48 CFR 18.124 - Electronic funds transfer.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 48 Federal Acquisition Regulations System 1 2014-10-01 2014-10-01 false Electronic funds transfer. 18.124 Section 18.124 Federal Acquisition Regulations System FEDERAL ACQUISITION REGULATION... Electronic funds transfer. Electronic funds transfer payments may be waived for acquisitions to support...

Suppression of electron temperature gradient turbulence via negative magnetic shear in NSTX.

PubMed

Yuh, H Y; Kaye, S M; Levinton, F M; Mazzucato, E; Mikkelsen, D R; Smith, D R; Bell, R E; Hosea, J C; LeBlanc, B P; Peterson, J L; Park, H K; Lee, W

2011-02-04

Negative magnetic shear is found to suppress electron turbulence and improve electron thermal transport for plasmas in the National Spherical Torus Experiment (NSTX). Sufficiently negative magnetic shear results in a transition out of a stiff profile regime. Density fluctuation measurements from high-k microwave scattering are verified to be the electron temperature gradient (ETG) mode by matching measured rest frequency and linear growth rate to gyrokinetic calculations. Fluctuation suppression under negligible E×B shear conditions confirm that negative magnetic shear alone is sufficient for ETG suppression. Measured electron temperature gradients can significantly exceed ETG critical gradients with ETG mode activity reduced to intermittent bursts, while electron thermal diffusivity improves to below 0.1 electron gyro-Bohms.

Protein electron transfer: Dynamics and statistics

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2013-07-01

Electron transfer between redox proteins participating in energy chains of biology is required to proceed with high energetic efficiency, minimizing losses of redox energy to heat. Within the standard models of electron transfer, this requirement, combined with the need for unidirectional (preferably activationless) transitions, is translated into the need to minimize the reorganization energy of electron transfer. This design program is, however, unrealistic for proteins whose active sites are typically positioned close to the polar and flexible protein-water interface to allow inter-protein electron tunneling. The high flexibility of the interfacial region makes both the hydration water and the surface protein layer act as highly polar solvents. The reorganization energy, as measured by fluctuations, is not minimized, but rather maximized in this region. Natural systems in fact utilize the broad breadth of interfacial electrostatic fluctuations, but in the ways not anticipated by the standard models based on equilibrium thermodynamics. The combination of the broad spectrum of static fluctuations with their dispersive dynamics offers the mechanism of dynamical freezing (ergodicity breaking) of subsets of nuclear modes on the time of reaction/residence of the electron at a redox cofactor. The separation of time-scales of nuclear modes coupled to electron transfer allows dynamical freezing. In particular, the separation between the relaxation time of electro-elastic fluctuations of the interface and the time of conformational transitions of the protein caused by changing redox state results in dynamical freezing of the latter for sufficiently fast electron transfer. The observable consequence of this dynamical freezing is significantly different reorganization energies describing the curvature at the bottom of electron-transfer free energy surfaces (large) and the distance between their minima (Stokes shift, small). The ratio of the two reorganization energies

Protein electron transfer: Dynamics and statistics.

PubMed

Matyushov, Dmitry V

2013-07-14

Electron transfer between redox proteins participating in energy chains of biology is required to proceed with high energetic efficiency, minimizing losses of redox energy to heat. Within the standard models of electron transfer, this requirement, combined with the need for unidirectional (preferably activationless) transitions, is translated into the need to minimize the reorganization energy of electron transfer. This design program is, however, unrealistic for proteins whose active sites are typically positioned close to the polar and flexible protein-water interface to allow inter-protein electron tunneling. The high flexibility of the interfacial region makes both the hydration water and the surface protein layer act as highly polar solvents. The reorganization energy, as measured by fluctuations, is not minimized, but rather maximized in this region. Natural systems in fact utilize the broad breadth of interfacial electrostatic fluctuations, but in the ways not anticipated by the standard models based on equilibrium thermodynamics. The combination of the broad spectrum of static fluctuations with their dispersive dynamics offers the mechanism of dynamical freezing (ergodicity breaking) of subsets of nuclear modes on the time of reaction/residence of the electron at a redox cofactor. The separation of time-scales of nuclear modes coupled to electron transfer allows dynamical freezing. In particular, the separation between the relaxation time of electro-elastic fluctuations of the interface and the time of conformational transitions of the protein caused by changing redox state results in dynamical freezing of the latter for sufficiently fast electron transfer. The observable consequence of this dynamical freezing is significantly different reorganization energies describing the curvature at the bottom of electron-transfer free energy surfaces (large) and the distance between their minima (Stokes shift, small). The ratio of the two reorganization energies

Electronic coupling in long-range electron transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newton, M.D.

