WorldWideScience

Sample records for electron transfer process

  1. Quantum tunneling resonant electron transfer process in Lorentzian plasmas

    International Nuclear Information System (INIS)

    Hong, Woo-Pyo; Jung, Young-Dae

    2014-01-01

    The quantum tunneling resonant electron transfer process between a positive ion and a neutral atom collision is investigated in nonthermal generalized Lorentzian plasmas. The result shows that the nonthermal effect enhances the resonant electron transfer cross section in Lorentzian plasmas. It is found that the nonthermal effect on the classical resonant electron transfer cross section is more significant than that on the quantum tunneling resonant charge transfer cross section. It is shown that the nonthermal effect on the resonant electron transfer cross section decreases with an increase of the Debye length. In addition, the nonthermal effect on the quantum tunneling resonant electron transfer cross section decreases with increasing collision energy. The variation of nonthermal and plasma shielding effects on the quantum tunneling resonant electron transfer process is also discussed

  2. Electron transfer and decay processes of highly charged iodine ions

    International Nuclear Information System (INIS)

    Sakaue, Hiroyuki A.; Danjo, Atsunori; Hosaka, Kazumoto

    2005-01-01

    In the present experimental work we have investigated multi-electron transfer processes in I q+ (q=10, 15, 20 and 25) + Ne, Ar, Kr and Xe collisions at 1.5q keV energy. The branching ratios between Auger and radiative decay channels have been measured in decay processes of multiply excited states formed by multi-electron transfer collisions. It has been shown that, in all the multi-electron transfer processes investigated, the Auger decays are far dominant over the radiative decay processes and the branching ratios are clearly characterized by the average principal quantum number of the initial excited states of projectile ions. We could express the branching ratios in high Rydberg states formed in multi-electron transfer processes by using the decay probability of one Auger electron emission. (author)

  3. Triboelectric effect: A new perspective on electron transfer process

    Science.gov (United States)

    Pan, Shuaihang; Zhang, Zhinan

    2017-10-01

    As interest in the triboelectric effect increases in line with the development of tribo-electrification related devices, the mechanisms involved in this phenomenon require more systematic review from the dual perspectives of developed classical insights and emerging quantum understanding. In this paper, the clear energy changing and transferring process of electrons have been proposed from the quantum point of view as the trigger for the charging initiation process in the triboelectric effect, and the phonon modes on the friction surfaces are believed to hold great importance as one of the main driving forces. Compatible with Maxwell Displacement Current theory, the complete consideration for charging steady state, i.e., the competition mechanisms between the breakdown process and the continuously charging process, and the balance mechanisms of phonon-electron interaction, built voltage, and induced polarization, are illustrated. In brief, the proposed theory emphasizes the fundamental role of electron transferring in tribo-electrical fields. By comparing certain experimental results from the previous studies, the theory is justified.

  4. Quantum electron transfer processes induced by thermo-coherent ...

    Indian Academy of Sciences (India)

    WINTEC

    Thermo-coherent state; electron transfer; quantum rate. 1. Introduction. The study ... two surfaces,16 namely, one electron two-centered exchange problem,7–10 many ... temperature classical regime for the single and the two-mode cases have ...

  5. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

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

  6. Charge amplification and transfer processes in the gas electron multiplier

    International Nuclear Information System (INIS)

    Bachmann, S.; Bressan, A.; Ropelewski, L.; Sauli, F.; Sharma, A.; Moermann, D.

    1999-01-01

    We report the results of systematic investigations on the operating properties of detectors based on the gas electron multiplier (GEM). The dependence of gain and charge collection efficiency on the external fields has been studied in a range of values for the hole diameter and pitch. The collection efficiency of ionization electrons into the multiplier, after an initial increase, reaches a plateau extending to higher values of drift field the larger the GEM voltage and its optical transparency. The effective gain, fraction of electrons collected by an electrode following the multiplier, increases almost linearly with the collection field, until entering a steeper parallel plate multiplication regime. The maximum effective gain attainable increases with the reduction in the hole diameter, stabilizing to a constant value at a diameter approximately corresponding to the foil thickness. Charge transfer properties appear to depend only on ratios of fields outside and within the channels, with no interaction between the external fields. With proper design, GEM detectors can be optimized to satisfy a wide range of experimental requirements: tracking of minimum ionizing particles, good electron collection with small distortions in high magnetic fields, improved multi-track resolution and strong ion feedback suppression in large volume and time-projection chambers

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

    International Nuclear Information System (INIS)

    Bertrand, Patrick

    2005-01-01

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

  8. 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....

  9. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions (updated 1993)

    International Nuclear Information System (INIS)

    Tawara, H.

    1993-04-01

    Following our previous compilations [IPPJ-AM-45 (1986), NIFS-DATA-7 (1990)], bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1980-1992 are included. For easy finding references for particular combination of collision partners, a simple list is also provided. (author) 1542 refs

  10. Photo-induced regeneration of hormones by electron transfer processes: Potential biological and medical consequences

    Science.gov (United States)

    Getoff, Nikola; Hartmann, Johannes; Schittl, Heike; Gerschpacher, Marion; Quint, Ruth Maria

    2011-08-01

    Based on the previous results concerning electron transfer processes in biological substances, it was of interest to investigate if hormone transients resulting by e.g. electron emission can be regenerated. The presented results prove for the first time that the hormone transients originating by the electron emission process can be successfully regenerated by the transfer of electrons from a potent electron donor, such as vitamin C (VitC). Investigations were performed using progesterone (PRG), testosterone (TES) and estrone (E1) as representatives of hormones. By irradiation with monochromatic UV light (λ=254 nm) in a media of 40% water and 60% ethanol, the degradation as well as the regeneration of the hormones was studied with each hormone individually and in the mixture with VitC as a function of the absorbed UV dose, using HPLC. Calculated from the obtained initial yields, the determined regeneration of PRG amounted to 52.7%, for TES to 58.6% and for E1 to 90.9%. The consumption of VitC was determined in the same way. The reported results concerning the regeneration of hormones by the transfer of electrons from an electron donor offer a new, promising method for the therapy with hormones. As a consequence of the regeneration of hormones, a decreased formation of carcinogenic metabolites is expected.

  11. Photo-induced regeneration of hormones by electron transfer processes: Potential biological and medical consequences

    Energy Technology Data Exchange (ETDEWEB)

    Getoff, Nikola, E-mail: nikola.getoff@univie.ac.a [Section of Radiation Biology, Faculty of Life Sciences, University of Vienna, A-1090 Vienna (Austria); Hartmann, Johannes [Department of Gynecologic Endocrinology and Reproduction, Medical University of Vienna, A-1090 Vienna (Austria); Schittl, Heike [Section of Radiation Biology, Faculty of Life Sciences, University of Vienna, A-1090 Vienna (Austria); Gerschpacher, Marion [Department of Gynecologic Endocrinology and Reproduction, Medical University of Vienna, A-1090 Vienna (Austria); Quint, Ruth Maria [Section of Radiation Biology, Faculty of Life Sciences, University of Vienna, A-1090 Vienna (Austria)

    2011-08-15

    Based on the previous results concerning electron transfer processes in biological substances, it was of interest to investigate if hormone transients resulting by e.g. electron emission can be regenerated. The presented results prove for the first time that the hormone transients originating by the electron emission process can be successfully regenerated by the transfer of electrons from a potent electron donor, such as vitamin C (VitC). Investigations were performed using progesterone (PRG), testosterone (TES) and estrone (E1) as representatives of hormones. By irradiation with monochromatic UV light ({lambda}=254 nm) in a media of 40% water and 60% ethanol, the degradation as well as the regeneration of the hormones was studied with each hormone individually and in the mixture with VitC as a function of the absorbed UV dose, using HPLC. Calculated from the obtained initial yields, the determined regeneration of PRG amounted to 52.7%, for TES to 58.6% and for E1 to 90.9%. The consumption of VitC was determined in the same way. The reported results concerning the regeneration of hormones by the transfer of electrons from an electron donor offer a new, promising method for the therapy with hormones. As a consequence of the regeneration of hormones, a decreased formation of carcinogenic metabolites is expected.

  12. Photo-induced regeneration of hormones by electron transfer processes: Potential biological and medical consequences

    International Nuclear Information System (INIS)

    Getoff, Nikola; Hartmann, Johannes; Schittl, Heike; Gerschpacher, Marion; Quint, Ruth Maria

    2011-01-01

    Based on the previous results concerning electron transfer processes in biological substances, it was of interest to investigate if hormone transients resulting by e.g. electron emission can be regenerated. The presented results prove for the first time that the hormone transients originating by the electron emission process can be successfully regenerated by the transfer of electrons from a potent electron donor, such as vitamin C (VitC). Investigations were performed using progesterone (PRG), testosterone (TES) and estrone (E1) as representatives of hormones. By irradiation with monochromatic UV light (λ=254 nm) in a media of 40% water and 60% ethanol, the degradation as well as the regeneration of the hormones was studied with each hormone individually and in the mixture with VitC as a function of the absorbed UV dose, using HPLC. Calculated from the obtained initial yields, the determined regeneration of PRG amounted to 52.7%, for TES to 58.6% and for E1 to 90.9%. The consumption of VitC was determined in the same way. The reported results concerning the regeneration of hormones by the transfer of electrons from an electron donor offer a new, promising method for the therapy with hormones. As a consequence of the regeneration of hormones, a decreased formation of carcinogenic metabolites is expected.

  13. Construction of Vibronic Diabatic Hamiltonian for Excited-State Electron and Energy Transfer Processes.

    Science.gov (United States)

    Xie, Yu; Jiang, Shengshi; Zheng, Jie; Lan, Zhenggang

    2017-12-21

    Photoinduced excited-state electron and energy transfer processes are crucial in biological photoharvesting systems and organic photovoltaic devices. We discuss the construction of a diabatic vibronic Hamiltonian for the proper treatment of these processes involving the projection approach acting on both electronic wave functions and vibrational modes. In the electronic part, the wave function projection approach is used to construct the diabatic Hamiltonian in which both local excited states and charge-transfer states are included on the same footing. For the vibrational degrees of freedom, the vibronic couplings in the diabatic Hamiltonian are obtained in the basis of the pseudonormal modes localized on each monomer site by applying delocalized-to-localized mode projection. This systematic approach allows us to construct the vibronic diabatic Hamiltonian in molecular aggregates.

  14. Direct observation of the ultrafast electron transfer process in a polymer/fullerene blend

    NARCIS (Netherlands)

    Cerullo, G.; Lanzani, G.; Silvestri, S. De; Brabec, Ch.J.; Zerza, G.; Sariciftci, N.S.; Hummelen, J.C.

    2000-01-01

    Photoinduced electron transfer in organic molecules is an extensively investigated topic both because of fundamental interest in the photophysics and for applications to artificial photosynthesis. Highly efficient ultrafast electron transfer from photoexcited conjugated polymers to C60 has been

  15. Regulation of electron transfer processes affects phototrophic mat structure and activity

    Science.gov (United States)

    Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan; Reardon, Patrick N.; Lindemann, Stephen R.; Fredrickson, James K.; Call, Douglas R.; Beyenal, Haluk

    2015-01-01

    Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA). We operated two reactors: graphite electrodes were polarized at potentials of -700 mVAg/AgCl [cathodic (CAT) mat system] and +300 mVAg/AgCl [anodic (AN) mat system] and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both AN and CAT mat systems. Interestingly, the CAT mats generated the highest reducing current at the same time points that the AN mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen (DO) and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR) imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the CAT mats than in the AN mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the CAT mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. These data suggested that variation in the

  16. Regulation of electron transfer processes affects phototrophic mat structure and activity

    Directory of Open Access Journals (Sweden)

    Haluk eBeyenal

    2015-09-01

    Full Text Available Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA. We operated two reactors: graphite electrodes were polarized at potentials of -700 mVAg/AgCl (cathodic mat system and +300 mVAg/AgCl (anodic mat system and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both anodic and cathodic mat systems. Interestingly, the cathodic mats generated the highest reducing current at the same time points that the anodic mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the cathodic mats than in the anodic mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the cathodic mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. These data suggested that

  17. Regulation of electron transfer processes affects phototrophic mat structure and activity.

    Science.gov (United States)

    Ha, Phuc T; Renslow, Ryan S; Atci, Erhan; Reardon, Patrick N; Lindemann, Stephen R; Fredrickson, James K; Call, Douglas R; Beyenal, Haluk

    2015-01-01

    Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located near Oroville (Washington, USA). We operated two reactors: graphite electrodes were polarized at potentials of -700 mVAg/AgCl [cathodic (CAT) mat system] and +300 mVAg/AgCl [anodic (AN) mat system] and the electron transfer rates between the electrode and mat were monitored. We observed a diel cycle of electron transfer rates for both AN and CAT mat systems. Interestingly, the CAT mats generated the highest reducing current at the same time points that the AN mats showed the highest oxidizing current. To characterize the physicochemical factors influencing electron transfer processes, we measured depth profiles of dissolved oxygen (DO) and sulfide in the mats using microelectrodes. We further demonstrated that the mat-to-electrode and electrode-to-mat electron transfer rates were light- and temperature-dependent. Using nuclear magnetic resonance (NMR) imaging, we determined that the electrode potential regulated the diffusivity and porosity of the microbial mats. Both porosity and diffusivity were higher in the CAT mats than in the AN mats. We also used NMR spectroscopy for high-resolution quantitative metabolite analysis and found that the CAT mats had significantly higher concentrations of osmoprotectants such as betaine and trehalose. Subsequently, we performed amplicon sequencing across the V4 region of the 16S rRNA gene of incubated mats to understand the impact of electrode potential on microbial community structure. These data suggested that variation in the

  18. Controlling electron transfer processes on insulating surfaces with the non-contact atomic force microscope.

    Science.gov (United States)

    Trevethan, Thomas; Shluger, Alexander

    2009-07-01

    We present the results of theoretical modelling that predicts how a process of transfer of single electrons between two defects on an insulating surface can be induced using a scanning force microscope tip. A model but realistic system is employed which consists of a neutral oxygen vacancy and a noble metal (Pt or Pd) adatom on the MgO(001) surface. We show that the ionization potential of the vacancy and the electron affinity of the metal adatom can be significantly modified by the electric field produced by an ionic tip apex at close approach to the surface. The relative energies of the two states are also a function of the separation of the two defects. Therefore the transfer of an electron from the vacancy to the metal adatom can be induced either by the field effect of the tip or by manipulating the position of the metal adatom on the surface.

  19. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions. Updated 1997

    International Nuclear Information System (INIS)

    Tawara, H.

    1997-04-01

    Following our previous compilations (IPPJ-AM-45 (1986), NIFS-DATA-7 (1990), NIFS-DATA-20 (1993)), bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1954-1996 are listed in the order of the publication year. For easy finding of the references for a combination of collision partners, a simple list is provided. (author)

  20. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions, updated 1990

    International Nuclear Information System (INIS)

    Tawara, H.

    1990-08-01

    Following a previous compilation, new bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1989 are surveyed. For easy finding references for particular combination of collision partners, a simple list is also provided. Furthermore, for convenience, a copy of the previous compilation (IPPJ-AM-45 (1986)) is included. (author) 1363 refs

  1. Regulation of electron transfer processes affects phototrophic mat structure and activity

    OpenAIRE

    Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan; Reardon, Patrick N.; Lindemann, Stephen R.; Fredrickson, James K.; Call, Douglas R.; Beyenal, Haluk

    2015-01-01

    Phototrophic microbial mats are among the most diverse ecosystems in nature. These systems undergo daily cycles in redox potential caused by variations in light energy input and metabolic interactions among the microbial species. In this work, solid electrodes with controlled potentials were placed under mats to study the electron transfer processes between the electrode and the microbial mat. The phototrophic microbial mat was harvested from Hot Lake, a hypersaline, epsomitic lake located ne...

  2. Electron transfer to sulfides:

    International Nuclear Information System (INIS)

    Meneses, Ana Belen; Antonello, Sabrina; Arevalo, Maria Carmen; Maran, Flavio

    2005-01-01

    The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the C-S bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph 2 CH - . The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated C-S bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π* radical anions and those going through the intermediacy of loose σ* radical anions

  3. Quantum molecular dynamics study on energy transfer to the secondary electron in surface collision process of an ion

    International Nuclear Information System (INIS)

    Shibahara, M; Satake, S; Taniguchi, J

    2008-01-01

    In the present study the quantum molecular dynamics method was applied to an energy transfer problem to an electron during ionic surface collision process in order to elucidate how energy of ionic collision transfers to the emitted electrons. Effects of various physical parameters, such as the collision velocity and interaction strength between the observed electron and the classical particles on the energy transfer to the electron were investigated by the quantum molecular dynamics method when the potassium ion was collided with the surface so as to elucidate the energy path to the electron and the predominant factor of energy transfer to the electron. Effects of potential energy between the ion and the electron and that between the surface molecule and the electron on the electronic energy transfer were shown in the present paper. The energy transfer to the observed secondary electron through the potential energy term between the ion and the electron was much dependent on the ion collision energy although the energy increase to the observed secondary electron was not monotonous through the potential energy between the ion and surface molecules with the change of the ion collision energy

  4. Efficient Long - Range Electron Transfer Processes in Polyfluorene – Perylene Diimide Blends

    KAUST Repository

    Isakova, Anna

    2018-05-17

    In bulk heterojunction donor-acceptor (D-A) blends, high photovoltaic yields require charge carrier separation to outcompete geminate recombination. Recently, evidence for long-range electron transfer mechanisms has been presented, avoiding strongly-bound interfacial charge transfer (CT) states. However, due to the lack of specific optical probes at the D-A interface, a detailed quantification of the long-range processes has not been feasible, until now. Here, we present a transient absorption study of long-range processes in a unique phase consisting of perylene diimide (PDI) crystals intercalated with polyfluorene (PFO), as widely used non-fullerene electron acceptor and donor, respectively. The intercalated PDI:PFO phase possesses specific well-separated spectral features for the excited states at the D-A interface. By use of femtosecond spectroscopy we reveal the excitation dynamics in this blend. PDI excitons undergo a clear symmetry-breaking charge separation in the PDI bulk, which occurs within several hundred femtoseconds, thus outcompeting excimer formation, known to limit charge separation yields when PDI is used as an acceptor. In contrast, PFO excitons are dissociated with very high yields in a one-step long-range process, enabled by large delocalization of the PFO exciton wavefunction. Moreover, both scenarios circumvent the formation of strongly-bound interfacial CT states and enable a targeted interfacial design for bulk heterojunction blends with near unity charge separation yields.

  5. Efficient Long - Range Electron Transfer Processes in Polyfluorene – Perylene Diimide Blends

    KAUST Repository

    Isakova, Anna; Karuthedath, Safakath; Arnold, Thomas; Howse, Jonathan; Topham, Paul D.; Toolan, Daniel Thomas William; Laquai, Fré dé ric; Lü er, Larry

    2018-01-01

    In bulk heterojunction donor-acceptor (D-A) blends, high photovoltaic yields require charge carrier separation to outcompete geminate recombination. Recently, evidence for long-range electron transfer mechanisms has been presented, avoiding strongly-bound interfacial charge transfer (CT) states. However, due to the lack of specific optical probes at the D-A interface, a detailed quantification of the long-range processes has not been feasible, until now. Here, we present a transient absorption study of long-range processes in a unique phase consisting of perylene diimide (PDI) crystals intercalated with polyfluorene (PFO), as widely used non-fullerene electron acceptor and donor, respectively. The intercalated PDI:PFO phase possesses specific well-separated spectral features for the excited states at the D-A interface. By use of femtosecond spectroscopy we reveal the excitation dynamics in this blend. PDI excitons undergo a clear symmetry-breaking charge separation in the PDI bulk, which occurs within several hundred femtoseconds, thus outcompeting excimer formation, known to limit charge separation yields when PDI is used as an acceptor. In contrast, PFO excitons are dissociated with very high yields in a one-step long-range process, enabled by large delocalization of the PFO exciton wavefunction. Moreover, both scenarios circumvent the formation of strongly-bound interfacial CT states and enable a targeted interfacial design for bulk heterojunction blends with near unity charge separation yields.

  6. Desulfurization of organic sulfur from lignite by an electron transfer process

    Energy Technology Data Exchange (ETDEWEB)

    Demirbas, A. [Selcuk University, Konya (Turkey). Dept. for Chemical Engineering

    2006-10-15

    This study is an attempt to desulfurize organic sulfur from lignite samples with ferrocyanide ion as the electron transferring agent. Effect of temperature, particle size and concentration of ferrocyanide ion on desulfurization from the lignite samples has been investigated. The desulfurization process has been found to be continuous and gradually increases with increase of temperature from 298 to 368 K. The particle size has no significant impact on sulfur removal from the lignite samples. Particle size has no profound impact on the amount of sulfur removal. The desulfurization reaction has been found to be dependent on the concentration of potassium ferrocyanide. Gradual increase in the concentration of potassium ferrocyanide raised the magnitude of desulfurization, but at a higher concentration, the variation is not significant.

  7. Electron pumping of the ground state of 21Ne. Transfers and multiple diffusion processes

    International Nuclear Information System (INIS)

    Stoeckel, F.; Lombardi, M.

    1978-01-01

    The electron-pumping process of the ground state of 21 Ne has been studied. It is demonstrated how in a neon cell at a pressure of 10 -4 to 10 -2 torr, a high frequency discharge can create a nuclear spin alignment in the fundamental level (I=3/2) when the excited levels are themselves aligned. The nuclear alignment is observed by monitoring the change of the linear polarization of several optical transitions during the magnetic resonance of the fundamental level. Various transfers of the alignments are investigated and a detailed study of the influence of the multiple diffusion is carried out. The multiple diffusion produces a depolarization and a relaxation of the nuclear spin. A theoretical calculation has been made for a two-level system with a J=1 radiative level and a J=0 ground state. Experimentally a relaxation time of the nuclear alignment varying from 37 ms to 240 ms is observed when the neon pressure decreases from 10 -2 to 10 -4 torr [fr

  8. Contribution of charge-transfer processes to ion-induced electron emission

    International Nuclear Information System (INIS)

    Roesler, M.; Garcia de Abajo, F.J.

    1996-01-01

    Charge changing events of ions moving inside metals are shown to contribute significantly to electron emission in the intermediate velocity regime via electrons coming from projectile ionization. Inclusion of equilibrium charge state fractions, together with two-electron Auger processes and resonant-coherent electron loss from the projectile, results in reasonable agreement with previous calculations for frozen protons, though a significant part of the emission is now interpreted in terms of charge exchange. The quantal character of the surface barrier transmission is shown to play an important role. The theory compares well with experimental observations for H projectiles. copyright 1996 The American Physical Society

  9. Nonadiabatic anharmonic electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, P. P. [Molecular Physics Research, 6547 Kristina Ursula Court, Falls Church, Virginia 22044 (United States)

    2013-03-28

    The effect of an inner sphere, local mode vibration on an electron transfer is modeled using the nonadiabatic transition probability (rate) expression together with both the anharmonic Morse and the harmonic oscillator potential. For an anharmonic inner sphere mode, a variational analysis uses harmonic oscillator basis functions to overcome the difficulties evaluating Morse-model Franck-Condon overlap factors. Individual matrix elements are computed with the use of new, fast, robust, and flexible recurrence relations. The analysis therefore readily addresses changes in frequency and/or displacement of oscillator minimums in the different electron transfer states. Direct summation of the individual Boltzmann weighted Franck-Condon contributions avoids the limitations inherent in the use of the familiar high-temperature, Gaussian form of the rate constant. The effect of harmonic versus anharmonic inner sphere modes on the electron transfer is readily seen, especially in the exoergic, inverted region. The behavior of the transition probability can also be displayed as a surface for all temperatures and values of the driving force/exoergicity {Delta}=-{Delta}G. The temperature insensitivity of the transfer rate is clearly seen when the exoergicity equals the collective reorganization energy ({Delta}={Lambda}{sub s}) along a maximum ln (w) vs. {Delta} ridge of the surface. The surface also reveals additional regions for {Delta} where ln (w) appears to be insensitive to temperature, or effectively activationless, for some kinds of inner sphere contributions.

  10. Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach

    Science.gov (United States)

    Prucker, V.; Bockstedte, M.; Thoss, M.; Coto, P. B.

    2018-03-01

    A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface. The results show a significant dependence of the ET on the orbital symmetry of the donor state and on the molecular and electronic structure of the spacer.

  11. Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach.

    Science.gov (United States)

    Prucker, V; Bockstedte, M; Thoss, M; Coto, P B

    2018-03-28

    A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface. The results show a significant dependence of the ET on the orbital symmetry of the donor state and on the molecular and electronic structure of the spacer.

  12. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  13. Electron-electron Thomas peak in fast transfer ionization

    International Nuclear Information System (INIS)

    Tolmanov, S. G.; McGuire, J. H.

    2000-01-01

    ''Thomas process'' is a name used for a family of singular two-step processes that can lead to electron transfer. The Thomas process of the ''second kind,'' occurring in reactions with both transfer and ionization, utilizes the e-e scattering in the second step, so this Thomas process requires the dynamics of the electron-electron interaction. We calculate numerically the second order element of an S matrix and corresponding cross sections for the transfer ionization process. We find that the position and shape of the Thomas peak depend on both electron-electron and the electron-nucleus interaction. Also the direct and exchange amplitudes are equal at the peak position. We test the peaking approximation used for transfer ionization. Our results can be compared to experimental results for p + +He→H+He 2+ +e - . (c) 2000 The American Physical Society

  14. Visible light induced electron transfer process over nitrogen doped TiO2 nanocrystals prepared by oxidation of titanium nitride

    International Nuclear Information System (INIS)

    Wu Zhongbiao; Dong Fan; Zhao Weirong; Guo Sen

    2008-01-01

    Nitrogen doped TiO 2 nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO 2 nanocrystals can be clearly attributed to the change of the additional electronic (N - ) states above the valence band of TiO 2 modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO 2 nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO 2

  15. Ultrafast Excited-State Dynamics of Diketopyrrolopyrrole (DPP)-Based Materials: Static versus Diffusion-Controlled Electron Transfer Process

    KAUST Repository

    Alsulami, Qana

    2015-06-25

    Singlet-to-triplet intersystem crossing (ISC) and photoinduced electron transfer (PET) of platinum(II) containing diketopyrrolopyrrole (DPP) oligomer in the absence and presence of strong electron-acceptor tetracyanoethylene (TCNE) were investigated using femtosecond and nanosecond transient absorption spectroscopy with broadband capabilities. The role of platinum(II) incorporation in those photophysical properties was evaluated by comparing the excited-state dynamics of DPP with and without the metal centers. The steady-state measurements reveal that platinum(II) incorporation facilitates dramatically the interactions between DPP-Pt(acac) and TCNE, resulting in charge transfer (CT) complex formation. The transient absorption spectra in the absence of TCNE reveal ultrafast ISC of DPP-Pt(acac) followed by their long-lived triplet state. In the presence of TCNE, PET from the excited DPP-Pt(acac) and DPP to TCNE, forming the radical ion pairs. The ultrafast PET which occurs statically from DPP-Pt(acac) to TCNE in picosecond regime, is much faster than that from DPP to TCNE (nanosecond time scale) which is diffusion-controlled process, providing clear evidence that PET rate is eventually controlled by the platinum(II) incorporation.

  16. Ultrafast Excited-State Dynamics of Diketopyrrolopyrrole (DPP)-Based Materials: Static versus Diffusion-Controlled Electron Transfer Process

    KAUST Repository

    Alsulami, Qana; Aly, Shawkat Mohammede; Goswami, Subhadip; Alarousu, Erkki; Usman, Anwar; Schanze, Kirk S.; Mohammed, Omar F.

    2015-01-01

    Singlet-to-triplet intersystem crossing (ISC) and photoinduced electron transfer (PET) of platinum(II) containing diketopyrrolopyrrole (DPP) oligomer in the absence and presence of strong electron-acceptor tetracyanoethylene (TCNE) were investigated using femtosecond and nanosecond transient absorption spectroscopy with broadband capabilities. The role of platinum(II) incorporation in those photophysical properties was evaluated by comparing the excited-state dynamics of DPP with and without the metal centers. The steady-state measurements reveal that platinum(II) incorporation facilitates dramatically the interactions between DPP-Pt(acac) and TCNE, resulting in charge transfer (CT) complex formation. The transient absorption spectra in the absence of TCNE reveal ultrafast ISC of DPP-Pt(acac) followed by their long-lived triplet state. In the presence of TCNE, PET from the excited DPP-Pt(acac) and DPP to TCNE, forming the radical ion pairs. The ultrafast PET which occurs statically from DPP-Pt(acac) to TCNE in picosecond regime, is much faster than that from DPP to TCNE (nanosecond time scale) which is diffusion-controlled process, providing clear evidence that PET rate is eventually controlled by the platinum(II) incorporation.

  17. Exocellular electron transfer in anaerobic microbial communities.

    Science.gov (United States)

    Stams, Alfons J M; de Bok, Frank A M; Plugge, Caroline M; van Eekert, Miriam H A; Dolfing, Jan; Schraa, Gosse

    2006-03-01

    Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory syntrophic consortia of proton-reducing acetogenic bacteria and hydrogen-consuming methanogenic archaea. Anaerobic microorganisms that use insoluble electron acceptors for growth, such as iron- and manganese-oxide as well as inert graphite electrodes in microbial fuel cells, also transfer electrons exocellularly. Soluble compounds, like humic substances, quinones, phenazines and riboflavin, can function as exocellular electron mediators enhancing this type of anaerobic respiration. However, direct electron transfer by cell-cell contact is important as well. This review addresses the mechanisms of exocellular electron transfer in anaerobic microbial communities. There are fundamental differences but also similarities between electron transfer to another microorganism or to an insoluble electron acceptor. The physical separation of the electron donor and electron acceptor metabolism allows energy conservation in compounds as methane and hydrogen or as electricity. Furthermore, this separation is essential in the donation or acceptance of electrons in some environmental technological processes, e.g. soil remediation, wastewater purification and corrosion.

  18. Quantum dynamical simulation of photoinduced electron transfer processes in dye-semiconductor systems: theory and application to coumarin 343 at TiO₂.

    Science.gov (United States)

    Li, Jingrui; Kondov, Ivan; Wang, Haobin; Thoss, Michael

    2015-04-10

    A recently developed methodology to simulate photoinduced electron transfer processes at dye-semiconductor interfaces is outlined. The methodology employs a first-principles-based model Hamiltonian and accurate quantum dynamics simulations using the multilayer multiconfiguration time-dependent Hartree approach. This method is applied to study electron injection in the dye-semiconductor system coumarin 343-TiO2. Specifically, the influence of electronic-vibrational coupling is analyzed. Extending previous work, we consider the influence of Dushinsky rotation of the normal modes as well as anharmonicities of the potential energy surfaces on the electron transfer dynamics.

  19. Electron capture and transfer-ionization processes in {sup 4}He{sup 2+}+Ar collision at 12.5 keV amu{sup -1}

    Energy Technology Data Exchange (ETDEWEB)

    Moretto-Capelle, P.; Bordenave-Montesquieu, D.; Bordenave-Montesquieu, A.; Benhenni, M. [Laboratoire Collisions, Agregats, Reactivite, IRSAMC, UMR 5589 CNRS and Universite Paul Sabatier, 31062 Toulouse Cedex (France)

    1998-05-14

    Electron emission in the {sup 4}He{sup 2+}+Ar collisional system has been investigated at 35 deg. and 12.5 keV amu{sup -1} collision velocity, in coincidence with the recoil target ion charges. Direct single ionization is found to be negligible with respect to single-electron capture. Contributions of transfer-ionization processes are stressed in the production of Ar{sup 2+} to Ar{sup 4+} ions; those of direct ionization, double excitation of the target and double capture into autoionization states of helium are instead found to be much less probable. Among the two-electron processes which explain the formation of Ar{sup 2+} ions, the double capture into autoionizing states of helium remains unimportant with respect to a pure transfer ionization process (one captured electron plus one ionized electron). The measured predominant production of Ar{sup 3+} ions illustrates the role played by three-electron processes, mainly a two-electron transfer accompanied by a single-target ionization. Finally, the formation of Ar{sup 4+} ions is connected with more complex transfer ionization processes. A qualitative analysis of these results is made within the quasimolecular approach. (author). Letter-to-the-editor.

  20. Fragment-based Quantum Mechanical/Molecular Mechanical Simulations of Thermodynamic and Kinetic Process of the Ru2+-Ru3+ Self-Exchange Electron Transfer.

    Science.gov (United States)

    Zeng, Xiancheng; Hu, Xiangqian; Yang, Weitao

    2012-12-11

    A fragment-based fractional number of electron (FNE) approach, is developed to study entire electron transfer (ET) processes from the electron donor region to the acceptor region in condensed phase. Both regions are described by the density-fragment interaction (DFI) method while FNE as an efficient ET order parameter is applied to simulate the electron transfer process. In association with the QM/MM energy expression, the DFI-FNE method is demonstrated to describe ET processes robustly with the Ru 2+ -Ru 3+ self-exchange ET as a proof-of-concept example. This method allows for systematic calculations of redox free energies, reorganization energies, and electronic couplings, and the absolute ET rate constants within the Marcus regime.

  1. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1995-01-01

    Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

  2. Nuclear reorganization barriers to electron transfer

    International Nuclear Information System (INIS)

    Sutin, N.; Brunschwig, B.S.; Creutz, C.; Winkler, J.R.

    1988-01-01

    The nuclear barrier to electron transfer arises from the need for reorganization of intramolecular and solvent internuclear distances prior to electron transfer. For reactions with relatively small driving force (''normal'' free-energy region) the nuclear factors and rates increase as intrinsic inner-shell and outer-shell barriers decrease; this is illustrated by data for transition metal complexes in their ground electronic states. By contrast, in the inverted free-energy region, rates and nuclear factors decrease with decreasing ''intrinsic'' barriers; this is illustrated by data for the decay of charge-transfer excited states. Several approaches to the evaluation of the outer-shell barrier are explored in an investigation of the distance dependence of the nuclear factor in intramolecular electron-transfer processes. 39 refs., 14 figs., 3 tabs

  3. Two-Electron Transfer Pathways.

    Science.gov (United States)

    Lin, Jiaxing; Balamurugan, D; Zhang, Peng; Skourtis, Spiros S; Beratan, David N

    2015-06-18

    The frontiers of electron-transfer chemistry demand that we develop theoretical frameworks to describe the delivery of multiple electrons, atoms, and ions in molecular systems. When electrons move over long distances through high barriers, where the probability for thermal population of oxidized or reduced bridge-localized states is very small, the electrons will tunnel from the donor (D) to acceptor (A), facilitated by bridge-mediated superexchange interactions. If the stable donor and acceptor redox states on D and A differ by two electrons, it is possible that the electrons will propagate coherently from D to A. While structure-function relations for single-electron superexchange in molecules are well established, strategies to manipulate the coherent flow of multiple electrons are largely unknown. In contrast to one-electron superexchange, two-electron superexchange involves both one- and two-electron virtual intermediate states, the number of virtual intermediates increases very rapidly with system size, and multiple classes of pathways interfere with one another. In the study described here, we developed simple superexchange models for two-electron transfer. We explored how the bridge structure and energetics influence multielectron superexchange, and we compared two-electron superexchange interactions to single-electron superexchange. Multielectron superexchange introduces interference between singly and doubly oxidized (or reduced) bridge virtual states, so that even simple linear donor-bridge-acceptor systems have pathway topologies that resemble those seen for one-electron superexchange through bridges with multiple parallel pathways. The simple model systems studied here exhibit a richness that is amenable to experimental exploration by manipulating the multiple pathways, pathway crosstalk, and changes in the number of donor and acceptor species. The features that emerge from these studies may assist in developing new strategies to deliver multiple

  4. Single-Molecule Interfacial Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Lu, H. Peter [Bowling Green State Univ., Bowling Green, OH (United States). Dept. of Chemistry and Center for Photochemical Sciences

    2017-11-28

    This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static and dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO2 nanoparticle surfaces by using ultrafast single

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

    International Nuclear Information System (INIS)

    Sobolewski, Andrzej L.; Domcke, Wolfgang

    2003-01-01

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

  6. Single Molecule Spectroscopy of Electron Transfer

    International Nuclear Information System (INIS)

    Holman, Michael; Zang, Ling; Liu, Ruchuan; Adams, David M.

    2009-01-01

    The objectives of this research are threefold: (1) to develop methods for the study electron transfer processes at the single molecule level, (2) to develop a series of modifiable and structurally well defined molecular and nanoparticle systems suitable for detailed single molecule/particle and bulk spectroscopic investigation, (3) to relate experiment to theory in order to elucidate the dependence of electron transfer processes on molecular and electronic structure, coupling and reorganization energies. We have begun the systematic development of single molecule spectroscopy (SMS) of electron transfer and summaries of recent studies are shown. There is a tremendous need for experiments designed to probe the discrete electronic and molecular dynamic fluctuations of single molecules near electrodes and at nanoparticle surfaces. Single molecule spectroscopy (SMS) has emerged as a powerful method to measure properties of individual molecules which would normally be obscured in ensemble-averaged measurement. Fluctuations in the fluorescence time trajectories contain detailed molecular level statistical and dynamical information of the system. The full distribution of a molecular property is revealed in the stochastic fluctuations, giving information about the range of possible behaviors that lead to the ensemble average. In the case of electron transfer, this level of understanding is particularly important to the field of molecular and nanoscale electronics: from a device-design standpoint, understanding and controlling this picture of the overall range of possible behaviors will likely prove to be as important as designing ia the ideal behavior of any given molecule.

  7. Electron Transfer from Triplet State of TIPS-Pentacene Generated by Singlet Fission Processes to CH3NH3PbI3 Perovskite.

    Science.gov (United States)

    Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho

    2017-02-16

    To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI 3 perovskite bilayer film (5 ns) compared with pristine MAPbI 3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI 3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI 3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI 3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.

  8. 75 FR 9120 - Electronic Fund Transfers

    Science.gov (United States)

    2010-03-01

    ... FEDERAL RESERVE SYSTEM 12 CFR Part 205 [Regulation E; Docket No. R-1343] Electronic Fund Transfers... implements the Electronic Fund Transfer Act, and the official staff commentary to the regulation. The final..., the Board adopted a final rule under Regulation E, which implements the Electronic Fund Transfer Act...

  9. Nonradiative electron and energy transfer. Explicit estimation of the influence of coherent and dephasing processes in a vibrational bath on electronic dynamics

    Czech Academy of Sciences Publication Activity Database

    Menšík, Miroslav; Král, Karel

    2009-01-01

    Roč. 27, č. 3 (2009), s. 671-684 ISSN 0137-1339. [International Conference on Electrical and Related Properties of Organic Solids /11./. Piechowice, 13.07.2008-17.07.2008] R&D Projects: GA AV ČR KAN401770651; GA ČR GA202/07/0643 Institutional research plan: CEZ:AV0Z40500505; CEZ:AV0Z10100520 Keywords : electron-vibrational interaction * non-adiabatic coupling * resonant energy transfer Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.384, year: 2009

  10. Defining Electron Bifurcation in the Electron-Transferring Flavoprotein Family.

    Science.gov (United States)

    Garcia Costas, Amaya M; Poudel, Saroj; Miller, Anne-Frances; Schut, Gerrit J; Ledbetter, Rhesa N; Fixen, Kathryn R; Seefeldt, Lance C; Adams, Michael W W; Harwood, Caroline S; Boyd, Eric S; Peters, John W

    2017-11-01

    energy conservation. Bifurcating enzymes couple thermodynamically unfavorable reactions with thermodynamically favorable reactions in an overall spontaneous process. Here we show that the electron-transferring flavoprotein (Etf) enzyme family exhibits far greater diversity than previously recognized, and we provide a phylogenetic analysis that clearly delineates bifurcating versus nonbifurcating members of this family. Structural modeling of proteins within these groups reveals key differences between the bifurcating and nonbifurcating Etfs. Copyright © 2017 American Society for Microbiology.

  11. Electron transfer processes in ion collisions with atomic hydrogen. Final report for period February 1, 1975--June 30, 1976

    International Nuclear Information System (INIS)

    Bayfield, J.E.

    1976-07-01

    Results of experiments completed with Yale equipment coupled to the Oak Ridge Test Bench and Tandem Accelerator facilities are presented. Electron transfer cross sections have been measured at keV collision energies for B, C, N and O ions colliding with H, H 2 , Ar and He gas targets. The ion charge states studied range from +2 through +5. Also reported are cross sections for Si and Fe ions on H, H 2 and Ar at energies between 1.5 and 14 MeV, with charge states varying between +5 and +13. Also measured were the cross sections for H + collisions with H, H 2 and Ar for energies between 0.8 and 2.5 MeV. At keV energies the cross sections for highly charged B, C, N and O ions are found to be 1 x 10 -14 cm 2 . The cross sections for 4 MeV Fe ions scale roughly with the square of the ion charge, and have values as high as 0.5 x 10 -14 cm 2 for Fe 10+ + H collisions. A strong energy dependence is found for Fe ion collisions between 4 and 14 MeV. Previous results for MeV H + + Ar collisions are nicely reproduced, while our first results for the fundamental MeV H + - H collision problem are cross sections higher than many theoretical predictions

  12. Exocellular electron transfer in anaerobic microbial communities

    NARCIS (Netherlands)

    Stams, A.J.M.; Bok, de F.A.M.; Plugge, C.M.; Eekert, van M.H.A.; Dolfing, J.; Schraa, G.

    2006-01-01

    Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory

  13. Transfer coating by electron initiated polymerization

    International Nuclear Information System (INIS)

    Nablo, S.V.

    1984-01-01

    The high speed and depth of cure possible with electron initiated monomer/oligomer coating systems provide many new opportunities for approaches to product finishing. Moreover, the use of transfer or cast coating using films or metallic surfaces offers the ability to precisely control the surface topology of liquid film surfaces during polymerization. Transfer coating such as with textiles has been a commercial process for many years and the synergistic addition of EB technology permits the manufacture of unusual new products. One of these, the casting paper used in the manufacture of vinyl and urethane fabrics, is the first EB application to use a drum surface for pattern replication in the coating. In this case the coated paper is cured against, and then released from, an engraved drum surface. Recent developments in the use of plastic films for transfer have been applied to the manufacture of transfer metallized and coated paper and paperboard products for packaging. Details of these and related processes are presented as well as a discussion of the typical product areas (e.g. photographic papers, release papers, magnetic media) using this high speed transfer technology

  14. Transfer coating by electron initiated polymerization

    International Nuclear Information System (INIS)

    Nablo, S.V.

    1985-01-01

    The high speed and depth of cure possible with electron initiated monomer/oligomer coating systems provide many new opportunities for approaches to product finishing. Moreover, the use of transfer or cast coating using films or metallic surfaces offers the ability to precisely control the surface topology of liquid film surfaces during polymerization. Transfer coating such as with textiles has been a commercial process for many years and the synergistic addition of EB technology permits the manufacture of unusual new products. One of these, the casting paper used in the manufacture of vinyl and urethane fabrics, is the first EB application to use a drum surface for pattern replication in the coating. In this case the coated paper is cured against, and then released from, an engraved drum surface. Recent developments in the use of plastic films for transfer have been applied to the manufacture of transfer metallized and coated paper and paperboard products for packaging. Details of these and related processes will be presented as well as a discussion of the typical product areas using this high speed transfer technology. (author)

  15. Electron-attachment processes

    International Nuclear Information System (INIS)

    Christophorou, L.G.; McCorkle, D.L.; Christodoulides, A.A.

    1982-01-01

    Topics covered include: (1) modes of production of negative ions, (2) techniques for the study of electron attachment processes, (3) dissociative electron attachment to ground-state molecules, (4) dissociative electron attachment to hot molecules (effects of temperature on dissociative electron attachment), (5) molecular parent negative ions, and (6) negative ions formed by ion-pair processes and by collisions of molecules with ground state and Rydberg atoms

  16. Hierarchical control of electron-transfer

    DEFF Research Database (Denmark)

    Westerhoff, Hans V.; Jensen, Peter Ruhdal; Egger, Louis

    1997-01-01

    In this chapter the role of electron transfer in determining the behaviour of the ATP synthesising enzyme in E. coli is analysed. It is concluded that the latter enzyme lacks control because of special properties of the electron transfer components. These properties range from absence of a strong...... back pressure by the protonmotive force on the rate of electron transfer to hierarchical regulation of the expression of the gens that encode the electron transfer proteins as a response to changes in the bioenergetic properties of the cell.The discussion uses Hierarchical Control Analysis...

  17. Numerical modeling of heat-transfer and the influence of process parameters on tailoring the grain morphology of IN718 in electron beam additive manufacturing

    International Nuclear Information System (INIS)

    Raghavan, Narendran; Dehoff, Ryan; Pannala, Sreekanth; Simunovic, Srdjan; Kirka, Michael; Turner, John; Carlson, Neil; Babu, Sudarsanam S.

