube synthesis via a galvanic replacement reaction. The progress of the gold nanotube synthesis was investigated using electron microscopy and UV-Vis spectroscopy. In addition, the reaction rates of gold nanotube formation in the early stage of the reaction were studied. The chlorine ion concentration linearly increased with the gold precursor concentration but deviated from the stoichiometric amounts. This deviation was probably due to AgCl precipitates formed by the reaction of chlorine ions with dissolved silver ions. The replacement reaction was promoted with increased temperature and was nonlinearly proportional to the gold ion concentration. The outcomes of this research will enhance the current understanding of the galvanic replacement reaction.

Electron correlation in highly-charged-ion collisions

International Nuclear Information System (INIS)

Hansen, J.P.; Taulbjerg, K.

1992-01-01

We have used the coupled-channel method to study the significance of electron correlation in the reaction mechanism for two-electron capture in C 5+ -He collisions. Two different sets of calculations were performed. While the static correlation energy was generally included in the calculations, further correlation effects were ignored in the first set of calculations. In the second set of calculations the so-called doubly excited symmetry basis (DESB) states were used to model the spatial electron correlation. The difference between the two sets of results is so profound that we can conclude that electron correlation plays an essential role in the reaction mechanism. The results of the DESB-based calculations are in good agreement with experimental data [Holt et al., Phys. Rev. A 43, 607 (1991)

Validated spectrophotometric methods for determination of Alendronate sodium in tablets through nucleophilic aromatic substitution reactions

Directory of Open Access Journals (Sweden)

Walash Mohamed I

2012-04-01

Full Text Available Abstract Background Alendronate (ALD is a member of the bisphosphonate family which is used for the treatment of osteoporosis, bone metastasis, Paget's disease, hypocalcaemia associated with malignancy and other conditions that feature bone fragility. ALD is a non-chromophoric compound so its determination by conventional spectrophotometric methods is not possible. So two derivatization reactions were proposed for determination of ALD through the reaction with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl and 2,4-dinitrofluorobenzene (DNFB as chromogenic derivatizing reagents. Results Three simple and sensitive spectrophotometric methods are described for the determination of ALD. Method I is based on the reaction of ALD with NBD-Cl. Method II involved heat-catalyzed derivatization of ALD with DNFB, while, Method III is based on micellar-catalyzed reaction of the studied drug with DNFB at room temperature. The reactions products were measured at 472, 378 and 374 nm, for methods I, II and III, respectively. Beer's law was obeyed over the concentration ranges of 1.0-20.0, 4.0-40.0 and 1.5-30.0 μg/mL with lower limits of detection of 0.09, 1.06 and 0.06 μg/mL for Methods I, II and III, respectively. The proposed methods were applied for quantitation of the studied drug in its pure form with mean percentage recoveries of 100.47 ± 1.12, 100.17 ± 1.21 and 99.23 ± 1.26 for Methods I, II and III, respectively. Moreover the proposed methods were successfully applied for determination of ALD in different tablets. Proposals of the reactions pathways have been postulated. Conclusion The proposed spectrophotometric methods provided sensitive, specific and inexpensive analytical procedures for determination of the non-chromophoric drug alendronate either per se or in its tablet dosage forms without interference from common excipients. Graphical abstract

The DQ and DQΦ electronic structure diabatization methods: Validation for general applications

Energy Technology Data Exchange (ETDEWEB)

Hoyer, Chad E.; Parker, Kelsey; Gagliardi, Laura, E-mail: gagliard@umn.edu, E-mail: truhlar@umn.edu; Truhlar, Donald G., E-mail: gagliard@umn.edu, E-mail: truhlar@umn.edu [Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431 (United States)

2016-05-21

We recently proposed the dipole-quadrupole (DQ) method for transforming adiabatic electronic states to diabatic states by using matrix elements of the dipole and quadrupole operators, and we applied the method to 3-state diabatizations of LiH and phenol. Here we extend the method to also include the electrostatic potential, and we call the resulting method the DQΦ method, which denotes the dipole–quadrupole–electrostatic-potential diabatization method. The electrostatic potential provides extra flexibility, and the goal of the present work is to test and illustrate the robustness of the methods for producing diabatic potential energy curves that tend to the adiabatic curves away from crossings and avoided crossings and are smooth in regions of crossings and avoided crossings. We illustrate the generality of the methods by an application to LiH with four states and by two-state diabatizations of HCl, (H{sub 2}){sub 2}, O{sub 3}, and the reaction Li + HF → LiF + H. We find that—if enough states are included—the DQ method does not have a significant dependence on the parameter weighting the quadrupole moment, and a geometry-independent value of 10 a{sub 0}{sup −2} is adequate in all cases tested. We also find that the addition of the electrostatic potential improves the diabatic potentials in some cases and provides an additional property useful for increasing the generality of the method for diabatization.

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

Method of determining the position of an irradiated electron beam

International Nuclear Information System (INIS)

Fukuda, Wataru.