1996-12-31

One of the quantities crucial in controlling electron transfer (et) kinetics is the donor/acceptor electronic coupling integral (HDA). Recent theoretical models for HDA will be presented, and the results of ab initio computational implementation will be reported and analyzed for several metal-to-metal ligand charge transfer processes in complex molecular aggregates. New procedures for defining diabatic states, including a generalization of the Mulliken-Hush model, allow applications to optical and excited state as well as ground state et in a many-state framework.

Electron transfer across a thermal gradient

PubMed Central

Craven, Galen T.

2016-01-01

Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for monitoring temperature at high temporal and spatial resolution, imply the need for considering electron transfer across thermal gradients. Here, a theory is developed for the rate of electron transfer and the associated heat transport between donor–acceptor pairs located at sites of different temperatures. To this end, through application of a generalized multidimensional transition state theory, the traditional Arrhenius picture of activation energy as a single point on a free energy surface is replaced with a bithermal property that is derived from statistical weighting over all configurations where the reactant and product states are equienergetic. The flow of energy associated with the electron transfer process is also examined, leading to relations between the rate of heat exchange among the donor and acceptor sites as functions of the temperature difference and the electronic driving bias. In particular, we find that an open electron transfer channel contributes to enhanced heat transport between sites even when they are in electronic equilibrium. The presented results provide a unified theory for charge transport and the associated heat conduction between sites at different temperatures. PMID:27450086

Suppression of shot noise and spontaneous radiation in electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Litvinenko,V.

2009-08-23

Shot noise in the electron beam distribution is the main source of noise in high-gain FEL amplifiers, which may affect applications ranging from single- and multi-stage HGHG FELs to an FEL amplifier for coherent electron cooling. This noise also imposes a fundamental limit of about 10{sup 6} on FEL gain, after which SASE FELs saturate. There are several advantages in strongly suppressing this shot noise in the electron beam, and the corresponding spontaneous radiation. For more than a half-century, a traditional passive method has been used successfully in practical low-energy microwave electronic devices to suppress shot noise. Recently, it wasmore » proposed for this purpose in FELs. However, being passive, the method has some significant limitations and is hardly suitable for the highly inhomogeneous beams of modern high-gain FELs. I present a novel active method of suppressing, by many orders-of-magnitude, the shot noise in relativistic electron beams. I give a theoretical description of the process, and detail its fundamental limitation.« less

Hot-electron transfer in quantum-dot heterojunction films.

PubMed

Grimaldi, Gianluca; Crisp, Ryan W; Ten Brinck, Stephanie; Zapata, Felipe; van Ouwendorp, Michiko; Renaud, Nicolas; Kirkwood, Nicholas; Evers, Wiel H; Kinge, Sachin; Infante, Ivan; Siebbeles, Laurens D A; Houtepen, Arjan J

2018-06-13

Thermalization losses limit the photon-to-power conversion of solar cells at the high-energy side of the solar spectrum, as electrons quickly lose their energy relaxing to the band edge. Hot-electron transfer could reduce these losses. Here, we demonstrate fast and efficient hot-electron transfer between lead selenide and cadmium selenide quantum dots assembled in a quantum-dot heterojunction solid. In this system, the energy structure of the absorber material and of the electron extracting material can be easily tuned via a variation of quantum-dot size, allowing us to tailor the energetics of the transfer process for device applications. The efficiency of the transfer process increases with excitation energy as a result of the more favorable competition between hot-electron transfer and electron cooling. The experimental picture is supported by time-domain density functional theory calculations, showing that electron density is transferred from lead selenide to cadmium selenide quantum dots on the sub-picosecond timescale.

Defining Electron Bifurcation in the Electron-Transferring Flavoprotein Family.