    2016-01-01

    The fabrication of 3-D parts from CAD models by additive manufacturing (AM) is a disruptive technology that is transforming the metal manufacturing industry. The correlation between solidification microstructure and mechanical properties has been well understood in the casting and welding processes over the years. This paper focuses on extending these principles to additive manufacturing to understand the transient phenomena of repeated melting and solidification during electron beam powder melting process to achieve site-specific microstructure control within a fabricated component. In this paper, we have developed a novel melt scan strategy for electron beam melting of nickel-base superalloy (Inconel 718) and also analyzed 3-D heat transfer conditions using a parallel numerical solidification code (Truchas) developed at Los Alamos National Laboratory. The spatial and temporal variations of temperature gradient (G) and growth velocity (R) at the liquid-solid interface of the melt pool were calculated as a function of electron beam parameters. By manipulating the relative number of voxels that lie in the columnar or equiaxed region, the crystallographic texture of the components can be controlled to an extent. The analysis of the parameters provided optimum processing conditions that will result in columnar to equiaxed transition (CET) during the solidification. The results from the numerical simulations were validated by experimental processing and characterization thereby proving the potential of additive manufacturing process to achieve site-specific crystallographic texture control within a fabricated component.

  18. Modeling and computations of the intramolecular electron transfer process in the two-heme protein cytochrome em>c>4

    DEFF Research Database (Denmark)

    Natzmutdinov, Renat R.; Bronshtein, Michael D.; Zinkicheva, Tamara T.

    2012-01-01

    force were determined using dielectric continuum models. We then calculated the electronic transmission coefficient of the intramolecular ET rate using perturbation theory combined with the electronic wave functions determined by the DFT calculations for different heme group orientations and Fe...

  19. Tunneling induced electron transfer between separated protons

    Science.gov (United States)

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

    2018-04-01

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

  20. Transient Exciplex Formation Electron Transfer Mechanism

    OpenAIRE

    Michael G. Kuzmin; Irina V. Soboleva; Elena V. Dolotova

    2011-01-01

    Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for c...

  1. Single-Molecule Interfacial Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Wilson [Univ. of California, Irvine, CA (United States)

    2018-02-03

    Interfacial electron transfer (ET) plays an important role in many chemical and biological processes. Specifically, interfacial ET in TiO2-based systems is important to solar energy technology, catalysis, and environmental remediation technology. However, the microscopic mechanism of interfacial ET is not well understood with regard to atomic surface structure, molecular structure, bonding, orientation, and motion. In this project, we used two complementary methodologies; single-molecule fluorescence spectroscopy, and scanning-tunneling microscopy and spectroscopy (STM and STS) to address this scientific need. The goal of this project was to integrate these techniques and measure the molecular dependence of ET between adsorbed molecules and TiO2 semiconductor surfaces and the ET induced reactions such as the splitting of water. The scanning probe techniques, STM and STS, are capable of providing the highest spatial resolution but not easily time-resolved data. Single-molecule fluorescence spectroscopy is capable of good time resolution but requires further development to match the spatial resolution of the STM. The integrated approach involving Peter Lu at Bowling Green State University (BGSU) and Wilson Ho at the University of California, Irvine (UC Irvine) produced methods for time and spatially resolved chemical imaging of interfacial electron transfer dynamics and photocatalytic reactions. An integral aspect of the joint research was a significant exchange of graduate students to work at the two institutions. This project bridged complementary approaches to investigate a set of common problems by working with the same molecules on a variety of solid surfaces, but using appropriate techniques to probe under ambient (BGSU) and ultrahigh vacuum (UCI) conditions. The molecular level understanding of the fundamental interfacial electron transfer processes obtained in this joint project will be important for developing efficient light harvesting

  2. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    Science.gov (United States)

    Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

    2016-10-01

    Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

  3. Electron transfer in organic glass. Distance and energy dependence

    International Nuclear Information System (INIS)

    Krongauz, V.V.

    1992-01-01

    The authors have investigated the distance and energy dependence of electron transfer in rigid organic glasses containing randomly dispersed electron donor and electron acceptor molecules. Pulsed radiolysis by an electron beam from a linear accelerator was used for ionization resulting in charge deposition on donor molecules. The disappearance kinetics of donor radical anions due to electron transfer to acceptor was monitored spectroscopically by the change in optical density at the wavelength corresponding to that of donor radical anion absorbance. It was found that the rate of the electron transfer observed experimentally was higher than that computed using the Marcus-Levich theory assuming that the electron-transfer activation barrier is equal to the binding energy of electron on the donor molecule. This discrepancy between the experimental and computed results suggests that the open-quotes inertclose quotes media in which electron-transfer reaction takes place may be participating in the process, resulting in experimentally observed higher electron-transfer rates. 32 refs., 3 figs., 2 tabs

  4. Analytical solutions of the planar cyclic voltammetry process for two soluble species with equal diffusivities and fast electron transfer using the method of eigenfunction expansions

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib; Lahti, Erik; Zhang, Jinsuo, E-mail: zhang.3558@osu.edu [Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19" t" h Avenue, Columbus, Ohio 43210 (United States)

    2015-08-15

    Cyclic voltammetry is a powerful tool that is used for characterizing electrochemical processes. Models of cyclic voltammetry take into account the mass transport of species and the kinetics at the electrode surface. Analytical solutions of these models are not well-known due to the complexity of the boundary conditions. In this study we present closed form analytical solutions of the planar voltammetry model for two soluble species with fast electron transfer and equal diffusivities using the eigenfunction expansion method. Our solution methodology does not incorporate Laplace transforms and yields good agreement with the numerical solution. This solution method can be extended to cases that are more general and may be useful for benchmarking purposes.

  5. Analytical solutions of the planar cyclic voltammetry process for two soluble species with equal diffusivities and fast electron transfer using the method of eigenfunction expansions

    International Nuclear Information System (INIS)

    th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Samin, Adib; th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Lahti, Erik; th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Zhang, Jinsuo

    2015-01-01

    Cyclic voltammetry is a powerful tool that is used for characterizing electrochemical processes. Models of cyclic voltammetry take into account the mass transport of species and the kinetics at the electrode surface. Analytical solutions of these models are not well-known due to the complexity of the boundary conditions. In this study we present closed form analytical solutions of the planar voltammetry model for two soluble species with fast electron transfer and equal diffusivities using the eigenfunction expansion method. Our solution methodology does not incorporate Laplace transforms and yields good agreement with the numerical solution. This solution method can be extended to cases that are more general and may be useful for benchmarking purposes

  6. GPU-accelerated computation of electron transfer.

    Science.gov (United States)

    Höfinger, Siegfried; Acocella, Angela; Pop, Sergiu C; Narumi, Tetsu; Yasuoka, Kenji; Beu, Titus; Zerbetto, Francesco

    2012-11-05

    Electron transfer is a fundamental process that can be studied with the help of computer simulation. The underlying quantum mechanical description renders the problem a computationally intensive application. In this study, we probe the graphics processing unit (GPU) for suitability to this type of problem. Time-critical components are identified via profiling of an existing implementation and several different variants are tested involving the GPU at increasing levels of abstraction. A publicly available library supporting basic linear algebra operations on the GPU turns out to accelerate the computation approximately 50-fold with minor dependence on actual problem size. The performance gain does not compromise numerical accuracy and is of significant value for practical purposes. Copyright © 2012 Wiley Periodicals, Inc.

  7. Charge transfer in gas electron multipliers

    Energy Technology Data Exchange (ETDEWEB)

    Ottnad, Jonathan; Ball, Markus; Ketzer, Bernhard; Ratza, Viktor; Razzaghi, Cina [HISKP, Bonn University, Nussallee 14-16, D-53115 Bonn (Germany)

    2015-07-01

    In order to efficiently employ a Time Projection Chamber (TPC) at interaction rates higher than ∝1 kHz, as foreseen e.g. in the ALICE experiment (CERN) and at CB-ELSA (Bonn), a continuous operation and readout mode is required. A necessary prerequisite is to minimize the space charge coming from the amplification system and to maintain an excellent spatial and energy resolution. Unfortunately these two goals can be in conflict to each other. Gas Electron Multipliers (GEM) are one candidate to fulfill these requirements. It is necessary to understand the processes within the amplification structure to find optimal operation conditions. To do so, we measure the charge transfer processes in and between GEM foils with different geometries and field configurations, and use an analytical model to describe the results. This model can then be used to predict and optimize the performance. The talk gives the present status of the measurements and describes the model.

  8. Advances in electron transfer chemistry, v.6

    CERN Document Server

    Mariano, PS

    1999-01-01

    It is clear that electron transfer chemisty is now one of the most active areas of chemical study. Advances in Electron Transfer Chemistry has been designed to allow scientists who are developing new knowledge in this rapidly expanding area to describe their most recent research findings. This volume will serve those interested in learning about current breakthroughs in this rapidly expanding area of chemical research.

  9. Dissociative electron attachment and charge transfer in condensed matter

    International Nuclear Information System (INIS)

    Bass, A.D.; Sanche, L.

    2003-01-01

    Experiments using energy-selected beams of electrons incident from vacuum upon thin vapour deposited solids show that, as in the gas-phase, scattering cross sections at low energies are dominated by the formation of temporary negative ions (or resonances) and that molecular damage may be effected via dissociative electron attachment (DEA). Recent results also show that charge transfer between anionic states of target molecules and their environment is often crucial in determining cross sections for electron driven processes. Here, we review recent work from our laboratory, in which charge transfer is observed. For rare gas solids, electron exchange between the electron-exciton complex and either a metal substrate or co-adsorbed molecule enhances the desorption of metastable atoms and/or molecular dissociation. We discuss how transient electron capture by surface electron states of a substrate and subsequent electron transfer to a molecular adsorbate enhances the effective cross sections for DEA. We also consider the case of DEA to CF 2 Cl 2 condensed on water and ammonia ices, where electron exchange between pre-solvated electron states of ice and transient molecular anions can also increase DEA cross sections. Electron transfer from molecular resonances into pre-solvated electron states of ice is also discussed

  10. Laser pulse control of bridge mediated heterogeneous electron transfer

    International Nuclear Information System (INIS)

    Wang Luxia; May, Volkhard

    2009-01-01

    Ultrafast heterogeneous electron transfer from surface attached dye molecules into semiconductor band states is analyzed. The focus is on systems where the dye is separated from the surface by different bridge anchor groups. To simulate the full quantum dynamics of the transfer process a model of reduced dimensionality is used. It comprises the electronic levels of the dye, the bridge anchor group electronic levels and the continuum of semiconductor band states, all defined versus a single intramolecular vibrational coordinate. The effect of the bridge states is demonstrated, firstly, in studying the injection dynamics following an impulsive excitation of the dye. Then, by discussing different control tasks it is demonstrate in which way the charge injection process can be influenced by tailored laser pulses. To highlight the importance of electron wave function interference emphasis is put on asymmetric two-bridge molecule systems which are also characterized by different and complex valued electronic transfer matrix elements.

  11. Electron transfer in gas surface collisions

    International Nuclear Information System (INIS)

    Wunnik, J.N.M. van.

    1983-01-01

    In this thesis electron transfer between atoms and metal surfaces in general is discussed and the negative ionization of hydrogen by scattering protons at a cesiated crystalline tungsten (110) surface in particular. Experimental results and a novel theoretical analysis are presented. In Chapter I a theoretical overview of resonant electron transitions between atoms and metals is given. In the first part of chapter II atom-metal electron transitions at a fixed atom-metal distance are described on the basis of a model developed by Gadzuk. In the second part the influence of the motion of the atom on the atomic charge state is incorporated. Measurements presented in chapter III show a strong dependence of the fraction of negatively charged H atoms scattered at cesiated tungsten, on the normal as well as the parallel velocity component. In chapter IV the proposed mechanism for the parallel velocity effect is incorporated in the amplitude method. The scattering process of protons incident under grazing angles on a cesium covered surface is studied in chapter V. (Auth.)

  12. Crossed-Beam Scattering Studies of Electron-Transfer Processes between the Dication CO22+ and Neutral CO2: Electronic States of Reactants and Products Involved

    Czech Academy of Sciences Publication Activity Database

    Žabka, Ján; Ricketts, Claire; Schröder, Detlef; Roithová, J.; Schwarz, H.; Thissen, R.; Dutuit, O.; Price, S. D.; Herman, Zdeněk

    2010-01-01

    Roč. 114, č. 23 (2010), s. 6463-6471 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400400702; GA ČR GA203/09/1223 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : charge transfer reactions * reactivity * CO2 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.732, year: 2010

  13. Transient Exciplex Formation Electron Transfer Mechanism

    Directory of Open Access Journals (Sweden)

    Michael G. Kuzmin

    2011-01-01

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

  14. A Doping Lattice of Aluminum and Copper with Accelerated Electron Transfer Process and Enhanced Reductive Degradation Performance

    Science.gov (United States)

    Zhang, Lin; Gao, Xue; Zhang, Zhixuan; Zhang, Mingbo; Cheng, Yiqian; Su, Jixin

    2016-08-01

    Treatment of azo dye effluents has received increasing concerns over the years due to their potential harms to natural environment and human health. The present study described the degrading ability of the as-synthesized crystalline Al-Cu alloys for removal of high-concentration Acid Scarlet 3R in alkaline aqueous solutions and its degradation mechanism. Al-Cu alloy particles with Al/Cu ratios 19:1 were successfully synthesized by high-energy mechanical milling. Characterization results showed that 10 h mechanical alloying process could lead to the formation of crystalline Al(Cu) solid solution. Batch experiment results confirmed the excellent ability of Al-Cu alloy particles for the degradation of 3R in aqueous solution. Under a certain condition ([Al-Cu]0 = 2 g/L, [3R]0 = 200 mg/L, [NaCl]0 = 25 g/L, initial pH = 10.9), the 3R could be completely degraded within only 3 min. It was also found that the degradation reaction followed zero-order kinetics model with respect to the initial dye concentration. The intermediate compounds were identified by UV-vis, FT-IR and HPLC-MS, and a pathway was proposed. Additionally, post-treatment Al-Cu alloy particles were characterized by SEM and TEM, and the results showed that the degradation might be attributed to the corrosion effect of Al-Cu alloys.

  15. Electron beam processing system

    International Nuclear Information System (INIS)

    Kashiwagi, Masayuki

    2004-01-01

    Electron beam Processing Systems (EPS) are used as useful and powerful tools in many industrial application fields such as the production of cross-linked wire, rubber tire, heat shrinkable film and tubing, curing, degradation of polymers, sterilization and environmental application. In this paper, the feature and application fields, the selection of machine ratings and safety measures of EPS will be described. (author)

  16. Comparison of silver(II), cobalt(III), and cerium(IV) as electron transfer mediators in the MEO mixed waste treatment process

    International Nuclear Information System (INIS)

    Smith, W.H.; Purdy, G.M.; McKee, S.D.

    1997-01-01

    Mediated electrochemical oxidation (MEO) has been developed as a method to treat mixed hazardous waste. The technology has for the most part been targeted toward wastes generated by the nuclear industry, consisting of a hazardous or non-hazardous organic material contaminated by a radioactive substance. The MEO process consists of the electrochemical generation of a powerful oxidizing agent, which serves as an electron transfer mediator to bring about the oxidation of the organic component. Numerous studies on a variety of organic substrates have demonstrated complete oxidation to carbon dioxide can be realized under the proper reaction conditions, with water serving as the source of oxygen. The radioactive component, usually an actinide element or heavy metal isotope, can then be recovered from the resulting organic free aqueous solution by standard methods such as ion exchange or solvent extraction. In addition to the variety of organic compounds tested, investigators have also looked at a number of process parameters including choice of mediator, temperature, concentration of mediator, current density, anode material, acid concentration, and cell separator material. From these studies it would appear that for a given organic substrate, the two most important process parameters are choice of mediator and temperature. The purpose of this work is to evaluate these two parameters for a given organic material, holding all other parameters constant. The organic material chosen for this study is the industry standard sulfonated styrene-divinyl benzene based cation exchange resin. This material is ubiquitous throughout the nuclear complex as a process residue, and is very resistant to chemical attack making it an ideal substrate to evaluate MEO capability. A high acid concentration is necessary to solubilize the mediator in its higher oxidation state, 6 M nitric acid was chosen since it is compatible with existing subsequent actinide element recovery processes

  17. Intramolecular photoinduced electron-transfer in azobenzene-perylene diimide

    International Nuclear Information System (INIS)

    Feng Wen-Ke; Wang Shu-Feng; Gong Qi-Huang; Feng Yi-Yu; Feng Wei; Yi Wen-Hui

    2010-01-01

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10 11 s −1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  18. Legal Risk Associated with Electronic Funds Transfer

    OpenAIRE

    Abdulah, Samahir

    2014-01-01

    The past thirty years have seen rapid advances in the technological component of banking services and as a consequence new legal issues have come to the fore, especially with regard to Electronic Fund Transfers (EFTs) which are now used to transfer money around the world, and have made fund transactions between payers and payees easier, faster and more secure. The method involves risks for both banks and customers, due to the possibility of unauthorized payments risks, credit and insolvency p...

  19. The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

    Science.gov (United States)

    Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

    2007-01-18

    Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

  20. Investigation by high resolution electron spectroscopy of the helium-like 3lnl' Rydberg series in double capture processes at low collision velocity: auto transfer to Rydberg states and electron stabilization

    Energy Technology Data Exchange (ETDEWEB)

    Bordenave-Montesquieu, A.; Moretto-Capelle, P.; Gonzalez, A.; Benhenni, M. (Toulouse-3 Univ., 31 (France)); Bachau, H.; Sanchez, I. (Bordeaux-1 Univ., 33 - Talence (France). Lab. des Collisions Atomiques)

    1994-09-28

    A high resolution electron spectrometry of the (3lnl') Ryberg series populated in N[sup 7+] + He and Ne[sup 10+] + He collisions at 10 q keV, 10[sup o] allows us to observe, for the first time by this method, two post-collisional effects. First, it is found with nitrogen ions that, when n increases from n = 4 to 9, the L-distribution peaks more and more on the high angular momentum states. This is qualitatively understood as a Stark deformation of the Rydberg orbit by the Coulomb field of the receding ion. Also, in the n range where the double capture process populates symmetrical 4l4l' states (n>9), an enhancement of the intensities of the 3lnl' Rydberg lines is observed for both collisonal systems. This is thought to be a signature of the so-called auto transfer to Rydberg states effect. The transfer of population from the 3l4l' to the 3lnl' states is found to be favoured against a direct autoionization of these 4l4l' states into the n = 2 continuum. These experimental findings together with preliminary spectroscopic calculations concerning the configuration interaction of the Ne[sup 8+] (4l4l') states with the Ne[sup 8+](3lnl') Rydberg series are also discussed within the context of the electron stabilization which follows a double capture. (Author).

  1. Investigation by high resolution electron spectroscopy of the helium-like 3lnl' Rydberg series in double capture processes at low collision velocity: auto transfer to Rydberg states and electron stabilization

    International Nuclear Information System (INIS)

    Bordenave-Montesquieu, A.; Moretto-Capelle, P.; Gonzalez, A.; Benhenni, M.; Bachau, H.; Sanchez, I.

    1994-01-01

    A high resolution electron spectrometry of the (3lnl') Ryberg series populated in N 7+ + He and Ne 10+ + He collisions at 10 q keV, 10 o allows us to observe, for the first time by this method, two post-collisional effects. First, it is found with nitrogen ions that, when n increases from n = 4 to 9, the L-distribution peaks more and more on the high angular momentum states. This is qualitatively understood as a Stark deformation of the Rydberg orbit by the Coulomb field of the receding ion. Also, in the n range where the double capture process populates symmetrical 4l4l' states (n>9), an enhancement of the intensities of the 3lnl' Rydberg lines is observed for both collisonal systems. This is thought to be a signature of the so-called auto transfer to Rydberg states effect. The transfer of population from the 3l4l' to the 3lnl' states is found to be favoured against a direct autoionization of these 4l4l' states into the n = 2 continuum. These experimental findings together with preliminary spectroscopic calculations concerning the configuration interaction of the Ne 8+ (4l4l') states with the Ne 8+ (3lnl') Rydberg series are also discussed within the context of the electron stabilization which follows a double capture. (Author)

  2. Facile Interfacial Electron Transfer of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Chunhai Fan

    2005-12-01

    Full Text Available Abstract: We herein describe a method of depositing hemoglobin (Hb and sulfonated polyaniline (SPAN on GC electrodes that facilitate interfacial protein electron transfer. Well-defined, reproducible, chemically reversible peaks of Hb and SPAN can be obtained in our experiments. We also observed enhanced peroxidase activity of Hb in SPAN films. These results clearly showed that SPAN worked as molecular wires and effectively exchanged electrons between Hb and electrodes.Mediated by Conjugated Polymers

  3. Elastic electron scattering at large momentum transfer

    International Nuclear Information System (INIS)

    Arnold, R.G.

    1979-05-01

    A review is given of elastic electron scattering at large momentum transfer (Q 2 > 20 fm -2 ) from nuclei with A less than or equal to 4. Recent experimental results are reviewed and the current problems in interpretation of these results are pointed out. Some questions for future experiments are posed, and a preview of possible future measurements is presented. 28 references

  4. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar...... biochar may enhance methane production from organic wastes under anaerobic conditions....

  5. Quantum effects in biological electron transfer

    Czech Academy of Sciences Publication Activity Database

    de la Lande, A.; Babcock, N. S.; Řezáč, Jan; Levy, B.; Sanders, B. C.; Salahub, D.

    2012-01-01

    Roč. 14, č. 17 (2012), s. 5902-5918 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506 Keywords : electron transfer * tunnelling * decoherence * semi-classical molecular dynamics * density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

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

    Science.gov (United States)

    Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

    2011-03-24

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

  7. Heat transfer between adsorbate and laser-heated hot electrons

    International Nuclear Information System (INIS)

    Ueba, H; Persson, B N J

    2008-01-01

    Strong short laser pulses can give rise to a strong increase in the electronic temperature at metal surfaces. Energy transfer from the hot electrons to adsorbed molecules may result in adsorbate reactions, e.g. desorption or diffusion. We point out the limitations of an often used equation to describe the heat transfer process in terms of a friction coupling. We propose a simple theory for the energy transfer between the adsorbate and hot electrons using a newly introduced heat transfer coefficient, which depends on the adsorbate temperature. We calculate the transient adsorbate temperature and the reaction yield for a Morse potential as a function of the laser fluency. The results are compared to those obtained using a conventional heat transfer equation with temperature-independent friction. It is found that our equation of energy (heat) transfer gives a significantly lower adsorbate peak temperature, which results in a large modification of the reaction yield. We also consider the heat transfer between different vibrational modes excited by hot electrons. This mode coupling provides indirect heating of the vibrational temperature in addition to the direct heating by hot electrons. The formula of heat transfer through linear mode-mode coupling of two harmonic oscillators is applied to the recent time-resolved study of carbon monoxide and atomic oxygen hopping on an ultrafast laser-heated Pt(111) surface. It is found that the maximum temperature of the frustrated translation mode can reach high temperatures for hopping, even when direct friction coupling to the hot electrons is not strong enough

  8. [Electron transfer, ionization, and excitation in atomic collisions

    International Nuclear Information System (INIS)

    1992-01-01

    Fundamental processes of electron transfer, ionization, and excitation in ion-atom and ion-ion collisions are studied. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-ion core can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. At intermediate collision energies (e.g., proton energies for p-He + collisions on the order of 100 kilo-electron volts), many electronic states are strongly coupled during the collision, a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. At higher collision energies (million electron-volt energies) the coupling is weaker with, however, many more states being coupled together, so that high-order perturbation theory is essential

  9. Electron transfer from nucleobase electron adducts to 5-bromouracil. Is guanine an ultimate sink for the electron in irradiated DNA?

    International Nuclear Information System (INIS)

    Nese, C.; Yuan, Z.; Schuchmann, M.N.; Sonntag, C. von

    1992-01-01

    Electron transfer to 5-bromouracil (5-BrU) from nucleobase (N) electron adducts (and their protonated forms) has been studied by product analysis and pulse radiolysis. When an electron is transferred to 5-BrU, the ensuing 5-BrU radical anion rapidly loses a bromide ion; the uracilyl radical thus formed reacts with added t-butanol, yielding uracil. From the uracil yields measured as the function of [N]/[5-BrU] after γ-radiolysis of Ar-saturated solutions it is concluded that thymine and adenine electron adducts and their heteroatom-protonated forms transfer electrons quantitatively to 5-BrU. The data raise the question whether in DNA the guanine moiety may act as the ultimate sink of the electron in competition with other processes such as protonation at C(6) of the thymine electron adduct. (Author)

  10. Mechanism of Intermolecular Electron Transfer in Bionanostructures

    Science.gov (United States)

    Gruodis, A.; Galikova, N.; Šarka, K.; Saulė, R.; Batiuškaitė, D.; Saulis, G.

    Hepatocellular carcinoma (HCC) is one of the most common malignant tumors worldwide. Most patients are inoperable and hepatoma cells are resistant to conventional chemotherapies. Thus, the development of novel therapies for HCC treatment is of paramount importance. Amongst different alimentary factors, vitamin C and vitamin K3 In the present work, it has been shown that the treatment of mouse hepatoma MH-22A cells by vitamin C and vitamin K3 at the ratio of 100:1 greatly enhanced their cytotoxicity. When cells were subjected to vitamin C at 200 μM or to vitamin K3 at 2 μM separately, their viability reduced by only about 10%. However, when vitamins C and K3 were combined at the same concentrations, they killed more than 90% of cells. To elucidate the mechanism of the synergistic cytotoxicity of the C&K3 mixture, theoretical quantum-chemical analysis of the dynamics of intermolecular electron transfer (IET) processes within the complexes containing C (five forms) and K3 (one form) has been carried out. Optimization of the ground state complex geometry has been provided by means of GAUSSIAN03 package. Simulation of the IET has been carried out using NUVOLA package, in the framework of molecular orbitals (MO). The rate of IET has been calculated using Fermi Golden rule. The results of simulations allow us to create the preliminary model of the reaction pathway.

  11. Electron Transfer in Chemistry and Biology - The Primary Events in ...

    Indian Academy of Sciences (India)

    transfers, occurs in a cascade in many biological processes, including photosynthesis. ... the model reactions of photosynthetic ... biological relevance. GENERAL I ARTICLE of electrons, respectively. This has entirely changed the earlier framework of interpreting reactions in chemistry and biology. This shift in emphasis ...

  12. Intramolecular electron transfer in single-site-mutated azurins

    DEFF Research Database (Denmark)

    Farver, O; Skov, L K; Pascher, T

    1993-01-01

    . Natl. Acad. Sci. U.S.A. 86, 6968-6972]. The RSSR- radical produced in the above reaction was reoxidized in a slower intramolecular electron-transfer process (30-70 s-1 at 298 K) concomitant with a further reduction of the Cu(II) ion. The temperature dependence of the latter rates was determined......, lambda = 135 kJ mol-1 for the reorganization energy was derived. When Trp48, situated midway between the donor and the acceptor, was replaced by Leu or Met, only a small change in the rate of intramolecular electron transfer was observed, indicating that the aromatic residue in this position...... is apparently only marginally involved in electron transfer in wild-type azurin. Pathway calculations also suggest that a longer, through-backbone path is more efficient than the shorter one involving Trp48. The former pathway yields an exponential decay factor, beta, of 6.6 nm-1. Another mutation, raising...

  13. Biotechnological Aspects of Microbial Extracellular Electron Transfer

    Science.gov (United States)

    Kato, Souichiro

    2015-01-01

    Extracellular electron transfer (EET) is a type of microbial respiration that enables electron transfer between microbial cells and extracellular solid materials, including naturally-occurring metal compounds and artificial electrodes. Microorganisms harboring EET abilities have received considerable attention for their various biotechnological applications, in addition to their contribution to global energy and material cycles. In this review, current knowledge on microbial EET and its application to diverse biotechnologies, including the bioremediation of toxic metals, recovery of useful metals, biocorrosion, and microbial electrochemical systems (microbial fuel cells and microbial electrosynthesis), were introduced. Two potential biotechnologies based on microbial EET, namely the electrochemical control of microbial metabolism and electrochemical stimulation of microbial symbiotic reactions (electric syntrophy), were also discussed. PMID:26004795

  14. Dynamics in electron transfer protein complexes

    OpenAIRE

    Bashir, Qamar

    2010-01-01

    Recent studies have provided experimental evidence for the existence of an encounter complex, a transient intermediate in the formation of protein complexes. We have used paramagnetic relaxation enhancement NMR spectroscopy in combination with Monte Carlo simulations to characterize and visualize the ensemble of encounter orientations in the short-lived electron transfer complex of yeast Cc and CcP. The complete conformational space sampled by the protein molecules during the dynamic part of ...

  15. Electron transfer from electronic excited states to sub-vacuum electron traps in amorphous ice

    International Nuclear Information System (INIS)

    Vichnevetski, E.; Bass, A.D.; Sanche, L.

    2000-01-01

    We investigate the electron stimulated yield of electronically excited argon atoms (Ar * ) from monolayer quantities of Ar deposited onto thin films of amorphous ice. Two peaks of narrow width ( - electron-exciton complex into exciton states, by the transfer of an electron into a sub-vacuum electron state within the ice film. However, the 10.7 eV feature is shifted to lower energy since electron attachment to Ar occurs within small pores of amorphous ice. In this case, the excess electron is transferred into an electron trap below the conduction band of the ice layer

  16. MASS TRANSFER IN FERMENTATION PROCESSES

    Directory of Open Access Journals (Sweden)

    A. Shevchenko

    2018-04-01

    Full Text Available The peculiarities of anaerobic fermentation processes with the accumulation of dissolved ethyl alcohol and carbon dioxide in the culture media are considered in the article.The solubility of CO2 is limited by the state of saturation in accordance with Henry’s law. This, with all else being equal, limits the mass transfer on the interface surface of yeast cells and the liquid phase of the medium. A phenomenological model of the media restoration technologies based on the unsaturation index on СО2 is developed. It is shown that this restoration in the existing technologies of fermentation of sugar-rich media occurs, to a limited extent, in self-organized flow circuits, with variable values of temperatures and hydrostatic pressures, due to the creation of unsaturated local zones.It is shown that increasing the height of the media in isovolumetric apparatuses leads to an increase in the levels of flow circuits organization and to the improvement of the desaturation and saturation modes of the liquid phase and intensification of mass transfer processes. Among the deterministic principles of restoring the saturation possibilities of the media, there are forced variables of pressures with time pauses on their lower and upper levels. In such cases, the possibilities of short-term intensive desaturations in full media volumes, the restoration of their saturation perception of CO2, and the activation of fermentation processes are achieved. This direction is technically feasible for active industrial equipment.The cumulative effect of the action of variable pressures and temperatures corresponds to the superposition principle, but at the final stages of fermentation, the pressure and temperature values are leveled, so the restoration of the unsaturation state slows down to the level of the bacteriostatic effect. The possibility of eliminating the disadvantages of the final stage of fermentation by means of programmable variable pressures is shown

  17. Electronic Handbooks Simplify Process Management

    Science.gov (United States)

    2012-01-01

    Getting a multitude of people to work together to manage processes across many organizations for example, flight projects, research, technologies, or data centers and others is not an easy task. Just ask Dr. Barry E. Jacobs, a research computer scientist at Goddard Space Flight Center. He helped NASA develop a process management solution that provided documenting tools for process developers and participants to help them quickly learn, adapt, test, and teach their views. Some of these tools included editable files for subprocess descriptions, document descriptions, role guidelines, manager worksheets, and references. First utilized for NASA's Headquarters Directives Management process, the approach led to the invention of a concept called the Electronic Handbook (EHB). This EHB concept was successfully applied to NASA's Small Business Innovation Research (SBIR) and Small Business Technology Transfer (STTR) programs, among other NASA programs. Several Federal agencies showed interest in the concept, so Jacobs and his team visited these agencies to show them how their specific processes could be managed by the methodology, as well as to create mockup versions of the EHBs.

  18. Promoting Interspecies Electron Transfer with Biochar

    Science.gov (United States)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Malvankar, Nikhil S.; Liu, Fanghua; Fan, Wei; Nevin, Kelly P.; Lovley, Derek R.

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were attached to the biochar, yet not in close contact, suggesting that electrons were likely conducted through the biochar, rather than biological electrical connections. The finding that biochar can stimulate DIET may be an important consideration when amending soils with biochar and can help explain why biochar may enhance methane production from organic wastes under anaerobic conditions. PMID:24846283

  19. Quality assurance and data collection -- Electronic Data Transfer

    International Nuclear Information System (INIS)

    Tomczak, L.M.; Lohner, W.G.; Ray, E.C.; Salesky, J.A.; Spitz, H.B.

    1993-05-01

    The Radiological Environmental Monitoring (REM) group at the Fernald Environmental Management Project is involved in an Electronic Data Transfer practice that will result in the improved quality assurance of collected data. This practice focuses on electronic data transfer from the recording instrument to reduce the manpower normally required for manual data entry and improve the quality of the data transferred. The application of this practice can enhance any data collection program where instruments with electronic memories and a signal output are utilized. Organizations employing this practice can strengthen the quality and efficiency of their data collection program. The use of these practices can assist in complying with Quality Assurance requirements under ASME NQA-1, RCRA, CERCLA, and DOE Order activities. Data from Pylon AB-5 instrumentation is typically configured to print data to a tape. The REM group has developed a process to electronically transfer stored data. The data are sent from the Pylon AB-5 field instrument to a HewlettPackard portable hand computer, model HP95LX. Data are recorded and stored on a 128 K-byte RAN card and later transferred to a PC database as an electronic file for analysis. The advantage of this system is twofold: (1) Data entry errors are eliminated and (2) considerable data collection and entry time is eliminated. Checks can then be conducted for data validity between recorded intervals due to light leaks etc. and the detection of outliers. This paper will discuss the interface and connector components that allow this transfer of data from the Pylon to the PC to take place and the process to perform that activity

  20. 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...

  1. Multiple-electron processes in fast ion-atom collisions

    International Nuclear Information System (INIS)

    Schlachter, A.S.

    1989-03-01

    Research in atomic physics at the Lawrence Berkeley Laboratory Super-HILAC and Bevalac accelerators on multiple-electron processes in fast ion-atom collisions is described. Experiments have studied various aspects of the charge-transfer, ionization, and excitation processes. Examples of processes in which electron correlation plays a role are resonant transfer and excitation and Auger-electron emission. Processes in which electron behavior can generally be described as uncorrelated include ionization and charge transfer in high-energy ion-atom collisions. A variety of experiments and results for energies from 1 MeV/u to 420 MeV/u are presented. 20 refs., 15 figs

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

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

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

  3. Double electron transfer in H- + H+ collisions

    International Nuclear Information System (INIS)

    Braeuning, H; Helm, H; Briggs, J S; Salzborn, E

    2007-01-01

    Absolute cross sections for double electron transfer in H - + H + collisions have been measured for center-of-mass energies from 0.5 keV to 12 keV. Clear oscillations in the cross section are observed which are in excellent agreement with earlier measurements at lower energies by Brouillard et al (1979) as well as Peart and Dolder (1979). After an oscillation maximum at 3 keV center-of-mass energy the cross section decreases for increasing energy with no indication of further oscillations

  4. Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

    Energy Technology Data Exchange (ETDEWEB)

    Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

    2006-02-01

    The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

  5. Electron transfer pathways in microbial oxygen biocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Freguia, Stefano, E-mail: stefano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Tsujimura, Seiya, E-mail: seiya@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Kano, Kenji, E-mail: kkano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan)

    2010-01-01

    The ability of some bacteria to enhance the rate of cathodic oxygen reduction to water has been recently discovered, opening the way to an entirely renewable and environmentally friendly concept of biocathode. In this study we reveal that several mechanisms may induce catalytic effects by bacteria. These comprise mechanisms that are putatively beneficial to the bacteria as well as mechanisms which are merely side effects, including quinone autoxidation and direct O{sub 2} reduction by heme compounds. Here we showed that 1 muM of ACNQ is able to generate a significant catalytic wave for oxygen reduction, with onset at approximately 0 V vs. SHE. Similarly, adsorption of hemin on a carbon surface catalyses O{sub 2} reduction to H{sub 2}O{sub 2} with an onset of +0.2 V vs. SHE. To evaluate the catalytic pathways of live cells on cathodic oxygen reduction, two species of electrochemically active bacteria were selected as pure cultures, namely Acinetobacter calcoaceticus and Shewanella putrefaciens. The former appears to exploit a self-excreted redox compound with redox characteristics matching those of pyrroloquinoline quinone (PQQ) for extracellular electron transfer. The latter appears to utilise outer membrane-bound redox compounds. Interaction of quinones and cytochromes with the membrane-bound electron transfer chain is yet to be proven.

  6. Electron accelerators for waste processing

    International Nuclear Information System (INIS)

    Kon'kov, N.G.

    1976-01-01

    The documents of the International symposium on radiation vaste processing are presented. Questions on waste utilization with the help of electron accelerators are considered. The electron accelerators are shown to have an advantage over some other ionizing radiation sources. A conclusion is made that radiation methods of waste processing are extensively elaborated in many developed countries. It has been pointed out that an electron accelerator is a most cheap and safe ionizing radiation source primarily for processing of gaseous and liquid wastes

  7. INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS

    NARCIS (Netherlands)

    Bartoloni, Fernando Heering; Monteiro Leite Ciscato, Luiz Francisco; Augusto, Felipe Alberto; Baader, Wilhelm Josef

    2010-01-01

    INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS. Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron

  8. ICAT and the NASA technology transfer process

    Science.gov (United States)

    Rifkin, Noah; Tencate, Hans; Watkins, Alison

    1993-01-01

    This paper will address issues related to NASA's technology transfer process and will cite the example of using ICAT technologies in educational tools. The obstacles to effective technology transfer will be highlighted, viewing the difficulties in achieving successful transfers of ICAT technologies.

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

    International Nuclear Information System (INIS)

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

    1985-01-01

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

  10. [Electron transfer, ionization and excitation in atomic collisions

    International Nuclear Information System (INIS)

    1991-01-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental atomic-collision processes of electron transfer, ionization, and excitation. Winter has focussed attention on intermediate and, more recently, higher collision energies -- proton energies of at least about 50 keV -- for which coupled-state approaches are appropriate. Alston has concentrated on perturbative approaches to symmetric ion-ion/atom collisions at high energies and to asymmetric collisions at intermediate to high energies

  11. Graphene transfer process and optimization of graphene coverage

    OpenAIRE

    Sabki Syarifah Norfaezah; Shamsuri Shafiq Hafly; Fauzi Siti Fazlina; Chon-Ki Meghashama Lim; Othman Noraini

    2017-01-01

    Graphene grown on transition metal is known to be high in quality due to its controlled amount of defects and potentially used for many electronic applications. The transfer process of graphene grown on transition metal to a new substrate requires optimization in order to ensure that high graphene coverage can be obtained. In this work, an improvement in the graphene transfer process is performed from graphene grown on copper foil. It has been observed that the graphene coverage is affected b...

  12. Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Kroneck, Peter M H; Zumft, Walter G

    2003-01-01

    Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have...... been studied and found to be dominated by pronounced interactions between the c and the d1 hemes. The interactions are expressed both in dramatic changes in the internal electron-transfer rates between these sites and in marked cooperativity in their electron affinity. The results constitute a prime...... example of intraprotein control of the electron-transfer rates by allosteric interactions....

  13. Introduction to electron beam processing

    Energy Technology Data Exchange (ETDEWEB)

    Kawakami, Waichiro [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

    1994-12-31

    The contents are general features in the irradiation of polymers, electron beam machines - low energy, medium energy, high energy; application of EB machine in industries, engineering of EB processing, dosimetry of EB (electron beam) safe operation of EB machine, recent topics on EB processing under development. 3 tabs., 4 figs., 17 refs.

  14. Introduction to electron beam processing

    International Nuclear Information System (INIS)

    Waichiro Kawakami

    1994-01-01

    The contents are general features in the irradiation of polymers, electron beam machines - low energy, medium energy, high energy; application of EB machine in industries, engineering of EB processing, dosimetry of EB (electron beam) safe operation of EB machine, recent topics on EB processing under development. 3 tabs., 4 figs., 17 refs

  15. Rapid long range intramolecular electron transfer within a steroid molecule with two electron binding groups

    International Nuclear Information System (INIS)

    Huddleston, R.K.; Miller, J.R.

    1983-01-01

    Intramolecular electron transfer has been observed to have occurred in less than 100 ns in a steroid molecule having two distinct electron binding groups separated by distances distributed from 7--11 A. Experiments were carried out in organic glasses at 77 K with pulse radiolysis techniques to create trapped electrons which were captured by a group on one end of the steroid molecule. Although one of the groups, benzoate, is held to the steroid spacer by a flexible linkage, the rigidity of the glassy matrices prevented movement to alter the initial distance. Interestingly, no effects of distance were seen: all ET processes appeared to have occurred much faster than our 100 ns time resolution, consistent with measurements of the rate of intermolecular electron transfer between the same functional groups in random solutions. Solvation energetics, on the other hand, had a remarkable influence on the extent and direction of electron transfer. A change in solvent polarity was observed to reverse the direction of electron transfer. Evidence was obtained for a distribution of solvation environments for ions in glasses which may be as broad as 0.15 eV

  16. Direct electron transfer based enzymatic fuel cells

    International Nuclear Information System (INIS)

    Falk, Magnus; Blum, Zoltan; Shleev, Sergey

    2012-01-01

    In this mini-review we briefly describe some historical developments made in the field of enzymatic fuel cells (FCs), discussing important design considerations taken when constructing mediator-, cofactor-, and membrane-less biological FCs (BFCs). Since the topic is rather extensive, only BFCs utilizing direct electron transfer (DET) reactions on both the anodic and cathodic sides are considered. Moreover, the performance of mostly glucose/oxygen biodevices is analyzed and compared. We also present some unpublished results on mediator-, cofactor-, and membrane-less glucose/oxygen BFCs recently designed in our group and tested in different human physiological fluids, such as blood, plasma, saliva, and tears. Finally, further perspectives for BFC applications are highlighted.

  17. Sensitivity of Electron Transfer Mediated Decay to Ion Pairing.

    Science.gov (United States)

    Pohl, Marvin N; Richter, Clemens; Lugovoy, Evgeny; Seidel, Robert; Slavíček, Petr; Aziz, Emad F; Abel, Bernd; Winter, Bernd; Hergenhahn, Uwe

    2017-08-17

    Ion pairing in electrolyte solutions remains a topic of discussion despite a long history of research. Very recently, nearest-neighbor mediated electronic de-excitation processes of core hole vacancies (electron transfer mediated decay, ETMD) were proposed to carry a spectral fingerprint of local solvation structure and in particular of contact ion pairs. Here, for the first time, we apply electron-electron coincidence detection to a liquid microjet, and record ETMD spectra of Li 1s vacancies in aqueous solutions of lithium chloride (LiCl) in direct comparison to lithium acetate (LiOAc). A change in the ETMD spectrum dependent on the electrolyte anion identity is observed for 4.5 M salt concentration. We discuss these findings within the framework of the formation and presence of contact ion pairs and the unique sensitivity of ETMD spectroscopy to ion pairing.

  18. Electron transfer oxidation of DNA radicals by paranitroacetophenone

    Energy Technology Data Exchange (ETDEWEB)

    Whillans, D W; Adams, G E [Mount Vernon Hospital, Northwood (UK)

    1975-12-01

    The reaction of a typical electron-affinic sensitizer, paranitroacetophenone (PNAP) with the model compounds thymine, thymidine, thymidylic acid, deoxyribose and single and double-stranded DNA has been investigated by pulse radiolysis. Radicals formed by one-electron reduction of the bases and of DNA reacted rapidly and efficiently with PNAP by electron transfer. A small yield of transfer (< 10 per cent) was also observed arising from oxidation of the radicals formed by the small proportion of OH which reacted at the sugar moieties in DNA. In contrast, electron transfer oxidation by PNAP of radicals formed by the addition of OH to the base moieties, e.g. thymine, was not an efficient process. Further, addition of the sensitizer to the thymine OH-adduct proceeded at a rate that was too low to measure the pulse radiolysis. We conclude that, since the major sites of OH reaction by DNA are the heterocyclic bases (> 80 per cent), oxidation of the resultant radicals is unlikely to be a major step in the mechanism of sensitization by this typical hypoxic-cell sensitizer.

  19. Electron Transfer Mechanisms of DNA Repair by Photolyase

    Science.gov (United States)

    Zhong, Dongping

    2015-04-01

    Photolyase is a flavin photoenzyme that repairs two DNA base damage products induced by ultraviolet (UV) light: cyclobutane pyrimidine dimers and 6-4 photoproducts. With femtosecond spectroscopy and site-directed mutagenesis, investigators have recently made significant advances in our understanding of UV-damaged DNA repair, and the entire enzymatic dynamics can now be mapped out in real time. For dimer repair, six elementary steps have been characterized, including three electron transfer reactions and two bond-breaking processes, and their reaction times have been determined. A unique electron-tunneling pathway was identified, and the critical residues in modulating the repair function at the active site were determined. The dynamic synergy between the elementary reactions for maintaining high repair efficiency was elucidated, and the biological nature of the flavin active state was uncovered. For 6-4 photoproduct repair, a proton-coupled electron transfer repair mechanism has been revealed. The elucidation of electron transfer mechanisms and two repair photocycles is significant and provides a molecular basis for future practical applications, such as in rational drug design for curing skin cancer.

  20. 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...

  1. Large scale oil lease automation and electronic custody transfer

    International Nuclear Information System (INIS)

    Price, C.R.; Elmer, D.C.