1967-01-01

The present invention relates to the method of determining the position of a radiated electron beam, in particular, the method of detecting the position of a p-n junction by a novel method when irradiating the electron beam on to the semi-conductor wafer, controlling the position of the electron beam from said junction. When the electron beam is irradiated on to the semi-conductor wafer which possesses the p-n junction, the position of the p-n junction may be ascertained to determine the position of the irradiated electron beam by detecting the electromotive force resulting from said p-n junction with a metal disposed in the proximity of but without mechanical contact with said semi-conductor wafer. Furthermore, as far as a semi-conductor wafer having at least one p-n junction is concerned, the present invention allows said p-n junction to be used to determine the position of an irradiated electron beam. Thus, according to the present invention, the electromotive force of the electron beam resulting from the p-n junction may easily be detected by electrostatic coupling, enabling the position of the irradiated electron beam to be accurately determined. (Masui, R.)

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.

Method for the enzymatic production of hydrogen

Science.gov (United States)

Woodward, J.; Mattingly, S.M.

1999-08-24

The present invention is an enzymatic method for producing hydrogen comprising the steps of: (a) forming a reaction mixture within a reaction vessel comprising a substrate capable of undergoing oxidation within a catabolic reaction, such as glucose, galactose, xylose, mannose, sucrose, lactose, cellulose, xylan and starch; the reaction mixture also comprising an amount of glucose dehydrogenase in an amount sufficient to catalyze the oxidation of the substrate, an amount of hydrogenase sufficient to catalyze an electron-requiring reaction wherein a stoichiometric yield of hydrogen is produced, an amount of pH buffer in an amount sufficient to provide an environment that allows the hydrogenase and the glucose dehydrogenase to retain sufficient activity for the production of hydrogen to occur and also comprising an amount of nicotinamide adenine dinucleotide phosphate sufficient to transfer electrons from the catabolic reaction to the electron-requiring reaction; (b) heating the reaction mixture at a temperature sufficient for glucose dehydrogenase and the hydrogenase to retain sufficient activity and sufficient for the production of hydrogen to occur, and heating for a period of time that continues until the hydrogen is no longer produced by the reaction mixture, wherein the catabolic reaction and the electron-requiring reactions have rates of reaction dependent upon the temperature; and (c) detecting the hydrogen produced from the reaction mixture. 8 figs.

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Titanium

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method covers procedures for measuring reaction rates by the activation reactions 46Ti(n,p) 46Sc + 47Ti(n, np)46Sc. Note 1—Since the cross section for the (n,np) reaction is relatively small for energies less than 12 MeV and is not easily distinguished from that of the (n,p) reaction, this test method will refer to the (n,p) reaction only. 1.2 The reaction is useful for measuring neutrons with energies above approximately 4.4 MeV and for irradiation times up to about 250 days (for longer irradiations, see Practice E 261). 1.3 With suitable techniques, fission-neutron fluence rates above 109 cm–2·s–1 can be determined. However, in the presence of a high thermal-neutron fluence rate, 46Sc depletion should be investigated. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.6 This standard does not purport to address all...

Multilayer electronic component systems and methods of manufacture

Science.gov (United States)

Thompson, Dane (Inventor); Wang, Guoan (Inventor); Kingsley, Nickolas D. (Inventor); Papapolymerou, Ioannis (Inventor); Tentzeris, Emmanouil M. (Inventor); Bairavasubramanian, Ramanan (Inventor); DeJean, Gerald (Inventor); Li, RongLin (Inventor)

2010-01-01

Multilayer electronic component systems and methods of manufacture are provided. In this regard, an exemplary system comprises a first layer of liquid crystal polymer (LCP), first electronic components supported by the first layer, and a second layer of LCP. The first layer is attached to the second layer by thermal bonds. Additionally, at least a portion of the first electronic components are located between the first layer and the second layer.

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.

Trojan Horse Method: a useful tool for electron screening effect investigation

Energy Technology Data Exchange (ETDEWEB)

Pizzone, R.G.; Spitaleri, C.; Cherubini, S.; La Cognata, M.; Lamia, L.; Romano, S.; Sergi, M.L. [Laboratori Nazionali del Sud-INFN and DMFCI Universita di Catania, Catania (Italy); Tumino, A. [Universita Kore, Enna (Italy); Li, C.; Wen, Q.; Zhou, S. [Department of Nuclear Physics, CIAE, Beijing (China); Burjan, V.; Kroha, V.; Mrazek, J. [Cyclotron Institute, Academy of Science, Rez, Czech Rep. (Czech Republic); Carlin, N.; Gimenez del Santo, M.; Szanto de Toledo, A. [Departamento de Fisica, Universidad de Sao Paulo (Brazil); Kubono, S.; Wakabayashi, T.; Yamaguchi, H. [CNS, University of Tokyo, Wako (Japan)