    1995-01-01

    Typically, oil field production operations have only been automated at fields with long term production profiles and enhanced recovery. The automation generally consists of monitoring and control at the wellhead and centralized facilities. However, Union Pacific Resources Co. (UPRC) has successfully implemented a large scale automation program for rapid-decline primary recovery Austin Chalk wells where purchasers buy and transport oil from each individual wellsite. This project has resulted in two significant benefits. First, operators are using the system to re-engineer their work processes. Second, an inter-company team created a new electronic custody transfer method. This paper will describe: the progression of the company's automation objectives in the area; the field operator's interaction with the system, and the related benefits; the research and development of the new electronic custody transfer method

  2. 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...

  3. Ab Initio Analysis of Auger-Assisted Electron Transfer.

    Science.gov (United States)

    Hyeon-Deuk, Kim; Kim, Joonghan; Prezhdo, Oleg V

    2015-01-15

    Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

  4. Photoinduced electron transfer process on emission spectrum of N,N‧-bis(salicylidene)-1,2-phenylenediamine as a Mg2+ cation chemosensor: A first principle DFT and TDDFT study

    Science.gov (United States)

    Taherpour, Avat (Arman); Jamshidi, Morteza; Rezaei, Omid; Belverdi, Ali Rezaei

    2018-06-01

    The electronic and optical properties of N,N‧-bis(salicylidene)-1,2-phenylenediamine (SPDA) ligand were studied as a chemical sensor of Mg2+ cation in two solvents (water and DMSO) using the ab initio theory through Density Functional Theory (DFT) and Time Dependent Density Functional theory (TDDFT) methods. The results show that the SPDA ligand has a high ability for chemical sensing of Mg2+. The results has also represented that HOMO-LUMO energy gap decreases 0.941 eV after the complex formation between SPDA and Mg2+. In addition, obvious changes are found in the UV-Vis absorption spectrum, optical analyses SPDA ligand and [SPDA.Mg]2+ complex, which it has the capability of detecting Mg2+ via the adsorptive UV-Vis and colorimetric methods. Emission spectrum calculations and photoinduced electron transfer (PET) process in water solution shows different wavelength emission spectrum in amount of 4.6 nm. An analysis of NBO (natural bond orbital) data indicates tangible changes in the electron transfers data from the electron pairs of ligand to the conjugated system, both prior and subsequent to Mg2+addition.

  5. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    Sutin, N.

    1977-01-01

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

  6. Penning ionization processes studied by electron spectroscopy

    International Nuclear Information System (INIS)

    Yencha, A.J.

    1978-01-01

    The technique of measuring the kinetic energy of electrons ejected from atomic or molecular species as a result of collisional energy transfer between a metastable excited rare gas atom and an atom or molecule is known as Penning ionization spectroscopy. Like the analogous photoionization process of photoelectron spectroscopy, a considerable amount of information has been gained about the ionization potentials of numerous molecular systems. It is, in fact, through the combined analyses of photoelectron and Penning electron spectra that affords a probe of the particle-particle interactions that occur in the Penning process. In this paper a short survey of the phenomenon of Penning ionization, as studied by electron spectroscopy, will be presented as it pertains to the ionization processes of simple molecules by metastable excited atoms. (author)

  7. Electron transfer, ionization, and excitation atomic collisions

    International Nuclear Information System (INIS)

    Winter, T.G.; Alston, S.G.

    1990-01-01

    Basic atomic-collision processes at intermediate and high energies are being studied theoretically at Penn State by Alston and Winter. In the high velocity regime, single-electron capture is treated using a high order multiple-scattering approach; extensive comparison with experiment and analysis of mechanisms have been made. Fitting the calculated amplitude with a simple analytic form, the asymptotic velocity dependence of the cross section is obtained. The effect on the capture amplitude of altering the inner part of the internuclear potential has also been explored. In the intermediate velocity regime, earlier work on collisions between protons and hydrogenic-ion targets using a coupled-state approach is being extended to the two-electron helium target. 29 refs

  8. Opto-electronic conversion logic behaviour through dynamic modulation of electron/energy transfer states at the TiO2-carbon quantum dot interface.

    Science.gov (United States)

    Wang, Fang; Zhang, Yonglai; Liu, Yang; Wang, Xuefeng; Shen, Mingrong; Lee, Shuit-Tong; Kang, Zhenhui

    2013-03-07

    Here we show a bias-mediated electron/energy transfer process at the CQDs-TiO(2) interface for the dynamic modulation of opto-electronic properties. Different energy and electron transfer states have been observed in the CQDs-TNTs system due to the up-conversion photoluminescence and the electron donation/acceptance properties of the CQDs decorated on TNTs.

  9. Heat Transfer in a Thermoacoustic Process

    Science.gov (United States)

    Beke, Tamas

    2012-01-01

    Thermoacoustic instability is defined as the excitation of acoustic modes in chambers with heat sources due to the coupling between acoustic perturbations and unsteady heat addition. The major objective of this paper is to achieve accurate theoretical results in a thermoacoustic heat transfer process. We carry out a detailed heat transfer analysis…

  10. Electron beam processing of polymers

    International Nuclear Information System (INIS)

    Silva, Leonardo G. Andrade e; Dias, Djalma B.; Calvo, Wilson A.P.; Miranda, Leila F. de

    2011-01-01

    The aim of this work is the use of electron beam produced by industrial electron accelerators to process polymers. There are several applications, such as, irradiation of wires and electric cables for automotive, aerospace, household appliance, naval and computing industries. The effect of different radiation doses in low density polyethylene (LDPE) was also studied. After irradiation and crosslinking it was thermally expanded forming LDPE foam. In addition, poly(N-vinyl-2-pyrrolidone) (PVP) hydrogels using electron beam processing were prepared. In all cases studied crosslinking percentages of the samples were determined. (author)

  11. Electron transfer, ionization, and excitation in atomic collisions

    International Nuclear Information System (INIS)

    Winter, T.G.; Alston, S.G.

    1992-01-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom (and ion-ion) collisions. The focus is on intermediate- and higher-energy collisions, corresponding to proton energies of about 25 kilo-electron-volts (keV) or larger. At intermediate energies, where the transition probabilities are not small, many states must be coupled in a large calculation, while at higher energies, perturbative approaches may be used. Several studies have been carried out in the current three-year period; most of these treat systems with only one or two electrons, so that fewer approximations need be made and the basic collisional mechanisms can be more clearly described

  12. Electronic transfer of sensitive patient data.

    Science.gov (United States)

    Detterbeck, A M W; Kaiser, J; Hirschfelder, U

    2015-01-01

    The purpose of this study was to develop decision-making aids and recommendations for dental practitioners regarding the utilization and sharing of sensitive digital patient data. In the current environment of growing digitization, healthcare professionals need detailed knowledge of secure data management to maximize confidentiality and minimize the risks involved in both archiving patient data and sharing it through electronic channels. Despite well-defined legal requirements, an all-inclusive technological solution does not currently exist. The need for a preliminary review and critical appraisal of common practices of data transfer prompted a search of the literature and the Web to identify viable methods of secure data exchange and to develop a flowchart. A strong focus was placed on the transmission of datasets both smaller than and larger than 10 MB, and on secure communication by smartphone. Although encryption of patient-related data should be routine, it is often difficult to implement. Pretty Good Privacy (PGP) and Secure/Multipurpose Internet Mail Extensions (S/MIME) are viable standards for secure e-mail encryption. Sharing of high-volume data should be accomplished with the help of file encryption. Careful handling of sensitive patient data is mandatory, and it is the end-user's responsibility to meet any requirements for encryption, preferably by using free, open-source (and hence transparent) software.

  13. Direct Electron Transfer of Dehydrogenases for Development of 3rd Generation Biosensors and Enzymatic Fuel Cells

    Directory of Open Access Journals (Sweden)

    Paolo Bollella

    2018-04-01

    Full Text Available Dehydrogenase based bioelectrocatalysis has been increasingly exploited in recent years in order to develop new bioelectrochemical devices, such as biosensors and biofuel cells, with improved performances. In some cases, dehydrogeases are able to directly exchange electrons with an appropriately designed electrode surface, without the need for an added redox mediator, allowing bioelectrocatalysis based on a direct electron transfer process. In this review we briefly describe the electron transfer mechanism of dehydrogenase enzymes and some of the characteristics required for bioelectrocatalysis reactions via a direct electron transfer mechanism. Special attention is given to cellobiose dehydrogenase and fructose dehydrogenase, which showed efficient direct electron transfer reactions. An overview of the most recent biosensors and biofuel cells based on the two dehydrogenases will be presented. The various strategies to prepare modified electrodes in order to improve the electron transfer properties of the device will be carefully investigated and all analytical parameters will be presented, discussed and compared.

  14. Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

    KAUST Repository

    Alsulami, Qana A.

    2016-11-30

    The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and

  15. Intercellular wiring enables electron transfer between methanotrophic archaea and bacteria.

    Science.gov (United States)

    Wegener, Gunter; Krukenberg, Viola; Riedel, Dietmar; Tegetmeyer, Halina E; Boetius, Antje

    2015-10-22

    The anaerobic oxidation of methane (AOM) with sulfate controls the emission of the greenhouse gas methane from the ocean floor. In marine sediments, AOM is performed by dual-species consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB) inhabiting the methane-sulfate transition zone. The biochemical pathways and biological adaptations enabling this globally relevant process are not fully understood. Here we study the syntrophic interaction in thermophilic AOM (TAOM) between ANME-1 archaea and their consortium partner SRB HotSeep-1 (ref. 6) at 60 °C to test the hypothesis of a direct interspecies exchange of electrons. The activity of TAOM consortia was compared to the first ANME-free culture of an AOM partner bacterium that grows using hydrogen as the sole electron donor. The thermophilic ANME-1 do not produce sufficient hydrogen to sustain the observed growth of the HotSeep-1 partner. Enhancing the growth of the HotSeep-1 partner by hydrogen addition represses methane oxidation and the metabolic activity of ANME-1. Further supporting the hypothesis of direct electron transfer between the partners, we observe that under TAOM conditions, both ANME and the HotSeep-1 bacteria overexpress genes for extracellular cytochrome production and form cell-to-cell connections that resemble the nanowire structures responsible for interspecies electron transfer between syntrophic consortia of Geobacter. HotSeep-1 highly expresses genes for pili production only during consortial growth using methane, and the nanowire-like structures are absent in HotSeep-1 cells isolated with hydrogen. These observations suggest that direct electron transfer is a principal mechanism in TAOM, which may also explain the enigmatic functioning and specificity of other methanotrophic ANME-SRB consortia.

  16. Nonadiabatic two-electron transfer mediated by an irregular bridge

    International Nuclear Information System (INIS)

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

    2004-01-01

    Nonadiabatic two-electron transfer (TET) mediated by a linear molecular bridge is studied theoretically. Special attention is put on the case of a irregular distribution of bridge site energies as well as on the inter-site Coulomb interaction. Based on the unified description of electron transfer reactions [J. Chem. Phys. 115 (2001) 7107] a closed set of kinetic equations describing the TET process is derived. A reduction of this set to a single exponential donor-acceptor (D-A) TET is performed together with a derivation of an overall D-A TET rate. The latter contains a contribution of the stepwise as well as of the concerted route of D-A TET. The stepwise contribution is determined by two single-electron steps each of them associated with a sequential and a superexchange pathway. A two-electron unistep superexchange transition between the D and A forms the concerted contribution to the overall rate. Both contributions are analyzed in their dependency on the bridge length. The irregular distribution of the bridge site energies as well as the influence of the Coulomb interaction facilitates the D-A TET via a modification of the stepwise and the concerted part of the overall rate. At low temperatures and for short bridges with a single or two units the concerted contribution exceeds the stepwise contribution. If the bridge contains more than two units, the stepwise contribution dominates the overall rate

  17. Exclusive processes at high momentum transfer

    CERN Document Server

    Radyushkin, Anatoly; Stoker, Paul

    2002-01-01

    This book focuses on the physics of exclusive processes at high momentum transfer and their description in terms of generalized parton distributions, perturbative QCD, and relativistic quark models. It covers recent developments in the field, both theoretical and experimental.

  18. Direct electron transfer from glucose oxidase immobilized on a nano-porous glassy carbon electrode

    International Nuclear Information System (INIS)

    Haghighi, Behzad; Tabrizi, Mahmoud Amouzadeh

    2011-01-01

    Highlights: → A direct electron transfer reaction of glucose oxidase was observed on the surface of a nano-porous glassy carbon electrode. → A pair of well-defined and reversible redox peaks was observed at the formal potential of approximately -0.439 V. → The apparent electron transfer rate constant was measured to be 5.27 s -1 . → A mechanism for the observed direct electron transfer reaction was proposed, which consists of a two-electron and a two-proton transfer. - Abstract: A pair of well-defined and reversible redox peaks was observed for the direct electron transfer (DET) reaction of an immobilized glucose oxidase (GOx) on the surface of a nano-porous glassy carbon electrode at the formal potential (E o ') of -0.439 V versus Ag/AgCl/saturated KCl. The electron transfer rate constant (k s ) was calculated to be 5.27 s -1 . The dependence of E o ' on pH indicated that the direct electron transfer of the GOx was a two-electron transfer process, coupled with two-proton transfer. The results clearly demonstrate that the nano-porous glassy carbon electrode is a cost-effective and ready-to-use scaffold for the fabrication of a glucose biosensor.

  19. Direct electron transfer from glucose oxidase immobilized on a nano-porous glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Behzad, E-mail: haghighi@iasbs.ac.ir [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of); Tabrizi, Mahmoud Amouzadeh [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of)

    2011-11-30

    Highlights: > A direct electron transfer reaction of glucose oxidase was observed on the surface of a nano-porous glassy carbon electrode. > A pair of well-defined and reversible redox peaks was observed at the formal potential of approximately -0.439 V. > The apparent electron transfer rate constant was measured to be 5.27 s{sup -1}. > A mechanism for the observed direct electron transfer reaction was proposed, which consists of a two-electron and a two-proton transfer. - Abstract: A pair of well-defined and reversible redox peaks was observed for the direct electron transfer (DET) reaction of an immobilized glucose oxidase (GOx) on the surface of a nano-porous glassy carbon electrode at the formal potential (E{sup o}') of -0.439 V versus Ag/AgCl/saturated KCl. The electron transfer rate constant (k{sub s}) was calculated to be 5.27 s{sup -1}. The dependence of E{sup o}' on pH indicated that the direct electron transfer of the GOx was a two-electron transfer process, coupled with two-proton transfer. The results clearly demonstrate that the nano-porous glassy carbon electrode is a cost-effective and ready-to-use scaffold for the fabrication of a glucose biosensor.

  20. 76 FR 709 - Electronic Funds Transfer of Depository Taxes; Correction

    Science.gov (United States)

    2011-01-06

    ... DEPARTMENT OF THE TREASURY Internal Revenue Service 26 CFR Parts 40 and 301 [TD 9507] RIN 1545-BJ13 Electronic Funds Transfer of Depository Taxes; Correction AGENCY: Internal Revenue Service (IRS...) providing guidance relating to Federal tax deposits (FTDs) by Electronic Funds Transfer (EFT). The temporary...

  1. 76 FR 708 - Electronic Funds Transfer of Depository Taxes; Correction

    Science.gov (United States)

    2011-01-06

    ... DEPARTMENT OF THE TREASURY Internal Revenue Service 26 CFR Parts 1, 31, 40, and 301 [TD 9507] RIN 1545-BJ13 Electronic Funds Transfer of Depository Taxes; Correction AGENCY: Internal Revenue Service... Electronic Funds Transfer (EFT). The temporary and final regulations provide rules under which depositors...

  2. 78 FR 66251 - Electronic Fund Transfers(Regulation E)

    Science.gov (United States)

    2013-11-05

    ... Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer Financial Protection. ACTION: Notice of... subpart B of Regulation E, which implements the Electronic Fund Transfer Act, and published this list on...-rule-amendment-to-regulation-e/ . SUPPLEMENTARY INFORMATION: The Bureau published its remittance rule...

  3. 78 FR 49365 - Electronic Fund Transfers (Regulation E); Correction

    Science.gov (United States)

    2013-08-14

    ... BUREAU OF CONSUMER FINANCIAL PROTECTION 12 CFR Part 1005 [Docket No. CFPB-2012-0050] RIN 3170-AA33 Electronic Fund Transfers (Regulation E); Correction AGENCY: Bureau of Consumer Financial Protection. ACTION... 2013 Final Rule, which along with three other final rules \\1\\ implements the Electronic Fund Transfer...

  4. THE ELECTRONIC COURSE OF HEAT AND MASS TRANSFER

    Directory of Open Access Journals (Sweden)

    Alexander P. Solodov

    2013-01-01

    Full Text Available The Electronic course of heat and mass transfer in power engineering is presented containing the full Electronic book as the structured hypertext document, the full set of Mathcad-documents with the whole set of educative computer models of heat and mass transfer, the computer labs, and selected educational presentations. 

  5. Shimmed electron beam welding process

    Science.gov (United States)

    Feng, Ganjiang; Nowak, Daniel Anthony; Murphy, John Thomas

    2002-01-01

    A modified electron beam welding process effects welding of joints between superalloy materials by inserting a weldable shim in the joint and heating the superalloy materials with an electron beam. The process insures a full penetration of joints with a consistent percentage of filler material and thereby improves fatigue life of the joint by three to four times as compared with the prior art. The process also allows variable shim thickness and joint fit-up gaps to provide increased flexibility for manufacturing when joining complex airfoil structures and the like.

  6. Theoretical treatment of charge transfer processes of relevance to astrophysics

    Energy Technology Data Exchange (ETDEWEB)

    Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

    1997-12-01

    Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture.

  7. Theoretical treatment of charge transfer processes of relevance to astrophysics

    International Nuclear Information System (INIS)

    Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

    1997-12-01

    Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture

  8. Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

    International Nuclear Information System (INIS)

    Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit; Chowdhury, Joydeep; Ganguly, Tapan

    2010-01-01

    UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (ε S ∼10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (ε S ∼37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

  9. Inelastic electron scattering at low momentum transfer

    International Nuclear Information System (INIS)

    Richter, A.

    1979-01-01

    Recent advances of high energy resolution (ΔE approx. 30 keV FWHM) inelastic electron scattering at low momentum transfer (q -1 ) using selected experimental data from the Darmstadt electron linear accelerator are discussed. Strong emphasis is given to a comparison of the data with theoretical nuclear model predictions. Of the low multipolarity electric transitions investigated, as examples only E1 transitions to unnatural parity states in 11 B and E2 transitions of the very fragmented isoscalar quadrupole giant resonance in 208 Pb are considered. In 11 B the role of the Os hole in the configuration of the 1/2 + , 3/2 + and 5/2 + states is quantitatively determined via an interference mechanism in the transition probability. By comparison of the high resolution data with RPA calculations the E2 EWSR in 208 Pb is found to be much less exhausted than anticipated from previous medium energy resolution (e,e) and hadron scattering experiments. In the case of M1 transitions it is shown that the simplest idealized independent particle shell-model prediction breaks down badly. In 28 Si, ground-state correlations influence largely the detected M1 strength and such ground-state correlations are also responsible for the occurence of a strong M1 transition to a state at Ex = 10.319 MeV in 40 Ca. In 90 Zr only about 10% of the theoretically expected M1 strength is seen in (e,e) and in 140 Ce and 208 Pb none (detection limit 1-2 μ 2 K). In the case of 208 Pb high resolution spectra exist now up to an excitation energy of Ex = approx. 12MeV. The continuous decrease of the M1 strength with mass number is corroborated by the behaviour of strong but very fragmented M2 transitions which are detected in 28 Si, 90 Zr, 140 Ce and 208 Pb concentrated at an excitation energy E x approx. 44A -1 / 3 MeV. In 90 Zr, the distribution of spacings and widths of the many Jπ = 2 states are consistent with a Wigner and Porter-Thomas distribution, respectively. (orig.) 891 KBE/orig. 892 ARA

  10. Molecular Insights into Variable Electron Transfer in Amphibian Cryptochrome

    DEFF Research Database (Denmark)

    Sjulstok, Emil; Lüdemann, Gesa; Kubař, Tomáš

    2018-01-01

    are mutated, radical-pair formation is still observed. In this study, we computationally investigate electron-transfer pathways in the X. laevis cryptochrome DASH by extensively equilibrating a previously established homology model using molecular dynamics simulations and then mutating key amino acids......Cryptochrome proteins are activated by the absorption of blue light, leading to the formation of radical pairs through electron transfer in the active site. Recent experimental studies have shown that once some of the amino acid residues in the active site of Xenopus laevis cryptochrome DASH...... involved in the electron transfer. The electron-transfer pathways are then probed by using tight-binding density-functional theory. We report the alternative electron-transfer pathways resolved at the molecular level and, through comparison of amino acid sequences for cryptochromes from different species...

  11. Transcriptomic and genetic analysis of direct interspecies electron transfer

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Summers, Zarath M

    2013-01-01

    The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens....... These results demonstrate that there are unique gene expression patterns that distinguish DIET from HIT and suggest that metatranscriptomics may be a promising route to investigate interspecies electron transfer pathways in more-complex environments....

  12. Electron transfer. 88. Cobalt(III)-bound phosphite and hypophosphite

    International Nuclear Information System (INIS)

    Linn, D.E. Jr.; Gould, E.S.

    1987-01-01

    Phosphite and hypophosphite coordinate to cobalt(III) in (NH 3 ) 5 Co/sup III/ through oxygen, rather than through phosphorus. The resulting complexes undergo electron-transfer reactions with Ru(NH 3 ) 6 2+ much more slowly than with Eu 2+ or V 2+ , indicating that the latter two reactants preferentially utilize ligand bridging. Reductions with Cr 2+ are shown to accompanied by transfer of the phosphorus-containing ligands, and reaction of the protonated phosphito (biphosphito) derivative (pK/sub A/ = 3.06 at 23 0 C) proceeds through a combination of acid-independent and inverse-acid paths, both routes yielding the same phosphito-bound Cr(III) product. The hypophosphito, but not the biphosphito, complex reacts with Ce(IV), producing Co 2+ in an induced electron-transfer process. The yield of Co 2+ falls off progressively as [Ce/sup IV/] is increased, pointing to a sequence in which a Co(III)-bound P(II) radical is formed in initial attack by Ce(IV) but subsequently undergoes partition between competing reaction paths, i.e. internal electron transfer to Co(III) vs external oxidation by a second Ce(IV) center. The hypophosphito complex, but not the biphosphito complex, smoothly decomposes in basic media via an internal redox reaction, yielding Co(II) quantitatively, along with a 1:1 mixture of phosphite, and hypophosphite. This transformation, which fails with mixtures of (NH 3 ) 5 Co(H 2 O) 3+ and H 2 PO 2 - appears to be catalyzed specifically by OH - . Deuterium-labeling experiments disclose a solvent isotope effect. Reaction mechanisms are suggested for all the observed results. 54 references, 5 tables

  13. Photoinduced electron transfer between the dendritic zinc phthalocyanines and anthraquinone

    Science.gov (United States)

    Chen, Kuizhi; Wen, Junri; Liu, Jiangsheng; Chen, Zhenzhen; Pan, Sujuan; Huang, Zheng; Peng, Yiru

    2015-03-01

    The intermolecular electron transfer between the novel dendritic zinc (II) phthalocyanines (G1-DPcB and G2-DPcB) and anthraquinone (AQ) was studied by steady-state fluorescence and UV/Vis absorption spectroscopic methods. The effect of dendron generation on intermolecular electron transfer was investigated. The results showed that the fluorescence emission of these dendritic phthalocyanines could be greatly quenched by AQ upon excitation at 610 nm. The Stern- Volmer constant (KSV) of electron transfer was decreased with increasing the dendron generations. Our study suggested that these novel dendritic phthalocyanines were effective new electron donors and transmission complexes and could be used as a potential artifical photosysthesis system.

  14. Controlling the digital transfer process

    Science.gov (United States)

    Brunner, Felix

    1997-02-01

    The accuracy of today's color management systems fails to satisfy the requirements of the graphic arts market. A first explanation for this is that color calibration charts on which these systems rely, because of print technical reasons, are subject to color deviations and inconsistencies. A second reason is that colorimetry describes the human visual perception of color differences and has no direct relation to the rendering technology itself of a proofing or printing device. The author explains that only firm process control of the many parameters in offset printing by means of a system as for example EUROSTANDARD System Brunner, can lead to accurate and consistent calibration of scanner, display, proof and print. The same principles hold for the quality management of digital presses.

  15. Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

    Energy Technology Data Exchange (ETDEWEB)

    Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India); Chowdhury, Joydeep [Sammilani Mahavidyalaya Baghajatin Station, West Bengal (India); Ganguly, Tapan, E-mail: sptg@mahendra.iacs.res.i [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India)

    2010-06-15

    UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (epsilon{sub S}approx10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (epsilon{sub S}approx37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

  16. METHOD OF ELECTRON BEAM PROCESSING

    DEFF Research Database (Denmark)

    2003-01-01

    As a rule, electron beam welding takes place in a vacuum. However, this means that the workpieces in question have to be placed in a vacuum chamber and have to be removed therefrom after welding. This is time−consuming and a serious limitation of a process the greatest advantage of which is the o......As a rule, electron beam welding takes place in a vacuum. However, this means that the workpieces in question have to be placed in a vacuum chamber and have to be removed therefrom after welding. This is time−consuming and a serious limitation of a process the greatest advantage of which...... is the option of welding workpieces of large thicknesses. Therefore the idea is to guide the electron beam (2) to the workpiece via a hollow wire, said wire thereby acting as a prolongation of the vacuum chamber (4) down to workpiece. Thus, a workpiece need not be placed inside the vacuum chamber, thereby...... exploiting the potential of electron beam processing to a greater degree than previously possible, for example by means of electron beam welding...

  17. Observation of electron-transfer-mediated decay in aqueous solution

    Science.gov (United States)

    Unger, Isaak; Seidel, Robert; Thürmer, Stephan; Pohl, Marvin N.; Aziz, Emad F.; Cederbaum, Lorenz S.; Muchová, Eva; Slavíček, Petr; Winter, Bernd; Kryzhevoi, Nikolai V.

    2017-07-01

    Photoionization is at the heart of X-ray photoelectron spectroscopy (XPS), which gives access to important information on a sample's local chemical environment. Local and non-local electronic decay after photoionization—in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively—have been well studied. However, electron-transfer-mediated decay (ETMD), which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low-energy electrons using liquid-microjet soft XPS. Experimental results are interpreted using molecular dynamics and high-level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion-solvent distances and solvent arrangement.

  18. A molecular shift register based on electron transfer

    Science.gov (United States)

    Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

    1988-01-01

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

  19. The process for technology transfer in Baltimore

    Science.gov (United States)

    Golden, T. S.

    1978-01-01

    Ingredients essential for a successful decision process relative to proper technological choices for a large city were determined during four years of experience in the NASA/Baltimore Applications Project. The general approach, rationale, and process of technology transfer are discussed.

  20. Covalent electron transfer chemistry of graphene with diazonium salts.

    Science.gov (United States)

    Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

    2013-01-15

    Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles.

  1. 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.

  2. Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

    Science.gov (United States)

    Wu, Yundang; Liu, Tongxu; Li, Xiaomin; Li, Fangbai

    2014-08-19

    Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

  3. 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...

  4. Extracellular electron transfer mechanisms between microorganisms and minerals

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Liang; Dong, Hailiang; Reguera, Gemma; Beyenal, Haluk; Lu, Anhuai; Liu, Juan; Yu, Han-Qing; Fredrickson, James K.

    2016-08-30

    Electrons can be transferred from microorganisms to multivalent metal ions that are associated with minerals and vice versa. As the microbial cell envelope is neither physically permeable to minerals nor electrically conductive, microorganisms have evolved strategies to exchange electrons with extracellular minerals. In this Review, we discuss the molecular mechanisms that underlie the ability of microorganisms to exchange electrons, such as c-type cytochromes and microbial nanowires, with extracellular minerals and with microorganisms of the same or different species. Microorganisms that have extracellular electron transfer capability can be used for biotechnological applications, including bioremediation, biomining and the production of biofuels and nanomaterials.

  5. Photoinduced electron transfer in some photosensitive molecules ...

    Indian Academy of Sciences (India)

    Unknown

    redox reactions of substrates like biological molecules,11,12 dyes,13,14 alcohols15,16 etc. Colloidal ... state which is characterised by a phenomenon of dual fluorescence. In the present ... The dried solid was transferred to quartz cell under vacuum ... Recently Grätzel et al34 have developed the dye-sensitized meso-.

  6. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive...... theory of charge transfer in polar media offers convenient tools for the treatment of experimental data for such systems, with due account of large-amplitude strongly anharmonic intramolecular reorganization. Equations for the activation barrier and free energy relationships are provided, incorporating...

  7. Stark-like electron transfer between quantum wells

    International Nuclear Information System (INIS)

    Dubovis, S.A.; Voronko, A.N.; Basharov, A.M.

    2008-01-01

    The Stark-like mechanism of electron transfer between two energy subband localized in remote quantum wells is examined theoretically. Estimations of major parameters of the problem in case of delta-function-wells model are adduced. Schematic model allowing experimental study of Stark-like transfer is proposed

  8. Distorted wave calculations for double electron transfer

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  9. High momentum transfer processes in QCD

    International Nuclear Information System (INIS)

    Efremov, A.V.; Radyushkin, A.V.

    1978-01-01

    A unified approach to the investigation of inclusive high momentum transfer processes in the QCD framework is proposed. A modified parton model (with parton distribution functions depending on an additional renormalization parameter) is shown to be valid in all orders of perturbation theory. The approach is also applicable for studying wide-angle elastic scattering processes of colourless bound states of quarks (the hadrons). The asymptotic behaviour of pion electromagnetic form factor is calculated as an example

  10. Technology Transfer, Labour and Local Learning Processes in Malaysian Industry

    DEFF Research Database (Denmark)

    Wangel, Arne

    1999-01-01

    The transfer of technologies by the foreign electronic industries operating in Malaysia involves training of workers for various purposes. The upgrading of skills to assimilate the transferred technology aims at increasing productivity and product quality. Communicating awareness about work hazards...... is meant to reduce breakdowns in production and workers' accidents. How do the training paradigms, which transnationals introduce in their subsidiaries in Malaysia, interact with the preconditions of learning with the local labour force? In shaping local learning processes, what is the scope for workers...

  11. 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...

  12. Concept Generation Process for Patient Transferring Device

    Science.gov (United States)

    Dandavate, A. L.; Sarje, S. H.

    2012-07-01

    In this paper, an attempt has been made to develop concepts for patient transferring tasks. The concept generation process of patient transferring device (PTD), which includes interviews of the customers, interpretation of the needs, organizing the needs into a hierarchy, establishing relative importance of the needs, establishing target specifications, and conceptualization has been discussed in this paper. The authors conducted the interviews of customers at Mobilink NGO, St. John's Hospital, Bangalore in order to know the needs and wants for the PTD. AHP technique was used for establishing and evaluating relative importance of needs, and based on the importance of the customer needs, concepts were developed through brainstorming.

  13. 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

  14. 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

  15. 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 ...

  16. Toddlers' word learning and transfer from electronic and print books.

    Science.gov (United States)

    Strouse, Gabrielle A; Ganea, Patricia A

    2017-04-01

    Transfer from symbolic media to the real world can be difficult for young children. A sample of 73 toddlers aged 17 to 23months were read either an electronic book displayed on a touchscreen device or a traditional print book in which a novel object was paired with a novel label. Toddlers in both conditions learned the label within the context of the book. However, only those who read the traditional format book generalized and transferred the label to other contexts. An older group of 28 toddlers aged 24 to 30months did generalize and transfer from the electronic book. Across ages, those children who primarily used screens to watch prerecorded video at home transferred less from the electronic book than those with more diverse home media experiences. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. 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.

  18. Electronic Energy Transfer in Polarizable Heterogeneous Environments

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Kongsted, Jacob

    2015-01-01

    such couplings provide important insight into the strength of interaction between photo-active pigments in protein-pigment complexes. Recently, attention has been payed to how the environment modifies or even controls the electronic couplings. To enable such theoretical predictions, a fully polarizable embedding......-order multipole moments. We use this extended model to systematically examine three different ways of obtaining EET couplings in a heterogeneous medium ranging from use of the exact transition density to a point-dipole approximation. Several interesting observations are made including that explicit use...... of transition densities in the calculation of the electronic couplings - also when including the explicit environment contribution - can be replaced by a much simpler transition point charge description without comprising the quality of the model predictions....

  19. Monitoring sequential electron transfer with EPR

    International Nuclear Information System (INIS)

    Thurnauer, M.C.; Feezel, L.L.; Snyder, S.W.; Tang, J.; Norris, J.R.; Morris, A.L.; Rustandi, R.R.

    1989-01-01

    A completely general model which treats electron spin polarization (ESP) found in a system in which radical pairs with different magnetic interactions are formed sequentially has been described. This treatment has been applied specifically to the ESP found in the bacterial reaction center. Test cases show clearly how parameters such as structure, lifetime, and magnetic interactions within the successive radical pairs affect the ESP, and demonstrate that previous treatments of this problem have been incomplete. The photosynthetic bacterial reaction center protein is an ideal system for testing the general model of ESP. The radical pair which exhibits ESP, P 870 + Q - (P 870 + is the oxidized, primary electron donor, a bacteriochlorophyll special pair and Q - is the reduced, primary quinone acceptor) is formed via sequential electron transport through the intermediary radical pair P 870 + I - (I - is the reduced, intermediary electron acceptor, a bacteriopheophytin). In addition, it is possible to experimentally vary most of the important parameters, such as the lifetime of the intermediary radical pair and the magnetic interactions in each pair. It has been shown how selective isotopic substitution ( 1 H or 2 H) on P 870 , I and Q affects the ESP of the EPR spectrum of P 870 + Q - , observed at two different microwave frequencies, in Fe 2+ -depleted bacterial reaction centers of Rhodobacter sphaeroides R26. Thus, the relative magnitudes of the magnetic properties (nuclear hyperfine and g-factor differences) which influence ESP development were varied. The results support the general model of ESP in that they suggest that the P 870 + Q - radical pair interactions are the dominant source of ESP production in 2 H bacterial reaction centers

  20. Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles

    DEFF Research Database (Denmark)

    Gilbert, Benjamin; Katz, Jordan E.; Huse, Nils

    2013-01-01

    photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported....... We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115...... a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer...

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  2. Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation

    Science.gov (United States)

    Delor, Milan; Archer, Stuart A.; Keane, Theo; Meijer, Anthony J. H. M.; Sazanovich, Igor V.; Greetham, Gregory M.; Towrie, Michael; Weinstein, Julia A.

    2017-11-01

    Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer donor-bridge-acceptor-bridge-donor 'fork' system: asymmetric 13C isotopic labelling of one of the two -C≡C- bridges makes the two parallel and otherwise identical donor→acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.

  3. Electron Transfer and Substrate Reduction in Nitrogenase

    OpenAIRE

    Danyal, Karamatullah

    2014-01-01

    Population growth over the past ~50 years accompanied by the changes in dietary habits due to economic growth have markedly increased the demand for fixed nitrogen. Aided by biological nitrogen fixation, the Haber-Bosch process has been able to fulfill these demands. However, due to its high temperature and pressure requirements, Haber-Bosch is an expensive process. Every year, approximately 2% of the total energy expenditure by man is used to manufacture fixed nitrogen. Biological systems, o...

  4. Characterization of Mullite-Zirconia Composite Processed by Non-Transferred and Transferred Arc Plasma

    International Nuclear Information System (INIS)

    Yugeswaran, S.; Selvarajan, V.; Lusvarghi, L.; Tok, A. I. Y.; Krishna, D. Siva Rama

    2009-01-01

    The arc plasma melting technique is a simple method to synthesize high temperature reaction composites. In this study, mullite-zirconia composite was synthesized by transferred and non-transferred arc plasma melting, and the results were compared. A mixture of alumina and zircon powders with a mole ratio of 3: 2 were ball milled for four hours and melted for two minutes in the transferred and non-transferred mode of plasma arcs. Argon and air were used as plasma forming gases. The phase and microstructural formation of melted samples were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). The microstructure of the composites was found to be affected by the mode of melting. In transferred arc melting, zirconia flowers with uniform lines along with mullite whiskers were obtained. In the case of non-transferred arc plasma melting, mullite whiskers along with star shape zirconia were formed. Differential thermal analysis (DTA) of the synthesized mullite-zirconia composites provided a deeper understanding of the mechanisms of mullite formation during the two different processes. (plasma technology)

  5. Selection rules for electron transfer to the continuum in ion-atom collision

    Energy Technology Data Exchange (ETDEWEB)

    Barrachina, R.O.; Bernardi, G.C.; Garibotti, C.R.

    1985-10-01

    We consider the process of electron transfer to the in first order Born approximation. We analyse the expansion of the double-differential cross section in series of electron velocity and ejection angle. We found that the coefficients obey precise selection rules. We discuss the relation of these rules, which predict an asymmetric shape for the electron loss to the continuum cusp, with the interpretation of recent experimental results.

  6. Electron transfer dynamics: Zusman equation versus exact theory

    International Nuclear Information System (INIS)

    Shi Qiang; Chen Liping; Nan Guangjun; Xu Ruixue; Yan Yijing

    2009-01-01

    The Zusman equation has been widely used to study the effect of solvent dynamics on electron transfer reactions. However, application of this equation is limited by the classical treatment of the nuclear degrees of freedom. In this paper, we revisit the Zusman equation in the framework of the exact hierarchical equations of motion formalism, and show that a high temperature approximation of the hierarchical theory is equivalent to the Zusman equation in describing electron transfer dynamics. Thus the exact hierarchical formalism naturally extends the Zusman equation to include quantum nuclear dynamics at low temperatures. This new finding has also inspired us to rescale the original hierarchical equations and incorporate a filtering algorithm to efficiently propagate the hierarchical equations. Numerical exact results are also presented for the electron transfer reaction dynamics and rate constant calculations.

  7. Screening of exciplex formation by distant electron transfer.

    Science.gov (United States)

    Fedorenko, S G; Khokhlova, S S; Burshtein, A I

    2012-01-12

    The excitation quenching by reversible exciplex formation, combined with irreversible but distant electron transfer, is considered by means of the integral encounter theory (IET). Assuming that the quenchers are in great excess, the set of IET equations for the excitations, free ions, and exciplexes is derived. Solving these equations gives the Laplace images of all these populations, and these are used to specify the quantum yields of the corresponding reaction products. It appears that diffusion facilitates the exciplex production and the electron transfer. On the other hand the stronger the electron transfer is, the weaker is the exciplex production. At slow diffusion the distant quenching of excitations by ionization prevents their reaching the contact where they can turn into exciplexes. This is a screening effect that is most pronounced when the ionization rate is large.

  8. Electron quantum optics as quantum signal processing

    OpenAIRE

    Roussel, B.; Cabart, C.; Fève, G.; Thibierge, E.; Degiovanni, P.

    2016-01-01

    The recent developments of electron quantum optics in quantum Hall edge channels have given us new ways to probe the behavior of electrons in quantum conductors. It has brought new quantities called electronic coherences under the spotlight. In this paper, we explore the relations between electron quantum optics and signal processing through a global review of the various methods for accessing single- and two-electron coherences in electron quantum optics. We interpret electron quantum optics...

  9. Numerical Simulation of Transient Moisture Transfer into an Electronic Enclosure

    DEFF Research Database (Denmark)

    Shojaee Nasirabadi, Parizad; Jabbaribehnam, Mirmasoud; Hattel, Jesper Henri

    2016-01-01

    Electronic systems are sometimes exposed to harsh environmental conditions of temperature and humidity. Moisturetransfer into electronic enclosures and condensation can cause several problems such as corrosion and alteration in thermalstresses. It is therefore essential to study the local climate...... inside the enclosures to be able to protect the electronic systems.In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce theCPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which...

  10. Dynamics of high momentum transfer processes

    International Nuclear Information System (INIS)

    Efremov, A.V.

    1977-01-01

    The high momentum transfer processes are considered in terms of field theory of quarks interacting through scalar or pseudoscalar gluons. This approach is based on an algorithm involving the consideration of the Feynman diagram asymptotical behaviour and its summation. The Parton model and quark counting power are an approximation of not too high momentum transfer when anti g 2 (q 2 )ln(-q 2 /Λ) 2 -invariant charge, Λ-boundary parameter. The violation of scaling beyond this region depends on the character of charge renormalization and is of the same kind as in the Wilson expansion approach. Scaling in this region is suppressed by anti g 4 factor for high psub(UPSILON) hadroproduction and wide angle elastic scattering, and by anti g 2 factor for inclusive lepton production and wide angle electro- and photoproduction. Parameter Λ is controlled by hadron masses and can be essential for not too high psub(UPSILON)

  11. Heat transfer in a thermoacoustic process

    International Nuclear Information System (INIS)

    Beke, Tamas

    2012-01-01

    Thermoacoustic instability is defined as the excitation of acoustic modes in chambers with heat sources due to the coupling between acoustic perturbations and unsteady heat addition. The major objective of this paper is to achieve accurate theoretical results in a thermoacoustic heat transfer process. We carry out a detailed heat transfer analysis aimed at determining the stability–instability border of the thermoacoustic system. In this paper, we present a project type of physical examination and modelling task. We employed an electrically heated Rijke tube in our thermoacoustic project work. The aim of our project is to help our students enlarge their knowledge about thermodynamics, mainly about thermoacoustics, and develop their applied information technology and mathematical skills. (paper)

  12. Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

    Science.gov (United States)

    Zeng, Zhirui; Tice, Michael M

    2018-01-01

    Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms. Key Words: Microbial iron reduction-Micropore-Electron transfer strategies-Microbial carbonate. Astrobiology 18, 28-36.

  13. Long-distance photoinitiated electron transfer through polyene molecular wires

    International Nuclear Information System (INIS)

    Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.; Kersey, K.M.; Cragg, D.E.; Minsek, D.W.

    1989-01-01

    Long-chain polyenes can be used as molecular wires to facilitate electron transfer between a photo-excited donor and an acceptor in an artificial photosynthetic system. The authors present data here on two Zn-porphyrin-polyene-anthraquinone molecules possessing either 5 or 9 all trans double bonds between the donor and acceptor, 1 and 2. The center-to-center distances between the porphyrin and the quinone in these relatively rigid molecules are 25 angstrom for 1 and 35 angstrom for 2. Selective picosecond laser excitation of the Zn-porphyrin and 1 and 2 results in the very rapid transfer of an electron to the anthraquinone in <2 ps and 10 ps, respectively. The resultant radical ion pairs recombine with τ = 10 ps for 1 and τ = 25 ps for 2. The electron transfer rates remain remarkably rapid over these long distances. The involvement of polyene radical cations in the mechanism of the radical ion pair recombination reaction is clear from the transient absorption spectra of 1 and 2, which show strong absorbances in the near-infrared. The strong electronic coupling between the Zn-porphyrin n the anthraquinone provided by low-lying states of the polyene make it possible to transfer an electron rapidly over very long distances

  14. Numerical simulation of transient moisture transfer into an electronic enclosure

    International Nuclear Information System (INIS)

    Nasirabadi, P. Shojaee; Jabbari, M.; Hattel, J. H.

    2016-01-01

    Electronic systems are sometimes exposed to harsh environmental conditions of temperature and humidity. Moisture transfer into electronic enclosures and condensation can cause several problems such as corrosion and alteration in thermal stresses. It is therefore essential to study the local climate inside the enclosures to be able to protect the electronic systems. In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce the CPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which the real 3D geometry is approximated by a 2D axial symmetry one. The results for 2D and 3D models were compared in order to calibrate the 2D representation. Furthermore, simulation results were compared with experimental data and good agreement was found.

  15. Numerical simulation of transient moisture transfer into an electronic enclosure

    Energy Technology Data Exchange (ETDEWEB)

    Nasirabadi, P. Shojaee; Jabbari, M.; Hattel, J. H. [Process Modelling Group, Department of Mechanical Engineering, Technical University of Denmark, Nils Koppels Allé, 2800 Kgs. Lyngby (Denmark)

    2016-06-08

    Electronic systems are sometimes exposed to harsh environmental conditions of temperature and humidity. Moisture transfer into electronic enclosures and condensation can cause several problems such as corrosion and alteration in thermal stresses. It is therefore essential to study the local climate inside the enclosures to be able to protect the electronic systems. In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce the CPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which the real 3D geometry is approximated by a 2D axial symmetry one. The results for 2D and 3D models were compared in order to calibrate the 2D representation. Furthermore, simulation results were compared with experimental data and good agreement was found.

  16. Conduction mechanism studies on electron transfer of disordered system

    Institute of Scientific and Technical Information of China (English)

    徐慧; 宋祎璞; 李新梅

    2002-01-01

    Using the negative eigenvalue theory and the infinite order perturbation theory, a new method was developed to solve the eigenvectors of disordered systems. The result shows that eigenvectors change from the extended state to the localized state with the increase of the site points and the disordered degree of the system. When electric field is exerted, the electrons transfer from one localized state to another one. The conductivity is induced by the electron transfer. The authors derive the formula of electron conductivity and find the electron hops between localized states whose energies are close to each other, whereas localized positions differ from each other greatly. At low temperature the disordered system has the character of the negative differential dependence of resistivity and temperature.

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

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

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

  18. Inelastic electron photon scattering at moderate four momentum transfers

    International Nuclear Information System (INIS)

    Berger, C.; Genzel, H.; Grigull, R.; Lackas, W.; Raupach, F.; Klovning, A.; Lillestoel, E.; Skard, J.A.; Ackermann, H.; Buerger, J.

    1980-10-01

    We present new high statistics data on hadron production in photon photon reactions. The data are analyzed in terms of an electron photon scattering formalism. The dependence of the total cross section on Q 2 , the four momentum transfer squared of the scattered electron, and on the mass W of the hadronic system is investigated. The data are compared to predictions from Vector Dominance and the quark model. (orig.)

  19. Simplistic graphene transfer process and its impact on contact resistance

    KAUST Repository

    Ghoneim, Mohamed T.; Smith, Casey; Hussain, Muhammad Mustafa

    2013-01-01

    Chemical vapor deposition based graphene grown on copper foil is attractive for electronic applications owing to its reliable growth process, large area coverage, and relatively defect free nature. However, transfer of the synthesized graphene to host substrate for subsequent device fabrication is extremely sensitive and can impact ultimate performance. Although ultra-high mobility is graphene's most prominent feature, problems with high contact resistance have severely limited its true potential. Therefore, we report a simple poly-(methyl methacrylate) based transfer process without post-annealing to achieve specific contact resistivity of 3.8 × 10−5 Ω cm2 which shows 80% reduction compared to previously reported values.

  20. Simplistic graphene transfer process and its impact on contact resistance

    KAUST Repository

    Ghoneim, Mohamed T.

    2013-05-09

    Chemical vapor deposition based graphene grown on copper foil is attractive for electronic applications owing to its reliable growth process, large area coverage, and relatively defect free nature. However, transfer of the synthesized graphene to host substrate for subsequent device fabrication is extremely sensitive and can impact ultimate performance. Although ultra-high mobility is graphene\\'s most prominent feature, problems with high contact resistance have severely limited its true potential. Therefore, we report a simple poly-(methyl methacrylate) based transfer process without post-annealing to achieve specific contact resistivity of 3.8 × 10−5 Ω cm2 which shows 80% reduction compared to previously reported values.

  1. Electron backscattering for process control in electron beam welding

    International Nuclear Information System (INIS)

    Ardenne, T. von; Panzer, S.

    1983-01-01

    A number of solutions to the automation of electron beam welding is presented. On the basis of electron backscattering a complex system of process control has been developed. It allows an enlarged imaging of the material's surface, improved adjustment of the beam focusing and definite focus positioning. Furthermore, both manual and automated positioning of the electron beam before and during the welding process has become possible. Monitoring of the welding process for meeting standard welding requirements can be achieved with the aid of a control quantity derived from the results of electronic evaluation of the high-frequency electron backscattering

  2. Transference of mass in fermentation process

    International Nuclear Information System (INIS)

    Rios E, R.; Buitrago H, G

    1998-01-01

    Based on bibliographical references, in a theoretical model based on a fermentation process, the relationship between the speed of oxygen transfer and the biochemistry demand is implemented, in order to discover the different conditions of aeration and of agitation speed, under those which the microbial growth is not affected by deficiency in the oxygen supply. This correlation was adapted to the cultivation of B. Thuringiensis, and of this form, maximum biomass concentration to the one, which is possible to supply oxygen efficiently with a group of defined operation conditions, could be estimated

  3. Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal

    Energy Technology Data Exchange (ETDEWEB)

    Lian, Tianquan

    2014-04-22

    The long-term goal of the proposed research is to understand electron transfer dynamics in nanoparticle/liquid interface. This knowledge is essential to many semiconductor nanoparticle based devices, including photocatalytic waste degradation and dye sensitized solar cells.

  4. Combining UV photodissociation with electron transfer for peptide structure analysis

    Czech Academy of Sciences Publication Activity Database

    Shaffer, C. J.; Marek, Aleš; Pepin, R.; Slováková, K.; Tureček, F.

    2015-01-01

    Roč. 50, č. 3 (2015), s. 470-475 ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : electron transfer dissociation * laser photodissociation * peptide ions * cation radical * chromophores * isomer distinction Subject RIV: CE - Biochemistry Impact factor: 2.541, year: 2015

  5. Electron Transfer in Chemistry and Biology – The Primary Events

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 2; Issue 12. Electron Transfer in Chemistry and Biology – The Primary Events in Photosynthesis. V Krishnan. General Article Volume 2 Issue 12 December 1997 pp 77-86. Fulltext. Click here to view fulltext PDF. Permanent link:

  6. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Boisen, Anja; Nielsen, Jens Ulrik

    2003-01-01

    We have studied the adsorption and electron-transfer dynamics of Saccharomyces cerevisiae (yeast) iso-l-cytochrome c adsorbed on Au(lll) electrodes in aqueous phosphate buffer media. This cytochrome possesses a thiol group dos e to the protein surface (Cysl02) suitable for linking the protein...

  7. 78 FR 30661 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2013-05-22

    ... Part 1005 Electronic Fund Transfers (Regulation E); Final Rule #0;#0;Federal Register / Vol. 78 , No... (Regulation E) AGENCY: Bureau of Consumer Financial Protection. ACTION: Final rule; official interpretation.../regulations/final-remittance-rule-amendment-regulation-e/ . SUPPLEMENTARY INFORMATION: I. Summary of the Final...

  8. Towards model-based testing of electronic funds transfer systems

    NARCIS (Netherlands)

    Asaadi, H.R.; Khosravi, R.; Mousavi, M.R.; Noroozi, N.; Arbab, F.; Sirjani, M.

    2012-01-01

    We report on our first experience with applying model-based testing techniques to an operational Electronic Funds Transfer (EFT) switch. The goal is to test the conformance of the EFT switch to the standard flows described by the ISO 8583 standard. To this end, we first make a formalization of the

  9. Towards model-based testing of electronic funds transfer systems

    NARCIS (Netherlands)

    Asaadi, H.R.; Khosravi, R.; Mousavi, M.R.; Noroozi, N.

    2010-01-01

    We report on our first experience with applying model-based testing techniques to an operational Electronic Funds Transfer (EFT) switch. The goal is to test the conformance of the EFT switch to the standard flows described by the ISO 8583 standard. To this end, we first make a formalization of the

  10. Electron transfer kinetics on mono- and multilayer graphene.

    Science.gov (United States)

    Velický, Matěj; Bradley, Dan F; Cooper, Adam J; Hill, Ernie W; Kinloch, Ian A; Mishchenko, Artem; Novoselov, Konstantin S; Patten, Hollie V; Toth, Peter S; Valota, Anna T; Worrall, Stephen D; Dryfe, Robert A W

    2014-10-28

    Understanding of the electrochemical properties of graphene, especially the electron transfer kinetics of a redox reaction between the graphene surface and a molecule, in comparison to graphite or other carbon-based materials, is essential for its potential in energy conversion and storage to be realized. Here we use voltammetric determination of the electron transfer rate for three redox mediators, ferricyanide, hexaammineruthenium, and hexachloroiridate (Fe(CN)(6)(3-), Ru(NH3)(6)(3+), and IrCl(6)(2-), respectively), to measure the reactivity of graphene samples prepared by mechanical exfoliation of natural graphite. Electron transfer rates are measured for varied number of graphene layers (1 to ca. 1000 layers) using microscopic droplets. The basal planes of mono- and multilayer graphene, supported on an insulating Si/SiO(2) substrate, exhibit significant electron transfer activity and changes in kinetics are observed for all three mediators. No significant trend in kinetics with flake thickness is discernible for each mediator; however, a large variation in kinetics is observed across the basal plane of the same flakes, indicating that local surface conditions affect the electrochemical performance. This is confirmed by in situ graphite exfoliation, which reveals significant deterioration of initially, near-reversible kinetics for Ru(NH3)(6)(3+) when comparing the atmosphere-aged and freshly exfoliated graphite surfaces.

  11. 75 FR 75897 - Electronic Funds Transfer of Depository Taxes

    Science.gov (United States)

    2010-12-07

    ... to the particular tax. (b) Income taxes. (1) For provisions relating to the deposits of income and... relating to Federal tax deposits (FTDs) by Electronic Funds Transfer (EFT). In response to the decision of... regulations amending the Income Tax Regulations (26 CFR part 1) and the Regulations on Procedure and...

  12. 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

  13. 31 CFR 208.3 - Payment by electronic funds transfer.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false Payment by electronic funds transfer. 208.3 Section 208.3 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY FINANCIAL MANAGEMENT SERVICE MANAGEMENT OF FEDERAL AGENCY...

  14. Charge-transfer properties in the gas electron multiplier

    International Nuclear Information System (INIS)

    Han, Sanghyo; Kim, Yongkyun; Cho, Hyosung

    2004-01-01

    The charge transfer properties of a gas electron multiplier (GEM) were systematically investigated over a broad range of electric field configurations. The electron collection efficiency and the charge sharing were found to depend on the external fields, as well as on the GEM voltage. The electron collection efficiency increased with the collection field up to 90%, but was essentially independent of the drift field strength. A double conical GEM has a 10% gain increase with time due to surface charging by avalanche ions whereas this effect was eliminated with the cylindrical GEM. The positive-ion feedback is also estimated. (author)

  15. Software engineering technology transfer: Understanding the process

    Science.gov (United States)

    Zelkowitz, Marvin V.

    1993-01-01

    Technology transfer is of crucial concern to both government and industry today. In this report, the mechanisms developed by NASA to transfer technology are explored and the actual mechanisms used to transfer software development technologies are investigated. Time, cost, and effectiveness of software engineering technology transfer is reported.

  16. Control of Electron Transfer from Lead-Salt Nanocrystals to TiO 2

    KAUST Repository

    Hyun, Byung-Ryool; Bartnik, A. C.; Sun, Liangfeng; Hanrath, Tobias; Wise, F. W.

    2011-01-01

    The roles of solvent reorganization energy and electronic coupling strength on the transfer of photoexcited electrons from PbS nanocrystals to TiO 2 nanoparticles are investigated. We find that the electron transfer depends only weakly

  17. Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

    Science.gov (United States)

    Vishnoi, Pratap; Rajesh, S; Manjunatha, S; Bandyopadhyay, Arkamita; Barua, Manaswee; Pati, Swapan K; Rao, C N R

    2017-11-03

    An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Vibrationally Assisted Electron Transfer Mechanism of Olfaction: Myth or Reality?

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Chang, Po-Yao; Schulten, Klaus

    2012-01-01

    to this suggestion an olfactory receptor is activated by electron transfer assisted through odorant vibrational excitation. The hundreds to thousands of different olfactory receptors in an animal recognize odorants over a discriminant landscape with surface properties and vibrational frequencies as the two major...... dimensions. In the present paper we introduce the vibrationally assisted mechanism of olfaction and demonstrate for several odorants that, indeed, a strong enhancement of an electron tunneling rate due to odorant vibrations can arise. We discuss in this regard the influence of odorant deuteration and explain...... olfactory receptors and odorants must obey for the vibrationally assisted electron transfer mechanism to function. We argue that the stated characteristics are feasible for realistic olfactory receptors, noting, though, that the receptor structure presently is still unknown, but can be studied through...

  19. Syntrophic Growth via Quinone-Mediated Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Jessica A Smith

    2015-02-01

    Full Text Available The mechanisms by which microbial species exchange electrons are of interest because interspecies electron transfer can expand the metabolic capabilities of microbial communities. Previous studies with the humic substance analog anthraquinone-2,6-disulfonate (AQDS suggested that quinone-mediated interspecies electron transfer (QUIET is feasible, but it was not determined if sufficient energy is available from QUIET to support the growth of both species. Furthermore, there have been no previous studies on the mechanisms for the oxidation of anthrahydroquinone-2,6-disulfonate (AHQDS. A co-culture of Geobacter metallireducens and Geobacter sulfurreducens metabolized ethanol with the reduction of fumarate much faster in the presence of AQDS, and there was an increase in cell protein. G. sulfurreducens was more abundant, consistent with G. sulfurreducens obtaining electrons from acetate that G. metallireducens produced from ethanol, as well as from AHQDS. Cocultures initiated with a citrate synthase-deficient strain of G. sulfurreducens that was unable to use acetate as an electron donor also metabolized ethanol with the reduction of fumarate and cell growth, but acetate accumulated over time. G. sulfurreducens and G. metallireducens were equally abundant in these co-cultures reflecting the inability of the citrate synthase-deficient strain of G. sulfurreducens to metabolize acetate. Evaluation of the mechanisms by which G. sulfurreducens accepts electrons from AHQDS demonstrated that a strain deficient in outer-surface c-type cytochromes that are required for AQDS reduction was as effective at QUIET as the wild-type strain. Deletion of additional genes previously implicated in extracellular electron transfer also had no impact on QUIET. These results demonstrate that QUIET can yield sufficient energy to support the growth of both syntrophic partners, but that the mechanisms by which electrons are derived from extracellular hydroquinones require

  20. Scaling laws in high energy electron-nuclear processes

    International Nuclear Information System (INIS)

    Chemtob, M.

    1980-11-01

    We survey the parton model description of high momentum transfer electron scattering processes with nuclei. We discuss both nucleon and quark parton models and confront the patterns of scaling laws violations, induced by binding effects, in the former, and perturbative QCD effects, in the latter

  1. Coherence and relaxation in energy transfer processes in condensed phases

    International Nuclear Information System (INIS)

    Shelby, R.M.

    1978-03-01

    Investigations of electronic triplet and vibrational energy transfer dynamics and relaxation processes are presented. Emphasis is placed on understanding the role of coherence and interactions which tend to destroy the coherence. In the case of triplet excitons at low temperatures, the importance of coherence in energy migration can be established, and the average coherence parameters can be experimentally determined. In the case of vibrational excitations, both picosecond spectroscopic studies of vibrational relaxation and spontaneous Raman spectroscopy are used to characterize the dynamics and give increased insight into the nature of the mechanisms responsible for vibrational dephasing. The design and operation of the picosecond apparatus used in these experiments is also described

  2. Electron spectroscopy in the fundamental process of electron-nucleus bremsstrahlung

    International Nuclear Information System (INIS)

    Hillenbrand, Pierre-Michel

    2013-07-01

    Within the scope of this thesis the fundamental process of electron-nucleus bremsstrahlung was studied in inverse kinematics at the Experimental Storage Ring ESR at GSI. For the system U 88+ + N 2 at 90 MeV/u it was shown, that by using inverse kinematics coincidence measurements between the scattered electron and the emitted photon can be performed for the case, in which the incoming electron transfers almost all of its kinetic energy onto the emitted photon. The sensitivity to the fundamental process could be achieved by measuring triple differential cross sections as a function of the emission angle of the photon and the scattered electron as well as the energy of the scattered electron. The optics of the magnetic electron spectrometer used were thoroughly revised and optimized to the experimental requirements. Analyzing different coincidences in this collision system, it was possible to determine the contributions to the electron distribution arising from radiative electron capture to the projectile continuum, nonradiative electron capture to the projectile continuum, and electron loss to the projectile continuum. The experimental results of each of these processes were compared to theoretical calculations. The electron spectra for the radiative and the nonradiative electron capture to continuum clearly reproduce the opposite asymmetry predicted by theory. Furthermore electron spectra for collisions of U 28+ with different gases were measured.

  3. Electron transfer by excited benzoquinone anions: slow rates for two-electron transitions.

    Science.gov (United States)

    Zamadar, Matibur; Cook, Andrew R; Lewandowska-Andralojc, Anna; Holroyd, Richard; Jiang, Yan; Bikalis, Jin; Miller, John R

    2013-09-05

    Electron transfer (ET) rate constants from the lowest excited state of the radical anion of benzoquinone, BQ(-•)*, were measured in THF solution. Rate constants for bimolecular electron transfer reactions typically reach the diffusion-controlled limit when the free-energy change, ΔG°, reaches -0.3 eV. The rate constants for ET from BQ(-•)* are one-to-two decades smaller at this energy and do not reach the diffusion-controlled limit until -ΔG° is 1.5-2.0 eV. The rates are so slow probably because a second electron must also undergo a transition to make use of the energy of the excited state. Similarly, ET, from solvated electrons to neutral BQ to form the lowest excited state, is slow, while fast ET is observed at a higher excited state, which can be populated in a transition involving only one electron. A simple picture based on perturbation theory can roughly account for the control of electron transfer by the need for transition of a second electron. The picture also explains how extra driving force (-ΔG°) can restore fast rates of electron transfer.

  4. Simulating Policy Processes through Electronic Mail.

    Science.gov (United States)

    Flynn, John P.

    1987-01-01

    Focuses on the use of electronic mail for teaching and learning about social welfare policy processes and compares electronic mail as a simulation medium to more structured computer applications. (Author)

  5. Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

    Energy Technology Data Exchange (ETDEWEB)

    Ramakrishnan, Raghunathan, E-mail: r.ramakrishnan@unibas.ch [Institute of Physical Chemistry, National Center for Computational Design and Discovery of Novel Materials (MARVEL), Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland); Nest, Mathias [Theoretische Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching (Germany)

    2015-01-13

    Highlights: • We model electron dynamics across cyano alkanethiolates attached to gold cluster. • We present electron transfer time scales from TD-DFT and TD-CI based simulations. • Both DFT and CI methods qualitatively predict the trend in time scales. • TD-CI predicts the experimental relative time scale very accurately. - Abstract: We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual π{sup ∗} molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process.

  6. Exploring the Critical Role of Motivation to Transfer in the Training Transfer Process

    Science.gov (United States)

    Grohmann, Anna; Beller, Johannes; Kauffeld, Simone

    2014-01-01

    The present study aims at exploring the critical role of motivation to transfer within the training transfer process. In a sample of N?=?252 employees of one industrial company, one peer rating and several self-ratings of transfer were used to investigate the mediating role of motivation to transfer in the relationship between training…

  7. When Creativity Met Transfer: Increasing Creativity and Transfer by Controlling the Styles of Processing

    Science.gov (United States)

    Kaniel, Shlomo

    2013-01-01

    The primary purpose of this article is to combine both transfer of learning (hereafter, transfer) and creativity into similar processes that can increase the products of transfer and creativity. Both transfer and creativity operate within reciprocal relationships between memory storage and working memory. Moreover, they are also based on moving…

  8. 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)

  9. Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation

    Science.gov (United States)

    Zeng, Zhirui; Tice, Michael M.

    2018-01-01

    Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms.

  10. Electron Transfer between Electrically Conductive Minerals and Quinones

    Directory of Open Access Journals (Sweden)

    Olga Taran

    2017-07-01

    Full Text Available Long-distance electron transfer in marine environments couples physically separated redox half-reactions, impacting biogeochemical cycles of iron, sulfur and carbon. Bacterial bio-electrochemical systems that facilitate electron transfer via conductive filaments or across man-made electrodes are well-known, but the impact of abiotic currents across naturally occurring conductive and semiconductive minerals is poorly understood. In this paper I use cyclic voltammetry to explore electron transfer between electrodes made of common iron minerals (magnetite, hematite, pyrite, pyrrhotite, mackinawite, and greigite, and hydroquinones—a class of organic molecules found in carbon-rich sediments. Of all tested minerals, only pyrite and magnetite showed an increase in electric current in the presence of organic molecules, with pyrite showing excellent electrocatalytic performance. Pyrite electrodes performed better than commercially available glassy carbon electrodes and showed higher peak currents, lower overpotential values and a smaller separation between oxidation and reduction peaks for each tested quinone. Hydroquinone oxidation on pyrite surfaces was reversible, diffusion controlled, and stable over a large number of potential cycles. Given the ubiquity of both pyrite and quinones, abiotic electron transfer between minerals and organic molecules is likely widespread in Nature and may contribute to several different phenomena, including anaerobic respiration of a wide variety of microorganisms in temporally anoxic zones or in the proximity of hydrothermal vent chimneys, as well as quinone cycling and the propagation of anoxic zones in organic rich waters. Finally, interactions between pyrite and quinones make use of electrochemical gradients that have been suggested as an important source of energy for the origins of life on Earth. Ubiquinones and iron sulfide clusters are common redox cofactors found in electron transport chains across all domains

  11. Electron Transfer Between Electrically Conductive Minerals and Quinones

    Science.gov (United States)

    Taran, Olga

    2017-07-01

    Long-distance electron transfer in marine environments couples physically separated redox half-reactions, impacting biogeochemical cycles of iron, sulfur and carbon. Bacterial bio-electrochemical systems that facilitate electron transfer via conductive filaments or across man-made electrodes are well known, but the impact of abiotic currents across naturally occurring conductive and semiconducitve minerals is poorly understood. In this paper I use cyclic voltammetry to explore electron transfer between electrodes made of common iron minerals (magnetite, hematite, pyrite, pyrrhotite, mackinawite and greigite), and hydroquinones - a class of organic molecules found in carbon-rich sediments. Of all tested minerals, only pyrite and magnetite showed an increase in electric current in the presence of organic molecules, with pyrite showing excellent electrocatalytic performance. Pyrite electrodes performed better than commercially available glassy carbon electrodes and showed higher peak currents, lower overpotential values and a smaller separation between oxidation and reduction peaks for each tested quinone. Hydroquinone oxidation on pyrite surfaces was reversible, diffusion controlled, and stable over a large number of potential cycles. Given the ubiquity of both pyrite and quinones, abiotic electron transfer between minerals and organic molecules is likely widespread in Nature and may contribute to several different phenomena, including anaerobic respiration of a wide variety of microorganisms in temporally anoxic zones or in the proximity of hydrothermal vent chimneys, as well as quinone cycling and the propagation of anoxic zones in organic rich waters. Finally, interactions between pyrite and quinones make use of electrochemical gradients that have been suggested as an important source of energy for the origins of life on Earth. Ubiquinones and iron sulfide clusters are common redox cofactors found in electron transport chains across all domains of life and

  12. Electron transfer and energy transfer reactions in photoexcited a-nonathiophene/C60 films and solutions

    NARCIS (Netherlands)

    Janssen, R.A.J.; Moses, D.; Sariciftci, N.S.; Heeger, A.J.

    1994-01-01

    Photoexcitation of a nonathiophene in film or solution across the p-p* energy gap produces a metastable triplet state. In the presence of C60, on the other hand, an ultra fast electron transfer from the photoexcited nonathiophene onto C60 is observed in films, whereas in solution C60 is involved in

  13. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...

  14. Electron-electron interaction and transfer ionization in fast ion-atom collisions

    International Nuclear Information System (INIS)

    Voitkiv, A B

    2008-01-01

    Recently it was pointed out that electron capture occurring in fast ion-atom collisions can proceed via a mechanism which earlier was not considered. In the present paper we study this mechanism in more detail. Similarly as in radiative capture, where the electron transfer occurs due to the interaction with the radiation field and proceeds via emission of a photon, within this mechanism the electron capture is caused by the interaction with another atomic electron leading mainly to the emission of the latter. In contrast to the electron-electron Thomas capture, this electron-electron (E-E) mechanism is basically a first-order one having similarities to the kinematic and radiative capture channels. It also possesses important differences with the latter two. Leading to transfer ionization, this first-order capture mechanism results in the electron emission mainly in the direction opposite to the motion of the projectile ion. The same, although less pronounced, feature is also characteristic for the momenta of the target recoil ions produced via this mechanism. It is also shown that the action of the E-E mechanism is clearly seen in recent experimental data on the transfer ionization in fast proton-helium collisions.

  15. Charge-transfer collisions involving few-electron systems

    International Nuclear Information System (INIS)

    Kirchner, T.

    2016-01-01

    Ion-atom collision systems that involve more than one electron constitute nonseparable few-body problems, whose full solution is difficult to say the least. At impact energies well below 1 keV/amu an expansion of the stationary scattering wave function in terms of a limited number of products of nuclear and molecular state wave functions (amended to satisfy scattering boundary conditions) is feasible and usually sufficient to obtain accurate charge-transfer cross sections provided the electronic wave functions include configuration interaction. At energies above 1 keV/amu this approach becomes inefficient and close-coupling methods within the semi classical approximation are better suited to treat the problem. For bare-ion collisions from helium target atoms explicit solutions of the two-electron time-dependent Schrödinger equation can be achieved, but are computationally costly and cannot be extended to problems which involve more than two electrons.

  16. Transfer function restoration in 3D electron microscopy via iterative data refinement

    International Nuclear Information System (INIS)

    Sorzano, C O S; Marabini, R; Herman, G T; Censor, Y; Carazo, J M

    2004-01-01

    Three-dimensional electron microscopy (3D-EM) is a powerful tool for visualizing complex biological systems. As with any other imaging device, the electron microscope introduces a transfer function (called in this field the contrast transfer function, CTF) into the image acquisition process that modulates the various frequencies of the signal. Thus, the 3D reconstructions performed with these CTF-affected projections are also affected by an implicit 3D transfer function. For high-resolution electron microscopy, the effect of the CTF is quite dramatic and limits severely the achievable resolution. In this work we make use of the iterative data refinement (IDR) technique to ameliorate the effect of the CTF. It is demonstrated that the approach can be successfully applied to noisy data

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

    Science.gov (United States)

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

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

  18. 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

  19. Electron transfer dynamics of triphenylamine dyes bound to TiO2 nanoparticles from femtosecond stimulated Raman spectroscopy

    KAUST Repository

    Hoffman, David P.; Lee, Olivia P.; Millstone, Jill E.; Chen, Mark S.; Su, Timothy A.; Creelman, Mark; Frechet, Jean; Mathies, Richard A.

    2013-01-01

    Interfacial electron transfer between sensitizers and semiconducting nanoparticles is a crucial yet poorly understood process. To address this problem, we have used transient absorption (TA) and femtosecond stimulated Raman spectroscopy (FSRS

  20. Syntrophic growth with direct interspecies electron transfer as the primary mechanism for energy exchange

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Aklujkar, Muktak

    2013-01-01

    Direct interspecies electron transfer (DIET) through biological electrical connections is an alternative to interspecies H2 transfer as a mechanism for electron exchange in syntrophic cultures. However, it has not previously been determined whether electrons received via DIET yield energy...... dehydrogenase, the pilus-associated c-type cytochrome OmcS and pili consistent with electron transfer via DIET. These results suggest that electrons transferred via DIET can serve as the sole energy source to support anaerobic respiration....

  1. Allenylidene Complexes of Ruthenium: Synthesis, Spectroscopy and Electron Transfer Properties

    Czech Academy of Sciences Publication Activity Database

    Winter, R. F.; Záliš, Stanislav

    2004-01-01

    Roč. 248, 15/16 (2004), s. 1565-1583 ISSN 0010-8545 R&D Projects: GA ČR GA203/03/0821; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * allenylidine complexes of ruthenium * electron transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.446, year: 2004

  2. Blocking layer modeling for temperature analysis of electron transfer ...

    African Journals Online (AJOL)

    In this article, we simulate thermal effects on the electron transfer rate from three quantum dots CdSe, CdS and CdTe to three metal oxides TiO2, SnO2 and ZnO2 in the presence of four blocking layers ZnS, ZnO, TiO2 and Al2O3, in a porous quantum dot sensitized solar cell (QDSSC) structure, using Marcus theory.

  3. Marcus wins nobel prize in chemistry for electron transfer theory

    International Nuclear Information System (INIS)

    Levi, B.G.

    1993-01-01

    This article describes the work of Rudolf Marcus of Caltech leading to his receipt of the 1992 Nobel Prize in Chemistry open-quotes for his contributions to the theory of electron transfer reactions in chemical systems.close quotes Applications of Marcus' theory include such diverse phenomena as photosynthesis, electrically conducting polymers, chemiluminescence, and corrosion. Historical aspects of his career are given. 10 refs., 1 fig

  4. Magnetic electron scattering from deuterium at low-momentum transfer

    International Nuclear Information System (INIS)

    Jones, E.C. Jr.; Bendel, W.L.; Fagg, L.W.; Lindgren, R.A.

    1980-01-01

    The elastic and inelastic cross sections of deuterium for 56.4 MeV electrons scattered at 180 0 , have been measured up to an excitation energy of 19 MeV. The experimental cross sections are compared with those calculated by Miller, by Durand, and by Arenhoevel and Fabian, and also with the sum rules of O'Connell. The results indicate that the contribution of meson exchange currents at this low-momentum transfer is significant

  5. Game theoretic aspect of production process transfer functions ...

    African Journals Online (AJOL)

    Game theoretic aspect of production process transfer functions. ... On the final analysis, it was shown that relating transfer function to Bayesian games and mechanism design would lead to optimal bids, optimal ... AJOL African Journals Online.

  6. Electron Transfer in Flavodoxin-based Redox Maquettes

    NARCIS (Netherlands)

    Alagaratnam, S.

    2005-01-01

    Small redox proteins play the role of electron taxis in the cell, picking electrons up at one location and delivering them at another. While it is known that these reactions are the basis for the processes of energy generation by respiration and photosynthesis, the means by which these 'taxis'

  7. Development of microforming process combined with thin film transfer printing

    Directory of Open Access Journals (Sweden)

    Koshimizu Kazushi

    2015-01-01

    Full Text Available Microforming receives a lot of attentions in the recent years due to the increased use of microparts in electronics and medical sectors. For the further functionalization of these micro devices, high functional surface with noble metals are strongly required for the devices in bio- and medical fields, such as bio-sensors. To realize the submillimeter structure of metal foils and micro to nanometer structures in one forming process, the present study proposes a combined process of microforming for metal foils and transfer printing of gold (Au thin films. To clarify the availability of the proposed combined process, transferability of Au thin films under micro bulging deformation are investigated. 0.1 mm-thick pure titanium (Ti foils and 100 nm-thick Au films were used as blank and functional materials, respectively. The forming tests of the proposed process were conducted. With increasing strain of Ti foils, Au TP areas increase. By this experiment, it’s confirmed that the hydrogen reduction of oxidation layers and the strain of Ti foil are significant factor for Au TP on Ti foils.

  8. Enhanced Electronic Properties of SnO2 via Electron Transfer from Graphene Quantum Dots for Efficient Perovskite Solar Cells.

    Science.gov (United States)

    Xie, Jiangsheng; Huang, Kun; Yu, Xuegong; Yang, Zhengrui; Xiao, Ke; Qiang, Yaping; Zhu, Xiaodong; Xu, Lingbo; Wang, Peng; Cui, Can; Yang, Deren

    2017-09-26

    Tin dioxide (SnO 2 ) has been demonstrated as an effective electron-transporting layer (ETL) for attaining high-performance perovskite solar cells (PSCs). However, the numerous trap states in low-temperature solution processed SnO 2 will reduce the PSCs performance and result in serious hysteresis. Here, we report a strategy to improve the electronic properties in SnO 2 through a facile treatment of the films with adding a small amount of graphene quantum dots (GQDs). We demonstrate that the photogenerated electrons in GQDs can transfer to the conduction band of SnO 2 . The transferred electrons from the GQDs will effectively fill the electron traps as well as improve the conductivity of SnO 2 , which is beneficial for improving the electron extraction efficiency and reducing the recombination at the ETLs/perovskite interface. The device fabricated with SnO 2 :GQDs could reach an average power conversion efficiency (PCE) of 19.2 ± 1.0% and a highest steady-state PCE of 20.23% with very little hysteresis. Our study provides an effective way to enhance the performance of perovskite solar cells through improving the electronic properties of SnO 2 .

  9. Fundamentals of electronic image processing

    CERN Document Server

    Weeks, Arthur R

    1996-01-01

    This book is directed to practicing engineers and scientists who need to understand the fundamentals of image processing theory and algorithms to perform their technical tasks. It is intended to fill the gap between existing high-level texts dedicated to specialists in the field and the need for a more practical, fundamental text on image processing. A variety of example images are used to enhance reader understanding of how particular image processing algorithms work.

  10. Effects of electrostatic interactions on electron transfer reactions

    International Nuclear Information System (INIS)

    Hickel, B.

    1987-01-01

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

  11. 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.

  12. Transfer process studies through a toarcian argilite

    International Nuclear Information System (INIS)

    Boisson, J.Y.

    1996-01-01

    Concerning long lived and high level radioactive wastes, the French Wastes Management Research Act (30th December 1991) has set three ways to be studied: separation and/or transmutation, conditioning processes and volumes reduction, and feasibility of geological disposal. ANDRA, in charge of this last point; has the responsibility to create and develop underground laboratories, to elaborate and propose the concept of the future disposal installations with safety demonstration, to be submitted to the French safety governmental authorities (Direction de la Surete des Installations Nucleaires). In order to asses these safety demonstrations, to build up its judgement, DSIN will ask technical advice, from Institut de Protection et de Surete Nucleaire (IPSN). To be able to meet these requirements, IPSN is developing, in the framework of its research and development safety programs, in situ research concerning the confining properties of geological formations. In order to perform experiments in representative conditions concerning mainly geotechnical and hydrogeological properties of very low permeability rocks, appropriate underground sites have been selected in the past in granite and shale formations. IPSN activities at the Tournemire site are the most important activities regarding specifically research about characterization of transfers through an argilite formation. This programme is developed in the framework of a cost sharing research contract between IPSN and EC. (author)

  13. Indirect processes in electron-ion scattering

    International Nuclear Information System (INIS)

    Bottcher, C.; Griffin, D.C.; Pindzola, M.S.; Phaneuf, R.A.

    1983-10-01

    A summary is given of an informal workshop held at Oak Ridge National Laboratory on June 22-23, 1983, in which the current status of theoretical calculations of indirect processes in electron-ion scattering was reviewed. Processes of particular interest in astrophysical and fusion plasmas were emphasized. Topics discussed include atomic structure effects, electron-impact ionization, and dielectronic recombination

  14. Indirect processes in electron-ion scattering

    Energy Technology Data Exchange (ETDEWEB)

    Bottcher, C.; Griffin, D.C.; Pindzola, M.S.; Phaneuf, R.A.

    1983-10-01

    A summary is given of an informal workshop held at Oak Ridge National Laboratory on June 22-23, 1983, in which the current status of theoretical calculations of indirect processes in electron-ion scattering was reviewed. Processes of particular interest in astrophysical and fusion plasmas were emphasized. Topics discussed include atomic structure effects, electron-impact ionization, and dielectronic recombination.

  15. Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy.

    Science.gov (United States)

    Zhang, Zhengyang; Lambrev, Petar H; Wells, Kym L; Garab, Győző; Tan, Howe-Siang

    2015-07-31

    During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

  16. Coulomb blockade and transfer of electrons one by one

    International Nuclear Information System (INIS)

    Pothier, Hugues

    1991-01-01

    Zero point fluctuations of the charge on the capacitance of a tunnel junction connected to a bias circuit are in almost all experimental situations larger than the electron charge. As a consequence, the effects of charge granularity are hidden, but in circuits with 'islands', which are electrodes connected to the rest of the circuit only through tunnel junctions and capacitors. The island charge being quantized, its fluctuations are blocked. If the island capacitance is sufficiently small, no electron can enter the island because of the increase of electrostatic energy that would occur. We have observed this effect, called 'Coulomb blockade', in the 'single electron box', where an island is formed between a tunnel junction and a capacitor. A bias voltage source coupled to the island through the capacitor allows to control the number of electrons. We have designed and operated two devices with nano-scale tunnel junctions based on this principle, the 'turnstile' and the 'pump', through which the current is controlled electron by electron. In our experiments, the precision of the transfer is of the order of one percent. It should be a million time better in versions of these devices with more junctions. One could then use them for a new measurement of the fine structure constant alpha. (author) [fr

  17. 77 FR 34127 - Financial Management Service; Proposed Collection of Information: Electronic Transfer Account...

    Science.gov (United States)

    2012-06-08

    ... Information: Electronic Transfer Account (ETA) Financial Agency Agreement AGENCY: Financial Management Service... of information described below: Title: Electronic Transfer Account (ETA) Financial Agency Agreement... public and other Federal agencies to take this opportunity to comment on a continuing information...

  18. Interspecies Electron Transfer during Propionate and Butyrate Degradation in Mesophilic, Granular Sludge

    OpenAIRE

    Schmidt, J. E.; Ahring, B. K.

    1995-01-01

    Granules from a mesophilic upflow anaerobic sludge blanket reactor were disintegrated, and bacteria utilizing only hydrogen or formate or both hydrogen and formate were added to investigate the role of interspecies electron transfer during degradation of propionate and butyrate. The data indicate that the major electron transfer occurred via interspecies hydrogen transfer, while interspecies formate transfer may not be essential for interspecies electron transfer in this system during degrada...

  19. Overpotential-induced lability of the electronic overlap factor in long-range electrochemical electron transfer: charge and distance dependence

    DEFF Research Database (Denmark)

    Kornyshev, A. A.; Kuznetsov, A. M.; Nielsen, Jens Ulrik

    2000-01-01

    Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly...

  20. 36 CFR 1235.48 - What documentation must agencies transfer with electronic records?

    Science.gov (United States)

    2010-07-01

    ... documentation for the following types of electronic records: (i) E-mail messages with attachments; (ii) Scanned... agencies transfer with electronic records? 1235.48 Section 1235.48 Parks, Forests, and Public Property... agencies transfer with electronic records? (a) General. Agencies must transfer documentation adequate to...

  1. Microbial interspecies electron transfer via electric currents through conductive minerals

    Science.gov (United States)

    Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

    2012-01-01

    In anaerobic biota, reducing equivalents (electrons) are transferred between different species of microbes [interspecies electron transfer (IET)], establishing the basis of cooperative behaviors and community functions. IET mechanisms described so far are based on diffusion of redox chemical species and/or direct contact in cell aggregates. Here, we show another possibility that IET also occurs via electric currents through natural conductive minerals. Our investigation revealed that electrically conductive magnetite nanoparticles facilitated IET from Geobacter sulfurreducens to Thiobacillus denitrificans, accomplishing acetate oxidation coupled to nitrate reduction. This two-species cooperative catabolism also occurred, albeit one order of magnitude slower, in the presence of Fe ions that worked as diffusive redox species. Semiconductive and insulating iron-oxide nanoparticles did not accelerate the cooperative catabolism. Our results suggest that microbes use conductive mineral particles as conduits of electrons, resulting in efficient IET and cooperative catabolism. Furthermore, such natural mineral conduits are considered to provide ecological advantages for users, because their investments in IET can be reduced. Given that conductive minerals are ubiquitously and abundantly present in nature, electric interactions between microbes and conductive minerals may contribute greatly to the coupling of biogeochemical reactions. PMID:22665802

  2. Integrated control system for electron beam processes

    Science.gov (United States)

    Koleva, L.; Koleva, E.; Batchkova, I.; Mladenov, G.

    2018-03-01

    The ISO/IEC 62264 standard is widely used for integration of the business systems of a manufacturer with the corresponding manufacturing control systems based on hierarchical equipment models, functional data and manufacturing operations activity models. In order to achieve the integration of control systems, formal object communication models must be developed, together with manufacturing operations activity models, which coordinate the integration between different levels of control. In this article, the development of integrated control system for electron beam welding process is presented as part of a fully integrated control system of an electron beam plant, including also other additional processes: surface modification, electron beam evaporation, selective melting and electron beam diagnostics.

  3. Extracellular Electron Transport Coupling Biogeochemical Processes Centimeters

    DEFF Research Database (Denmark)

    Risgaard-Petersen, Nils; Fossing, Henrik; Christensen, Peter Bondo

    2010-01-01

    of the oxygen uptake in laboratory incubations of initially homogenized and stabilized sediment. Using microsensors and process rate measurements we further investigated the effect of the electric currents on sediment biogeochemistry. Dissolved sulfide readily donated electrons to the networks and could...... confirmed the depth range of the electric communication and indicated donation of electrons directly from organotrophic bacteria. The separation of oxidation and reduction processes created steep pH gradients eventually causing carbonate precipitation at the surface. The results indicate that electron...... exchanging organisms have major biogeochemical importance as they allow widely separated electron donors and acceptors to react with one another....

  4. 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

  5. Convective and conduction heat transfer study on a mig-type electron gun

    International Nuclear Information System (INIS)

    Patire Junior, H.; Barroso, J.J.

    1996-01-01

    A convective and conducting heat transfer study of a magnetron injection electron gun has been made to minimize the temperature distribution in the gun elements while keeping the required operating temperature at 1000 0 C of the emitter. Appropriate materials were selected to reduce thermal losses and to improve the gun design from a constructional point of view aiming at extending the capabilities of the electron gun. A thermal probe to determine the air velocity and the convective heat transfer coefficient has been constructed to determine the external boundary condition of the ceramic shell and external flanges. A study the contact resistance for all the gun elements has been made to minimize the conduction thermal losses. A software has been used to simulate a thermal model considering the three processes of thermal transfer, namely, conduction, convection and radiation and the influence of the physical properties of the materials used. (author). 7 refs., 5 figs., 1 tab

  6. Hydrodynamics and mass transfer in trickle leaching process

    International Nuclear Information System (INIS)

    Jin Suoqing; Xiang Qinfang; Guo Jianzheng

    1995-01-01

    The initial research results of the hydrodynamic behavior and mass transfer of the trickle leaching process are summarized. It was shown that the dropping mode, the height of uranium ore heap and the flow rate of the dropping fluid affect the mass transfer of the trickle leaching process. Based on the concept of the keeping form of liquid in ore particle bed and the diffusion in porous medium, a mass transfer pattern, i.e. 'double-membrane transfer process' controlled by porous diffusion, was presented and proved for trickle leaching process

  7. Electron Transfer and Solvent-Mediated Electronic Localization in Molecular Photocatalysis

    DEFF Research Database (Denmark)

    Dohn, Asmus Ougaard; Kjær, Kasper Skov; Harlang, Tobias B.

    2016-01-01

    This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born–Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate...

  8. 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

  9. 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

  10. Towards model-based testing of electronic funds transfer systems

    OpenAIRE

    Asaadi, H.R.; Khosravi, R.; Mousavi, M.R.; Noroozi, N.

    2010-01-01

    We report on our first experience with applying model-based testing techniques to an operational Electronic Funds Transfer (EFT) switch. The goal is to test the conformance of the EFT switch to the standard flows described by the ISO 8583 standard. To this end, we first make a formalization of the transaction flows specified in the ISO 8583 standard in terms of a Labeled Transition System (LTS). This formalization paves the way for model-based testing based on the formal notion of Input-Outpu...

  11. Exciplex formation and electron transfer in polychromophoric systems

    International Nuclear Information System (INIS)

    Yang, N.C.C.; Minsek, D.W.; Johnson, D.G.; Wasielewski, M.R.

    1989-01-01

    This paper discusses the rates of excited anthracene decay and intramolecular exciplex formation from biochromophoric molecules containing an anthryl group and an amine donor which vary with the length of the chain link, the nature of the amine donor and the viscosity of the medium. According to the authors, the results indicate that the intramolecular exciplex formation may proceed via more than one pathway. Experimental results suggest that electron transfer from the amino donor to the excited anthryl group may play a role in the exciplex formation in viscous alkanes

  12. Large momentum transfer electron scattering from few-nucleon systems

    International Nuclear Information System (INIS)

    Arnold, R.G.

    1979-08-01

    A review is given of the experimental results from a series of measurements at SLAC of large momentum transfer (Q 2 > 20 fm -2 ) electron scattering at forward angles from nuclei with A less than or equal to 4. Theoretical interpretations of these data in terms of traditional nuclear physics models and in terms of quark constituent models are described. Some physics questions for future experiments are explored, and a preview of possible future measurements of magnetic structure functions of light nuclei at large Q 2 is given

  13. 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.

  14. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  15. Powering microbes with electricity: direct electron transfer from electrodes to microbes.

    Science.gov (United States)

    Lovley, Derek R

    2011-02-01

    The discovery of electrotrophs, microorganisms that can directly accept electrons from electrodes for the reduction of terminal electron acceptors, has spurred the investigation of a wide range of potential applications. To date, only a handful of pure cultures have been shown to be capable of electrotrophy, but this process has also been inferred in many studies with undefined consortia. Potential electron acceptors include: carbon dioxide, nitrate, metals, chlorinated compounds, organic acids, protons and oxygen. Direct electron transfer from electrodes to cells has many advantages over indirect electrical stimulation of microbial metabolism via electron shuttles or hydrogen production. Supplying electrons with electrodes for the bioremediation of chlorinated compounds, nitrate or toxic metals may be preferable to adding organic electron donors or hydrogen to the subsurface or bioreactors. The most transformative application of electrotrophy may be microbial electrosynthesis in which carbon dioxide and water are converted to multi-carbon organic compounds that are released extracellularly. Coupling photovoltaic technology with microbial electrosynthesis represents a novel photosynthesis strategy that avoids many of the drawbacks of biomass-based strategies for the production of transportation fuels and other organic chemicals. The mechanisms for direct electron transfer from electrodes to microorganisms warrant further investigation in order to optimize envisioned applications. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

  16. 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)

  17. Effect of electrostatic interactions on electron-transfer reactions

    International Nuclear Information System (INIS)

    Hickel, B.

    1987-01-01

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

  18. Effects of energy, distance and orientation on electron transfer rates studied by pulse radiolysis in organic media

    International Nuclear Information System (INIS)

    Miller, J.R.