2010-03-01

Direct measurements in the last decades have highlighted a new problem related to the lowering of the Coulomb barrier between the interacting nuclei due to the presence of the 'electron screening' in the laboratory measurements. It was systematically observed that the presence of the electronic cloud around the interacting ions in measurements of nuclear reactions cross sections at astrophysical energies gives rise to an enhancement of the astrophysical S(E)-factor as lower and lower energies are explored [H. Assenbaum, K. Langanke, C. Rolfs, Z. Phys. 327 (1987) 461]. Moreover, at present such an effect is not well understood as the value of the potential for screening extracted from these measurements is higher than the upper limit of theoretical predictions (adiabatic limit). On the other hand, the electron screening potential in laboratory measurement is different from that occurring in stellar plasmas thus the quantity of interest in astrophysics is the so-called 'bare nucleus cross section'. This quantity can only be extrapolated in direct measurements. These are the reasons that led to a considerable growth on interest in indirect measurement techniques and in particular the Trojan Horse Method (THM) [G. Baur, Phys. Lett. B 178, (1986) 135; S. Cherubini et al. Ap. J. 457, (1996) 855] Results concerning the bare nucleus cross sections measurements will be shown in several cases of astrophysical interest. In those cases the screening potential evaluated by means of the THM will be compared with the adiabatic limit and results arising from extrapolation in direct measurements.

14 CFR 1274.931 - Electronic funds transfer payment methods.

Science.gov (United States)

2010-01-01

... cooperative agreement will be made by the Government by electronic funds transfer through the Treasury Fedline... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.931 Electronic...

Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

Science.gov (United States)

Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

2011-10-01

When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

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

Fourier spectral methods for fractional-in-space reaction-diffusion equations

KAUST Repository

Bueno-Orovio, Alfonso; Kay, David; Burrage, Kevin

2014-01-01

approximation of these models is demanding and imposes a number of computational constraints. In this paper, we introduce Fourier spectral methods as an attractive and easy-to-code alternative for the integration of fractional-in-space reaction

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

A data driven method to measure electron charge mis-identification rate

CERN Document Server

Bakhshiansohi, Hamed

2009-01-01

Electron charge mis-measurement is an important challenge in analyses which depend on the charge of electron. To estimate the probability of {\\it electron charge mis-measurement} a data driven method is introduced and a good agreement with MC based methods is achieved.\\\\ The third moment of $\\phi$ distribution of hits in electron SuperCluster is studied. The correlation between this variable and the electron charge is also investigated. Using this `new' variable and some other variables the electron charge measurement is improved by two different approaches.

Resonating group method as applied to the spectroscopy of α-transfer reactions

Science.gov (United States)

Subbotin, V. B.; Semjonov, V. M.; Gridnev, K. A.; Hefter, E. F.

1983-10-01

In the conventional approach to α-transfer reactions the finite- and/or zero-range distorted-wave Born approximation is used in liaison with a macroscopic description of the captured α particle in the residual nucleus. Here the specific example of 16O(6Li,d)20Ne reactions at different projectile energies is taken to present a microscopic resonating group method analysis of the α particle in the final nucleus (for the reaction part the simple zero-range distorted-wave Born approximation is employed). In the discussion of suitable nucleon-nucleon interactions, force number one of the effective interactions presented by Volkov is shown to be most appropriate for the system considered. Application of the continuous analog of Newton's method to the evaluation of the resonating group method equations yields an increased accuracy with respect to traditional methods. The resonating group method description induces only minor changes in the structures of the angular distributions, but it does serve its purpose in yielding reliable and consistent spectroscopic information. NUCLEAR STRUCTURE 16O(6Li,d)20Ne; E=20 to 32 MeV; calculated B(E2); reduced widths, dσdΩ extracted α-spectroscopic factors. ZRDWBA with microscope RGM description of residual α particle in 20Ne; application of continuous analog of Newton's method; tested and applied Volkov force No. 1; direct mechanism.

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.

Thermodynamics, Gibbs Method and Statistical Physics of Electron Gases Gibbs Method and Statistical Physics of Electron Gases

CERN Document Server

Askerov, Bahram M

2010-01-01

This book deals with theoretical thermodynamics and the statistical physics of electron and particle gases. While treating the laws of thermodynamics from both classical and quantum theoretical viewpoints, it posits that the basis of the statistical theory of macroscopic properties of a system is the microcanonical distribution of isolated systems, from which all canonical distributions stem. To calculate the free energy, the Gibbs method is applied to ideal and non-ideal gases, and also to a crystalline solid. Considerable attention is paid to the Fermi-Dirac and Bose-Einstein quantum statistics and its application to different quantum gases, and electron gas in both metals and semiconductors is considered in a nonequilibrium state. A separate chapter treats the statistical theory of thermodynamic properties of an electron gas in a quantizing magnetic field.

On possibility of transuranium element by the method of transport reactions

International Nuclear Information System (INIS)

Sinitsyna, G.S.; Krashenitsyn, G.N.; Shestakov, B.I.