    1987-01-01

    In the past few years the methods of radiation chemistry in organic media have made an enormous change in how we view electron transfer processes, as these media have proved the most useful for studying long distance electron transfer between molecules. This paper briefly summarizes a few of the aspects of this area and discusses some of the attributes and limitations of radiation tehniques, particularly pulse radiolysis, in organic solvents. 14 refs., 2 figs

  19. Photoinduced electron-transfer from imidazole derivative to nano-semiconductors.

    Science.gov (United States)

    Karunakaran, C; Jayabharathi, J; Jayamoorthy, K; Devi, K Brindha

    2012-04-01

    Bioactive imidazole derivative absorbs in the UV region at 305 nm. The interaction of imidazole derivative with nanoparticulate WO3, Fe2O3, Fe3O4, CuO, ZrO2 and Al2O3 has been studied by UV-visible absorption, FT-IR and fluorescence spectroscopies. The imidazole derivative adsorbs strongly on the surfaces of nanosemiconductor, the apparent binding constants for the association between nanomaterials and imidazole derivative have been determined from the fluorescence quenching. In the case of nanocrystalline insulator, fluorescence quenching through electron transfer from the excited state of the imidazole derivative to alumina is not possible. However, a possible mechanism for the quenching of fluorescence by the insulator is energy transfer, that is, energy transferred from the organic molecule to the alumina lattice. Based on Forster's non-radiation energy transfer theory, the distance between the imidazole derivative and nanoparticles (r0∼2.00 nm) as well as the critical energy transfer distance (R0∼1.70 nm) has been calculated. The interaction between the imidazole derivative and nanosurfaces occurs through static quenching mechanism. The free energy change (ΔGet) for electron transfer process has been calculated by applying Rehm-Weller equation. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  1. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu; Aly, Shawkat Mohammede; Usman, Anwar; Parida, Manas R.; Del Gobbo, Silvano; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  2. Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission† †Electronic supplementary information (ESI) available: Actinic pump spectrum, discussion on ground state addition process, peak fitting procedure, transient absorption data, power dependence measurements, etalon pulse shaping, TIPS-pentacene FSRS data, and optimized geometry and frequency calculation results. See DOI: 10.1039/c7sc03496b

    Science.gov (United States)

    Hart, Stephanie M.; Silva, W. Ruchira

    2017-01-01

    Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes. PMID:29675170

  3. Photons emission processes in electron scattering

    International Nuclear Information System (INIS)

    Soto Vargas, C.W.

    1996-01-01

    The investigations involving the scattering sections arising in virtual an real photon emission processes of electron and positron scattering by an atomic nucleus, have the need for thorough and complete calculations of the virtual photon spectrum and then introduce the distorted wave formulation, which is mathematically involved an numerically elaborated, but accessible to its use in experimental electron scattering facilities. (author) [es

  4. Studies of collision dynamics in electron capture processes

    International Nuclear Information System (INIS)

    Hansen, J.P.

    1990-12-01

    This thesis presents some recent development in time-dependent coupled channel methods for one- and two-electron systems. The methods have been applied to detailed studies on several different aspects of charge transfer processes in ion-atom collisions at intermediate to low energies. Measurable quantities, such as partial and total cross sections, partial cross sections in projectile energy gain, orientation and alignment fractions, have been calculated. Confrontation with experiments has in general given good agreement. 29 refs

  5. Studies of collision dynamics in electron capture processes

    International Nuclear Information System (INIS)

    Hansen, J.P.

    1989-12-01

    The thesis presents some recent development in time-dependent coupled channel methods for one- and two-electron systems. The methods have been applied to detailed studies on several different aspects of charge transfer processes in ion-atom collisions at intermediate to low energies. Measurable quantities, such as partial and total cross sections, partial cross sections in projectile energy gain, orientation and alignment fractions, have been calculated. Confrontation with experiments has in general given good agreement. 14 refs., 2 figs

  6. Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

    Science.gov (United States)

    Laborda, Eduardo; Gómez-Gil, José María; Molina, Angela

    2017-06-28

    A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

  7. Optical absorption and energy transfer processes in dendrimers

    International Nuclear Information System (INIS)

    Reineker, P.; Engelmann, A.; Yudson, V.I.

    2004-01-01

    For dendrimers of various sizes the energy transfer and the optical absorption is investigated theoretically. The molecular subunits of a dendrimer are modeled as two-level systems. The electronic interaction between them is described via transfer integrals and the influence of vibrational degrees of freedom is taken into account in a first approach using a stochastic model. We discuss the time dependence of the energy transport and show that rim states of the dendrimer dominate the absorption spectra, that in general the electronic excitation energy is concentrated on peripheric molecules, and that the energetically lowest absorption peak is redshifted with increasing dendrimer size due to delocalization of the electronic excitation

  8. Multiple electron processes of He and Ne by proton impact

    Science.gov (United States)

    Terekhin, Pavel Nikolaevich; Montenegro, Pablo; Quinto, Michele; Monti, Juan; Fojon, Omar; Rivarola, Roberto

    2016-05-01

    A detailed investigation of multiple electron processes (single and multiple ionization, single capture, transfer-ionization) of He and Ne is presented for proton impact at intermediate and high collision energies. Exclusive absolute cross sections for these processes have been obtained by calculation of transition probabilities in the independent electron and independent event models as a function of impact parameter in the framework of the continuum distorted wave-eikonal initial state theory. A binomial analysis is employed to calculate exclusive probabilities. The comparison with available theoretical and experimental results shows that exclusive probabilities are needed for a reliable description of the experimental data. The developed approach can be used for obtaining the input database for modeling multiple electron processes of charged particles passing through the matter.

  9. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

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

    Science.gov (United States)

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

    2018-02-01

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

  11. Numerical simulation of heat transfer process in automotive brakes

    OpenAIRE

    Gonzalo Voltas, David

    2013-01-01

    This master thesis concerns the theoretical investigations of the heat transfer process in automotive brakes. The process of heat generation and heat transfer to ambient air in automotive brake was presented. The two–dimensional, axi-symmetrical model of transient heat conduction for the brake was applied. The relevant boundary conditions, that describe the heat generated in the brake and the heat transferred to ambient air, were used. The unsteady heat conduction problem was solved by the...

  12. The competence accumulation process in the technology transference strategy

    OpenAIRE

    Souza, André Silva de; Segatto-Mendes, Andréa Paula

    2008-01-01

    The present article evaluates and measures the technological competence accumulation in an automation area enterprise to distribution centers, Knapp Sudamérica Logistic and Automation Ltd, in the interval of the technology transference process previous period (1998-2001) and during the technology transference process (2002-2005). Therefore, based on an individual case study, the study identified the technology transference strategy and mechanism accorded between the head office and the branch...

  13. Ion beam processing of advanced electronic materials

    International Nuclear Information System (INIS)

    Cheung, N.W.; Marwick, A.D.; Roberto, J.B.

    1989-01-01

    This report contains research programs discussed at the materials research society symposia on ion beam processing of advanced electronic materials. Major topics include: shallow implantation and solid-phase epitaxy; damage effects; focused ion beams; MeV implantation; high-dose implantation; implantation in III-V materials and multilayers; and implantation in electronic materials. Individual projects are processed separately for the data bases

  14. Improvement Of Search Process In Electronic Catalogues

    Directory of Open Access Journals (Sweden)

    Titas Savickas

    2014-05-01

    Full Text Available The paper presents investigation on search in electronic catalogues. The chosen problem domain is the search system in the electronic catalogue of Lithuanian Academic Libraries. The catalogue uses ALEPH system with MARC21 bibliographic format. The article presents analysis of problems pertaining to the current search engine and user expectations related to the search system of the electronic catalogue of academic libraries. Subsequent to analysis, the research paper presents the architecture for a semantic search system in the electronic catalogue that uses search process designed to improve search results for users.

  15. Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

    Science.gov (United States)

    Tiwari, Vivek; Peters, William K.; Jonas, David M.

    2017-10-01

    Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

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

    Science.gov (United States)

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

    2018-02-14

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

  17. Process of international kaizen transfer in the Netherlands

    NARCIS (Netherlands)

    Yokozawa, Kodo; Steenhuis, H.J.; de Bruijn, E.J.

    2011-01-01

    This study sheds light on the international kaizen transfer process. Two research questions were explored: what are the major stages in the kaizen transfer process? And what are the activities, positive and negative factors influencing each stage? Case studies with 15 Japanese manufacturers in the

  18. Electron beam processing of wastewater in Malaysia

    International Nuclear Information System (INIS)

    Zulkafli Ghazali; Khairul Zaman Dahlan; Ting Teo Ming; Khomsaton A. Bakar

    2006-01-01

    Electron beam processing technology started in Malaysia in 1991 when two accelerators were installed through JICA cooperation to perform medical product sterilization project. Since then several private companies have installed electron accelerators to develop in removing volatile organic materials and to demonstrate flue gas treatment. In this country report, effort on electron beam processing of wastewater or contaminated groundwater is presented: After de-coloration tests using gamma rays as function of radiation doses, electron beam treatment of textile industry wastewater as function of beam energy and current intensity as well as with combined treatment such as aeration or biological treatment to examine the effectiveness in color and BOD or COD change has been carried out and the main results are reported. Furthermore, the present technique was examined to apply in river water treatment for use as drinking water. Techno-economic feasibility study for recycling of industrial waste water using electron beam technology is now underway. (S. Ohno)

  19. Electronic devices for analog signal processing

    CERN Document Server

    Rybin, Yu K

    2012-01-01

    Electronic Devices for Analog Signal Processing is intended for engineers and post graduates and considers electronic devices applied to process analog signals in instrument making, automation, measurements, and other branches of technology. They perform various transformations of electrical signals: scaling, integration, logarithming, etc. The need in their deeper study is caused, on the one hand, by the extension of the forms of the input signal and increasing accuracy and performance of such devices, and on the other hand, new devices constantly emerge and are already widely used in practice, but no information about them are written in books on electronics. The basic approach of presenting the material in Electronic Devices for Analog Signal Processing can be formulated as follows: the study with help from self-education. While divided into seven chapters, each chapter contains theoretical material, examples of practical problems, questions and tests. The most difficult questions are marked by a diamon...

  20. Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II,Rh(III Supramolecular Complexes

    Directory of Open Access Journals (Sweden)

    Karen J. Brewer

    2010-08-01

    Full Text Available Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and time-resolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II,Rh(III supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer excited state. The details of the photophysics of Ru(II,Rh(III and Ru(II,Rh(III,Ru(II systems as probed by steady-state and time-resolved emission spectroscopy will be highlighted.

  1. Theoretical perspectives on electron transfer and charge separation events in photochemical water cleavage systems

    International Nuclear Information System (INIS)

    Kozak, J.J.; Lenoir, P.M.; Musho, M.K.; Tembe, B.L.

    1984-01-01

    We study in this paper the dynamics induced by models for photochemical water cleavage systems, focusing on the spatial and temporal factors influencing electron transfer and charge separation processes in such systems. The reaction-diffusion theory is formulated in full generality and the consequences explored in a number of spatio-temporal regimes, viz. the spatially homogeneous system in the long-time limit (i.e. the steady state for a well-stirred system), the spatially homogeneous system in evolution, and the spatially inhomogeneous system in evolution (where, in the latter study, we consider electron transfer at the cluster surface to be governed by a rate constant that reflects the localized nature of such processes). The results of numerical simulations are presented for all three cases and used to highlight the importance of heterogeneous environments in enhancing the cage escape yield of charge separated species, and to demonstrate the dependence of the hydrogen yield on the localization of electron-transfer processes in the vicinity of the microcatalyst surface

  2. Layered Black Phosphorus: Strongly Anisotropic Magnetic, Electronic, and Electron-Transfer Properties.

    Science.gov (United States)

    Sofer, Zdeněk; Sedmidubský, David; Huber, Štěpán; Luxa, Jan; Bouša, Daniel; Boothroyd, Chris; Pumera, Martin

    2016-03-01

    Layered elemental materials, such as black phosphorus, exhibit unique properties originating from their highly anisotropic layered structure. The results presented herein demonstrate an anomalous anisotropy for the electrical, magnetic, and electrochemical properties of black phosphorus. It is shown that heterogeneous electron transfer from black phosphorus to outer- and inner-sphere molecular probes is highly anisotropic. The electron-transfer rates differ at the basal and edge planes. These unusual properties were interpreted by means of calculations, manifesting the metallic character of the edge planes as compared to the semiconducting properties of the basal plane. This indicates that black phosphorus belongs to a group of materials known as topological insulators. Consequently, these effects render the magnetic properties highly anisotropic, as both diamagnetic and paramagnetic behavior can be observed depending on the orientation in the magnetic field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane

    2015-01-01

    in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant...... cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

  4. Electron beam flue gas treatment process. Review

    International Nuclear Information System (INIS)

    Honkonen, V.A.

    1996-01-01

    The basis of the process for electron beam flue gas treatment are presented in the report. In tabular form the history of the research is reviewed. Main dependences of SO 2 and NO x removal efficiencies on different physico-chemical parameters are discussed. Trends concerning industrial process implementation are presented in the paper,finally. (author). 74 refs, 11 figs, 1 tab

  5. Electron beam processing of combustion flue gases

    International Nuclear Information System (INIS)

    1987-07-01

    This report contains the papers presented at the consultants' meeting on electron beam processing of combustion flue gases. The meeting provided an excellent opportunity for exchanging information and reviewing the current status of technology development. Characteristics of the electron beam processing recognized by the meeting are: capability of simultaneous removals of SO 2 and NO x , safe technology and simplicity of control, dry process without waste water to be treated, cost benefit of electron beam processing compared with conventional technology and the conversion of SO 2 and NO x to a by-product that can be used as agricultural fertilizer. A separate abstract was prepared for each of the 22 papers in this technical report

  6. Electron transfer flavoprotein deficiency: Functional and molecular aspects

    DEFF Research Database (Denmark)

    Schiff, M; Froissart, R; Olsen, Rikke Katrine Jentoft

    2006-01-01

    Multiple acyl-CoA dehydrogenase deficiency (MADD) is a recessively inherited metabolic disorder that can be due to a deficiency of electron transfer flavoprotein (ETF) or its dehydrogenase (ETF-ubiquinone oxidoreductase). ETF is a mitochondrial matrix protein consisting of alpha- (30kDa) and beta......- (28kDa) subunits encoded by the ETFA and ETFB genes, respectively. In the present study, we have analysed tissue samples from 16 unrelated patients with ETF deficiency, and we report the results of ETF activity, Western blot analysis and mutation analysis. The ETF assay provides a reliable diagnostic...... tool to confirm ETF deficiency in patients suspected to suffer from MADD. Activity ranged from less than 1 to 16% of controls with the most severely affected patients disclosing the lowest activity values. The majority of patients had mutations in the ETFA gene while only two of them harboured...

  7. Facile direct electron transfer in glucose oxidase modified electrodes

    International Nuclear Information System (INIS)

    Wang Dan; Chen Liwei

    2009-01-01

    Glucose oxidase (GOx) is widely used in the glucose biosensor industry. However, mediatorless direct electron transfer (DET) from GOx to electrode surfaces is very slow. Recently, mediatorless DET has been reported via the incorporation of nanomaterials such as carbon nanotubes and nanoparticles in the modification of electrodes. Here we report GOx electrodes showing DET without the need for any nanomaterials. The enzyme after immobilization with poly-L-lysine (PLL) and Nafion retains the biocatalytic activities and oxidizes glucose efficiently. The amperometric response of Nafion-PLL-GOx modified electrode is linearly proportional to the concentration of glucose up to 10 mM with a sensitivity of 0.75 μA/mM at a low detection potential (-0.460 V vs. Ag/AgCl). The methodology developed in this study will have impact on glucose biosensors and biofuel cells and may potentially simplify enzyme immobilization in other biosensing systems.

  8. 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

  9. Bond charges and electronic charge transfer in ternary semiconductors

    International Nuclear Information System (INIS)

    Pietsch, U.

    1986-01-01

    By means of a simple molecule-theoretic model of 'linear superposition of two-electron molecules' the bond charges between nearest neighbours and the effective charges of ions are calculated for ternary zinc-blende structure alloys as well as chalcopyrite semiconductors. Taking into account both, the charge transfer among the ions caused by the differences of electronegativities of atoms used and between the bonds created by the internal stress of the lattice a nearly unvaried averaged bond charge amount of the alloy is found, but rather dramatically changed local bond charge parameters in comparison with the respective values of binary compounds used. This fact should influence the noncentral force interaction in such semiconductors. (author)

  10. Electronic Processes at Organic−Organic Interfaces: Insight from Modeling and Implications for Opto-electronic Devices †

    KAUST Repository

    Beljonne, David

    2011-02-08

    We report on the recent progress achieved in modeling the electronic processes that take place at interfaces between π-conjugated materials in organic opto-electronic devices. First, we provide a critical overview of the current computational techniques used to assess the morphology of organic: organic heterojunctions; we highlight the compromises that are necessary to handle large systems and multiple time scales while preserving the atomistic details required for subsequent computations of the electronic and optical properties. We then review some recent theoretical advances in describing the ground-state electronic structure at heterojunctions between donor and acceptor materials and highlight the role played by charge-transfer and long-range polarization effects. Finally, we discuss the modeling of the excited-state electronic structure at organic:organic interfaces, which is a key aspect in the understanding of the dynamics of photoinduced electron-transfer processes. © 2010 American Chemical Society.

  11. Simulation of solution phase electron transfer in a compact donor-acceptor dyad.

    Science.gov (United States)

    Kowalczyk, Tim; Wang, Lee-Ping; Van Voorhis, Troy

    2011-10-27

    Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide-anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis-trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems.

  12. 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.

  13. Study of the electron transfer in analog compounds of the Prussia blue

    International Nuclear Information System (INIS)

    Romero V, S.; Damaso C, L.F.; Reguera R, E.; Yee M, H.T.

    2006-01-01

    As answer to the necessity of the search of new nano structured materials, the present work was carried out that it studies the electron transfer in compound similar of the Prussia blue (CAAP), which are representative molecular materials, because its chromophore, magnetic, and electric properties, depend mainly on the processes that are made in their levels or orbital energy. It is known that these made up with octahedra symmetry that its are presented in form of powders, suffer processes of electron transfer when its are exposed to external stimulation by means of light (embracing the regions from the ultraviolet one until the infrared in the electromagnetic spectrum), because they are made up of mixed valency. To know that types of electronic transfers are those that are made in the study materials, 4 series of CAAP its were synthesized by the method of mixtures of aqueous solutions: M[Fe +3 CN) 6 ] 2 nH 2 O, M[Cr +3 (CN) 6 ] 2 nH 2 O, M[Mn +3 (CN) 6 ] 3 nH 2 O y M[Co +3 (CN) 6 ] 3 nH 2 O, and later on studied by means of the electron spectroscopy technique with a UV-SENSE spectrophotometer (Perkin-Elmer) in or n range of work of 250 to 1100 nm. Because to discuss the electronic structures of any compound, it is required the calculation of the energy levels, they took like reference the data tabulated by John Alexander and Harry Gray calculated by the modified theoretical approach of Wolfsberg-Helmhoz. When comparing the obtained spectra with the theoretical data, it was concludes that in the CAAP, its are carried out electronic transfers among orbital molecular metallic of the type d → d, and load transfer (TC) among orbital molecular of the ligand and metal. When being carried out a load transfer in the CAAP that initially are made up of under-spin these its are photoinduced to an excited state of high spin. In consequence it is possible to vary the interactions among the metals of transition of the CAAP and the ligands, allowing the extension of coordinated

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  15. Nanoscale charge transfer in redox proteins and DNA: Towards biomolecular electronics

    International Nuclear Information System (INIS)

    Artés, Juan Manuel; López-Martínez, Montserrat; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

    2014-01-01

    Understanding how charges move through and between biomolecules is a fundamental question that constitutes the basis for many biological processes. On the other hand, it has potential applications in the design of sensors based on biomolecules and single molecule devices. In this review we introduce the study of the electron transfer (ET) process in biomolecules, providing an overview of the fundamental theory behind it and the different experimental approaches. The ET in proteins is introduced by reviewing a complete electronic characterization of a redox protein (azurin) using electrochemical scanning tunnelling microscopy (ECSTM). The ET process in DNA is overviewed and results from different experimental approaches are discussed. Finally, future directions in the study of the ET process in biomolecules are introduced as well as examples of possible technological applications

  16. A note on the standard electron transfer potential at the interface between two immiscible electrolyte solutions

    Czech Academy of Sciences Publication Activity Database

    Samec, Zdeněk

    2009-01-01

    Roč. 55, č. 2 (2009), s. 75-81 ISSN 0034-6691 R&D Projects: GA ČR(CZ) GA203/07/1257 Institutional research plan: CEZ:AV0Z40400503 Keywords : interface between two immiscible electrolyte solutions * interfacial electron transfer * standard electron trasfer potential * homogeneous electron transfer Subject RIV: CG - Electrochemistry

  17. 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

  18. Feedback Specificity, Information Processing, and Transfer of Training

    Science.gov (United States)

    Goodman, Jodi S.; Wood, Robert E.; Chen, Zheng

    2011-01-01

    This study examines the effects of feedback specificity on transfer of training and the mechanisms through which feedback can enhance or inhibit transfer. We used concurrent verbal protocol methodology to elicit and operationalize the explicit information processing activities used by 48 trainees performing the Furniture Factory computer…

  19. Light- induced electron transfer and ATP synthesis in a carotene synthesizing insect

    Science.gov (United States)

    Valmalette, Jean Christophe; Dombrovsky, Aviv; Brat, Pierre; Mertz, Christian; Capovilla, Maria; Robichon, Alain

    2012-08-01

    A singular adaptive phenotype of a parthenogenetic insect species (Acyrthosiphon pisum) was selected in cold conditions and is characterized by a remarkable apparition of a greenish colour. The aphid pigments involve carotenoid genes well defined in chloroplasts and cyanobacteria and amazingly present in the aphid genome, likely by lateral transfer during evolution. The abundant carotenoid synthesis in aphids suggests strongly that a major and unknown physiological role is related to these compounds beyond their canonical anti-oxidant properties. We report here that the capture of light energy in living aphids results in the photo induced electron transfer from excited chromophores to acceptor molecules. The redox potentials of molecules involved in this process would be compatible with the reduction of the NAD+ coenzyme. This appears as an archaic photosynthetic system consisting of photo-emitted electrons that are in fine funnelled into the mitochondrial reducing power in order to synthesize ATP molecules.

  20. Carbonate radical anion-induced electron transfer in bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Ravi [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)]. E-mail: rjudrin@yahoo.com; Mukherjee, T. [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2006-07-15

    Reaction of native and thermally denatured bovine serum albumin (BSA) with carbonate radical anion (CO{sub 3}{sup -} radical) has been studied using pulse radiolysis technique. Scavenging of CO{sub 3}{sup -} radical by native BSA and consequent electron transfer from tyrosine to tryptophan radical has been observed to occur with almost same rate constant (k{approx}1.7x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}) at pH 8.8. Effect of structural changes, due to thermal denaturation, on scavenging of CO{sub 3}{sup -} radical and the electron transfer process have been studied and discussed in this paper.

  1. Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

    Science.gov (United States)

    2018-01-01

    Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present. PMID:29392173

  2. Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

    Directory of Open Access Journals (Sweden)

    Kaiyu Fu

    2018-01-01

    Full Text Available Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present.

  3. Transfer of spectral weight in spectroscopies of correlated electron systems

    International Nuclear Information System (INIS)

    Rozenberg, M.J.; Kotliar, G.; Kajueter, H.

    1996-01-01

    We study the transfer of spectral weight in the photoemission and optical spectra of strongly correlated electron systems. Within the local impurity self-consistent approximation, that becomes exact in the limit of large lattice coordination, we consider and compare two models of correlated electrons, the Hubbard model and the periodic Anderson model. The results are discussed in regard to recent experiments. In the Hubbard model, we predict an anomalous enhancement optical spectral weight as a function of temperature in the correlated metallic state which is in qualitative agreement with optical measurements in V 2 O 3 . We argue that anomalies observed in the spectroscopy of the metal are connected to the proximity to a crossover region in the phase diagram of the model. In the insulating phase, we obtain excellent agreement with the experimental data, and present a detailed discussion on the role of magnetic frustration by studying the k-resolved single-particle spectra. The results for the periodic Anderson model are discussed in connection to recent experimental data of the Kondo insulators Ce 3 Bi 4 Pt 3 and FeSi. The model can successfully explain the thermal filling of the optical gap and the corresponding changes in the photoemission density of states. The temperature dependence of the optical sum rule is obtained, and its relevance to the interpretation of the experimental data discussed. Finally, we argue that the large scattering rate measured in Kondo insulators cannot be described by the periodic Anderson model. copyright 1996 The American Physical Society

  4. Process variation in electron beam sterilization

    International Nuclear Information System (INIS)

    Beck, Jeffrey A.

    2012-01-01

    The qualification and control of electron beam sterilization can be improved by the application of proven statistical analysis techniques such as Analysis of Variance (ANOVA) and Statistical Tolerance Limits. These statistical techniques can be useful tools in: •Locating and quantifying the minimum and maximum absorbed dose in a product. •Estimating the expected process maximum dose, given a minimum sterilizing dose. •Setting a process minimum dose target, based on an allowance for random measurement and process variation. •Determining the dose relationship between a reference dosimeter and process minimum and maximum doses. This study investigates and demonstrates the application of these tools in qualifying electron beam sterilization, and compares the conclusions obtained with those obtained using practices recommended in Guide for Process Control in Radiation Sterilization. The study supports the following conclusions for electron beam processes: 1.ANOVA is a more effective tool for evaluating the equivalency of absorbed doses than methods suggested in . 2.Process limits computed using statistical tolerance limits more accurately reflect actual process variability than the AAMI method, which applies +/−2 sample standard deviations (s) regardless of sample size. 3.The use of reference dose ratios lends itself to qualification using statistical tolerance limits. The current AAMI recommended approach may result in an overly optimistic estimate of the reference dose adjustment factor, as it is based on application of +/−2(s) tolerances regardless of sample size.

  5. Two-photon-induced hot-electron transfer to a single molecule in a scanning tunneling microscope

    International Nuclear Information System (INIS)

    Wu, S. W.; Ho, W.

    2010-01-01

    The junction of a scanning tunneling microscope (STM) operating in the tunneling regime was irradiated with femtosecond laser pulses. A photoexcited hot electron in the STM tip resonantly tunnels into an excited state of a single molecule on the surface, converting it from the neutral to the anion. The electron-transfer rate depends quadratically on the incident laser power, suggesting a two-photon excitation process. This nonlinear optical process is further confirmed by the polarization measurement. Spatial dependence of the electron-transfer rate exhibits atomic-scale variations. A two-pulse correlation experiment reveals the ultrafast dynamic nature of photoinduced charging process in the STM junction. Results from these experiments are important for understanding photoinduced interfacial charge transfer in many nanoscale inorganic-organic structures.

  6. Correlation properties of surface and percolation transfer of electrons

    International Nuclear Information System (INIS)

    Bakunin, O.G.

    2002-01-01

    In this work was received equation, connecting correlatively properties of surface with electrons distribution function. Usually for equilibrium is necessary a large number of collisions. Collisions are 'destroying' correlations. In case rare collisions large importance have correlations and 'memory' effects. Non-Markov's character of emitting particles by surface lead to strongly nonequilibrium condition of 'gas'. Here kinetic equation of diffusive form does not apply. Classical kinetic equation are described only conditions near to equilibrium. This work offers to use ideas anomal diffusion in phase-space. The correlation properties of surface describe by correlations of velocities of emitting electrons: B(t). We offer to use functional equation for probability collision instead of kinetic equation: ∫ 0 ν 0 W noncoll F(ν) dv = 1 - B(t). This functional allow to consider 'memory' effects. It is important for consideration of electrons and clusters near surfaces. Distribution function become direct connected with correlations. In classical Kubo-Mory theory of transfer is necessary to get nondivergences integral: D ∝ ∫ 0 ∞ B(t). In considering case we can use even 'power function'. It was used 'slow' correlation function as Kohlraush in calculations. The information about kinetics and correlations properties are containing in one functional equation. It was received solution of this equation in form Levy function: F(ν) ∝ 1/ν α exp(-1/ν). The solution of this form can not be get with help asymptotic methods of kinetic theory. Asymptotics of solution have scale-invariant character F(V) ∝ 1/V α . This indicate on fractal properties phase-space. (author)

  7. 77 FR 6310 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ... business'' in the definition of ``remittance transfer provider.'' This definition determines whether a... remittance transfers in the ``normal course of its business'' from the definition of ``remittance transfer... ``normal course of business'' for purposes of the definition of ``remittance transfer provider.'' Second...

  8. Control of Electron Transfer from Lead-Salt Nanocrystals to TiO 2

    KAUST Repository

    Hyun, Byung-Ryool

    2011-05-11

    The roles of solvent reorganization energy and electronic coupling strength on the transfer of photoexcited electrons from PbS nanocrystals to TiO 2 nanoparticles are investigated. We find that the electron transfer depends only weakly on the solvent, in contrast to the strong dependence in the nanocrystal-molecule system. This is ascribed to the larger size of the acceptor in this system, and is accounted for by Marcus theory. The electronic coupling of the PbS and TiO 2 is varied by changing the length, aliphatic and aromatic structure, and anchor groups of the linker molecules. Shorter linker molecules consistently lead to faster electron transfer. Surprisingly, linker molecules of the same length but distinct chemical structures yield similar electron transfer rates. In contrast, the electron transfer rate can vary dramatically with different anchor groups. © 2011 American Chemical Society.

  9. Experimental investigations of laser-induced forward transfer process of organic thin films

    International Nuclear Information System (INIS)

    Thomas, Benjamin; Alloncle, Anne Patricia; Delaporte, Philippe; Sentis, Marc; Sanaur, Sebastien; Barret, Michael; Collot, Philippe

    2007-01-01

    This paper deals with transfer induced by laser of thin layers of a conducting polymer, the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), for applications in plastic electronics. This relatively simple technique of direct writing offers the ability to make surface micro-patterning by localized deposits of material. The study of the various mechanisms (ablation, transfer and deposit) has been carried out according to different conditions of irradiation: wavelength (from ultraviolet to infrared radiation), pulse duration (nanosecond and sub-nanosecond) and fluence. The morphology of the transferred patterns has been analyzed by optical microscopy and scanning electronic microscopy. Our objective is to understand the different mechanisms involved in the process in order to optimize it in terms of geometrical resolution while preserving the properties of the transferred material

  10. Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

    Science.gov (United States)

    Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

    2015-08-03

    We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 78 FR 14233 - Electronic Retirement Processing

    Science.gov (United States)

    2013-03-05

    ... as the private key, is used to verify the signature. Digitized signature means a graphical image of a... recipients of the electronic document. Smart card means a plastic card, typically the size of a credit card, containing an embedded integrated circuit or ``chip'' that can generate, store, or process data. A smart card...

  12. Process mining for electronic data interchange

    NARCIS (Netherlands)

    Engel, R.; Krathu, W.; Zapletal, M.; Pichler, C.; Aalst, van der W.M.P.; Werthner, H.; Huemer, C.; Setzer, T.

    2011-01-01

    Choreography modeling and service integration received a lot of attention in the last decade. However, most real-world implementations of inter-organizational systems are still realized by traditional Electronic Data Interchange (EDI) standards. In traditional EDI standards, the notion of process or

  13. Short-Range Electron Transfer in Reduced Flavodoxin: Ultrafast Nonequilibrium Dynamics Coupled with Protein Fluctuations.

    Science.gov (United States)

    Kundu, Mainak; He, Ting-Fang; Lu, Yangyi; Wang, Lijuan; Zhong, Dongping

    2018-05-03

    Short-range electron transfer (ET) in proteins is an ultrafast process on the similar timescales as local protein-solvent fluctuations thus the two dynamics are coupled. Here, we use semiquinone flavodoxin and systematically characterized the photoinduced redox cycle with eleven mutations of different aromatic electron donors (tryptophan and tyrosine) and local residues to change redox properties. We observed the forward and backward ET dynamics in a few picoseconds, strongly following a stretched behavior resulting from a coupling between local environment relaxations and these ET processes. We further observed the hot vibrational-state formation through charge recombination and the subsequent cooling dynamics also in a few picoseconds. Combined with the ET studies in oxidized flavodoxin, these results coherently reveal the evolution of the ET dynamics from single to stretched exponential behaviors and thus elucidate critical timescales for the coupling. The observed hot vibration-state formation is robust and should be considered in all photoinduced back ET processes in flavoproteins.

  14. Accelerators in industrial electron beam processing

    International Nuclear Information System (INIS)

    Becker, R.C.

    1984-01-01

    High power electron beam accelerators are being used for a variety of industrial processes. Such machines can process a wide range of products at very high thruput rates and at very low unit processing costs. These industrial accelerators are now capable of producing up to 200 kW of electron beam power at 4.0 MV and 100 kW at 5.0 MV. At this writing, even larger units are contemplated. The reliability of these high power devices also makes it feasible to consider bremsstrahlung (x-ray) processing as well. In addition to the advance of accelerator technology, microprocessor control systems now provide the capability to coordinate all the operations of the irradiation facility, including the accelerator, the material handling system, the personnel safety system and various auxiliary services. Facility designs can be adapted to many different industrial processes, including use of the dual purpose electron/x-ray accelerator, to ensure satisfactory product treatment with good dose uniformity, high energy efficiency and operational safety and simplicity. In addition, equipment manufacturers like RDI are looking beyond their conventional DC accelerator technology; looking at high power 10-12 MeV linear accelerators with power levels up to 25 kW or more. These high power linear accelerators could be the ideal processing tool for many sterilization and food irradiation applications. (author)

  15. Type IV pili of Acidithiobacillus ferrooxidans can transfer electrons from extracellular electron donors.

    Science.gov (United States)

    Li, Yongquan; Li, Hongyu

    2014-03-01

    Studies on Acidithiobacillus ferrooxidans accepting electrons from Fe(II) have previously focused on cytochrome c. However, we have discovered that, besides cytochrome c, type IV pili (Tfp) can transfer electrons. Here, we report conduction by Tfp of A. ferrooxidans analyzed with a conducting-probe atomic force microscope (AFM). The results indicate that the Tfp of A. ferrooxidans are highly conductive. The genome sequence of A. ferrooxidans ATCC 23270 contains two genes, pilV and pilW, which code for pilin domain proteins with the conserved amino acids characteristic of Tfp. Multiple alignment analysis of the PilV and PilW (pilin) proteins indicated that pilV is the adhesin gene while pilW codes for the major protein element of Tfp. The likely function of Tfp is to complete the circuit between the cell surface and Fe(II) oxides. These results indicate that Tfp of A. ferrooxidans might serve as biological nanowires transferring electrons from the surface of Fe(II) oxides to the cell surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Self-reduction process and enhanced blue emission in SrAl{sub 2}Si{sub 2}O{sub 8}: Eu, Tb via electron transfer from Tb{sup 3+} to Eu{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Hongwei; Wang, Lili; Li, Minhong; Ran, Weiguang; Deng, Zhihan; Houzong, Ruizhi; Shi, Jinsheng [Department of Chemistry and Pharmaceutical Science, Qingdao Agricultural University, Qingdao 266109, Shandong, (China)

    2017-06-15

    Eu, Tb co-doped SrAl{sub 2}Si{sub 2}O{sub 8} luminescent materials were synthesized via a high-temperature solid-state reaction. Excitation spectra of SrAl{sub 2}Si{sub 2}O{sub 8}: Eu{sup 2+} gives two broad excitation bands maximizing at 270 and 330 nm, resulting from splitting Eu{sup 2+} energy levels in octahedral crystal field. Eu single doped SrAl{sub 2}Si{sub 2}O{sub 8} luminescent material exhibits two emission bands at about 406 and 616 nm. Intensity of the blue emission from Eu{sup 2+} is always strong, compared with that of the red emission band of Eu{sup 3+}. Reduction from Eu{sup 3+} to Eu{sup 2+} can be explained with the model of charge compensation. Blue emission in SrAl{sub 2}Si{sub 2}O{sub 8}: xEu was strengthened after incorporation of Tb, which can be explained by electron transfer from Tb{sup 3+} to Eu{sup 3+} (Tb{sup 3+} + Eu{sup 3+} → Tb{sup 4+} + Eu{sup 2+}). Under 230 nm excitation, intensity of Tb{sup 3+} emission was nearly unchanged and that of Eu{sup 2+} was increased, obviously due to the delivery of more electrons to Eu{sup 3+}. The strongest emission of Eu{sup 2+} in 0.09Eu/0.06Tb co-doped SrAl{sub 2}Si{sub 2}O{sub 8} and excited at 270 and 330 nm was remarkably enhanced by about four times compared to that of 0.15Eu Single doped SrAl{sub 2}Si{sub 2}O{sub 8}. All of the results indicate that SrAl{sub 2}Si{sub 2}O{sub 8}:xEu, yTb are potential blue emitting luminescent materials for UV-LEDs. More importantly, this research may provide a new perspective in designing broad band blue luminescent materials. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2014-08-07

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

  18. Guide for selection of dosimetry system for electron processing

    International Nuclear Information System (INIS)

    Mehta, K.

    1988-01-01

    Correct applications of radiation processing depend on accurate measurements of absorbed radiation dose. Radiation dosimetry plays several important roles in radiation processing. In particular, there are three stages for any radiation process during which dosimetry is a key to success: basic laboratory research, commissioning of the process and quality control. Radiation dosimeters may be divided into various classes depending upon their areas of applications and their relative quality: primary standard dosimeter, reference standard dosimeter, transfer standard dosimeter and routine in-house dosimeter. Several commercially available dosimeters are described under each class, and their advantages and limitations are discussed. Finally, recommendations are made as to which dosimeter is most suitable for each of the three stages of electron-beam processing. 124 refs

  19. 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.

  20. Flat Graphene-Enhanced Electron Transfer Involved in Redox Reactions.

    Science.gov (United States)

    Pan, Meilan; Zhang, Yanyang; Shan, Chao; Zhang, Xiaolin; Gao, Guandao; Pan, Bingcai

    2017-08-01

    Graphene is easily warped in the out-of-plane direction because of its high in-plane Young's modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

  1. Coherence transfer and electron T1-, T2-relaxation in nitroxide spin labels

    DEFF Research Database (Denmark)

    Marsh, Derek

    2017-01-01

    -hyperfine anisotropies of isolated nitroxide spin labels. Results compatible with earlier treatments by Redfield theory are obtained without specifically evaluating matrix elements. Extension to single-transition operators for isolated nitroxides predicts electron coherence transfer by pseudosecular electron...

  2. Kinetics of electron transfer through ferrocene-terminated alkanethiol monolayers on gold

    Energy Technology Data Exchange (ETDEWEB)

    Smalley, J.F.; Feldberg, S.W.; Newton, M.D.; Liu, Y.P. [Brookhaven National Lab., Upton, NY (United States); Chidsey, C.E.D.; Linford, M.R. [Stanford Univ., CA (United States)

    1995-08-31

    The kinetics of electron transfer between a substrate gold electrode and a self-assembled monolayer formed from CH{sub 3}(CH{sub 2}){sub n-1}SH and ({eta}{sup 5} C{sub 5}H{sub 5})Fe ({eta}{sup 5}-C{sub 5}H{sub 4})CO{sub 2}(CH{sub 2}){sub n}SH were studied as a function of n, the number of methylenes in the alkyl chain tethering the ferrocene moiety to the electrode, using the indirect laser-induced temperature jump method (ILIT). For 5 {<=} n {<=} 9 the standard electron-transfer rate constants vary according to {kappa}{sub {tau}a,n=0} exp[-{beta}{sub n}n] where {kappa}{sub {tau}a,n=0} is the (extrapolated) rate constant for the electron transfer at n = 0. At {Tau} = 25{degree}C, {kappa}{sub {tau}a,n} 0 {approx_equal} 6 x 10{sup 8} s{sup -1} and {beta}{sub n} = 1.21 x 0.05. The ILIT method allows rates to be measured that are too fast to be measured by conventional chronoamperometry at a macroelectrode, which is limited to rate constants of {<=} 10{sup 4} s{sup -1}. Using a Marcus formalism, the reorganization energy, {lambda}, for the electron-transfer process at a given n was determined from the slope of an Arrhenius plot over the temperature range 15-55{degree}C. Values of {lambda} determined from Arrhenius slopes for n = 8 and 9 using ILIT are in reasonable agreement with the value of {lambda} previously deduced from the potential dependence of the rate constant for n = 16. 39 refs., 13 figs., 3 tabs.

  3. Electron beam processing - status and prospects

    International Nuclear Information System (INIS)

    Cleland, M.R.

    1989-01-01

    A variety of commercial products now on the market are being produced by electron beam processing, which involves the treatment of materials with high-energy electrons to obtain beneficial effects. Ongoing applications include the high-speed curing of printing inks, clear and pigmented coatings, release coatings and adhesive films, the crosslinking of plastic film, foam, tubing, pipe, molded parts, electrical wire and cable, the cold vulcanization of rubber sheets for automobile tires and factory roofing as well as the sterilization of medical devices and packaging materials, and the preservation of food. Continuing growth is being driven by some inherent advantages of electron beam processing over alternative chemical and thermal treatment processes, such as enhanced product quality and lower unit costs that result from higher production rates, dynamic process control, quicker process start-up and shutdown, and reductions in scrap loss, energy consumption, floor space requirements, and toxic residues. Other potential applications that have not yet reached commercial fruition are focused on environmental protection and the reclamation of waste materials. These include the disinfection of potable water supplies, municipal waste water, sewage sludge, and the infectious wastes from hospitals and airports, the modification of toxic chemicals, the degradation of cellulosic materials, the cracking of crude oil and residual tars from refineries, and the extraction of sulfur and nitrogen oxides from combustion gases to reduce the effects of acid rain

  4. Coupled quantum-classical method for long range charge transfer: relevance of the nuclear motion to the quantum electron dynamics

    International Nuclear Information System (INIS)

    Da Silva, Robson; Hoff, Diego A; Rego, Luis G C

    2015-01-01

    Charge and excitonic-energy transfer phenomena are fundamental for energy conversion in solar cells as well as artificial photosynthesis. Currently, much interest is being paid to light-harvesting and energy transduction processes in supramolecular structures, where nuclear dynamics has a major influence on electronic quantum dynamics. For this reason, the simulation of long range electron transfer in supramolecular structures, under environmental conditions described within an atomistic framework, has been a difficult problem to study. This work describes a coupled quantum mechanics/molecular mechanics method that aims at describing long range charge transfer processes in supramolecular systems, taking into account the atomistic details of large molecular structures, the underlying nuclear motion, and environmental effects. The method is applied to investigate the relevance of electron–nuclei interaction on the mechanisms for photo-induced electron–hole pair separation in dye-sensitized interfaces as well as electronic dynamics in molecular structures. (paper)

  5. Photoinduced electron transfer and persistent spectral hole-burning in natural emerald.

    Science.gov (United States)

    Riesen, Hans

    2011-06-02

    Wavelength-selective excited-state lifetime measurements and absorption, luminescence, and hole-burning spectra of a natural African emerald crystal are reported. The (2)E excited-state lifetime displays an extreme wavelength dependence, varying from 190 to 37 μs within 1.8 nm of the R(1)-line. Overall, the excited state is strongly quenched, in comparison to laboratory-created emerald (τ=1.3 ms), with an average quenching rate of ∼6 × 10(3) s(-1) at 2.5 K. This quenching is attributed to photoinduced electron transfer caused by a relatively high concentration of Fe(2+) ions. The forward electron-transfer rate, k(f), from the nearest possible Fe(2+) sites at around 5 Å is estimated to be ∼20 × 10(3) s(-1) at 2.5 K. The photoreductive quenching of the excited Cr(3+) ions by Fe(2+) is followed by rapid electron back-transfer in the ground state upon deactivation. The exchange interaction based quenching can be modeled by assuming a random quencher distribution within the possible Fe(2+) sites with the forward electron-transfer rate, k(f), given as a function of acceptor-donor separation R by exp[(R(f)-R)/a(f)]; R(f) and a(f) values of 13.5 and 2.7 Å are obtained at 2.5 K. The electron transfer/back-transfer reorganizes the local crystal lattice, occasionally leading to a minor variation of the short-range structure around the Cr(3+) ions. This provides a mechanism for spectral hole-burning for which a moderately high quantum efficiency of about ∼0.005% is observed. Spectral holes are subject to spontaneous hole-filling and spectral diffusion, and both effects can be quantified within the standard two-level systems for non-photochemical hole-burning. Importantly, the absorbance increases on both sides of broad spectral holes, and isosbestic points are observed, in accord with the expected distribution of the "photoproduct" in a non-photochemical hole-burning process. © 2011 American Chemical Society

  6. Electron transfer reactions in some complexes of V+2, Co+3 and Eu+3

    International Nuclear Information System (INIS)

    Lellis, F.T.P.

    1983-01-01

    The stability constants β 1 , β 2 , β 3 for the mono-,bis-and tris-substituted complexes from vanadium (III) ions with the pyridine-2-carboxilate liquid are determined potentiometrically. The tris-substituted complex in aqueous solutions by electronic spectra and reversible cyclic voltammetry using gold electrodes is extensively characterized. In the investigation of electron tranfer kinetics involving mild oxidizing complexes, such as Co(NH 3 ) 3+ 6 , Co(en) 3+ 3 , Co(en) 2 gly 2+ , Co (histidinate) + 2 , Ru(NH 3 ) 3+ 6 and Eu 3+ ions, the tris (picolinate) vanadate (III) complex is used. Electron transfer kinetics for the Eu 3+ / 2+ couple in terms of a pseudo-first order process is analysed. The results, in terms of a tunneling mechanism, involving a set of similar, nuclear coordinates for the reactants and products, are explained. (M.J.C.) [pt

  7. 77 FR 50243 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-08-20

    ... transfers. DATES: This rule is effective February 7, 2013. FOR FURTHER INFORMATION CONTACT: Eric Goldberg... variation in the demand for remittance transfers, the Bureau believes that an annual figure is the most...

  8. Electron transfer precedes ATP hydrolysis during nitrogenase catalysis

    Science.gov (United States)

    Duval, Simon; Danyal, Karamatullah; Shaw, Sudipta; Lytle, Anna K.; Dean, Dennis R.; Hoffman, Brian M.; Antony, Edwin; Seefeldt, Lance C.

    2013-01-01

    The biological reduction of N2 to NH3 catalyzed by Mo-dependent nitrogenase requires at least eight rounds of a complex cycle of events associated with ATP-driven electron transfer (ET) from the Fe protein to the catalytic MoFe protein, with each ET coupled to the hydrolysis of two ATP molecules. Although steps within this cycle have been studied for decades, the nature of the coupling between ATP hydrolysis and ET, in particular the order of ET and ATP hydrolysis, has been elusive. Here, we have measured first-order rate constants for each key step in the reaction sequence, including direct measurement of the ATP hydrolysis rate constant: kATP = 70 s−1, 25 °C. Comparison of the rate constants establishes that the reaction sequence involves four sequential steps: (i) conformationally gated ET (kET = 140 s−1, 25 °C), (ii) ATP hydrolysis (kATP = 70 s−1, 25 °C), (iii) Phosphate release (kPi = 16 s−1, 25 °C), and (iv) Fe protein dissociation from the MoFe protein (kdiss = 6 s−1, 25 °C). These findings allow completion of the thermodynamic cycle undergone by the Fe protein, showing that the energy of ATP binding and protein–protein association drive ET, with subsequent ATP hydrolysis and Pi release causing dissociation of the complex between the Feox(ADP)2 protein and the reduced MoFe protein. PMID:24062462

  9. Electron transfer precedes ATP hydrolysis during nitrogenase catalysis.

    Science.gov (United States)

    Duval, Simon; Danyal, Karamatullah; Shaw, Sudipta; Lytle, Anna K; Dean, Dennis R; Hoffman, Brian M; Antony, Edwin; Seefeldt, Lance C

    2013-10-08

    The biological reduction of N2 to NH3 catalyzed by Mo-dependent nitrogenase requires at least eight rounds of a complex cycle of events associated with ATP-driven electron transfer (ET) from the Fe protein to the catalytic MoFe protein, with each ET coupled to the hydrolysis of two ATP molecules. Although steps within this cycle have been studied for decades, the nature of the coupling between ATP hydrolysis and ET, in particular the order of ET and ATP hydrolysis, has been elusive. Here, we have measured first-order rate constants for each key step in the reaction sequence, including direct measurement of the ATP hydrolysis rate constant: kATP = 70 s(-1), 25 °C. Comparison of the rate constants establishes that the reaction sequence involves four sequential steps: (i) conformationally gated ET (kET = 140 s(-1), 25 °C), (ii) ATP hydrolysis (kATP = 70 s(-1), 25 °C), (iii) Phosphate release (kPi = 16 s(-1), 25 °C), and (iv) Fe protein dissociation from the MoFe protein (kdiss = 6 s(-1), 25 °C). These findings allow completion of the thermodynamic cycle undergone by the Fe protein, showing that the energy of ATP binding and protein-protein association drive ET, with subsequent ATP hydrolysis and Pi release causing dissociation of the complex between the Fe(ox)(ADP)2 protein and the reduced MoFe protein.

  10. Diameter dependent electron transfer kinetics in semiconductor-enzyme complexes.

    Science.gov (United States)

    Brown, Katherine A; Song, Qing; Mulder, David W; King, Paul W

    2014-10-28

    Excited state electron transfer (ET) is a fundamental step for the catalytic conversion of solar energy into chemical energy. To understand the properties controlling ET between photoexcited nanoparticles and catalysts, the ET kinetics were measured for solution-phase complexes of CdTe quantum dots and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) using time-resolved photoluminescence spectroscopy. Over a 2.0-3.5 nm diameter range of CdTe nanoparticles, the observed ET rate (kET) was sensitive to CaI concentration. To account for diameter effects on CaI binding, a Langmuir isotherm and two geometric binding models were created to estimate maximal CaI affinities and coverages at saturating concentrations. Normalizing the ET kinetics to CaI surface coverage for each CdTe diameter led to k(ET) values that were insensitive to diameter, despite a decrease in the free energy for photoexcited ET (ΔGET) with increasing diameter. The turnover frequency (TOF) of CaI in CdTe-CaI complexes was measured at several molar ratios. Normalization for diameter-dependent changes in CaI coverage showed an increase in TOF with diameter. These results suggest that k(ET) and H2 production for CdTe-CaI complexes are not strictly controlled by ΔG(ET) and that other factors must be considered.

  11. Electrochemical Measurement of Electron Transfer Kinetics by Shewanella oneidensis MR-1*

    Science.gov (United States)

    Baron, Daniel; LaBelle, Edward; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

    2009-01-01

    Shewanella oneidensis strain MR-1 can respire using carbon electrodes and metal oxyhydroxides as electron acceptors, requiring mechanisms for transferring electrons from the cell interior to surfaces located beyond the cell. Although purified outer membrane cytochromes will reduce both electrodes and metals, S. oneidensis also secretes flavins, which accelerate electron transfer to metals and electrodes. We developed techniques for detecting direct electron transfer by intact cells, using turnover and single turnover voltammetry. Metabolically active cells attached to graphite electrodes produced thin (submonolayer) films that demonstrated both catalytic and reversible electron transfer in the presence and absence of flavins. In the absence of soluble flavins, electron transfer occurred in a broad potential window centered at ∼0 V (versus standard hydrogen electrode), and was altered in single (ΔomcA, ΔmtrC) and double deletion (ΔomcA/ΔmtrC) mutants of outer membrane cytochromes. The addition of soluble flavins at physiological concentrations significantly accelerated electron transfer and allowed catalytic electron transfer to occur at lower applied potentials (−0.2 V). Scan rate analysis indicated that rate constants for direct electron transfer were slower than those reported for pure cytochromes (∼1 s−1). These observations indicated that anodic current in the higher (>0 V) window is due to activation of a direct transfer mechanism, whereas electron transfer at lower potentials is enabled by flavins. The electrochemical dissection of these activities in living cells into two systems with characteristic midpoint potentials and kinetic behaviors explains prior observations and demonstrates the complementary nature of S. oneidensis electron transfer strategies. PMID:19661057

  12. Tungsten Trioxide/Zinc Tungstate Bilayers: Electrochromic Behaviors, Energy Storage and Electron Transfer

    International Nuclear Information System (INIS)

    Wei, Huige; Ding, Daowei; Yan, Xingru; Guo, Jiang; Shao, Lu; Chen, Haoran; Sun, Luyi; Colorado, Henry A.; Wei, Suying; Guo, Zhanhu

    2014-01-01

    Highlights: • Tungsten oxide and zinc tungstate bilayers have been prepared via a facile sol-gel method for integrated applications of electrochromic behaviors and energy storage;. • Electron transfer behaviors between the semiconductor bilayer films have been found dependent on the bilayer assembly sequence;. • Methylene blue (MB) has been employed for the first time as an indicator to study the electron transfer phenomenon in the bilayer films. - Abstract: Pair-sequentially spin-coated tungsten trioxide (WO 3 ) and zinc tungstate (ZnWO 4 ) bilayer films onto indium tin oxide (ITO) coated glass slides have been prepared via sol-gel methods followed by annealing. The bilayers (ZnWO 4 /WO 3 denoting the bilayer film with the inner layer of ZnWO 4 and the outer layer of WO 3 on the ITO while WO 3 /ZnWO 4 standing for the bilayer film with the inner layer of WO 3 and the outer layer of ZnWO 4 on the ITO) exhibit integrated functions of electrochromic and energy storage behaviors as indicated by the in situ spectroelectrochemistry and cyclic voltammetry (CV) results. Accordingly, blue color was observed for the bilayer films at -1 V in 0.5 M H 2 SO 4 solution. An areal capacitance of 140 and 230 μF/cm 2 was obtained for the ZnWO 4 /WO 3 , and WO 3 /ZnWO 4 film, respectively, at a scan rate of 0.05 V/s in the CV measurements. The CV results also unveiled the electron transfer behavior between the semiconductor films in the oxidation process, suggesting a sequence-dependent electrochemical response in the bilayer films. Meanwhile, methylene blue (MB) was used as an indicator to study the electron transfer phenomenon during the reduction process at negative potentials of -0.4 and -0.8 V, in 0.5 M Na 2 SO 4 . The results indicated that the electrons transfer across the bilayers was enhanced at more negative potentials

  13. Wafer-Level Membrane-Transfer Process for Fabricating MEMS

    Science.gov (United States)

    Yang, Eui-Hyeok; Wiberg, Dean

    2003-01-01

    A process for transferring an entire wafer-level micromachined silicon structure for mating with and bonding to another such structure has been devised. This process is intended especially for use in wafer-level integration of microelectromechanical systems (MEMS) that have been fabricated on dissimilar substrates. Unlike in some older membrane-transfer processes, there is no use of wax or epoxy during transfer. In this process, the substrate of a wafer-level structure to be transferred serves as a carrier, and is etched away once the transfer has been completed. Another important feature of this process is that two electrodes constitutes an electrostatic actuator array. An SOI wafer and a silicon wafer (see Figure 1) are used as the carrier and electrode wafers, respectively. After oxidation, both wafers are patterned and etched to define a corrugation profile and electrode array, respectively. The polysilicon layer is deposited on the SOI wafer. The carrier wafer is bonded to the electrode wafer by using evaporated indium bumps. The piston pressure of 4 kPa is applied at 156 C in a vacuum chamber to provide hermetic sealing. The substrate of the SOI wafer is etched in a 25 weight percent TMAH bath at 80 C. The exposed buried oxide is then removed by using 49 percent HF droplets after an oxygen plasma ashing. The SOI top silicon layer is etched away by using an SF6 plasma to define the corrugation profile, followed by the HF droplet etching of the remaining oxide. The SF6 plasma with a shadow mask selectively etches the polysilicon membrane, if the transferred membrane structure needs to be patterned. Electrostatic actuators with various electrode gaps have been fabricated by this transfer technique. The gap between the transferred membrane and electrode substrate is very uniform ( 0.1 m across a wafer diameter of 100 mm, provided by optimizing the bonding control). Figure 2 depicts the finished product.

  14. Geobacter sulfurreducens adapts to low electrode potential for extracellular electron transfer

    International Nuclear Information System (INIS)

    Peng, Luo; Zhang, Xiao-Ting; Yin, Jie; Xu, Shuo-Yuan; Zhang, Yong; Xie, De-Ti; Li, Zhen-Lun

    2016-01-01

    Microbial extracellular electron transfer (EET) occurring in natural and engineering processes is attracting increasing interests. While a meaningful question for bioenergetics, microbial physiology and microbial electrochemical systems; less is known about the lower limit of electron acceptor reduction potential for EET. It is also unclear how microbes adapt to weak electron acceptors. This study evaluated Geobacter sulfurreducens biofilms grown with an electrode poised at −0.25 V vs. SHE. This potential was found to be sufficient for microbial metabolism and proliferation. The turnover cyclic voltammetries found that these biofilms had a half-saturation potential of −0.242 ± 0.004 V, in contrast to −0.151 ± 0.003 V for that of the biofilms grown under 0.2 V. For the biofilms grown under 0.2 V, differential pulse voltammetry showed that the metabolic current was mediated by interfacial cofactors with mid-point potential around −0.16 V performing single-electron electron transfer (ET). The major electron conduits for the biofilms respiring under −0.25 V had mid-point potentials of −0.22 V or −0.26 V, which appeared to perform two-electron ET. Under the non-turnover condition, both biofilms showed similar patterns in voltammograms and the low-potential conduits largely disappeared for the biofilms grown under −0.25 V. Transcriptome analysis identified 17 cytochrome-c genes significantly up-regulated for the biofilms grown under −0.25 V, together with many other genes linked to the ET system. It was also noted that, lowering the poised potential from −0.25 V to −0.28 V (the fuel standard oxidation potential) did not fully inhibit microbial respiration.

  15. The Iron-Sulfur Cluster of Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO) is the Electron Acceptor for Electron Transfer Flavoprotein†

    Science.gov (United States)

    Swanson, Michael A.; Usselman, Robert J.; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

    2011-01-01

    Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the ubiquinone-pool. It contains one [4Fe-4S]2+,1+ and one FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. The mutations did not alter the optical spectra, EPR g-values, spin-lattice relaxation rates, or the [4Fe-4S]2+,1+ to FAD point-dipole interspin distances. The mutations had no impact on the reduction potential for the iron-sulfur cluster, which was monitored by changes in the continuous wave EPR signals of the [4Fe-4S]+ at 15 K. For the FAD semiquinone, significantly different potentials were obtained by monitoring the titration at 100 or 293 K. Based on spectra at 293 K the N338T mutation shifted the first and second midpoint potentials for the FAD from +47 mV and −30 mV for wild type to −11 mV and −19 mV, respectively. The N338A mutation decreased the potentials to −37 mV and −49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF1e− catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone, but not in electron transfer from ETF to ETF-QO. Therefore the iron-sulfur cluster is the immediate acceptor from ETF. PMID:18672901

  16. Applications of free-electron lasers to measurements of energy transfer in biopolymers and materials

    Science.gov (United States)

    Edwards, Glenn S.; Johnson, J. B.; Kozub, John A.; Tribble, Jerri A.; Wagner, Katrina

    1992-08-01

    Free-electron lasers (FELs) provide tunable, pulsed radiation in the infrared. Using the FEL as a pump beam, we are investigating the mechanisms for energy transfer between localized vibrational modes and between vibrational modes and lattice or phonon modes. Either a laser-Raman system or a Fourier transform infrared (FTIR) spectrometer will serve as the probe beam, with the attribute of placing the burden of detection on two conventional spectroscopic techniques that circumvent the limited response of infrared detectors. More specifically, the Raman effect inelastically shifts an exciting laser line, typically a visible frequency, by the energy of the vibrational mode; however, the shifted Raman lines also lie in the visible, allowing for detection with highly efficient visible detectors. With regards to FTIR spectroscopy, the multiplex advantage yields a distinct benefit for infrared detector response. Our group is investigating intramolecular and intermolecular energy transfer processes in both biopolymers and more traditional materials. For example, alkali halides contain a number of defect types that effectively transfer energy in an intermolecular process. Similarly, the functioning of biopolymers depends on efficient intramolecular energy transfer. Understanding these mechanisms will enhance our ability to modify biopolymers and materials with applications to biology, medecine, and materials science.

  17. Energy transfer processes in Er-doped crystals

    International Nuclear Information System (INIS)

    Georgescu, Serban; Toma, Octavian

    2005-01-01

    In this paper, the microparameters characteristic to various energy-transfer processes in erbium doped crystals are estimated using the Dexter theory. For all the investigated processes, electric dipole-dipole interaction between donor and acceptor ions is assumed. The spectra appearing in Dexter's expression of the microparameter are simulated as a superposition of Lorentzian lines, knowing the positions of both initial and final Stark levels, and calibrated using the Judd-Ofelt model. This approach can give an estimation of the importance of the energy-transfer processes. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  18. Photoinduced bimolecular electron transfer kinetics in small unilamellar vesicles

    International Nuclear Information System (INIS)

    Choudhury, Sharmistha Dutta; Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas

    2007-01-01

    Photoinduced electron transfer (ET) from N,N-dimethylaniline to some coumarin derivatives has been studied in small unilamellar vesicles (SUVs) of the phospholipid, DL-α-dimyristoyl-phosphatidylcholine, using steady-state and time-resolved fluorescence quenching, both below and above the phase transition temperature of the vesicles. The primary interest was to examine whether Marcus inversion [H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986)] could be observed for the present ET systems in these organized assemblies. The influence of the topology of SUVs on the photophysical properties of the reactants and consequently on their ET kinetics has also been investigated. Absorption and fluorescence spectral data of the coumarins in SUVs and the variation of their fluorescence decays with temperature indicate that the dyes are localized in the bilayer of the SUVs. Time-resolved area normalized emission spectra analysis, however, reveals that the dyes are distributed in two different microenvironments in the SUVs, which we attribute to the two leaflets of the bilayer, one toward bulk water and the other toward the inner water pool. The microenvironments in the two leaflets are, however, not indicated to be that significantly different. Time-resolved anisotropy decays were biexponential for all the dyes in SUVs, and this has been interpreted in terms of the compound motion model according to which the dye molecules can experience a fast wobbling-in-cone type of motion as well as a slow overall rotating motion of the cone containing the molecule. The expected bimolecular diffusion-controlled rates in SUVs, as estimated by comparing the microviscosities in SUVs (determined from rotational correlation times) and that in acetonitrile solution, are much slower than the observed fluorescence quenching rates, suggesting that reactant diffusion (translational) does not play any role in the quenching kinetics in the present systems. Accordingly, clear inversions are

  19. Direct interaction between linear electron transfer chains and solute transport systems in bacteria

    NARCIS (Netherlands)

    Elferink, Marieke G.L.; Hellingwerf, Klaas J.; Belkum, Marco J. van; Poolman, Bert; Konings, Wil N.

    1984-01-01

    In studies on alanine and lactose transport in Rhodopseudomonas sphaeroides we have demonstrated that the rate of solute uptake in this phototrophic bacterium is regulated by the rate of light-induced cyclic electron transfer. In the present paper the interaction between linear electron transfer

  20. 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

  1. Photoinduced energy and electron transfer in rubrene-benzoquinone and rubrene-porphyrin systems

    KAUST Repository

    Khan, Jafar Iqbal

    2014-11-01

    Excited-state electron and energy transfer from singlet excited rubrene (Ru) to benzoquinone (BQ) and tetra-(4-aminophenyl) porphyrin (TAPP) were investigated by steady-state absorption and emission, time-resolved transient absorption, and femtosecond (fs)-nanosecond (ns) fluorescence spectroscopy. The low reduction potential of BQ provides the high probability of electron transfer from the excited Ru to BQ. Steady-state and time-resolved results confirm such an excited electron transfer scenario. On the other hand, strong spectral overlap between the emission of Ru and absorption of TAPP suggests that energy transfer is a possible deactivation pathway of the Ru excited state.

  2. Electronic equipment for spectrometric data processing

    International Nuclear Information System (INIS)

    Antonov, L.J.; Trenev, A.M.; Todorova, E.I.; Dimitrov, V.D.

    1978-01-01

    Electronic equipment carrying out logical operations and a full set of the arithmetic operations was developed for spectrometric data processing. The flowsheet of the computing part of the device, made on the basis of a specialized integral circuit, is given. The device includes input registers, multiplexor, matrix commutator, arithmetic unit and indication unit. The equipment is rated to carry out calculations according to comparatively complex formulae in several seconds

  3. Digital processing of ionospheric electron content data

    Science.gov (United States)

    Bernhardt, P. A.

    1979-01-01

    Ionospheric electron content data contain periodicities that are produced by a diversity of sources including hydromagnetic waves, gravity waves, and lunar tides. Often these periodicities are masked by the strong daily variation in the data. Digital filtering can be used to isolate the weaker components. The filtered data can then be further processed to provide estimates of the source properties. In addition, homomorphic filtering may be used to identify nonlinear interactions in the ionosphere.

  4. Effect of resonant-to-bulk electron momentum transfer on the efficiency of electron-cyclotron current-drive

    International Nuclear Information System (INIS)

    Matsuda, Y.; Smith, G.R.; Cohen, R.H.

    1989-01-01

    Efficiency of current drive by electron cyclotron waves is investigated numerically by a bounce-averaged Fokker-Planck code to ellucidate the effects of momentum transfer from resonant to bulk-electrons, finite bulk temperature relative to the energy of resonant electrons, and trapped electrons. Comparisons are made with existing theories to assess their validity and quantitative difference between theory and code results. Difference of nearly a factor of 2 was found in efficiency between some theory and code results. (author)

  5. Protein electron transfer: is biology (thermo)dynamic?

    International Nuclear Information System (INIS)

    Matyushov, Dmitry V

    2015-01-01

    Simple physical mechanisms are behind the flow of energy in all forms of life. Energy comes to living systems through electrons occupying high-energy states, either from food (respiratory chains) or from light (photosynthesis). This energy is transformed into the cross-membrane proton-motive force that eventually drives all biochemistry of the cell. Life’s ability to transfer electrons over large distances with nearly zero loss of free energy is puzzling and has not been accomplished in synthetic systems. The focus of this review is on how this energetic efficiency is realized. General physical mechanisms and interactions that allow proteins to fold into compact water-soluble structures are also responsible for a rugged landscape of energy states and a broad distribution of relaxation times. Specific to a protein as a fluctuating thermal bath is the protein-water interface, which is heterogeneous both dynamically and structurally. The spectrum of interfacial fluctuations is a consequence of protein’s elastic flexibility combined with a high density of surface charges polarizing water dipoles into surface nanodomains. Electrostatics is critical to the protein function and the relevant questions are: (i) What is the spectrum of interfacial electrostatic fluctuations? (ii) Does the interfacial biological water produce electrostatic signatures specific to proteins? (iii) How is protein-mediated chemistry affected by electrostatics? These questions connect the fluctuation spectrum to the dynamical control of chemical reactivity, i.e. the dependence of the activation free energy of the reaction on the dynamics of the bath. Ergodicity is often broken in protein-driven reactions and thermodynamic free energies become irrelevant. Continuous ergodicity breaking in a dense spectrum of relaxation times requires using dynamically restricted ensembles to calculate statistical averages. When applied to the calculation of the rates, this formalism leads to the nonergodic

  6. Electron - ion recombination processes - an overview

    International Nuclear Information System (INIS)

    Hahn, Yukap

    1997-01-01

    Extensive theoretical and experimental studies have been carried out for the past 20 years on electron - ion recombination processes, as they are applied to the analysis of astrophysical and laboratory plasmas. We review the basic understanding gained through these efforts, with emphasis on some of the more recent progress made in recombination theory as the recombining system is affected by time-dependent electric fields and plasma particles at low temperature. Together with collisional ionization and excitation processes, recombination is important in determining ionization balance and excited-state population in non-equilibrium plasmas. The radiation emitted by plasmas is usually the principal medium with which to study the plasma condition, as it is produced mainly during the recombination and decay of excited states of ions inside the plasma. This is especially true when the plasma under study is not readily accessible by direct probes, as in astrophysical plasmas. Moreover, external probes may sometimes cause undesirable disturbances of the plasma. Electron-ion recombination proceeds in several different modes. The direct modes include three-body recombination (TBR) and one-step radiative recombination (RR), all to the ground- and singly-excited states of the target ions. By contrast, the indirect resonant mode is a two-step dielectronic recombination (DR), which proceeds first with the formation of doubly-excited states by radiationless excitation/capture. The resonant states thus formed may relax by autoionization and/or radiative cascades. For more exotic modes of recombination, we consider off-shell dielectronic recombination (radiative DR = RDR), in which an electron capture is accompanied by simultaneous radiative emission and excitation of the target ion. Some discussion on attachment of electrons to neutral atoms, resulting in the formation of negative ions, is also given. When resonance states involve one or more electrons in high Rydberg states

  7. Demonstration of Lignin-to-Peroxidase Direct Electron Transfer

    Science.gov (United States)

    Sáez-Jiménez, Verónica; Baratto, Maria Camilla; Pogni, Rebecca; Rencoret, Jorge; Gutiérrez, Ana; Santos, José Ignacio; Martínez, Angel T.; Ruiz-Dueñas, Francisco Javier

    2015-01-01

    Versatile peroxidase (VP) is a high redox-potential peroxidase of biotechnological interest that is able to oxidize phenolic and non-phenolic aromatics, Mn2+, and different dyes. The ability of VP from Pleurotus eryngii to oxidize water-soluble lignins (softwood and hardwood lignosulfonates) is demonstrated here by a combination of directed mutagenesis and spectroscopic techniques, among others. In addition, direct electron transfer between the peroxidase and the lignin macromolecule was kinetically characterized using stopped-flow spectrophotometry. VP variants were used to show that this reaction strongly depends on the presence of a solvent-exposed tryptophan residue (Trp-164). Moreover, the tryptophanyl radical detected by EPR spectroscopy of H2O2-activated VP (being absent from the W164S variant) was identified as catalytically active because it was reduced during lignosulfonate oxidation, resulting in the appearance of a lignin radical. The decrease of lignin fluorescence (excitation at 355 nm/emission at 400 nm) during VP treatment under steady-state conditions was accompanied by a decrease of the lignin (aromatic nuclei and side chains) signals in one-dimensional and two-dimensional NMR spectra, confirming the ligninolytic capabilities of the enzyme. Simultaneously, size-exclusion chromatography showed an increase of the molecular mass of the modified residual lignin, especially for the (low molecular mass) hardwood lignosulfonate, revealing that the oxidation products tend to recondense during the VP treatment. Finally, mutagenesis of selected residues neighboring Trp-164 resulted in improved apparent second-order rate constants for lignosulfonate reactions, revealing that changes in its protein environment (modifying the net negative charge and/or substrate accessibility/binding) can modulate the reactivity of the catalytic tryptophan. PMID:26240145

  8. Pulse radiolytic and electrochemical investigations of intramolecular electron transfer in carotenoporphyrins and carotenoporphyrin-quinone triads

    International Nuclear Information System (INIS)

    Land, E.J.; Lexa, D.; Bensasson, R.V.; Gust, D.; Moore, T.A.; Moore, A.L.; Liddell, P.A.; Nemeth, G.A.

    1987-01-01

    Thermodynamic and kinetic aspects of intramolecular electron-transfer reactions in carotenoporphyrin dyads and carotenoid-porphyrin-quinone triads have been studied by using pulse radiolysis and cyclic voltammetry. Rapid (<1 μs) electron transfer from carotenoid radical anions to attached porphyrins has been inferred. Carotenoid cations, on the other hand, do not readily accept electrons from attached porphyrins or pyropheophorbides. Electrochemical studies provide the thermodynamic basis for these observations and also allow estimation of the energetics of photoinitiated two-step electron transfer and two-step charge recombination in triad models for photosynthetic charge separation

  9. Statistical process control for electron beam monitoring.

    Science.gov (United States)

    López-Tarjuelo, Juan; Luquero-Llopis, Naika; García-Mollá, Rafael; Quirós-Higueras, Juan David; Bouché-Babiloni, Ana; Juan-Senabre, Xavier Jordi; de Marco-Blancas, Noelia; Ferrer-Albiach, Carlos; Santos-Serra, Agustín

    2015-07-01

    To assess the electron beam monitoring statistical process control (SPC) in linear accelerator (linac) daily quality control. We present a long-term record of our measurements and evaluate which SPC-led conditions are feasible for maintaining control. We retrieved our linac beam calibration, symmetry, and flatness daily records for all electron beam energies from January 2008 to December 2013, and retrospectively studied how SPC could have been applied and which of its features could be used in the future. A set of adjustment interventions designed to maintain these parameters under control was also simulated. All phase I data was under control. The dose plots were characterized by rising trends followed by steep drops caused by our attempts to re-center the linac beam calibration. Where flatness and symmetry trends were detected they were less-well defined. The process capability ratios ranged from 1.6 to 9.3 at a 2% specification level. Simulated interventions ranged from 2% to 34% of the total number of measurement sessions. We also noted that if prospective SPC had been applied it would have met quality control specifications. SPC can be used to assess the inherent variability of our electron beam monitoring system. It can also indicate whether a process is capable of maintaining electron parameters under control with respect to established specifications by using a daily checking device, but this is not practical unless a method to establish direct feedback from the device to the linac can be devised. Copyright © 2015 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  10. Materials and processing approaches for foundry-compatible transient electronics

    Science.gov (United States)

    Chang, Jan-Kai; Fang, Hui; Bower, Christopher A.; Song, Enming; Yu, Xinge; Rogers, John A.

    2017-07-01

    Foundry-based routes to transient silicon electronic devices have the potential to serve as the manufacturing basis for “green” electronic devices, biodegradable implants, hardware secure data storage systems, and unrecoverable remote devices. This article introduces materials and processing approaches that enable state-of-the-art silicon complementary metal-oxide-semiconductor (CMOS) foundries to be leveraged for high-performance, water-soluble forms of electronics. The key elements are (i) collections of biodegradable electronic materials (e.g., silicon, tungsten, silicon nitride, silicon dioxide) and device architectures that are compatible with manufacturing procedures currently used in the integrated circuit industry, (ii) release schemes and transfer printing methods for integration of multiple ultrathin components formed in this way onto biodegradable polymer substrates, and (iii) planarization and metallization techniques to yield interconnected and fully functional systems. Various CMOS devices and circuit elements created in this fashion and detailed measurements of their electrical characteristics highlight the capabilities. Accelerated dissolution studies in aqueous environments reveal the chemical kinetics associated with the underlying transient behaviors. The results demonstrate the technical feasibility for using foundry-based routes to sophisticated forms of transient electronic devices, with functional capabilities and cost structures that could support diverse applications in the biomedical, military, industrial, and consumer industries.

  11. Single-Nanoparticle Resolved Biomimetic Long-Range Electron Transfer and Electrocatalysis of Mixed-Valence Nanoparticles

    DEFF Research Database (Denmark)

    Zhu, Nan; Hao, Xian; Ulstrup, Jens

    2016-01-01

    Long-range electron transfer (LRET) is a core elementary step in a wealth of processes central to chemistry and biology, including photosynthesis, respiration, and catalysis. In nature, biological catalysis is performed by enzymes. However, enzymes are structurally fragile and have limited stabil...

  12. Electron transfer among the CuA-, heme b- and a3-centers of Thermus thermophilus cytochrome ba3

    DEFF Research Database (Denmark)

    Farver, Ole; Chen, Ying; Fee, James A

    2006-01-01

    The 1-methyl-nicotinamide radical (MNA(*)), produced by pulse radiolysis has previously been shown to reduce the Cu(A)-site of cytochromes aa(3), a process followed by intramolecular electron transfer (ET) to the heme a but not to the heme a(3) [Farver, O., Grell, E., Ludwig, B., Michel, H. and P...

  13. 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...

  14. Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors

    Science.gov (United States)

    Sivakumar, V.; Ponnamma, Deepalekshmi; Hussein, Yasser H. A.

    2017-02-01

    Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQT) but not the triplets AQT or AQST. However in aqueous medium, AN quenches AQST and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQT or AQST while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications.

  15. Surface Immobilized His-tagged Azurin as a Model Interface for the Investigation of Vectorial Electron Transfer in Biological Systems

    International Nuclear Information System (INIS)

    Casalini, Stefano; Berto, Marcello; Kovtun, Alessandro; Operamolla, Alessandra; Di Rocco, Giulia; Facci, Paolo; Liscio, Andrea; Farinola, Gianluca M.; Borsari, Marco; Bortolotti, Carlo A.

    2015-01-01

    A model system for the electrochemical investigation of vectorial electron transfer in biological systems was designed, assembled and characterized. Gold electrodes, functionalized with a -OCH_3 terminated, aromatic self-assembled monolayer, were used as a substrate for the adsorption of variants of copper-containing, redox metalloprotein azurin. The engineered azurin bears a polyhistidine tag at its C-terminus. Thanks to the presence of the solvent exposed tag, which chelates Cu"2"+ ions in solution, we introduced an exogenous redox centre. The different reduction potentials of the two redox centres and their positioning with respect to the surface are such that electron transfer from the exogenous copper centre and the electrode is mediated by the native azurin active site, closely paralleling electron transfer processes in naturally occurring multicentre metalloproteins.

  16. Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex.

    Science.gov (United States)

    Santos, Willy G; Budkina, Darya S; Deflon, Victor M; Tarnovsky, Alexander N; Cardoso, Daniel R; Forbes, Malcolm D E

    2017-06-14

    Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (k obs < 10 12 s -1 ) and twisted (k obs ∼ 10 10 s -1 ) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V •+ ).

  17. Electron beam processing programme: Wastewater and sludge treatment in Brazil

    International Nuclear Information System (INIS)

    Sampa, M.H.O.; Rela, P.R.; Duarte, C.L.; Borrely, S.I.; Vieira, J.M.

    1998-01-01

    The Institute for Energetic and Nuclear Research, working on environmental applications, has an extensive research programme using high energy electron beam in treating industrial wastewater and sludge. The experiments are being conducted in a pilot plant using an industrial electron beam 1.5MeV, 25mA, where the streams are presented to the scanned electron beam in counter flow. This pilot plant is designed to process approximately 3.0m 3 /h with an average dose 5kGy and the absorbed dose measurement is performed continuously by calorimetric system in real time. Combined biological and radiation treatment of domestic sewage and sludge were carried out to investigate disinfestation and removal of organic matter. The experiments showed that total and fecal coliforms were decreased by about 5 logs cycles with a 3.0kGy radiation dose in raw sewage and biological effluents, respectively. Concerning the industrial wastewater in the first stage of the programme, the irradiation was conducted using batch systems with samples originating from a Governmental Wastewater Treatment Plant. The data showed a significant color reduction effect when delivered dose was increased, and the opposite was noted for turbidity and total suspended solids. Other experiments were focused to process real industrial effluents from one of the most important chemical and pharmaceutical industries in Brazil. A special transport truck was used to transfer the liquid waste from the Industry to the Electron Beam Pilot Plant. Large quantities of liquid waste were irradiated with and without air addition with the doses from 2kGy to 20kGy. Such experiences performed in association with the Industry demonstrated that this technology has a great potential to be transferred and to contribute with a permanent cleanup alternative for hazardous wastes

  18. Positronium Inhibition and Quenching by Organic Electron Acceptors and Charge Transfer Complexes

    DEFF Research Database (Denmark)

    Jansen, P.; Eldrup, Morten Mostgaard; Jensen, Bror Skytte

    1975-01-01

    Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex...... in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data....

  19. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    Energy Technology Data Exchange (ETDEWEB)

    Haverkate, Lucas A.; Mulder, Fokko M. [Reactor Institute Delft, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629JB Delft (Netherlands); Zbiri, Mohamed, E-mail: zbiri@ill.fr; Johnson, Mark R. [Institut Laue Langevin, 38042 Grenoble Cedex 9 (France); Carter, Elizabeth [Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, NSW 2008 (Australia); Kotlewski, Arek; Picken, S. [ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL/136 Delft (Netherlands); Kearley, Gordon J. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia)

    2014-01-07

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup −2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  20. Radiation processing with the Messina electron linac

    International Nuclear Information System (INIS)

    Auditore, L.; Barna, R.C.; De Pasquale, D.; Emanuele, U.; Loria, D.; Morgana, E.; Trifiro, A.; Trimarchi, M.

    2008-01-01

    In the last decades radiation processing has been more and more applied in several fields of industrial treatments and scientific research as a safe, reliable and economic technique. In order to improve existing industrial techniques and to develop new applications of this technology, at the Physics Department of Messina University a high power 5 MeV electron linac has been studied and set-up. The main features of the accelerating structure will be described together with the distinctive features of the delivered beam and several results obtained by electron beam irradiations, such as improvement of the characteristics of polymers and polymer composite materials, synthesis of new hydrogels for pharmaceutical and biomedical applications, reclaim of culture ground, sterilization of medical devices, development of new dosimeters for very high doses and dose rates required for monitoring of industrial irradiations

  1. 77 FR 6193 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ...''); Manuel Orozco, Inter- American Dialogue, Migration and Remittances in Times of Recession: Effects on... Reserve Bank of India; study was not limited to transfers from the United States); see also Manuel Orozco..., transfers). \\10\\ Elizabeth M. Grieco, Patricia de la Cruz et al., Who in the United States Sends and...

  2. Secondary Electron Emission from Plasma Processed Accelerating Cavity Grade Niobium

    Energy Technology Data Exchange (ETDEWEB)

    Basovic, Milos [Old Dominion Univ., Norfolk, VA (United States)

    2016-05-01

    Advances in the particle accelerator technology have enabled numerous fundamental discoveries in 20th century physics. Extensive interdisciplinary research has always supported further development of accelerator technology in efforts of reaching each new energy frontier. Accelerating cavities, which are used to transfer energy to accelerated charged particles, have been one of the main focuses of research and development in the particle accelerator field. Over the last fifty years, in the race to break energy barriers, there has been constant improvement of the maximum stable accelerating field achieved in accelerating cavities. Every increase in the maximum attainable accelerating fields allowed for higher energy upgrades of existing accelerators and more compact designs of new accelerators. Each new and improved technology was faced with ever emerging limiting factors. With the standard high accelerating gradients of more than 25 MV/m, free electrons inside the cavities get accelerated by the field, gaining enough energy to produce more electrons in their interactions with the walls of the cavity. The electron production is exponential and the electron energy transfer to the walls of a cavity can trigger detrimental processes, limiting the performance of the cavity. The root cause of the free electron number gain is a phenomenon called Secondary Electron Emission (SEE). Even though the phenomenon has been known and studied over a century, there are still no effective means of controlling it. The ratio between the electrons emitted from the surface and the impacting electrons is defined as the Secondary Electron Yield (SEY). A SEY ratio larger than 1 designates an increase in the total number of electrons. In the design of accelerator cavities, the goal is to reduce the SEY to be as low as possible using any form of surface manipulation. In this dissertation, an experimental setup was developed and used to study the SEY of various sample surfaces that were treated

  3. Secondary electron emission from plasma processed accelerating cavity grade niobium

    Science.gov (United States)

    Basovic, Milos

    Advances in the particle accelerator technology have enabled numerous fundamental discoveries in 20th century physics. Extensive interdisciplinary research has always supported further development of accelerator technology in efforts of reaching each new energy frontier. Accelerating cavities, which are used to transfer energy to accelerated charged particles, have been one of the main focuses of research and development in the particle accelerator field. Over the last fifty years, in the race to break energy barriers, there has been constant improvement of the maximum stable accelerating field achieved in accelerating cavities. Every increase in the maximum attainable accelerating fields allowed for higher energy upgrades of existing accelerators and more compact designs of new accelerators. Each new and improved technology was faced with ever emerging limiting factors. With the standard high accelerating gradients of more than 25 MV/m, free electrons inside the cavities get accelerated by the field, gaining enough energy to produce more electrons in their interactions with the walls of the cavity. The electron production is exponential and the electron energy transfer to the walls of a cavity can trigger detrimental processes, limiting the performance of the cavity. The root cause of the free electron number gain is a phenomenon called Secondary Electron Emission (SEE). Even though the phenomenon has been known and studied over a century, there are still no effective means of controlling it. The ratio between the electrons emitted from the surface and the impacting electrons is defined as the Secondary Electron Yield (SEY). A SEY ratio larger than 1 designates an increase in the total number of electrons. In the design of accelerator cavities, the goal is to reduce the SEY to be as low as possible using any form of surface manipulation. In this dissertation, an experimental setup was developed and used to study the SEY of various sample surfaces that were treated

  4. Tape transfer printing of a liquid metal alloy for stretchable RF electronics.

    Science.gov (United States)

    Jeong, Seung Hee; Hjort, Klas; Wu, Zhigang

    2014-09-03

    In order to make conductors with large cross sections for low impedance radio frequency (RF) electronics, while still retaining high stretchability, liquid-alloy-based microfluidic stretchable electronics offers stretchable electronic systems the unique opportunity to combine various sensors on our bodies or organs with high-quality wireless communication with the external world (devices/systems), without sacrificing enhanced user comfort. This microfluidic approach, based on printed circuit board technology, allows large area processing of large cross section conductors and robust contacts, which can handle a lot of stretching between the embedded rigid active components and the surrounding system. Although it provides such benefits, further development is needed to realize its potential as a high throughput, cost-effective process technology. In this paper, tape transfer printing is proposed to supply a rapid prototyping batch process at low cost, albeit at a low resolution of 150 μm. In particular, isolated patterns can be obtained in a simple one-step process. Finally, a stretchable radio frequency identification (RFID) tag is demonstrated. The measured results show the robustness of the hybrid integrated system when the tag is stretched at 50% for 3000 cycles.

  5. Tape Transfer Printing of a Liquid Metal Alloy for Stretchable RF Electronics

    Directory of Open Access Journals (Sweden)

    Seung Hee Jeong

    2014-09-01

    Full Text Available In order to make conductors with large cross sections for low impedance radio frequency (RF electronics, while still retaining high stretchability, liquid-alloy-based microfluidic stretchable electronics offers stretchable electronic systems the unique opportunity to combine various sensors on our bodies or organs with high-quality wireless communication with the external world (devices/systems, without sacrificing enhanced user comfort. This microfluidic approach, based on printed circuit board technology, allows large area processing of large cross section conductors and robust contacts, which can handle a lot of stretching between the embedded rigid active components and the surrounding system. Although it provides such benefits, further development is needed to realize its potential as a high throughput, cost-effective process technology. In this paper, tape transfer printing is proposed to supply a rapid prototyping batch process at low cost, albeit at a low resolution of 150 μm. In particular, isolated patterns can be obtained in a simple one-step process. Finally, a stretchable radio frequency identification (RFID tag is demonstrated. The measured results show the robustness of the hybrid integrated system when the tag is stretched at 50% for 3000 cycles.

  6. Sub-picosecond timing fluctuation suppression in laser-based atmospheric transfer of microwave signal using electronic phase compensation

    Science.gov (United States)

    Chen, Shijun; Sun, Fuyu; Bai, Qingsong; Chen, Dawei; Chen, Qiang; Hou, Dong

    2017-10-01

    We demonstrated a timing fluctuation suppression in outdoor laser-based atmospheric radio-frequency transfer over a 110 m one-way free-space link using an electronic phase compensation technique. Timing fluctuations and Allan Deviation are both measured to characterize the instability of transferred frequency incurred during the transfer process. With transferring a 1 GHz microwave signal over a timing fluctuation suppressed transmission link, the total root-mean-square (rms) timing fluctuation was measured to be 920 femtoseconds in 5000 s, with fractional frequency instability on the order of 1 × 10-12 at 1 s, and order of 2 × 10-16 at 1000 s. This atmospheric frequency transfer scheme with the timing fluctuation suppression technique can be used to fast build an atomic clock-based frequency free-space transmission link since its stability is superior to a commercial Cs and Rb clock.

  7. Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

    KAUST Repository

    Alsulami, Qana

    2016-01-01

    , electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance

  8. Modulation transfer function and detective quantum efficiency of electron bombarded charge coupled device detector for low energy electrons

    Czech Academy of Sciences Publication Activity Database

    Horáček, Miroslav

    2005-01-01

    Roč. 76, č. 9 (2005), 093704:1-6 ISSN 0034-6748 R&D Projects: GA ČR(CZ) GA202/03/1575 Keywords : electron bombarded CCD * modulation transfer function * detective quantum efficiency Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 1.235, year: 2005

  9. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek R. [Univ. of Massachusetts, Amherst, MA (United States)

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  10. Enhanced Performance of Dye-Sensitized Solar Cells with Nanostructure Graphene Electron Transfer Layer

    Directory of Open Access Journals (Sweden)

    Chih-Hung Hsu

    2014-01-01

    Full Text Available The utilization of nanostructure graphene thin films as electron transfer layer in dye-sensitized solar cells (DSSCs was demonstrated. The effect of a nanostructure graphene thin film in DSSC structure was examined. The nanostructure graphene thin films provides a great electron transfer channel for the photogenerated electrons from TiO2 to indium tin oxide (ITO glass. Obvious improvements in short-circuit current density of the DSSCs were observed by using the graphene electron transport layer modified photoelectrode. The graphene electron transport layer reduces effectively the back reaction in the interface between the ITO transparent conductive film and the electrolyte in the DSSC.

  11. Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

    Science.gov (United States)

    Nishio, Koichi; Pornpitra, Tunanunkul; Izawa, Seiichiro; Nishiwaki-Ohkawa, Taeko; Kato, Souichiro; Hashimoto, Kazuhito; Nakanishi, Shuji

    2015-06-01

    Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  12. Synergistic electron transfer effect-based signal amplification strategy for the ultrasensitive detection of dopamine.

    Science.gov (United States)

    Lu, Qiujun; Chen, Xiaogen; Liu, Dan; Wu, Cuiyan; Liu, Meiling; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

    2018-05-15

    The selective and sensitive detection of dopamine (DA) is of great significance for the identification of schizophrenia, Huntington's disease, and Parkinson's disease from the perspective of molecular diagnostics. So far, most of DA fluorescence sensors are based on the electron transfer from the fluorescence nanomaterials to DA-quinone. However, the limited electron transfer ability of the DA-quinone affects the level of detection sensitivity of these sensors. In this work, based on the DA can reduce Ag + into AgNPs followed by oxidized to DA-quinone, we developed a novel silicon nanoparticles-based electron transfer fluorescent sensor for the detection of DA. As electron transfer acceptor, the AgNPs and DA-quinone can quench the fluorescence of silicon nanoparticles effectively through the synergistic electron transfer effect. Compared with traditional fluorescence DA sensors, the proposed synergistic electron transfer-based sensor improves the detection sensitivity to a great extent (at least 10-fold improvement). The proposed sensor shows a low detection limit of DA, which is as low as 0.1 nM under the optimal conditions. This sensor has potential applicability for the detection of DA in practical sample. This work has been demonstrated to contribute to a substantial improvement in the sensitivity of the sensors. It also gives new insight into design electron transfer-based sensors. Copyright © 2018. Published by Elsevier B.V.