1983-01-01

A possibility to use chemical transport reaction for separation of uranium, plutonium and some transplutonium elements is shown. The method is based on the use of the known plutonium property to form tetrachloride existing only in the gaseous phase in chlorine atmosphere, which is transported ever the temperature gradiept. Two ways of transport reaction realization - the method of flow and the method of diffusion in closed volume are tested. The experiments are made using specially synthesized plutonium dioxide, containing uranium, americium, curium, lanthanum, terbium, barium. Chlorination is realized by the mixture of chlorine and carbon tetrachloride at temperatures 723-953 K. Plutonium trichloride is deposited in the range 613-653 K, uranium - in the range 473-523 K, curium, americium, lanthanum, terbium, barium remain in the start zone if its temperature does not exceed 873 K

Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

Directory of Open Access Journals (Sweden)

Oyunbileg G

2018-02-01

Full Text Available The oxygen reduction reaction (ORR is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM and a transmission electron microscope (TEM analyses confirm the formation of the star-shaped nanoparticles. Among the investigated nanostar catalysts, an AuNS5 with smaller size and a few branches showed the higher electrocatalytic activity towards ORR than other catalysts with a bigger size. In addition, the electron numbers transferred for all the catalysts are approximately two. The present study results infer that the size of the Au-based nanostars may influence greatly on their catalytic activity. The present study results show that the further improvement is needed for Au-based nanostar catalysts towards the ORR reaction.

Entropy methods for reaction-diffusion equations: slowly growing a-priori bounds

KAUST Repository

Desvillettes, Laurent; Fellner, Klemens

2008-01-01

In the continuation of [Desvillettes, L., Fellner, K.: Exponential Decay toward Equilibrium via Entropy Methods for Reaction-Diffusion Equations. J. Math. Anal. Appl. 319 (2006), no. 1, 157-176], we study reversible reaction-diffusion equations via entropy methods (based on the free energy functional) for a 1D system of four species. We improve the existing theory by getting 1) almost exponential convergence in L1 to the steady state via a precise entropy-entropy dissipation estimate, 2) an explicit global L∞ bound via interpolation of a polynomially growing H1 bound with the almost exponential L1 convergence, and 3), finally, explicit exponential convergence to the steady state in all Sobolev norms.

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

Numerical methods in electron magnetic resonance

International Nuclear Information System (INIS)

Soernes, A.R.

1998-01-01

The focal point of the thesis is the development and use of numerical methods in the analysis, simulation and interpretation of Electron Magnetic Resonance experiments on free radicals in solids to uncover the structure, the dynamics and the environment of the system

Numerical methods in electron magnetic resonance

Energy Technology Data Exchange (ETDEWEB)

Soernes, A.R

1998-07-01

The focal point of the thesis is the development and use of numerical methods in the analysis, simulation and interpretation of Electron Magnetic Resonance experiments on free radicals in solids to uncover the structure, the dynamics and the environment of the system.

Electron beam-cured coating

International Nuclear Information System (INIS)

Kishi, Naoyuki

1976-01-01

The method for hardening coatings by the irradiation with electron beams is reviewed. The report is divided into seven parts, namely 1) general description and characteristics of electron beam-cured coating, 2) radiation sources of curing, 3) hardening conditions and reaction behaviour, 4) uses and advantages, 5) latest trends of the industry, 6) practice in the field of construction materials, and 7) economy. The primary characteristics of the electron beam hardening is that graft reaction takes place between base resin and coating to produce strong adhesive coating without any pretreatment. A variety of base resins are developed. High class esters of acrylic acid monomers and methacrylic acid monomers are mainly used as dilutants recently. At present, scanning type accelerators are used, but the practical application of the system producing electron beam of curtain type is expected. The dose rate dependence, the repetitive irradiation and the irradiation atmosphere are briefly described. The filed patent applications on the electron beam hardening were analyzed by the officer of Japan Patent Agency. The production lines for coatings by the electron beam hardening in the world are listed. In the electron beam-cured coating, fifty percent of given energy is consumed effectively for the electron beam hardening, and the solvents discharged from ovens and polluting atmosphere are not used, because the paints of high solid type is used. The running costs of the electron beam process are one sixth of the thermal oven process. (Iwakiri, K.)

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....

Applications of the Trojan Horse method in nuclear astrophysics

Energy Technology Data Exchange (ETDEWEB)

Spitaleri, Claudio, E-mail: spitaleri@lns.infn.it [Dipartimento di Fisica e Astronomia, Università di Catania, Catania, Italy and Laboratori Nazionali del Sud-INFN, Catania (Italy)

2015-02-24

The study of the energy production in stars and related nucleosyntesis processes requires increasingly precise knowledge of the nuclear reaction cross section and reaction rates at interaction energy. In order to overcome the experimental difficulties, arising from small cross-sections involved in charge particle induced reactions at astrophysical energies, and from the presence of electron screening, it was necessary to introduce indirect methods. Trough these methods it is possible to measure cross sections at very small energies and retrieve information on electron screening effect when ultra-low energy direct measurements are available. The Trojan Horse Method (THM) represents the indirect technique to determine the bare nucleus astrophysical S-factor for reactions between charged particles at astrophysical energies. The basic theory of the THM is discussed in the case of non-resonant.

A method for integrating and ranking the evidence for biochemical pathways by mining reactions from text

Science.gov (United States)

Miwa, Makoto; Ohta, Tomoko; Rak, Rafal; Rowley, Andrew; Kell, Douglas B.; Pyysalo, Sampo; Ananiadou, Sophia

2013-01-01

Motivation: To create, verify and maintain pathway models, curators must discover and assess knowledge distributed over the vast body of biological literature. Methods supporting these tasks must understand both the pathway model representations and the natural language in the literature. These methods should identify and order documents by relevance to any given pathway reaction. No existing system has addressed all aspects of this challenge. Method: We present novel methods for associating pathway model reactions with relevant publications. Our approach extracts the reactions directly from the models and then turns them into queries for three text mining-based MEDLINE literature search systems. These queries are executed, and the resulting documents are combined and ranked according to their relevance to the reactions of interest. We manually annotate document-reaction pairs with the relevance of the document to the reaction and use this annotation to study several ranking methods, using various heuristic and machine-learning approaches. Results: Our evaluation shows that the annotated document-reaction pairs can be used to create a rule-based document ranking system, and that machine learning can be used to rank documents by their relevance to pathway reactions. We find that a Support Vector Machine-based system outperforms several baselines and matches the performance of the rule-based system. The success of the query extraction and ranking methods are used to update our existing pathway search system, PathText. Availability: An online demonstration of PathText 2 and the annotated corpus are available for research purposes at http://www.nactem.ac.uk/pathtext2/. Contact: makoto.miwa@manchester.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23813008

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

Science.gov (United States)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

Evaluation of photonuclear reaction cross-sections using the reduction method for large systematic uncertainties

International Nuclear Information System (INIS)

Varlamov, V.V.; Efimkin, N.G.; Ishkhanov, B.S.; Sapunenko, V.V.

1994-12-01

The authors describe a method based on the reduction method for the evaluation of photonuclear reaction cross-sections obtained under conditions where there are large systematic uncertainties (different instrumental functions, calibration and normalization errors). The evaluation method involves using the actual instrumental function (photon spectrum) of each individual experiment to reduce the data to a representation generated by an instrumental function of better quality. The objective is to find the most reasonably achievable monoenergetic representation of the information on the reaction cross-section derived from the results of various experiments and to take into account the calibration and normalization errors in these experiments. The method was used to obtain the evaluated total photoneutron reaction cross-section (γ,xn) for a large number of nuclei. Data obtained for 16 O and 208 Pb are presented. (author). 36 refs, 6 figs, 4 tabs

AN UPDATED 6Li(p, α)3He REACTION RATE AT ASTROPHYSICAL ENERGIES WITH THE TROJAN HORSE METHOD

International Nuclear Information System (INIS)

Lamia, L.; Spitaleri, C.; Sergi, M. L.; Pizzone, R. G.; Tumino, A.; La Cognata, M.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Pappalardo, L.

2013-01-01

The lithium problem influencing primordial and stellar nucleosynthesis is one of the most interesting unsolved issues in astrophysics. 6 Li is the most fragile of lithium's stable isotopes and is largely destroyed in most stars during the pre-main-sequence (PMS) phase. For these stars, the convective envelope easily reaches, at least at its bottom, the relatively low 6 Li ignition temperature. Thus, gaining an understanding of 6 Li depletion also gives hints about the extent of convective regions. For this reason, charged-particle-induced reactions in lithium have been the subject of several studies. Low-energy extrapolations of these studies provide information about both the zero-energy astrophysical S(E) factor and the electron screening potential, U e . Thanks to recent direct measurements, new estimates of the 6 Li(p, α) 3 He bare-nucleus S(E) factor and the corresponding U e value have been obtained by applying the Trojan Horse method to the 2 H( 6 Li, α 3 He)n reaction in quasi-free kinematics. The calculated reaction rate covers the temperature window 0.01 to 2T 9 and its impact on the surface lithium depletion in PMS models with different masses and metallicities has been evaluated in detail by adopting an updated version of the FRANEC evolutionary code.

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...