  13. Long-range intramolecular electron transfer in aromatic radical anions and binuclear transition metal complexes

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic ra...

  14. 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...

  15. 48 CFR 52.232-33 - Payment by Electronic Funds Transfer-Central Contractor Registration.

    Science.gov (United States)

    2010-10-01

    ... Government under this contract shall be made by electronic funds transfer (EFT), except as provided in... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Payment by Electronic... CONTRACT CLAUSES Text of Provisions and Clauses 52.232-33 Payment by Electronic Funds Transfer—Central...

  16. Electron Transfer in Donor-Bridge-Acceptor Systems and Derived Materials

    NARCIS (Netherlands)

    Oosterbaan, W.D.

    2002-01-01

    Some aspects of photoinduced electron transfer (ET) in (electron donor)-bridge-(electron acceptor) compounds (D-B-A) and derived materials are investigated. Aim I is to determine how and to which extent non-conjugated double bonds in an otherwise saturated hydrocarbon bridge affect the rate of

  17. Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces

    Science.gov (United States)

    Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.

    2017-07-01

    During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical

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

    Science.gov (United States)

    Matasović, Brunislav; Bonifačić, Marija

    2011-06-01

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

  19. Effect of Electromagnetic Fields on Transfer Processes in Heterogeneous Systems

    Czech Academy of Sciences Publication Activity Database

    Levdansky, V.V.; Kim, H. Y.; Kim, H. C.; Smolík, Jiří; Moravec, Pavel

    2001-01-01

    Roč. 44, č. 5 (2001), s. 1065-1071 ISSN 0017-9310 Institutional research plan: CEZ:AV0Z4072921 Keywords : electromagnetic field * transfer processes * heterogeneous system Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.240, year: 2001

  20. Mass transfer processes in crystalline aggregates containing a fluid phase

    NARCIS (Netherlands)

    Visser, H.J.M.

    1999-01-01

    Understanding mass transfer processes in porous crystalline aggregates containing a fluid phase is of major importance for modelling partially molten regions of the Earth's mantle, such as those under mid-ocean spreading ridges. Despite the fact that mid-ocean ridges can be considered the

  1. Mass transfer processes in crystalline aggregates containing a fluid phase

    NARCIS (Netherlands)

    Visser, H.J.M.

    1999-01-01

    Understanding mass transfer processes in porous crystalline aggregates containing a fluid phase is of major importance for modelling partially molten regions of the Earth's mantle, such as those under mid-ocean spreading ridges. Despite the fact that mid-ocean ridges can be considered the simplest

  2. Trust, Knowledge Creation and Mediating Effects of Knowledge Transfer Processes

    Directory of Open Access Journals (Sweden)

    Anna Sankowska

    2016-01-01

    Full Text Available This paper investigates how organizational trust contributes to knowledge transfer processes and knowledge creation both directly and indirectly. The mediation analyses were used. The findings using cross-sectional data from Polish companies suggest a new way of thinking in respect of how crucial is trust to creation of knowledge unconnected to organizational memory.

  3. Photoinduced electron transfer for an eosin-tyrosine conjugate. Activity of the tyrosinate anion in long-range electron transfer in a protein-like polymer matrix

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G. II; Feng, Z.; Oh, C. [Boston Univ., MA (United States)

    1995-03-23

    The Xanthene dye eosin Y has been modified via a thiohydantoin link to the amine terminus of the amino acid L-tyrosine. Photochemical electron transfer involving the singlet state of the dye and the attached phenol-containing residue led to a reduction in eosin fluorescence quantum yield and lifetime for aqueous solutions at elevated pH. The conjugate provided an electron transfer product of relatively long lifetime (1 {mu}s range) observed by flash photolysis of solutions at pH 12.0, conditions under which the tyrosine moiety is ionized. The effects of binding of the conjugate in the polymer poly(vinylpyrrolidone) (PVP) on the rates of electron transfer of species of different charge type were examined. 30 refs., 5 figs., 1 tab.

  4. Electron transfer in silicon-bridged adjacent chromophores: the source for blue-green emission.

    Science.gov (United States)

    Bayda, Malgorzata; Angulo, Gonzalo; Hug, Gordon L; Ludwiczak, Monika; Karolczak, Jerzy; Koput, Jacek; Dobkowski, Jacek; Marciniak, Bronislaw

    2017-05-10

    Si-Bridged chromophores have been proposed as sources for blue-green emission in several technological applications. The origin of this dual emission is to be found in an internal charge transfer reaction. The current work is an attempt to describe the details of these processes in these kinds of substances, and to design a molecular architecture to improve their performance. Nuclear motions essential for intramolecular charge transfer (ICT) can involve processes from twisted internal moieties to dielectric relaxation of the solvent. To address these issues, we studied ICT between adjacent chromophores in a molecular compound containing N-isopropylcarbazole (CBL) and 1,4-divinylbenzene (DVB) linked by a dimethylsilylene bridge. In nonpolar solvents emission arises from the local excited state (LE) of carbazole whereas in solvents of higher polarity dual emission was detected (LE + ICT). The CT character of the additional emission band was concluded from the linear dependence of the fluorescence maxima on solvent polarity. Electron transfer from CBL to DVB resulted in a large excited-state dipole moment (37.3 D) as determined from a solvatochromic plot and DFT calculations. Steady-state and picosecond time-resolved fluorescence experiments in butyronitrile (293-173 K) showed that the ICT excited state arises from the LE state of carbazole. These results were analyzed and found to be in accordance with an adiabatic version of Marcus theory including solvent relaxation.

  5. Intramolecular electron transfer through a bridging carboxylate group coordinated to two cobalt(III)-ions

    International Nuclear Information System (INIS)

    Wieghardt, K.

    1978-01-01

    Reduction of the binuclear μ-p-nitrobenzoato -di-μ-hydroxo -bis[triammine cobalt(III)] cation with (CH 3 ) 2 COH radicals yields a radical cation with the p-nitrobenzoato radical being coordinated to two cobalt(III) ions at the carboxylic group. The unprotonated form of this species undergoes intramolecular electron transfer producing Co(II) (k = (3.3 +- 0.3). x 10 3 s -1 ). The role of the carboxylate group in the intramolecular electron transfer process is tentatively assessed in terms of an intramolecular outer-sphere reaction because of lack of overlap of the donor orbitals (π) and the acceptor orbital (sigma). The protonated form of the radical cation (pKsub(a) = 2.5) disproportionates via a bimolecular process without production of Co(II). The effect of two coordinated Co(III) ions as compared to only one on the properties of the nitrobenzoate radical anion are discussed. (orig.) 891 HK 892 GM [de

  6. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    Energy Technology Data Exchange (ETDEWEB)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India); Datta, Anindya, E-mail: anindya@chem.iitb.ac.in [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India)

    2012-11-15

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p{sub 6} with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: Black-Right-Pointing-Pointer Modulation of PET of biologically active fluorophores and Methyl viologen. Black-Right-Pointing-Pointer Static and Dynamic Quenching present. Black-Right-Pointing-Pointer PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. Black-Right-Pointing-Pointer Rotational anisotropy has significant contribution in quenching.

  7. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    International Nuclear Information System (INIS)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam; Datta, Anindya

    2012-01-01

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p 6 with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: ► Modulation of PET of biologically active fluorophores and Methyl viologen. ► Static and Dynamic Quenching present. ► PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. ► Rotational anisotropy has significant contribution in quenching.

  8. Theoretical insights into multiscale electronic processes in organic photovoltaics

    Science.gov (United States)

    Tretiak, Sergei

    Present day electronic devices are enabled by design and implementation of precise interfaces that control the flow of charge carriers. This requires robust and predictive multiscale approaches for theoretical description of underlining complex phenomena. Combined with thorough experimental studies such approaches provide a reliable estimate of physical properties of nanostructured materials and enable a rational design of devices. From this perspective I will discuss first principle modeling of small-molecule bulk-heterojunction organic solar cells and push-pull chromophores for tunable-color organic light emitters. The emphasis is on electronic processes involving intra- and intermolecular energy or charge transfer driven by strong electron-phonon coupling inherent to pi-conjugated systems. Finally I will describe how precise manipulation and control of organic-organic interfaces in a photovoltaic device can increase its power conversion efficiency by 2-5 times in a model bilayer system. Applications of these design principles to practical architectures like bulk heterojunction devices lead to an enhancement in power conversion efficiency from 4.0% to 7.0%. These interface manipulation strategies are universally applicable to any donor-acceptor interface, making them both fundamentally interesting and technologically important for achieving high efficiency organic electronic devices.

  9. Dipole and Coulomb forces in electron capture dissociation and electron transfer dissociation mass spectroscopy.

    Science.gov (United States)

    Świerszcz, Iwona; Skurski, Piotr; Simons, Jack

    2012-02-23

    Ab initio electronic structure calculations were performed on a doubly charged polypeptide model H(+)-Lys(Ala)(19)-CO-CH(NH(2))-CH(2)-SS-CH(2)-(NH(2))CH-CO-(Ala)(19)-Lys-H(+) consisting of a C-terminal protonated Lys followed by a 19-Ala α-helix with a 20th Ala-like unit whose side chain is linked by a disulfide bond to a corresponding Ala-like unit connected to a second 19-Ala α-helix terminated by a second C-terminal-protonated Lys. The Coulomb potentials arising from the two charged Lys residues and dipole potentials arising from the two oppositely directed 72 D dipoles of the α-helices act to stabilize the SS bond's σ* orbital. The Coulomb potentials provide stabilization of 1 eV, while the two large dipoles generate an additional 4 eV. Such stabilization allows the SS σ* orbital to attach an electron and thereby generate disulfide bond cleavage products. Although calculations are performed only on SS bond cleavage, discussion of N-C(α) bond cleavage caused by electron attachment to amide π* orbitals is also presented. The magnitudes of the stabilization energies as well as the fact that they arise from Coulomb and dipole potentials are supported by results on a small model system consisting of a H(3)C-SS-CH(3) molecule with positive and negative fractional point charges to its left and right designed to represent (i) two positive charges ca. 32 Å distant (i.e., the two charged Lys sites of the peptide model) and (ii) two 72 D dipoles (i.e., the two α-helices). Earlier workers suggested that internal dipole forces in polypeptides could act to guide incoming free electrons (i.e., in electron capture dissociation (ECD)) toward the positive end of the dipole and thus affect the branching ratios for cleaving various bonds. Those workers argued that, because of the huge mass difference between an anion donor and a free electron, internal dipole forces would have a far smaller influence over the trajectory of a donor (i.e., in electron transfer dissociation

  10. Phase change heat transfer device for process heat applications

    International Nuclear Information System (INIS)

    Sabharwall, Piyush; Patterson, Mike; Utgikar, Vivek; Gunnerson, Fred

    2010-01-01

    The next generation nuclear plant (NGNP) will most likely produce electricity and process heat, with both being considered for hydrogen production. To capture nuclear process heat, and transport it to a distant industrial facility requires a high temperature system of heat exchangers, pumps and/or compressors. The heat transfer system is particularly challenging not only due to the elevated temperatures (up to ∼1300 K) and industrial scale power transport (≥50 MW), but also due to a potentially large separation distance between the nuclear and industrial plants (100+ m) dictated by safety and licensing mandates. The work reported here is the preliminary analysis of two-phase thermosyphon heat transfer performance with alkali metals. A thermosyphon is a thermal device for transporting heat from one point to another with quite extraordinary properties. In contrast to single-phased forced convective heat transfer via 'pumping a fluid', a thermosyphon (also called a wickless heat pipe) transfers heat through the vaporization/condensing process. The condensate is further returned to the hot source by gravity, i.e., without any requirement of pumps or compressors. With this mode of heat transfer, the thermosyphon has the capability to transport heat at high rates over appreciable distances, virtually isothermally and without any requirement for external pumping devices. Two-phase heat transfer by a thermosyphon has the advantage of high enthalpy transport that includes the sensible heat of the liquid, the latent heat of vaporization, and vapor superheat. In contrast, single-phase forced convection transports only the sensible heat of the fluid. Additionally, vapor-phase velocities within a thermosyphon are much greater than single-phase liquid velocities within a forced convective loop. Thermosyphon performance can be limited by the sonic limit (choking) of vapor flow and/or by condensate entrainment. Proper thermosyphon requires analysis of both.

  11. Electronic processes in organic electronics bridging nanostructure, electronic states and device properties

    CERN Document Server

    Kudo, Kazuhiro; Nakayama, Takashi; Ueno, Nobuo

    2015-01-01

    The book covers a variety of studies of organic semiconductors, from fundamental electronic states to device applications, including theoretical studies. Furthermore, innovative experimental techniques, e.g., ultrahigh sensitivity photoelectron spectroscopy, photoelectron yield spectroscopy, spin-resolved scanning tunneling microscopy (STM), and a material processing method with optical-vortex and polarization-vortex lasers, are introduced. As this book is intended to serve as a textbook for a graduate level course or as reference material for researchers in organic electronics and nanoscience from electronic states, fundamental science that is necessary to understand the research is described. It does not duplicate the books already written on organic electronics, but focuses mainly on electronic properties that arise from the nature of organic semiconductors (molecular solids). The new experimental methods introduced in this book are applicable to various materials (e.g., metals, inorganic and organic mater...

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

    Science.gov (United States)

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

    2016-11-10

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

  13. The Competence Accumulation Process in the Technology Transference Strategy

    Directory of Open Access Journals (Sweden)

    André Silva de Souza

    2008-04-01

    Full Text Available The present article evaluates and measures the technological competence accumulation in an automation area enterprise to distribution centers, Knapp Sudamérica Logistic and Automation Ltd, in the interval of the technology transference process previous period (1998-2001 and during the technology transference process(2002-2005. Therefore, based on an individual case study, the study identified the technology transference strategy and mechanism accorded between the head office and the branch office, the technological functions and activities developed by the receiver and, at last, the critical factors present in this process. The echnological competences accumulation exam was accomplished based on an analytical structure existent in the literature that was adapted to the researched segment analysis. The obtained results showed that the planed, organized, controlled and continuous effort to generating and disseminating knowledge allowed the enterprise to speed up the accumulation process of technological competences promoting the converting of this process from individual level to the organizational one: besides, it also allowed the identification of barriers and facilitators involved in this process.

  14. [Electron transfer, ionization, and excitation in atomic collisions]. Final technical report, June 15, 1986 - June 14, 1998

    International Nuclear Information System (INIS)

    1998-01-01

    The research on theoretical atomic collisions that was funded at The Pennsylvania State University's Wilkes-Barre Campus by DOE from 1986 to 1998 was carried out by Winger from 1986 to 1989 and by Winter and Alston from 1989 to 1998. The fundamental processes of electron transfer, ionization, and excitation in ion-ion, ion-atom, and, more recently, ion-molecule collisions were addressed. These collision processes were treated in the context of simple one-electron, quasi-one-electron, or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. Winter's work generally focused on the intermediate projectile-energy range corresponding to proton energies from about ten to a few hundred keV. In this velocity-matching energy range, the electron-transfer cross section reaches a peak, and many states, including electron-transfer and ionization states, contribute to the overall electron-cloud distribution and transition probabilities; a large number of states are coupled, and therefore perturbative approaches are generally inappropriate. These coupled-state calculations were sometimes also extended to higher energies to join with perturbative results. Alston concentrated on intermediate-energy asymmetric collision systems, for which coupling with the projectile is weaker, but many target states are included, and on high energies (MeV energies). Thus, while perturbation theory for electron transfer is valid, it is not adequate to first order. The studies by Winter and Alston described were often done in parallel. Alston also developed formal perturbative approaches not tied to any particular system. Materials studied included He + , Li 2+ , Be 3+ , B 4+ , C 5+ , and the H + + Na system

  15. Match properties of heat transfer and coupled heat and mass transfer processes in air-conditioning system

    International Nuclear Information System (INIS)

    Zhang Tao; Liu Xiaohua; Zhang Lun; Jiang Yi

    2012-01-01

    Highlights: ► Investigates match properties of heat or mass transfer processes in HVAC system. ► Losses are caused by limited transfer ability, flow and parameter mismatching. ► Condition of flow matching is the same heat capacity of the fluids. ► Parameter matching is only reached along the saturation line in air–water system. ► Analytical solutions of heat and mass transfer resistance are derived. - Abstract: Sensible heat exchangers and coupled heat and mass transfer devices between humid air and water/desiccant are commonly used devices in air-conditioning systems. This paper focuses on the match properties of sensible heat transfer processes and coupled heat and mass transfer processes in an effort to understand the reasons for performance limitations in order to optimize system performance. Limited heat transfer capability and flow mismatching resulted in heat resistance of the sensible heat transfer process. Losses occurred during the heat and mass transfer processes due to limited transfer capability, flow mismatching, and parameter mismatching. Flow matching was achieved when the heat capacities of the fluids were identical, and parameter matching could only be reached along the saturation line in air–water systems or the iso-concentration line in air–desiccant systems. Analytical solutions of heat transfer resistance and mass transfer resistance were then derived. The heat and mass transfer process close to the saturation line is recommended, and heating sprayed water resulted in better humidification performance than heating inlet air in the air humidifier.

  16. Role of coherence and delocalization in photo-induced electron transfer at organic interfaces

    Science.gov (United States)

    Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.; Abramavicius, D.

    2016-09-01

    Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

  17. 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

  18. Electronic and photophysical properties of 2-(2′-hydroxyphenyl)benzoxazole and its derivatives enhancing in the excited-state intramolecular proton transfer processes: A TD-DFT study on substitution effect

    Energy Technology Data Exchange (ETDEWEB)

    Daengngern, Rathawat; Kungwan, Nawee, E-mail: naweekung@gmail.com

    2015-11-15

    The effect of electron donating and withdrawing substituents on the enol absorption and keto emission spectra of 2-(2′-hydroxyphenyl)benzoxazole (HBO) and its derivatives has been systematically investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The enol absorption spectra of HBO were simulated by using five different DFTs with various exchange-correlation functions to validate a suitable functional prior to being further used as a method of choice to study the effect of substituents on the spectral characteristics of HBO derivatives. The popular B3LYP (Becke, three-parameter, Lee–Yang–Parr) exchange-correlation functional is found to provide the best desirable result in predicting the absorption spectrum close to experimental data. In the ground state, enol forms of HBO and its derivatives are more stable than those of keto forms, while in the first lowest excited state, keto forms are found to be more stable than their enol forms. Overall, simulated absorption and emission spectra of HBO and its derivatives from TD-B3LYP calculations are in good agreement with the experimental data. For enol, absorption maxima of HBO derivatives having electron-withdrawing groups are red-shift corresponding to their lower HOMO–LUMO energy gaps compared to that of HBO. For keto emission, HBO having electron donating groups (m-MeHBO and MHBO) and withdrawing group (CNHBO) at 4′-position on the phenol fragment as well as electron donating groups (HBOMe and HBOM) at 6-position on the benzoxazole fragment make the position of keto emission peak shift to shorter wavelength (blue-shift). However, HBO derivatives with electron withdrawing groups (HBOF, HBOCl, HBOA and HBOE) at 6-position give redshifted emission compared to the parent compound (HBO). The type of substituent on both 4′- and 6-positions certainly has a pronounced effect on the absorption and emission spectra of HBO derivatives. - Highlights: • Simulated spectra

  19. Electronic and photophysical properties of 2-(2′-hydroxyphenyl)benzoxazole and its derivatives enhancing in the excited-state intramolecular proton transfer processes: A TD-DFT study on substitution effect

    International Nuclear Information System (INIS)

    Daengngern, Rathawat; Kungwan, Nawee

    2015-01-01

    The effect of electron donating and withdrawing substituents on the enol absorption and keto emission spectra of 2-(2′-hydroxyphenyl)benzoxazole (HBO) and its derivatives has been systematically investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The enol absorption spectra of HBO were simulated by using five different DFTs with various exchange-correlation functions to validate a suitable functional prior to being further used as a method of choice to study the effect of substituents on the spectral characteristics of HBO derivatives. The popular B3LYP (Becke, three-parameter, Lee–Yang–Parr) exchange-correlation functional is found to provide the best desirable result in predicting the absorption spectrum close to experimental data. In the ground state, enol forms of HBO and its derivatives are more stable than those of keto forms, while in the first lowest excited state, keto forms are found to be more stable than their enol forms. Overall, simulated absorption and emission spectra of HBO and its derivatives from TD-B3LYP calculations are in good agreement with the experimental data. For enol, absorption maxima of HBO derivatives having electron-withdrawing groups are red-shift corresponding to their lower HOMO–LUMO energy gaps compared to that of HBO. For keto emission, HBO having electron donating groups (m-MeHBO and MHBO) and withdrawing group (CNHBO) at 4′-position on the phenol fragment as well as electron donating groups (HBOMe and HBOM) at 6-position on the benzoxazole fragment make the position of keto emission peak shift to shorter wavelength (blue-shift). However, HBO derivatives with electron withdrawing groups (HBOF, HBOCl, HBOA and HBOE) at 6-position give redshifted emission compared to the parent compound (HBO). The type of substituent on both 4′- and 6-positions certainly has a pronounced effect on the absorption and emission spectra of HBO derivatives. - Highlights: • Simulated spectra

  20. Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

    Science.gov (United States)

    Farnum, Byron H; Morseth, Zachary A; Brennaman, M Kyle; Papanikolas, John M; Meyer, Thomas J

    2015-06-18

    Degenerately doped In2O3:Sn semiconductor nanoparticles (nanoITO) have been used to study the photoinduced interfacial electron-transfer reactivity of surface-bound [Ru(II)(bpy)2(4,4'-(PO3H2)2-bpy)](2+) (RuP(2+)) molecules as a function of driving force over a range of 1.8 eV. The metallic properties of the ITO nanoparticles, present within an interconnected mesoporous film, allowed for the driving force to be tuned by controlling their Fermi level with an external bias while their optical transparency allowed for transient absorption spectroscopy to be used to monitor electron-transfer kinetics. Photoinduced electron transfer from excited-state -RuP(2+*) molecules to nanoITO was found to be dependent on applied bias and competitive with nonradiative energy transfer to nanoITO. Back electron transfer from nanoITO to oxidized -RuP(3+) was also dependent on the applied bias but without complication from inter- or intraparticle electron diffusion in the oxide nanoparticles. Analysis of the electron injection kinetics as a function of driving force using Marcus-Gerischer theory resulted in an experimental estimate of the reorganization energy for the excited-state -RuP(3+/2+*) redox couple of λ* = 0.83 eV and an electronic coupling matrix element, arising from electronic wave function overlap between the donor orbital in the molecule and the acceptor orbital(s) in the nanoITO electrode, of Hab = 20-45 cm(-1). Similar analysis of the back electron-transfer kinetics yielded λ = 0.56 eV for the ground-state -RuP(3+/2+) redox couple and Hab = 2-4 cm(-1). The use of these wide band gap, degenerately doped materials provides a unique experimental approach for investigating single-site electron transfer at the surface of oxide nanoparticles.

  1. Bi-directional magnetic resonance based wireless power transfer for electronic devices

    International Nuclear Information System (INIS)

    Kar, Durga P.; Nayak, Praveen P.; Bhuyan, Satyanarayan; Mishra, Debasish

    2015-01-01

    In order to power or charge electronic devices wirelessly, a bi-directional wireless power transfer method has been proposed and experimentally investigated. In the proposed design, two receiving coils are used on both sides of a transmitting coil along its central axis to receive the power wirelessly from the generated magnetic fields through strongly coupled magnetic resonance. It has been observed experimentally that the maximum power transfer occurs at the operating resonant frequency for optimum electric load connected across the receiving coils on both side. The optimum wireless power transfer efficiency is 88% for the bi-directional power transfer technique compared 84% in the one side receiver system. By adopting the developed bi-directional power transfer method, two electronic devices can be powered up or charged simultaneously instead of a single device through usual one side receiver system without affecting the optimum power transfer efficiency

  2. Bi-directional magnetic resonance based wireless power transfer for electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Kar, Durga P.; Nayak, Praveen P.; Bhuyan, Satyanarayan; Mishra, Debasish [Department of Electronics and Instrumentation Engineering, Institute of Technical Education and Research, Siksha ‘O’ Anushandhan University, Bhubaneswar 751030 (India)

    2015-09-28

    In order to power or charge electronic devices wirelessly, a bi-directional wireless power transfer method has been proposed and experimentally investigated. In the proposed design, two receiving coils are used on both sides of a transmitting coil along its central axis to receive the power wirelessly from the generated magnetic fields through strongly coupled magnetic resonance. It has been observed experimentally that the maximum power transfer occurs at the operating resonant frequency for optimum electric load connected across the receiving coils on both side. The optimum wireless power transfer efficiency is 88% for the bi-directional power transfer technique compared 84% in the one side receiver system. By adopting the developed bi-directional power transfer method, two electronic devices can be powered up or charged simultaneously instead of a single device through usual one side receiver system without affecting the optimum power transfer efficiency.

  3. Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

    Energy Technology Data Exchange (ETDEWEB)

    Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

    2016-02-15

    The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

  4. Fast electron transfer through a single molecule natively structured redox protein

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Macdonald, J. Emyr

    2012-01-01

    The electron transfer properties of proteins are normally measured as molecularly averaged ensembles. Through these and related measurements, proteins are widely regarded as macroscopically insulating materials. Using scanning tunnelling microscopy (STM), we present new measurements of the conduc...

  5. 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.

  6. 77 FR 71035 - Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT...

    Science.gov (United States)

    2012-11-28

    ... DEPARTMENT OF THE TREASURY Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT) Market Research Study AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION: Notice and Request for comments. SUMMARY: The Financial Management...

  7. Heterogeneous electron transfer kinetics and electrocatalytic behaviour of mixed self-assembled ferrocenes and SWCNT layers

    CSIR Research Space (South Africa)

    Nkosi, D

    2010-01-01

    Full Text Available The electron transfer dynamics and electrocatalytic behaviour of ferrocene-terminated self-assembled monolayers (SAMs), co-adsorbed with single-walled carbon nanotubes (SWCNTs) on a gold electrode, have been interrogated for the first time...

  8. Multidimensional Quantum Mechanical Modeling of Electron Transfer and Electronic Coherence in Plant Cryptochromes: The Role of Initial Bath Conditions.

    Science.gov (United States)

    Mendive-Tapia, David; Mangaud, Etienne; Firmino, Thiago; de la Lande, Aurélien; Desouter-Lecomte, Michèle; Meyer, Hans-Dieter; Gatti, Fabien

    2018-01-11

    A multidimensional quantum mechanical protocol is used to describe the photoinduced electron transfer and electronic coherence in plant cryptochromes without any semiempirical, e.g., experimentally obtained, parameters. Starting from a two-level spin-boson Hamiltonian we look at the effect that the initial photoinduced nuclear bath distribution has on an intermediate step of this biological electron transfer cascade for two idealized cases. The first assumes a slow equilibration of the nuclear bath with respect to the previous electron transfer step that leads to an ultrafast decay with little temperature dependence; while the second assumes a prior fast bath equilibration on the donor potential energy surface leading to a much slower decay, which contrarily displays a high temperature dependence and a better agreement with previous theoretical and experimental results. Beyond Marcus and semiclassical pictures these results unravel the strong impact that the presence or not of equilibrium initial conditions has on the electronic population and coherence dynamics at the quantum dynamics level in this and conceivably in other biological electron transfer cascades.

  9. An 80 Mbytes/s data transfer and processing system

    International Nuclear Information System (INIS)

    Belusevic, R.; Nixon, G.; Shaw, D.

    1990-05-01

    We describe hardware and software aspects of a very fast and versatile, yet conceptually simple, data transfer and processing system for use with future accelerators. It consists of a transputer-based crate controller (CC), which includes an Intel i860 microcomputer, and of a set of readout cards (RC), each containing a digital signal processor (DSP) for fast data parametrisation and compaction. The reduced data is written into a dual port memory (DPM), where it can be accessed concurrently by the transputer and transferred to a common DPM on the CC card. A crateful of data thus assembled at one place can further be processed by the powerful i860 microcomputer. Address generators (simple binary counters) are included on the crate controller and each readout card to enable direct memory access (DMA) operations, resulting in a considerable increase in data transfer speed (maximum 80 Mbytes/s). The use of a transputer as the sole controller processor, in conjunction with DPMs, renders bus arbitration unnecessary leading to very simple interfacing logic and operating software. The four high speed serial links of the transputer greatly facilitate downloading of programs and intercrate communications. An Intel i960CA processor, situated on the CC card, is used for fast data transfer between crates by means of its 32-bit wide DMA channel. The operating software is written in the Occam language, which was specially developed for programming concurrent systems based on transputers. (author)

  10. An 80 Mbytes/s data transfer and processing system

    International Nuclear Information System (INIS)

    Belusevic, R.; Nixon, G.; Shaw, D.

    1990-01-01

    We describe hardware and software aspects of a very fast and versatile, yet conceptually simple, data transfer and processing system for use with future accelerators. It consists of a transputer-based crate controller (CC), which includes an Intel i860 microcomputer, and of a set of readout cards (RC), each containing a digital signal processor (DSP) for fast data parametrisation and compaction. The reduced data is written into a dual port memory (DPM), where it can be accessed concurrently by the transputer and transferred to a common DPM on the CC card. A crateful of data thus assembled at one place can further be processed by the powerful i860 microcomputer. Address generators (simple binary counters) are included on the crate controller and each readout card to enable direct memory access (DMA) operations, resulting in a considerable increase in data transfer speed (maximum 80 Mbytes/s). The use of a transputer as the sole controlling processor, in conjunction with DPMs, renders bus arbitration unnecessary, leading to very simple interfacing logic and operating software. The four high-speed serial links of the transputer greatly facilitate downloading of programs and intercrate communications. An Intel i960CA processor, situated on the CC card, is used for fast data transfer between crates by means of its 32-bit wide DMA channel. The operating software is written in the Occam language, which was specially developed for programming concurrent systems based on transputers. (orig.)

  11. Heat and mass transfer enhancement in absorbing processes

    International Nuclear Information System (INIS)

    Hijikata, Kunio; Lee, S.K.

    1993-01-01

    The key to improving the performance of absorption-type heat machines lies in the enhancement of the mass transfer of the vapor into the absorbant solution, since the mass diffusivity in the solution is very small compared to the thermal diffusivity. The absorption process is influenced by many factors including physical properties of the fluids, the flow pattern and others, especially the velocity profile near the interface is the most important. From these stand points, the heat and mass transfer in the absorption was investigated by following three steps. First, an augmentation of the absorption to a liquid film flowing in groove was theoretically investigated, in which the interface between the vapor and liquid film is cooled by the grooved surfaces. Secondly, systematical experiments were carried out on several factors that affect the absorption process, which were the cooling wall temperature, the inlet solution subcooling, and the fin configuration. Finally, a numerical study of the heat and mass transfer enhancement due to flow agitation by the periodically grooved channel was conducted. That flow realized by fabricating ridges on the fin surface. A secondary flow due to these ridges is expected to enhance the heat and mass transfer. These results were compared with experimental ones. (orig.)

  12. Remote process cell mercury transfer pumps for DWPF

    International Nuclear Information System (INIS)

    Nielsen, M.G.; Vaughn, V.G.

    1986-01-01

    Final design and the results of the testing performed thus far show that the water displacement of mercury to a height of 40 feet is feasible with just 6 gallons of motive water. Control of the transfer is achieved by monitoring the pump discharge pressure. An air actuated plug valve configuration successfully contained the required discharge pressure of 260 psi. The requirements of low flow and maximum separation of mercury from particulates are achieved due to the configuration of the pressure canister. The pump is capable of transferring a discrete amount of mercury with little additional slurry particulates. The success of this new pumping configuration is highlighted by the fact that it was the inspiration for other remote transfer applications tested at SRP. These application include the dual canister sample pump shown in Figure 7, as well as a successful prototype pump designed at Pacific Northwest Laboratories (PNL). The PNL pump was designed for the purpose of metering waste slurries to an electric melter. Upon completion of final pump fabrication, the Defense Waste Processing facility (DWPF) facility will have a simple and highly reliable method of remotely transferring small discrete batches of mercury as required from radioactive process vessels. 3 refs., 7 figs., 1 tab

  13. Freezing hot electrons. Electron transfer and solvation dynamics at D{sub 2}O and NH{sub 3}-metal interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Staehler, A.J.

    2007-05-15

    The present work investigates the electron transfer and solvation dynamics at the D{sub 2}O/Cu(111), D{sub 2}O/Ru(001), and NH{sub 3}/Cu(111) interfaces using femtosecond time-resolved two-photon photoelectron spectroscopy. Within this framework, the influence of the substrate, adsorbate structure and morphology, solvation site, coverage, temperature, and solvent on the electron dynamics are studied, yielding microscopic insight into the underlying fundamental processes. Transitions between different regimes of ET, substrate-dominated, barrier-determined, strong, and weak coupling are observed by systematic variation of the interfacial properties and development of empirical model descriptions. It is shown that the fundamental steps of the interfacial electron dynamics are similar for all investigated systems: Metal electrons are photoexcited to unoccupied metal states and transferred into the adlayer via the adsorbate's conduction band. The electrons localize at favorable sites and are stabilized by reorientations of the surrounding polar solvent molecules. Concurrently, they decay back two the metal substrate, as it offers a continuum of unoccupied states. However, the detailed characteristics vary for the different investigated interfaces: For amorphous ice-metal interfaces, the electron transfer is initially, right after photoinjection, dominated by the substrate's electronic surface band structure. With increasing solvation, a transient barrier evolves at the interface that increasingly screens the electrons from the substrate. Tunneling through this barrier becomes the rate-limiting step for ET. The competition of electron decay and solvation leads to lifetimes of the solvated electrons in the order of 100 fs. Furthermore, it is shown that the electrons bind in the bulk of the ice layers, but on the edges of adsorbed D{sub 2}O clusters and that the ice morphology strongly influences the electron dynamics. For the amorphous NH{sub 3}/Cu(111

  14. Reversible assembly of protein-DNA nanostructures triggered by mediated electron transfer

    International Nuclear Information System (INIS)

    Vogt, Stephan; Wenderhold-Reeb, Sabine; Nöll, Gilbert

    2017-01-01

    Stable protein-DNA nanostructures have been assembled by reconstitution of the multi-ligand binding flavoprotein dodecin on top of flavin-terminated dsDNA monolayers on gold electrodes. These structures could be disassembled by electrochemical flavin reduction via mediated electron transfer. For this purpose a negative potential was applied at the Au working electrode in the presence of the redox mediator bis-(ammoniumethyl)-4,4′-bipyridinium tetrabromide. The stepwise formation of the flavin-terminated dsDNA monolayers as well as the binding and electrochemically triggered release of apododecin were monitored by surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) measurements. The assembly and disassembly of the protein-DNA nanostructures were fully reversible processes, which could be carried out multiple times at the same flavin-dsDNA modified surface. When a negative potential was applied in the absence of a redox mediator apododecin could not be released, i.e. direct electron transfer was not possible. As alternative redox mediators also methylene blue and phenosafranine were studied, but in the presence of these molecules apododecin was released without applying a potential, probably because the tricyclic aromatic compounds are able to replace the flavins at the binding sites.

  15. Transformation of methano[60]fullerenes in dihydrofullerofuranes induced by electron transfer

    International Nuclear Information System (INIS)

    Yanilkin, V.V.; Toropchina, A.V.; Morozov, V.I.; Nastapova, N.V.; Gubskaya, V.P.; Sibgatullina, F.G.; Azancheev, N.M.; Efremov, Yu.Ya.; Nuretdinov, I.A.

    2004-01-01

    The electrochemical reduction of methano[60]fullerenes (61-acetyl-61-(diethoxyphosphoryl)methano-60-fullerene 1, 61-acetyl-61-(diisopropoxyphosphoryl)methano-60-fullerene 2, 61-(2,2-diethoxyacetyl)-61-(diethoxy-phosphoryl)methano-60-fullerene 3, 61-phenyl-61-(1,2-dioxo-3,3-dimethyl-buthyl)methano-60-fullerene 4) in o-dichlorobenzene-DMF (3:1 v/v)/0.1 M Bu 4 NBF 4 on a glass-carbon electrode proceeds in a few steps. The reversible transfer of the first electron results in the formation of radical anions registered by ESR method. The subsequent reduction proceeds differently because of the various stability of anionic intermediates. The radical anions of the methanofullerenes 3 and 4 are less stable than the radical anions of compounds 1 and 2 and less stable than the radical anions of methanofullerenes, which contain an ester and/or a phosphonate group. The opening of a cyclopropane ring occurs during the stage of the formation of radical trianions of methanofullerenes 1, 2. The same process for compounds 3, 4 proceeds slowly in radical anions and fast in dianions. The opening of cyclopropane ring for all compounds is not accompanied by the elimination of methanogroup and results in the formation of dihydrofullerenofurane derivatives. The transformation of methanofullerene 3 induced by single electron transfer proceeds via a chain reaction mechanism

  16. Transferred metal electrode films for large-area electronic devices

    International Nuclear Information System (INIS)

    Yang, Jin-Guo; Kam, Fong-Yu; Chua, Lay-Lay

    2014-01-01

    The evaporation of metal-film gate electrodes for top-gate organic field-effect transistors (OFETs) limits the minimum thickness of the polymer gate dielectric to typically more than 300 nm due to deep hot metal atom penetration and damage of the dielectric. We show here that the self-release layer transfer method recently developed for high-quality graphene transfer is also capable of giving high-quality metal thin-film transfers to produce high-performance capacitors and OFETs with superior dielectric breakdown strength even for ultrathin polymer dielectric films. Dielectric breakdown strengths up to 5–6 MV cm −1 have been obtained for 50-nm thin films of polystyrene and a cyclic olefin copolymer TOPAS ® (Zeon). High-quality OFETs with sub-10 V operational voltages have been obtained this way using conventional polymer dielectrics and a high-mobility polymer semiconductor poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene-2,5-diyl]. The transferred metal films can make reliable contacts without damaging ultrathin polymer films, self-assembled monolayers and graphene, which is not otherwise possible from evaporated or sputtered metal films

  17. Tritium transfer process using the CRNL wetproof catalyst

    International Nuclear Information System (INIS)

    Chuang, K.T.; Holtslander, W.J.

    1980-01-01

    The recovery of tritium from heavy water in CANDU reactor systems requires the transfer of the tritium atoms from water to hydrogen molecules prior to tritium concentration by cryogenic distillation. Isotopic exchange between liquid water and hydrogen using the CRNL-developed wetproof catalyst provides an effective method for the tritium transfer process. The development of this process has required the translation of the technology from a laboratory demonstration of catalyst activity for the exchange reaction to proving and demonstration that the process will meet the practical restraints in a full-scale tritium recovery plant. This has led to a program to demonstrate acceptable performance of the catalyst at operating conditions that will provide data for design of large plants. Laboratory and pilot plant work has shown adequate catalyst lifetimes, demonstrated catalyst regeneration techniques and defined and required feedwater purification systems to ensure optimum catalyst performance. The ability of the catalyst to promote the exchange of hydrogen isotopes between water and hydrogen has been shown to be technically feasible for the tritium transfer process

  18. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO2 were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  19. Charge transfer in quasi-one-electron systems at 'high' energy

    Energy Technology Data Exchange (ETDEWEB)

    Gay, T.J.; Redd, E.; Blankenship, D.M.; Park, J.T.; Peacher, J.L.; Seeley, D.G.

    1988-08-14

    We have made absolute and relative measurements of differential cross sections for single-electron transfer in collisions between Mg/sup +/ (30-150 keV) and Be/sup +/ (56.25 keV) ions and He atoms. The behaviour of transfer probability as a function of impact parameter can be understood qualitatively from recent molecular orbital calculations of quasi-one-electron systems.

  20. One-electron redox potentials and rate of electron transfer in aqueous micellar solution. Partially solubilized quinones

    International Nuclear Information System (INIS)

    Almgren, M.; Grieser, F.; Thomas, J.K.

    1979-01-01

    The electron transfer equilibrium between AQS/AQS - and DQ/DQ - (where AQS is sodium 9,10-arthraquinone-2-sulfonate and DQ, duroquinone) has been studied by pulse radiolysis in aqueous micellar solutions of sodium lauryl sulfate. The equilibrium constant is changed as would be expected if AQS, AQS - , and DQ- were all mainly in the aqueous solution, and DQ distributed between the micelles and the aqueous phase with a distribution constant of K/sub D//N = 150 M -1 , in agreement with the independently determined value of this constant. The kinetics of the equilibration show, however, that electron transfer at the micelle surface is important, indicating that also AQS and DQ - are associated with the micelle to some extent. With reasonable assumptions regarding the distribution constants of these species (that have some independent support), the observed catalytic effect of the micelles on the electron transfer from DQ - to AQS can be understood

  1. Double electron transfer in ion-atom collisions

    International Nuclear Information System (INIS)

    Martinez, A.E

    1990-01-01

    Continuum distorted wave (CDW) and CDW-EIS (electron-ion scattering) approximations are used to study the resonant double capture by collision of alpha particles on He targets for intermediate and high energies. Calculations of total cross-sections based on the Independent Event Approximation are presented. A good agreement with experimental results was found, even without the inclusion of the dynamic and angular correlation of captured electrons. (Author). 11 refs., 1 fig

  2. Molecular Computational Investigation of Electron Transfer Kinetics across Cytochrome-Iron Oxide Interfaces

    International Nuclear Information System (INIS)

    Kerisit, Sebastien N.; Rosso, Kevin M.; Dupuis, Michel; Valiev, Marat

    2007-01-01

    The interface between electron transfer proteins such as cytochromes and solid phase mineral oxides is central to the activity of dissimilatory-metal reducing bacteria. A combination of potential-based molecular dynamics simulations and ab initio electronic structure calculations are used in the framework of Marcus' electron transfer theory to compute elementary electron transfer rates from a well-defined cytochrome model, namely the small tetraheme cytochrome (STC) from Shewanella oneidensis, to surfaces of the iron oxide mineral hematite (a-Fe2O3). Room temperature molecular dynamics simulations show that an isolated STC molecule favors surface attachment via direct contact of hemes I and IV at the poles of the elongated axis, with electron transfer distances as small as 9 Angstroms. The cytochrome remains attached to the mineral surface in the presence of water and shows limited surface diffusion at the interface. Ab initio electronic coupling matrix element (VAB) calculations of configurations excised from the molecular dynamics simulations reveal VAB values ranging from 1 to 20 cm-1, consistent with nonadiabaticity. Using these results, together with experimental data on the redox potential of hematite and hemes in relevant cytochromes and calculations of the reorganization energy from cluster models, we estimate the rate of electron transfer across this model interface to range from 1 to 1000 s-1 for the most exothermic driving force considered in this work, and from 0.01 to 20 s-1 for the most endothermic. This fairly large range of electron transfer rates highlights the sensitivity of the rate upon the electronic coupling matrix element, which is in turn dependent on the fluctuations of the heme configuration at the interface. We characterize this dependence using an idealized bis-imidazole heme to compute from first principles the VAB variation due to porphyrin ring orientation, electron transfer distance, and mineral surface termination. The electronic

  3. Effect of resonant-to-bulk electron momentum transfer on the efficiency of electron-cyclotron current drive

    International Nuclear Information System (INIS)

    Matsuda, Y.; Smith, G.R.; Cohen, R.H.

    1988-01-01

    Efficiency of current drive by electron-cyclotron waves is investigated numerically by a bounce-average Fokker-Planck code to elucidate the effects of momentum transfer from resonant to bulk electrons, finite bulk temperature relative to the energy of resonant electrons, and trapped electrons. Comparisons are made with existing theories to assess their validity and quantitative difference between theory and code results. Difference of nearly a factor of 2 was found in efficiency between some theory and code results. 4 refs., 4 figs

  4. Optimization of equipment for electron radiation processing

    Science.gov (United States)

    Tartz, M.; Hartmann, E.; Lenk, M.; Mehnert, R.

    1999-05-01

    In the course of the last decade, IOM Leipzig has developed low-energy electron accelerators for electron beam curing of polymer coatings and printing inks. In order to optimize the electron irradiation field, electron optical calculations have been carried out using the commercially available EGUN code. The present study outlines the design of the diode-type low-energy electron accelerators LEA and EBOGEN, taking into account the electron optical effects of secondary components such as the retaining rods installed in the cathode assembly.

  5. Optimization of equipment for electron radiation processing

    International Nuclear Information System (INIS)

    Tartz, M.; Hartmann, E.; Lenk, M.; Mehnert, R.