Solid state reaction studies in Fe3O4–TiO2 system by diffusion couple method

International Nuclear Information System (INIS)

Ren, Zhongshan; Hu, Xiaojun; Xue, Xiangxin; Chou, Kuochih

2013-01-01

Highlights: •The solid state reactions of Fe2O3-TiO2 system was studied by the diffusion couple method. •Different products were formed by diffusion, and the FeTiO3 was more stable phase. •The inter-diffusion coefficients and diffusion activation energy were estimated. -- Abstract: The solid state reactions in Fe 3 O 4 –TiO 2 system has been studied by diffusion couple experiments at 1323–1473 K, in which the oxygen partial pressure was controlled by the CO–CO 2 gas mixture. The XRD analysis was used to confirm the phases of the inter-compound, and the concentration profiles were determined by electron probe microanalysis (EPMA). Based on the concentration profile of Ti, the inter-diffusion coefficients in Fe 3 O 4 phase, which were both temperature and concentration of Ti ions dependent, were calculated by the modified Boltzmann–Matano method. According to the relation between the thickness of diffusion layer and temperature, the diffusion coefficient of the Fe 3 O 4 –TiO 2 system was obtained. According to the Arrhenius equation, the estimated diffusion activation energy was about 282.1 ± 18.8 kJ mol −1

Photocatalytic fluoroalkylation reactions of organic compounds

OpenAIRE

Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto

2017-01-01

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photoc...

Transition Metal Donor-Peptide-Acceptor Complexes: From Intramolecular Electron Transfer Reactions to the Study of Reactive Intermediates

Energy Technology Data Exchange (ETDEWEB)

Isied, Stephan S.

2003-03-11

The trans-polyproline (PII) oligomers (Figure 1) are unusually rigid peptide structures which have been extensively studied by our group for peptide mediated intramolecular electron transfer (ET) at long distances. We have previously studied ET across a series of metal ion donor (D) acceptor (A) oligoproline peptides with different distances, driving forces and reorganizational energies. The majority of these experiments involve generating the ET intermediate using pulse radiolysis methods, although more recently photochemical methods are also used. Results of these studies showed that ET across peptides can vary by more than twelve orders of magnitude. Using ruthenium bipyridine donors, ET reaction rate constants across several proline residues (n = 4 - 9) occurred in the millisecond (ms) to {micro}s timescale, thus limiting the proline peptide conformational motions to only minor changes (far smaller than the large changes that occur on the ms to sec timescale, such as trans to cis proline isomerization). The present report describes our large data base of experimental results for D-peptide-A complexes in terms of a model where the involvement of both superexchange and hopping (hole and electron) mechanisms account for the long range ET rate constants observed. Our data shows that the change from superexchange to hopping mechanisms occurs at different distances depending on the type of D and A and their interactions with the peptides. Our model is also consistent with generalized models for superexchange and hopping which have been put forward by a number of theoretical groups to account for long range ET phenomena.

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...

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,…

Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction

DEFF Research Database (Denmark)

Taarning, Esben; Madsen, Robert

2008-01-01

A one-pot procedure is described for using alpha,beta-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes...

The Trojan Horse Method in nuclear astrophysics

Energy Technology Data Exchange (ETDEWEB)

Spitaleri, C., E-mail: spitaleri@lns.infn.it [Universita degli Studi di Catania, Dipartimento di Fisica e Astronomia (Italy); Mukhamedzhanov, A. M. [Texas A and M University, Cyclotron Institute (United States); Blokhintsev, L. D. [Moscow State University, Skobeltsyn Institute of Nuclear Physics (Russian Federation); Cognata, M. La [Universita degli Studi di Catania, Dipartimento di Fisica e Astronomia (Italy); Pizzone, R. G.; Tumino, A. [INFN, Laboratori Nazionali del Sud (Italy)

2011-12-15

The study of energy production and nucleosynthesis in stars requires an increasingly precise knowledge of the nuclear reaction rates at the energies of interest. To overcome the experimental difficulties arising from the small cross sections at those energies and from the presence of the electron screening, the Trojan Horse Method has been introduced. The method provides a valid alternative path to measure unscreened low-energy cross sections of reactions between charged particles, and to retrieve information on the electron screening potential when ultra-low energy direct measurements are available.

Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

Energy Technology Data Exchange (ETDEWEB)

Leleux, P [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

1998-06-01

In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

Energy Technology Data Exchange (ETDEWEB)

Ovacik, Meric A. [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Androulakis, Ioannis P., E-mail: yannis@rci.rutgers.edu [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Biomedical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States)

2013-09-15

Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy.

Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

International Nuclear Information System (INIS)

Ovacik, Meric A.; Androulakis, Ioannis P.

2013-01-01

Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy

Numerical simulation methods for electron and ion optics

International Nuclear Information System (INIS)

Munro, Eric

2011-01-01

This paper summarizes currently used techniques for simulation and computer-aided design in electron and ion beam optics. Topics covered include: field computation, methods for computing optical properties (including Paraxial Rays and Aberration Integrals, Differential Algebra and Direct Ray Tracing), simulation of Coulomb interactions, space charge effects in electron and ion sources, tolerancing, wave optical simulations and optimization. Simulation examples are presented for multipole aberration correctors, Wien filter monochromators, imaging energy filters, magnetic prisms, general curved axis systems and electron mirrors.

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.

Growth of polyaniline nanofibers for supercapacitor applications using successive ionic layer adsorption and reaction (SILAR) method

Energy Technology Data Exchange (ETDEWEB)

Deshmukh, P. R.; Pusawale, S. N.; Shinde, N. M.; Lokhande, C. D. [Shivaji University, Kolhapur (India)

2014-07-15

We report the synthesis of polyaniline nanofibers using the successive ionic layer adsorption and reaction (SILAR) method. The structural study shows the amorphous nature of polyaniline. The formation of polyaniline nanofibers has been revealed by scanning electron microscopy (SEM) whereas the confirmation of polyaniline material is obtained from Fourier transform infrared (FT-IR) spectroscopy. A plausible explanation illustrating the growth mechanism is presented. A maximum specific capacitance of 1078 F·g{sup -1} at a scan rate of 5 mV·s{sup -1} is obtained. The charge-discharge behavior shows a maximum specific power of 1.2 kW·kg{sup -1} and specific energy of 64 Wh·kg{sup -1}. The ease of the synthesis and the interesting electrochemical properties indicate that polyaniline nanofibers are promising materials for supercapacitor applications.

Growth of polyaniline nanofibers for supercapacitor applications using successive ionic layer adsorption and reaction (SILAR) method

International Nuclear Information System (INIS)

Deshmukh, P. R.; Pusawale, S. N.; Shinde, N. M.; Lokhande, C. D.

2014-01-01

We report the synthesis of polyaniline nanofibers using the successive ionic layer adsorption and reaction (SILAR) method. The structural study shows the amorphous nature of polyaniline. The formation of polyaniline nanofibers has been revealed by scanning electron microscopy (SEM) whereas the confirmation of polyaniline material is obtained from Fourier transform infrared (FT-IR) spectroscopy. A plausible explanation illustrating the growth mechanism is presented. A maximum specific capacitance of 1078 F·g -1 at a scan rate of 5 mV·s -1 is obtained. The charge-discharge behavior shows a maximum specific power of 1.2 kW·kg -1 and specific energy of 64 Wh·kg -1 . The ease of the synthesis and the interesting electrochemical properties indicate that polyaniline nanofibers are promising materials for supercapacitor applications.

Fast electronic structure methods for strongly correlated molecular systems

International Nuclear Information System (INIS)

Head-Gordon, Martin; Beran, Gregory J O; Sodt, Alex; Jung, Yousung

2005-01-01

A short review is given of newly developed fast electronic structure methods that are designed to treat molecular systems with strong electron correlations, such as diradicaloid molecules, for which standard electronic structure methods such as density functional theory are inadequate. These new local correlation methods are based on coupled cluster theory within a perfect pairing active space, containing either a linear or quadratic number of pair correlation amplitudes, to yield the perfect pairing (PP) and imperfect pairing (IP) models. This reduces the scaling of the coupled cluster iterations to no worse than cubic, relative to the sixth power dependence of the usual (untruncated) coupled cluster doubles model. A second order perturbation correction, PP(2), to treat the neglected (weaker) correlations is formulated for the PP model. To ensure minimal prefactors, in addition to favorable size-scaling, highly efficient implementations of PP, IP and PP(2) have been completed, using auxiliary basis expansions. This yields speedups of almost an order of magnitude over the best alternatives using 4-center 2-electron integrals. A short discussion of the scope of accessible chemical applications is given

Study of the 17O(n,α)14C reaction: Extension of the Trojan Horse Method to neutron induced reactions

International Nuclear Information System (INIS)

Guardo, G. L.; Lamia, L.; Spitaleri, C.; Cherubini, S.; Rapisarda, G. G.; Sergi, M. L.; Gulino, M.; Tang, X. D.; Bucher, B.; Couder, M.; Davies, P.; Boer, R. de; Fang, X.; Lamm, L.; Ma, C.; Notani, M.; OBrien, S.; Roberson, D.; Tan, W.; Wiescher, M.

2014-01-01

The experimental study of the 17 O(n,α) 14 C reaction has been performed in the energy range 0-350 keV. This reaction could play an important role in explaining heavy elements (s-process) nucleosynthesis in various astrophysical scenario. To overcome the practical problems arising from the neutrons production, a new application of the Trojan Horse Method has been recently suggested. In more details, the 17 O(n,α) 14 C reaction has been studied using the quasi-free 2 H( 17 O,α 14 C) 1 H reaction, induced at an energy of 43.5 MeV. The measurement allows one to investigate the ℓ=3, 75 keV resonance (E*=8.125 MeV, J π =5 − ), absent in the available direct measurements because of centrifugal suppression effects

Method of reduction of nitroaromatics by enzymatic reaction with redox enzymes

Science.gov (United States)

Shah, Manish M.

2000-01-01

A method for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with redox enzymes, such as Oxyrase (Trademark of Oxyrase, Inc., Mansfield, Ohio).

AN INVESTIGATION ON THE EFFECT OF FUNCTIONALISED GRAPHENE COMPOSITED WITH NCNT AND FE-NCNT ON THE OXYGEN REDUCTION REACTION VIA PHYSICAL MIXING METHOD

Directory of Open Access Journals (Sweden)

CHONG W.Z.