    1999-01-01

    In the course of the last decade, IOM Leipzig has developed low-energy electron accelerators for electron beam curing of polymer coatings and printing inks. In order to optimize the electron irradiation field, electron optical calculations have been carried out using the commercially available EGUN code. The present study outlines the design of the diode-type low-energy electron accelerators LEA and EBOGEN, taking into account the electron optical effects of secondary components such as the retaining rods installed in the cathode assembly

  6. New memory devices based on the proton transfer process

    International Nuclear Information System (INIS)

    Wierzbowska, Małgorzata

    2016-01-01

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

  7. New memory devices based on the proton transfer process

    Science.gov (United States)

    Wierzbowska, Małgorzata

    2016-01-01

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

  8. Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

    KAUST Repository

    Van Regemorter, Tanguy; Guillaume, Maxime; Sini, Gjergji; Sears, John S.; Geskin, Victor; Bré das, Jean-Luc; Beljonne, David; Cornil, Jé rô me

    2012-01-01

    In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

  9. Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

    KAUST Repository

    Van Regemorter, Tanguy

    2012-09-15

    In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

  10. Oxidation of the FAD cofactor to the 8-formyl-derivative in human electron-transferring flavoprotein

    Science.gov (United States)

    Augustin, Peter; Toplak, Marina; Fuchs, Katharina; Gerstmann, Eva Christine; Prassl, Ruth; Winkler, Andreas; Macheroux, Peter

    2018-01-01

    The heterodimeric human (h) electron-transferring flavoprotein (ETF) transfers electrons from at least 13 different flavin dehydrogenases to the mitochondrial respiratory chain through a non-covalently bound FAD cofactor. Here, we describe the discovery of an irreversible and pH-dependent oxidation of the 8α-methyl group to 8-formyl-FAD (8f-FAD), which represents a unique chemical modification of a flavin cofactor in the human flavoproteome. Furthermore, a set of hETF variants revealed that several conserved amino acid residues in the FAD-binding pocket of electron-transferring flavoproteins are required for the conversion to the formyl group. Two of the variants generated in our study, namely αR249C and αT266M, cause glutaric aciduria type II, a severe inherited disease. Both of the variants showed impaired formation of 8f-FAD shedding new light on the potential molecular cause of disease development. Interestingly, the conversion of FAD to 8f-FAD yields a very stable flavin semiquinone that exhibited slightly lower rates of electron transfer in an artificial assay system than hETF containing FAD. In contrast, the formation of 8f-FAD enhanced the affinity to human dimethylglycine dehydrogenase 5-fold, indicating that formation of 8f-FAD modulates the interaction of hETF with client enzymes in the mitochondrial matrix. Thus, we hypothesize that the FAD cofactor bound to hETF is subject to oxidation in the alkaline (pH 8) environment of the mitochondrial matrix, which may modulate electron transport between client dehydrogenases and the respiratory chain. This discovery challenges the current concepts of electron transfer processes in mitochondria. PMID:29301933

  11. The dipole moment of the electron carrier adrenodoxin is not critical for redox partner interaction and electron transfer.

    Science.gov (United States)

    Hannemann, Frank; Guyot, Arnaud; Zöllner, Andy; Müller, Jürgen J; Heinemann, Udo; Bernhardt, Rita

    2009-07-01

    Dipole moments of proteins arise from helical dipoles, hydrogen bond networks and charged groups at the protein surface. High protein dipole moments were suggested to contribute to the electrostatic steering between redox partners in electron transport chains of respiration, photosynthesis and steroid biosynthesis, although so far experimental evidence for this hypothesis was missing. In order to probe this assumption, we changed the dipole moment of the electron transfer protein adrenodoxin and investigated the influence of this on protein-protein interactions and electron transfer. In bovine adrenodoxin, the [2Fe-2S] ferredoxin of the adrenal glands, a dipole moment of 803 Debye was calculated for a full-length adrenodoxin model based on the Adx(4-108) and the wild type adrenodoxin crystal structures. Large distances and asymmetric distribution of the charged residues in the molecule mainly determine the observed high value. In order to analyse the influence of the resulting inhomogeneous electric field on the biological function of this electron carrier the molecular dipole moment was systematically changed. Five recombinant adrenodoxin mutants with successively reduced dipole moment (from 600 to 200 Debye) were analysed for their redox properties, their binding affinities to the redox partner proteins and for their function during electron transfer-dependent steroid hydroxylation. None of the mutants, not even the quadruple mutant K6E/K22Q/K24Q/K98E with a dipole moment reduced by about 70% showed significant changes in the protein function as compared with the unmodified adrenodoxin demonstrating that neither the formation of the transient complex nor the biological activity of the electron transfer chain of the endocrine glands was affected. This is the first experimental evidence that the high dipole moment observed in electron transfer proteins is not involved in electrostatic steering among the proteins in the redox chain.

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

    Science.gov (United States)

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

    2013-12-18

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

  13. Fundamental studies of energy-and hole/electron- transfer in hydroporphyrin architectures

    Energy Technology Data Exchange (ETDEWEB)

    Bocian, David F. [University of California, Riverside, CA (United States)

    2014-08-20

    The long-term objective of the Bocian/Holten/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten group), and electrochemical, electron paramagnetic resonance, and resonance Raman studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (1) Determination of the rates of ground-state hole/electron transfer between (hydro)porphyrins in multipigment arrays as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (2) Examination of excited-state energy transfer among hydroporphyrins in multipigment arrrays, including both pairwise and non-adjacent transfer, with a chief aim to identify the relative contributions of through-space (Förster) and through-bond (Dexter) mechanisms of energy transfer, including the roles of site of linker connection and frontier molecular orbital composition. (3) Elucidation of the role of substituents in tuning the spectral and electronic properties of bacteriochlorins, with a primary aim of learning how to shift the long-wavelength absorption band deeper into the near-infrared region. (4) Continued development of the software package PhotochemCAD for spectral manipulations and calculations through the compilation of a database

  14. 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.

  15. Using CASE to Exploit Process Modeling in Technology Transfer

    Science.gov (United States)

    Renz-Olar, Cheryl

    2003-01-01

    A successful business will be one that has processes in place to run that business. Creating processes, reengineering processes, and continually improving processes can be accomplished through extensive modeling. Casewise(R) Corporate Modeler(TM) CASE is a computer aided software engineering tool that will enable the Technology Transfer Department (TT) at NASA Marshall Space Flight Center (MSFC) to capture these abilities. After successful implementation of CASE, it could then go on to be applied in other departments at MSFC and other centers at NASA. The success of a business process is dependent upon the players working as a team and continuously improving the process. A good process fosters customer satisfaction as well as internal satisfaction in the organizational infrastructure. CASE provides a method for business process success through functions consisting of systems and processes business models; specialized diagrams; matrix management; simulation; report generation and publishing; and, linking, importing, and exporting documents and files. The software has an underlying repository or database to support these functions. The Casewise. manual informs us that dynamics modeling is a technique used in business design and analysis. Feedback is used as a tool for the end users and generates different ways of dealing with the process. Feedback on this project resulted from collection of issues through a systems analyst interface approach of interviews with process coordinators and Technical Points of Contact (TPOCs).

  16. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    International Nuclear Information System (INIS)

    Jiang, Li-lin; Liu, Wei-long; Song, Yun-fei; He, Xing; Wang, Yang; Wang, Chang; Wu, Hong-lin; Yang, Fang; Yang, Yan-qiang

    2014-01-01

    Highlights: • Mechanism of PIET reaction process for the Rh101 + /DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101 +∗ occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101 + ) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101 +∗ occurs on a time scale of τ FET = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of τ BET = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of τ IVR = 2.77–5.39 ps

  17. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Li-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); School of Mechanical and Electronic Engineering, Hezhou University, Hezhou 542800 (China); Liu, Wei-long; Song, Yun-fei; He, Xing; Wang, Yang; Wang, Chang; Wu, Hong-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); Yang, Fang [National Key Laboratory of Science and Technology on Tunable Laser, Department of Optoelectronics Information Science Technology, Harbin Institute of Technology, Harbin 150001 (China); Yang, Yan-qiang, E-mail: yqyang@hit.edu.cn [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang 621900, Sichuan (China)

    2014-01-31

    Highlights: • Mechanism of PIET reaction process for the Rh101{sup +}/DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101{sup +∗} occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101{sup +}) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101{sup +∗} occurs on a time scale of τ{sub FET} = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of τ{sub BET} = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of τ{sub IVR} = 2.77–5.39 ps.

  18. Photoinduced electron-transfer from pi-conjugated polymers onto buckminsterfullerene, fulleroids, and methanofullerenes

    NARCIS (Netherlands)

    Janssen, R. A. J.; Hummelen, J. C.; Lee, Kwanghee; Pakbaz, K.; Sariciftci, N. S.; Heeger, A. J.; Wudl, F

    1995-01-01

    We present near-steady-state photoinduced absorption (PIA), photoluminescence, and light-induced electron spin resonance (LESR) studies on photoinduced electron transfer reactions from poly(bis-2,5-epi-cholestanoxy-1,4-phenylene vinylene) (BeCHA-PPV) as a donor to Buckminsterfullerene (C60) and a

  19. 77 FR 10373 - Greenhouse Gas Reporting Program: Electronics Manufacturing: Revisions to Heat Transfer Fluid...

    Science.gov (United States)

    2012-02-22

    ... Greenhouse Gas Reporting Program: Electronics Manufacturing: Revisions to Heat Transfer Fluid Provisions... technical revisions to the electronics manufacturing source category of the Greenhouse Gas Reporting Rule... final rule will also be available through the WWW on the EPA's Greenhouse Gas Reporting Program Web site...

  20. Potential for direct interspecies electron transfer in methanogenic wastewater digester aggregates

    DEFF Research Database (Denmark)

    Morita, Masahiko; Malvankar, Nikhil S; Franks, Ashley E

    2011-01-01

    Mechanisms for electron transfer within microbial aggregates derived from an upflow anaerobic sludge blanket reactor converting brewery waste to methane were investigated in order to better understand the function of methanogenic consortia. The aggregates were electrically conductive, with conduc...... for electron exchange in some methanogenic systems....

  1. Modulating indium doped tin oxide electrode properties for laccase electron transfer enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Diaconu, Mirela [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Chira, Ana [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania); Radu, Lucian, E-mail: gl_radu@chim.upb.ro [Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania)

    2014-08-28

    Indium doped tin oxide (ITO) electrodes were functionalized with gold nanoparticles (GNPs) and cysteamine monolayer to enhance the heterogeneous electron transfer process of laccase from Trametes versicolor. The assembly of GNP on ITO support was performed through generation of H{sup +} species at the electrode surface by hydroquinone electrooxidation at 0.9 V vs Ag/AgCl. Uniform distribution of gold nanoparticle aggregates on electrode surfaces was confirmed by atomic force microscopy. The size of GNP aggregates was in the range of 200–500 nm. The enhanced charge transfer at the GNP functionalized ITO electrodes was observed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy. Electrocatalytic behavior of laccase immobilized on ITO modified electrode toward oxygen reduction reaction was evaluated using CV in the presence of 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulfuric acid (ABTS). The obtained sigmoidal-shaped voltammograms for ABTS reduction in oxygen saturated buffer solution are characteristic for a catalytic process. The intensity of catalytic current increased linearly with mediator concentration up to 6.2 × 10{sup −4} M. The registered voltammogram in the absence of ABTS mediator clearly showed a significant faradaic current which is the evidence of the interfacial oxygen reduction. - Highlights: • Assembly of gold nanoparticles on indium tin oxide support at positive potentials • Electrochemical and morphological evaluation of the gold nanoparticle layer assembly • Bioelectrocatalytic oxygen reduction on laccase modified electrode.

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

    Science.gov (United States)

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    transfer and proton-coupled electron transfer in chemical and biological processes.

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

    International Nuclear Information System (INIS)

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

    transfer and proton-coupled electron transfer in chemical and biological processes

  4. Electron transfer driven decomposition of adenine and selected analogs as probed by experimental and theoretical methods

    Science.gov (United States)

    Cunha, T.; Mendes, M.; Ferreira da Silva, F.; Eden, S.; García, G.; Bacchus-Montabonel, M.-C.; Limão-Vieira, P.

    2018-04-01

    We report on a combined experimental and theoretical study of electron-transfer-induced decomposition of adenine (Ad) and a selection of analog molecules in collisions with potassium (K) atoms. Time-of-flight negative ion mass spectra have been obtained in a wide collision energy range (6-68 eV in the centre-of-mass frame), providing a comprehensive investigation of the fragmentation patterns of purine (Pu), adenine (Ad), 9-methyl adenine (9-mAd), 6-dimethyl adenine (6-dimAd), and 2-D adenine (2-DAd). Following our recent communication about selective hydrogen loss from the transient negative ions (TNIs) produced in these collisions [T. Cunha et al., J. Chem. Phys. 148, 021101 (2018)], this work focuses on the production of smaller fragment anions. In the low-energy part of the present range, several dissociation channels that are accessible in free electron attachment experiments are absent from the present mass spectra, notably NH2 loss from adenine and 9-methyl adenine. This can be understood in terms of a relatively long transit time of the K+ cation in the vicinity of the TNI tending to enhance the likelihood of intramolecular electron transfer. In this case, the excess energy can be redistributed through the available degrees of freedom inhibiting fragmentation pathways. Ab initio theoretical calculations were performed for 9-methyl adenine (9-mAd) and adenine (Ad) in the presence of a potassium atom and provided a strong basis for the assignment of the lowest unoccupied molecular orbitals accessed in the collision process.

  5. 77 FR 30923 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-05-24

    ... similar to a debit card that is linked to a traditional checking account. The Bureau is particularly interested in learning more about this product, including its costs, benefits, and risks to consumers. The... methods: Electronic: http://www.regulations.gov . Follow the instructions for submitting comments. Mail...

  6. Interspecies electron transfer in methanogenic propionate degrading consortia

    NARCIS (Netherlands)

    Bok, de F.A.M.; Plugge, C.M.; Stams, A.J.M.

    2004-01-01

    Propionate is a key intermediate in the conversion of complex organic matter under methanogenic conditions. Oxidation of this compound requires obligate syntrophic consortia of acetogenic proton- and bicarbonate reducing bacteria and methanogenic archaea. Although H-2 acts as an electron-carrier in

  7. Numerical Analysis of Heat Transfer During Quenching Process

    Science.gov (United States)

    Madireddi, Sowjanya; Krishnan, Krishnan Nambudiripad; Reddy, Ammana Satyanarayana

    2018-04-01

    A numerical model is developed to simulate the immersion quenching process of metals. The time of quench plays an important role if the process involves a defined step quenching schedule to obtain the desired characteristics. Lumped heat capacity analysis used for this purpose requires the value of heat transfer coefficient, whose evaluation requires large experimental data. Experimentation on a sample work piece may not represent the actual component which may vary in dimension. A Fluid-Structure interaction technique with a coupled interface between the solid (metal) and liquid (quenchant) is used for the simulations. Initial times of quenching shows boiling heat transfer phenomenon with high values of heat transfer coefficients (5000-2.5 × 105 W/m2K). Shape of the work piece with equal dimension shows less influence on the cooling rate Non-uniformity in hardness at the sharp corners can be reduced by rounding off the edges. For a square piece of 20 mm thickness, with 3 mm fillet radius, this difference is reduced by 73 %. The model can be used for any metal-quenchant combination to obtain time-temperature data without the necessity of experimentation.

  8. NO-γ emissions from streamer discharges: direct electron impact excitation versus resonant energy transfer

    International Nuclear Information System (INIS)

    Liu Ningyu; Pasko, Victor P

    2010-01-01

    It has been established that production of NO-γ emission in pulsed corona discharges is dominated by the energy transfer from N 2 (A 3 Σ u + ) to the NO ground state NO(X 2 Π r ) while direct excitation by electron impact is negligible. However, recent studies suggest that the electron impact excitation plays a more important role. In this work, we report modelling results of NO-γ emission associated with streamer discharges using two cross section data sets available in the literature. The first set was originally reported by Mojarrabi et al (1996 Phys. Rev. A 54 2977-82) and later updated by Brunger et al (2000 J. Phys. B: At. Mol. Opt. Phys. 33 809-19); the second set was published by Hayashi (1990 Nonequilibrium Processes in Partially Ionized Gases (NATO Advanced Science Institutes Series, Series B, Physics vol 220) ed M Capitelli and J N Bardsley (New York: Plenum) pp 333-40). According to the results, the role played by the electron impact excitation in the production of NO-γ is drastically different when different cross sections are used. The results indicate that the first data set leads to better agreement with experimental measurements. (fast track communication)

  9. Effects of electron-transfer chemical modification on the electrical characteristics of graphene

    International Nuclear Information System (INIS)

    Fan Xiaoyan; Tanigaki, Katsumi; Nouchi, Ryo; Yin Lichang

    2010-01-01

    Because of the large reactivity of single layer graphene to electron-transfer chemistries, 4-nitrobenzene diazonium tetrafluoroborate is employed to modify the electrical properties of graphene field-effect transistors. After modification, the transfer characteristics of chemically modified graphene show a reduction in the minimum conductivity, electron-hole mobility asymmetry, a decrease in the electron/hole mobility, and a positive shift of the charge neutrality point with broadening of the minimum conductivity region. These phenomena are attributed to a dediazoniation reaction and the adsorbates on the graphene surface.

  10. Effects of electron-transfer chemical modification on the electrical characteristics of graphene

    Energy Technology Data Exchange (ETDEWEB)

    Fan Xiaoyan; Tanigaki, Katsumi [Department of Physics, Graduate School of Science, Tohoku University, Sendai 980-8578 (Japan); Nouchi, Ryo [WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8578 (Japan); Yin Lichang, E-mail: nouchi@sspns.phys.tohoku.ac.jp [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China)

    2010-11-26

    Because of the large reactivity of single layer graphene to electron-transfer chemistries, 4-nitrobenzene diazonium tetrafluoroborate is employed to modify the electrical properties of graphene field-effect transistors. After modification, the transfer characteristics of chemically modified graphene show a reduction in the minimum conductivity, electron-hole mobility asymmetry, a decrease in the electron/hole mobility, and a positive shift of the charge neutrality point with broadening of the minimum conductivity region. These phenomena are attributed to a dediazoniation reaction and the adsorbates on the graphene surface.

  11. The application and processing of paints hardened by electron beams

    International Nuclear Information System (INIS)

    Anon.

    1984-01-01

    Electron beam hardening is a process for changing liquid surface coatings of different thicknesses by irradiation with electrons of high energy into solid, hard, elastic films. In contrast to the UV process, one can harden pigmented paints with electron beams. An electron accelerator, which remits free electrons is used as the energy source for starting the chemical reaction in the coating material. In order to irradiate flat parts, which were coated with liquid paint by rolling, pouring or spraying, equally with electrons, one must produce an 'electron curtain', similar to that in a paint pouring machine. (orig./PW) [de

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-06-15

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

  13. Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

    Science.gov (United States)

    Rinfray, Corentin; Izzet, Guillaume; Pinson, Jean; Gam Derouich, Sarra; Ganem, Jean-Jacques; Combellas, Catherine; Kanoufi, Frédéric; Proust, Anna

    2013-10-04

    Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\\rm N}{{+\\hfill \\atop 2\\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electronic-excitation energy transfer in heterogeneous dye solutions under laser excitation

    International Nuclear Information System (INIS)

    Levshin, L.V.; Mukushev, B.T.; Saletskii, A.M.

    1995-01-01

    An experimental study has been made of electronic-excitation energy transfer (EEET) among dye molecules of different types for different exciting-fight wavelengths and temperatures. Upon selective laser excitation of the donor, the inhomogeneous broadening of molecular levels increases the probability of EEET from the donor to acceptor molecules. The efficiency of this process is directly proportional to the acceptor molecule concentration and is temperature dependent. The EEET is accompanied by the spectral migration of energy among donor molecules, which reduces the fluorescence quantum efficiency of the donor. Increasing the frequency of the exciting light decreases in the donor fluorescence quantum efficiency. An increase in the acceptor molecule concentration results in a decrease of the spectral migration of excitation in the donor molecule system. 5 refs., 5 figs

  15. Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

    International Nuclear Information System (INIS)

    Zhang, Yan; Hao, Huilian; Wang, Linlin

    2016-01-01

    Highlights: • Different morphologies of ERGO on the surface of GCE were prepared via different methods. • The defect densities of ERGO were controlled by tuning the mass or concentration of GO. • A higher defect density of ERGO accelerates electron transfer rate. • ERGO with more exposed edge planes shows significantly higher electron transfer kinetics. • Both edge planes and defect density contribute to electron transfer of ERGO. - Abstract: Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k"0) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k"0 values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k"0 valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

  16. Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan, E-mail: yanzhang@sues.edu.cn [School of Material Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China); Hao, Huilian, E-mail: huilian.hao@sues.edu.cn [School of Material Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China); Wang, Linlin, E-mail: wlinlin@mail.ustc.edu.cn [College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China)

    2016-12-30

    Highlights: • Different morphologies of ERGO on the surface of GCE were prepared via different methods. • The defect densities of ERGO were controlled by tuning the mass or concentration of GO. • A higher defect density of ERGO accelerates electron transfer rate. • ERGO with more exposed edge planes shows significantly higher electron transfer kinetics. • Both edge planes and defect density contribute to electron transfer of ERGO. - Abstract: Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k{sup 0}) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k{sup 0} values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k{sup 0} valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

  17. Properties of the transfer matrices of deflecting magnet systems for free electron laser

    International Nuclear Information System (INIS)

    Takao, Masaru

    1993-01-01

    The oscillation of the free electron laser (FEL) requires the high current and low emittance electron beam. The beam transport system should be achromatic and isochronous to preserve the brightness and the emittance of the electron beam. In this paper we clarify the algebraic properties of the transfer matrices of the magnetic deflection system, which is a key component in the beam transport line. (author)

  18. A how-to approach for a 3D simulation of charge transfer characteristics in a gas electron multiplier (GEM)

    CERN Document Server

    Sharma, A

    1999-01-01

    In this paper a detailed description of how to simulate charge transfer processes in a gaseous device is presented, taking the gas electron multiplier (GEM) as an example. A 3-dimensional simulation of the electric field and avalanche is performed. Results on charge transport are compared to experiment and agree within experimental errors; the avalanche mechanism and positive ion feedback are studied. The procedures used in the simulation are described in detail, and program scripts are appended. (15 refs).

  19. Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer

    Science.gov (United States)

    Tiwari, Vivek; Jonas, David M.

    2018-02-01

    Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Förster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a

  20. Three-dimensional hollow graphene efficiently promotes electron transfer of Ag3PO4 for photocatalytically eliminating phenol

    Science.gov (United States)

    Song, Shaoqing; Meng, Aiyun; Jiang, Shujuan; Cheng, Bei

    2018-06-01

    The effective transport of photo-induced carriers over semiconductor photocatalyst is critical for enhancing the photocatalytic performance under light excitation. Although oxidized graphene (GO) and/or reduced graphene oxide (rGO) has been used as cocatalyst to promote the transfer and utilization of electrons, however, random diffusion and transfer of photo-induced charges are inevitable from all sides over these actual graphene owing to the limitation of the preparation process and theory. Herein, we utilized three-dimensional hollow carbon graphene (HCG) to promote the efficient electron transfer of Ag3PO4 in the photocatalytic process. Owing to the confinement-induced electron field of HCG, the constructed HCG-Ag3PO4 photocatalytic system demonstrated the enhanced visible-light adsorption, improved transfer of photo-induced charges, and suitable redox potentials as revealed by transient photo-current spectroscopic, surface photovoltage spectroscopy, and electron paramagnetic resonance (EPR). EPR spectra of oxygen species and gas chromatography-mass spectra exhibited high efficiency activity over HCG-Ag3PO4 with Z-scheme photocatalytic mechanism for phenol decomposition by reaction between hexanoic acid and radOH and radO2-. It is noteworthy that photocatalytic performance over optimal HCG-Ag3PO4 is 6, 3.43, 1.92 times of pristine Ag3PO4, GO-Ag3PO4, and rGO-Ag3PO4, respectively. The results may supply a novel perspective to enhance transfer of photo-induced charges for the promotion of photocatalytic technology.

  1. The modification of glassy carbon and gold electrodes with aryl diazonium salt: The impact of the electrode materials on the rate of heterogeneous electron transfer

    International Nuclear Information System (INIS)

    Liu Guozhen; Liu Jingquan; Boecking, Till; Eggers, Paul K.; Gooding, J. Justin

    2005-01-01

    The heterogeneous electron-transfer properties of ferrocenemethylamine coupled to a series of mixed 4-carboxyphenyl/phenyl monolayers on glassy carbon (GC) and gold electrodes were investigated, by cyclic voltammetry, in aqueous buffer solutions. The electrodes were derivatized in a step-wise process. Electrochemical reduction of mixtures of 4-carboxyphenyl and phenyl diazonium salts on the electrode surfaces yielded stable monolayers. The introduction of carboxylic acid moieties onto the surfaces was verified by X-ray photoelectron spectroscopy. Subsequently the 4-carboxyphenyl moieties were activated using water-soluble carbodiimide and N-hydroxysuccinimide and reacted with ferrocenemethylamine. The rate constants of electron transfer through the monolayer systems were determined from cyclic voltammograms using the Marcus theory for electron transfer and were found to be an order of magnitude higher for the ferrocene-modified monolayer systems on gold than those on GC electrodes. The results suggest the electrode material has an important influence on the rate of electron transfer

  2. Designed Surface Residue Substitutions in [NiFe] Hydrogenase that Improve Electron Transfer Characteristics

    Directory of Open Access Journals (Sweden)

    Isaac T. Yonemoto

    2015-01-01

    Full Text Available Photobiological hydrogen production is an attractive, carbon-neutral means to convert solar energy to hydrogen. We build on previous research improving the Alteromonas macleodii “Deep Ecotype” [NiFe] hydrogenase, and report progress towards creating an artificial electron transfer pathway to supply the hydrogenase with electrons necessary for hydrogen production. Ferredoxin is the first soluble electron transfer mediator to receive high-energy electrons from photosystem I, and bears an electron with sufficient potential to efficiently reduce protons. Thus, we engineered a hydrogenase-ferredoxin fusion that also contained several other modifications. In addition to the C-terminal ferredoxin fusion, we truncated the C-terminus of the hydrogenase small subunit, identified as the available terminus closer to the electron transfer region. We also neutralized an anionic patch surrounding the interface Fe-S cluster to improve transfer kinetics with the negatively charged ferredoxin. Initial screening showed the enzyme tolerated both truncation and charge neutralization on the small subunit ferredoxin-binding face. While the enzyme activity was relatively unchanged using the substrate methyl viologen, we observed a marked improvement from both the ferredoxin fusion and surface modification using only dithionite as an electron donor. Combining ferredoxin fusion and surface charge modification showed progressively improved activity in an in vitro assay with purified enzyme.

  3. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    KAUST Repository

    Li, Jingrui

    2015-07-29

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  4. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    KAUST Repository

    Li, Jingrui; Li, Hong; Winget, Paul; Bredas, Jean-Luc

    2015-01-01

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  5. Charge Transfer Processes in Collisions of Si4+ Ions with He Atoms at Intermediate Energies

    Science.gov (United States)

    Suzuki, R.; Watanabe, A.; Sato, H.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Kimura, M.; Stancil, P. C.

    Charge transfer in collisions of Si4+ ions with He atoms below 100 keV/u is studied by using a molecular orbital representation within both the semiclassical and quantal representations. Single transfer reaction Si4++He →Si3++He+ has been studied by a number of theoretical investigations. In addition to the reaction (1), the first semiclassical MOCC calculations are performed for the double transfer channel Si4++HE→Si2++He2+ Nine molecular states that connect both with single and double electron transfer processes are considered in the present model. Electronic states and corresponding couplings are determined by the multireference single- and double- excitation configuration interaction method. The present cross sections tie well with the earlier calculations of Stancil et al., Phys. Rev. A 55, 1064 (1997) at lower energies, but show a rather different magnitude from those of Bacchus-Montabonel and Ceyzeriat, Phys. Rev. A 58, 1162 (1998). The present rate constant is found to be significantly different from the experimental finding of Fang and Kwong, Phys. Rev. A 59, 342 (1996) at 4,600 K, and hence does not support the experiment.

  6. Carbon nanoparticle stabilised liquid|liquid micro-interfaces for electrochemically driven ion-transfer processes

    International Nuclear Information System (INIS)

    MacDonald, Stuart M.; Fletcher, Paul D.I.; Cui Zhenggang; Opallo, Marcin; Chen Jingyuan; Marken, Frank

    2007-01-01

    Stabilised liquid|liquid interfaces between an organic 4-(3-phenylpropyl)-pyridine (PPP) phase and an aqueous electrolyte phase are obtained in the presence of suitable nanoparticles. The use of nanoparticulate stabilisers (ca. 30 nm diameter laponite or 9-18 nm diameter carbon) in 'Pickering' emulsion systems allows stable organic microdroplets to be formed and these are readily deposited onto conventional tin-doped indium oxide (ITO) electrodes. In contrast to the electrically insulating laponite nanoparticles, conducting carbon nanoparticles are shown to effectively catalyse the simultaneous electron transfer and ion transfer process at triple phase boundary junctions. Anion transfer processes between the aqueous and organic phase are driven electrochemically at the extensive triple phase junction carbon nanoparticle|4-(3-phenylpropyl)-pyridine|aqueous electrolyte. The organic phase consists of a redox active reagent 5,10,15,20-tetraphenyl-21H,23H-porphinato manganese(III) (MnTPP + ), 5,10,15,20-tetraphenyl-21H,23H-porphinato iron(III) (FeTPP + ), or proto-porphyrinato-IX iron(III) (hemin) dissolved in 4-(3-phenylpropyl)-pyridine (PPP). The composition of the aqueous electrolyte phase determines the reversible potential for the Nernstian anion transfer process. The methodology is shown to be versatile and, in future, could be applied more generally in liquid|liquid electroanalysis

  7. Femtosecond dynamics of electron transfer in a neutral organic mixed-valence compound

    International Nuclear Information System (INIS)

    Maksimenka, Raman; Margraf, Markus; Koehler, Juliane; Heckmann, Alexander; Lambert, Christoph; Fischer, Ingo

    2008-01-01

    In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 x 10 12 s -1 in benzonitrile through 8.3 x 10 11 s -1 in MTBE, around 1.6 x 10 11 s -1 in dibutylether and toluene and to 3.8 x 10 9 s -1 in n-hexane

  8. Electron transfer capacity dependence of quinone-mediated Fe(III) reduction and current generation by Klebsiella pneumoniae L17.

    Science.gov (United States)

    Li, Xiaomin; Liu, Liang; Liu, Tongxu; Yuan, Tian; Zhang, Wei; Li, Fangbai; Zhou, Shungui; Li, Yongtao

    2013-06-01

    Quinone groups in exogenous electron shuttles can accelerate extracellular electron transfer (EET) from bacteria to insoluble terminal electron acceptors, such as Fe(III) oxides and electrodes, which are important in biogeochemical redox processes and microbial electricity generation. However, the relationship between quinone-mediated EET performance and electron-shuttling properties of the quinones remains incompletely characterized. This study investigates the effects of a series of synthetic quinones (SQs) on goethite reduction and current generation by a fermenting bacterium Klebsiella pneumoniae L17. In addition, the voltammetric behavior and electron transfer capacities (ETCs) of SQ, including electron accepting (EAC) and donating (EDC) capacities, is also examined using electrochemical methods. The results showed that SQ can significantly increase both the Fe(III) reduction rates and current outputs of L17. Each tested SQ reversibly accepted and donated electrons as indicated by the cyclic voltammograms. The EAC and EDC results showed that Carmine and Alizarin had low relative capacities of electron transfer, whereas 9,10-anthraquinone-2,6-disulfonic acid (AQDS), 2-hydroxy-1,4-naphthoquinone (2-HNQ), and 5-hydroxy-1,4-naphthoquinone (5-HNQ) showed stronger relative ETC, and 9,10-anthraquinone-2-carboxylic acid (AQC) and 9,10-anthraquinone-2-sulfonic acid (AQS) had high relative ETC. Enhancement of microbial goethite reduction kinetics and current outputs by SQ had a good linear relationship with their ETC, indicating that the effectiveness of quinone-mediated EET may be strongly dependent on the ETC of the quinones. Therefore, the presence of quinone compounds and fermenting microorganisms may increase the diversity of microbial populations that contribute to element transformation in natural environments. Moreover, ETC determination of different SQ would help to evaluate their performance for microbial EET under anoxic conditions. Copyright © 2013 Elsevier

  9. Localized electron transfer rates and microelectrode-based enrichment of microbial communities within a phototrophic microbial mat

    Directory of Open Access Journals (Sweden)

    Jerome eBabauta

    2014-01-01

    Full Text Available Phototrophic microbial mats frequently exhibit sharp, light-dependent redox gradients that regulate microbial respiration on specific electron acceptors as a function of depth. In this work, a benthic phototrophic microbial mat from Hot Lake, a hypersaline, epsomitic lake located near Oroville in north-central Washington, was used to develop a microscale electrochemical method to study local electron transfer processes within the mat. To characterize the physicochemical variables influencing electron transfer, we initially quantified redox potential, pH and dissolved oxygen gradients by depth in the mat under photic and aphotic conditions. We further demonstrated that power output of a mat fuel cell was light-dependent. To study local electron transfer processes, we deployed a microscale electrode (microelectrode with tip size ~20 µm. To enrich a subset of microorganisms capable of interacting with the microelectrode, we anodically polarized the microelectrode in the mat. Subsequently, to characterize the microelectrode-associated community and compare it to the neighboring mat community, we performed amplicon sequencing of the V1-V3 region of the 16S gene. Differences in Bray-Curtis beta diversity, illustrated by large changes in relative abundance at the phylum level, suggested successful enrichment of specific mat community members on the microelectrode surface. The microelectrode-associated community exhibited substantially reduced alpha diversity and elevated relative abundances of Prosthecochloris, Loktanella, Catellibacterium, other unclassified members of Rhodobacteraceae, Thiomicrospira, and Limnobacter, compared with the community at an equivalent depth in the mat. Our results suggest that local electron transfer to an anodically polarized microelectrode selected for a specific microbial population, with substantially more abundance and diversity of sulfur-oxidizing phylotypes compared with the neighboring mat community.

  10. Localized electron transfer rates and microelectrode-based enrichment of microbial communities within a phototrophic microbial mat.

    Science.gov (United States)

    Babauta, Jerome T; Atci, Erhan; Ha, Phuc T; Lindemann, Stephen R; Ewing, Timothy; Call, Douglas R; Fredrickson, James K; Beyenal, Haluk

    2014-01-01

    Phototrophic microbial mats frequently exhibit sharp, light-dependent redox gradients that regulate microbial respiration on specific electron acceptors as a function of depth. In this work, a benthic phototrophic microbial mat from Hot Lake, a hypersaline, epsomitic lake located near Oroville in north-central Washington, was used to develop a microscale electrochemical method to study local electron transfer processes within the mat. To characterize the physicochemical variables influencing electron transfer, we initially quantified redox potential, pH, and dissolved oxygen gradients by depth in the mat under photic and aphotic conditions. We further demonstrated that power output of a mat fuel cell was light-dependent. To study local electron transfer processes, we deployed a microscale electrode (microelectrode) with tip size ~20 μm. To enrich a subset of microorganisms capable of interacting with the microelectrode, we anodically polarized the microelectrode at depth in the mat. Subsequently, to characterize the microelectrode-associated community and compare it to the neighboring mat community, we performed amplicon sequencing of the V1-V3 region of the 16S gene. Differences in Bray-Curtis beta diversity, illustrated by large changes in relative abundance at the phylum level, suggested successful enrichment of specific mat community members on the microelectrode surface. The microelectrode-associated community exhibited substantially reduced alpha diversity and elevated relative abundances of Prosthecochloris, Loktanella, Catellibacterium, other unclassified members of Rhodobacteraceae, Thiomicrospira, and Limnobacter, compared with the community at an equivalent depth in the mat. Our results suggest that local electron transfer to an anodically polarized microelectrode selected for a specific microbial population, with substantially more abundance and diversity of sulfur-oxidizing phylotypes compared with the neighboring mat community.

  11. Nanoscale and single-molecule interfacial electron transfer

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Wackerbarth, Hainer; Nielsen, Jens Ulrik

    2003-01-01

    for comprehensive later theoretical work and data interpretation in many areas of chemistry, electrochemistry, and biology. We discuss here some new areas of theoretical electrochemical ET science, with focus on nanoscale electrochemical and bioelectrochemical sciences. Particular attention is given to in situ...... scanning tunneling microscopy (STM) and single-electron tunneling (SET, or Coulomb blockade) in electrochemical. systems directly in aqueous electrolyte solution and at room temperature. We illustrate the new theoretical formalism and its perspectives by recent cases of electrochemical SET, negative...... differential resistance patterns, and by ET dynamics of organized assemblies of biological macromolecules, such as redox metalloproteins and oligonucleotides on single-crystal Au(III)-electrode surfaces....

  12. Correlation between biological activity and electron transferring of bovine liver catalase: Osmolytes effects

    International Nuclear Information System (INIS)

    Tehrani, H. Sepasi; Moosavi-Movahedi, A.A.; Ghourchian, H.

    2013-01-01

    Highlights: • Proline increases ET in Bovine Liver Catalase (BLC) whereas histidine decreases it. • Proline also increased the biological activity, whereas histidine decreased it. • Electron transferring and biological activity for BLC are directly correlated. • Proline causes favorable ET for BLC shown by positive E 1/2 (E°′) and negative ΔG. • Histidine makes ET unfavorable for BLC, manifested by E 1/2 (E°′) 0. -- Abstract: Catalase is a crucial antioxidant enzyme that protects life against detrimental effects of H 2 O 2 by disproportionating it into water and molecular oxygen. Effect of proline as a compatible and histidine as a non compatible osmolyte on the electron transferring and midpoint potential of catalase has been investigated. Proline increases the midpoint potential (ΔE m > 0), therefore causing the ΔG ET to be less positive and making the electron transfer reaction more facile whereas histidine decreases the E m (ΔE m ET , thereby rendering the electron transfer reaction less efficient. These results indicate the inhibitory effect of histidine evident by a −37% decrease in the cathodic peak current compared to 16% increase in the case of proline indicative of activation. The insight paves the tedious way towards our ultimate goal of elucidating a correlation between biological activity and electron transferring

  13. Imaging the Ultrafast Photoelectron Transfer Process in Alizarin-TiO2

    Directory of Open Access Journals (Sweden)

    Tatiana Gomez

    2015-07-01

    Full Text Available In this work, we adopt a quantum mechanical approach based on time-dependent density functional theory (TDDFT to study the optical and electronic properties of alizarin supported on TiO2 nano-crystallites, as a prototypical dye-sensitized solar cell. To ensure proper alignment of the donor (alizarin and acceptor (TiO2 nano-crystallite levels, static optical excitation spectra are simulated using time-dependent density functional theory in response. The ultrafast photoelectron transfer from the dye to the cluster is simulated using an explicitly time-dependent, one-electron TDDFT ansatz. The model considers the δ-pulse excitation of a single active electron localized in the dye to the complete set of energetically accessible, delocalized molecular orbitals of the dye/nano-crystallite complex. A set of quantum mechanical tools derived from the transition electronic flux density is introduced to visualize and analyze the process in real time. The evolution of the created wave packet subject to absorbing boundary conditions at the borders of the cluster reveal that, while the electrons of the aromatic rings of alizarin are heavily involved in an ultrafast charge redistribution between the carbonyl groups of the dye molecule, they do not contribute positively to the electron injection and, overall, they delay the process.

  14. An Electronic Structure Approach to Charge Transfer and Transport in Molecular Building Blocks for Organic Optoelectronics

    Science.gov (United States)

    Hendrickson, Heidi Phillips

    technological design and development. Time dependent perturbation theory, employed by non-equilibrium Green's function formalism, is utilized to study the effect of quantum coherences on electron transport and the effect of symmetry breaking on the electronic spectra of model molecular junctions. The fourth part of this thesis presents the design of a physical chemistry course based on a pedagogical approach called Writing-to-Teach. The nature of inaccuracies expressed in student-generated explanations of quantum chemistry topics, and the ability of a peer review process to engage these inaccuracies, is explored within this context.

  15. Electron accelerators for radiation processing: Criterions of selection and exploitation

    International Nuclear Information System (INIS)

    Zimek, Zbigniew

    2001-01-01

    The progress in accelerator technology is tightly attached to the continuously advanced development in many branches of technical activity. Although the present level of accelerators development can satisfy most of the commercial requirements, this field continues to expand and improve quality by offering efficient, cheap, reliable, high average beam power commercial units. Accelerator construction must be a compromised between size, efficiency and cost with respect to the field of its application. High power accelerators have been developed to meet specific demands of flue gas treatment and other high throughput to increase the capacity of the progress and reduced unit cost of operation. Automatic control, reliability and reduced maintenance, adequate adoption to process conditions, suitable electron energy and beam power are the basic features of modern accelerator construction. Accelerators have the potential to serve as industrial radiation sources and eventually may replace the isotope sources in future. Electron beam plants can transfer much higher amounts of energy into the irradiated objects than other types of facilities including gamma plants. This provides the opportunity to construct technological lines with high capacity that are more technically and economically suitable with high throughputs, short evidence time and grate versatility

  16. Process heat transfer principles, applications and rules of thumb

    CERN Document Server

    Serth, Robert W

    2014-01-01

    Process Heat Transfer is a reference on the design and implementation of industrial heat exchangers. It provides the background needed to understand and master the commercial software packages used by professional engineers in the design and analysis of heat exchangers. This book focuses on types of heat exchangers most widely used by industry: shell-and-tube exchangers (including condensers, reboilers and vaporizers), air-cooled heat exchangers and double-pipe (hairpin) exchangers. It provides a substantial introduction to the design of heat exchanger networks using pinch technology, the mos

  17. Isotope separation process by transfer of vibrational energy

    International Nuclear Information System (INIS)

    Angelie, C.; Cauchetier, M.; Paris, J.

    1983-01-01

    This process consists in exciting A molecules by absorption of a pulsed light beam, then in exciting until their dissociation X molecules, present in several isotopic forms, by a vibrational transfer between the A molecules and the X molecules, the A molecules having a dissociation energy greater than that of the X molecules, the duration and energy of the light pulses being such that the absorption time by the A molecules is less than the excitation time of the X molecules and the temperature conditions such that the thermal width of the vibration rays is at the most near the isotopic difference between the resonance rays of the two isotopic varieties [fr

  18. Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

    KAUST Repository

    Alsam, Amani Abdu

    2017-03-14

    Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

  19. Mediatorless electron transfer in glucose dehydrogenase/laccase system adsorbed on carbon nanotubes

    International Nuclear Information System (INIS)

    Ratautas, D.; Marcinkevičienė, L.; Meškys, R.; Kulys, J.

    2015-01-01

    Highlights: • Glucose dehydrogenase from Ewingella americana (GDH) demonstrated an effective mediatorless oxidation of glucose on single-walled carbon nanotubes (SWCNT). • Laccase from Trichaptum abietinum (LAC) exhibited mediatorless oxygen reduction when the enzyme was adsorbed on SWCNT. • Simultaneous adsorption of GDH and LAC on SWCNT formed an electron transfer chain in which glucose and lactose were oxidized by oxygen in mediatorless manner. - Abstract: A mediatorless electron transfer in the chain of glucose dehydrogenase (GDH) and laccase (LAC) catalysing the oxidation of glucose by molecular oxygen was studied. To demonstrate mediatorless processes, the GDH from Ewingella americana was adsorbed on single-walled carbon nanotubes (SWCNT). The effective mediatorless oxidation of glucose proceeded at 0.2–0.4 V vs. SCE. The electrode was most active at pH 6.1, and generated 0.8 mA cm −2 biocatalytic current in the presence of 50 mM glucose. The electrode showed a bell-shaped pH dependence with pK a values of 4.1 and 7.5. LAC from Trichaptum abietinum adsorbed on SWCNT exhibited mediatorless oxygen reduction at electrode potential less than 0.65 V. The electrode was most active at pH 3.0–4.0 and generated 1.1 mA cm −2 biocatalytic current in the presence of 0.254 mM oxygen, with an apparent pK a of 1.0 and 5.4. The electrodes prepared by simultaneous adsorption of GDH and LAC on SWCNT exhibited glucose oxidation at a potential higher than 0.25 V. The oxygen consumption in the chain was demonstrated using a Clark-type oxygen electrode. The dependence of oxygen consumption on glucose and lactose concentrations as well as activity of the system on pH were measured. A model of the pH dependence as well as mediatorless consecutive glucose oxidation with oxygen catalysed by LAC/GDH system is presented. This work provides a novel approach towards the synthesis of artificial multi enzyme systems by wiring oxidoreductases with SWCNT, and offers a better

  20. Preparation of high performance NBR/HNTs nanocomposites using an electron transferring interaction method

    Science.gov (United States)

    Yang, Shuyan; Zhou, Yanxue; Zhang, Peng; Cai, Zhuodi; Li, Yangping; Fan, Hongbo

    2017-12-01

    Interfacial interaction is one of the key factors to improve comprehensive properties of polymer/inorganic filler nanocomposites. In this work, a new interfacial interaction called electron transferring interaction is reported in the nitrile-butadiene rubber/halloysite nanotubes (NBR/HNTs) nanocomposites. The X-ray photoelectron spectroscopy (XPS) and in-situ controlling temperature Fourier transform infrared spectroscopy (FTIR) have confirmed that electrons of electron-rich -CN groups in NBR can transfer to the electron-deficiency aluminum atoms of HNTs, which packs a part of NBR molecules onto the surface of HNTs to form bound rubber and stabilize the homogeneous dispersion of HNTs with few agglomeration as revealed by scanning electron microscope (SEM) and dynamic mechanical analysis (DMA) performances, even at high HNTs addition, resulting in high light transmittance. The tensile strength of NBR/30wt%HNTs nanocomposites is about 291% higher than pure NBR, without sacrificing the elongation at break.