2016-02-01

Full Text Available Oxygen reduction reaction plays a major role in fuel cell applications to generate electricity by an electrochemical reaction. In this study, functionalised graphene composited with Fe-NCNT or NCNT were investigated on its ORR activity using a physical mixing method. Initially, functionalised graphene was produced via oxidation of graphene. NCNT and Fe-NCNT was obtained from the previously prepared samples using chemical vapour deposition technique and electrochemical reduction method for Fe-NCNT. The physical mixing between functionalised graphene and NCNT or Fe-NCNT was performed using sonication with the presence of pyrrole to produce the desired nanocatalyst. The surface morphologies and microstructures of the synthesised nanocatalysts were studied using field emission scanning electron microscopy. Surface chemical functionality of the nanocatalysts was investigated using X-ray photoelectron microscopy. Meanwhile, the ORR performance of nanocatalysts in a half cell were investigated using cyclic voltammetry techniques in both alkaline and acidic electrolytes. From this study, agglomeration of functionalised graphene (f-graphene was observed on the Fe-NCNTs indicating a hindrance in transfer of electrons within the catalyst surface. NCNT/f-graphene showed to contain higher percentage of pyridinic-N which claimed to have favored the catalytic activity compared to Fe-NCNT/f-graphene. Likewise, a higher onset potential was recorded for NCNT/f-graphene which indicated a higher ORR activity than the Fe-NCNT/f-graphene.

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

A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

DEFF Research Database (Denmark)

Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

2016-01-01

A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

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

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

Modified Monte Carlo method for study of electron transport in degenerate electron gas in the presence of electron-electron interactions, application to graphene

Science.gov (United States)

Borowik, Piotr; Thobel, Jean-Luc; Adamowicz, Leszek

2017-07-01

Standard computational methods used to take account of the Pauli Exclusion Principle into Monte Carlo (MC) simulations of electron transport in semiconductors may give unphysical results in low field regime, where obtained electron distribution function takes values exceeding unity. Modified algorithms were already proposed and allow to correctly account for electron scattering on phonons or impurities. Present paper extends this approach and proposes improved simulation scheme allowing including Pauli exclusion principle for electron-electron (e-e) scattering into MC simulations. Simulations with significantly reduced computational cost recreate correct values of the electron distribution function. Proposed algorithm is applied to study transport properties of degenerate electrons in graphene with e-e interactions. This required adapting the treatment of e-e scattering in the case of linear band dispersion relation. Hence, this part of the simulation algorithm is described in details.

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.)

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Science.gov (United States)

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

2003-04-01

The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

Synthesisofc-lifepo4 composite by solid state reaction method

Science.gov (United States)

Rahayu, I.; Hidayat, S.; Noviyanti, A. R.; Rakhmawaty, D.; Ernawati, E.

2017-02-01

In this research, the enhancement of LiFePO4 conductivity was conducted by doping method with carbon materials. Carbon-based materials were obtained from the mixture of sucrose, and the precursor of LiH2PO4 and α-Fe2O3 was synthesized by solid state reaction. Sintering temperature was varied at 700°C, 800°C, 900°C and 1,000°C. The result showed that C-LiFePO4 could be synthesized by using solid state reaction method. Based on the XRD and FTIR spectrums, C-LiFePO4 can be identified as the type of crystal, characterized by the appearance of sharp signal on (011), (211) and typical peak of LiFePO4 materials. The result of conductivity measurement from C-LiFePO4 at sintering temperature of 900°C and 1,000°C was 2×10-4 S/cm and 4×10-4S/cm, respectively. The conductivity value at sintering temperature of 700°C and 800°C was very small (<10-6 S/cm), which cannot be measured by the existing equipment.

Analysis of electron interactions in dielectric gases

International Nuclear Information System (INIS)

Olivet, Aurelio; Duque, Daniel; Vega, Lourdes F.

2007-01-01

We present and discuss results concerning electron interactions processes of dielectric gases and their relationship with the macroscopic behavior of these gases, in particular, with their dielectric strength. Such analysis is based on calculating energies of reactions for molecular ionization, dissociative ionization, parent negative ion formation, and dissociative electron attachment processes. We hypothesize that the estimation of the required energy for a reduced number of processes that take place in electrically stressed gases could be related to the gas' capability to manage the electron flow during an electrical discharge. All calculations were done with semiempirical quantum chemistry methods, including an initial optimization of molecular geometry and heat of formation of the dielectric gases and all of species that appear during electron interaction reactions. The performance of semiempirical methods Austin model 1 and Parametric model 3 (PM3) was compared for several compounds, PM3 being superior in most cases. Calculations performed for a sample of nine dielectric gases show that electron attachment and detachment processes occur in different energy bands that do not overlap for any value of the dielectric strength. We have also analyzed the relationship between dielectric strength and two physical properties: electron affinity and ionization energy. Calculations performed for 43 dielectric gases show no clear correlation between them, although certain guidelines for the qualitative estimation of dielectric strength can still be assessed