PubMed

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

Electron bifurcation is the coupling of exergonic and endergonic redox reactions to simultaneously generate (or utilize) low- and high-potential electrons. It is the third recognized form of energy conservation in biology and was recently described for select electron-transferring flavoproteins (Etfs). Etfs are flavin-containing heterodimers best known for donating electrons derived from fatty acid and amino acid oxidation to an electron transfer respiratory chain via Etf-quinone oxidoreductase. Canonical examples contain a flavin adenine dinucleotide (FAD) that is involved in electron transfer, as well as a non-redox-active AMP. However, Etfs demonstrated to bifurcate electrons contain a second FAD in place of the AMP. To expand our understanding of the functional variety and metabolic significance of Etfs and to identify amino acid sequence motifs that potentially enable electron bifurcation, we compiled 1,314 Etf protein sequences from genome sequence databases and subjected them to informatic and structural analyses. Etfs were identified in diverse archaea and bacteria, and they clustered into five distinct well-supported groups, based on their amino acid sequences. Gene neighborhood analyses indicated that these Etf group designations largely correspond to putative differences in functionality. Etfs with the demonstrated ability to bifurcate were found to form one group, suggesting that distinct conserved amino acid sequence motifs enable this capability. Indeed, structural modeling and sequence alignments revealed that identifying residues occur in the NADH- and FAD-binding regions of bifurcating Etfs. Collectively, a new classification scheme for Etf proteins that delineates putative bifurcating versus nonbifurcating members is presented and suggests that Etf-mediated bifurcation is associated with surprisingly diverse enzymes. IMPORTANCE Electron bifurcation has recently been recognized as an electron transfer mechanism used by microorganisms to maximize

Defining Electron Bifurcation in the Electron-Transferring Flavoprotein Family

PubMed Central

Garcia Costas, Amaya M.; Poudel, Saroj; Miller, Anne-Frances; Schut, Gerrit J.; Ledbetter, Rhesa N.; Seefeldt, Lance C.; Adams, Michael W. W.

2017-01-01

ABSTRACT Electron bifurcation is the coupling of exergonic and endergonic redox reactions to simultaneously generate (or utilize) low- and high-potential electrons. It is the third recognized form of energy conservation in biology and was recently described for select electron-transferring flavoproteins (Etfs). Etfs are flavin-containing heterodimers best known for donating electrons derived from fatty acid and amino acid oxidation to an electron transfer respiratory chain via Etf-quinone oxidoreductase. Canonical examples contain a flavin adenine dinucleotide (FAD) that is involved in electron transfer, as well as a non-redox-active AMP. However, Etfs demonstrated to bifurcate electrons contain a second FAD in place of the AMP. To expand our understanding of the functional variety and metabolic significance of Etfs and to identify amino acid sequence motifs that potentially enable electron bifurcation, we compiled 1,314 Etf protein sequences from genome sequence databases and subjected them to informatic and structural analyses. Etfs were identified in diverse archaea and bacteria, and they clustered into five distinct well-supported groups, based on their amino acid sequences. Gene neighborhood analyses indicated that these Etf group designations largely correspond to putative differences in functionality. Etfs with the demonstrated ability to bifurcate were found to form one group, suggesting that distinct conserved amino acid sequence motifs enable this capability. Indeed, structural modeling and sequence alignments revealed that identifying residues occur in the NADH- and FAD-binding regions of bifurcating Etfs. Collectively, a new classification scheme for Etf proteins that delineates putative bifurcating versus nonbifurcating members is presented and suggests that Etf-mediated bifurcation is associated with surprisingly diverse enzymes. IMPORTANCE Electron bifurcation has recently been recognized as an electron transfer mechanism used by microorganisms to

75 FR 33681 - Electronic Fund Transfers

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-15

... FEDERAL RESERVE SYSTEM 12 CFR Part 205 [Regulation E; Docket No. R-1343] Electronic Fund Transfers June 4, 2010. AGENCY: Board of Governors of the Federal Reserve System. ACTION: Final rule; correction..., published on June 4, 2010 (75 FR 31665) make the following correction: PART 205--ELECTRONIC FUND TRANSFERS...

Tunneling induced electron transfer between separated protons

NASA Astrophysics Data System (ADS)

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.

Quantum tunneling resonant electron transfer process in Lorentzian plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Woo-Pyo; Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr; Department of Applied Physics and Department of Bionanotechnology, Hanyang University, Ansan, Kyunggi-Do 426-791

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 tunnelingmore » 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.« less

Two-Electron Transfer Pathways.

PubMed

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

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Boning; Liang, Min; Zmich, Nicole

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

Wu, Boning; Liang, Min; Zmich, Nicole; ...

2018-01-29

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Reactions of electron-transfer flavoprotein and electron-transfer flavoprotein: ubiquinone oxidoreductase.

PubMed Central

Ramsay, R R; Steenkamp, D J; Husain, M

1987-01-01

Electron-transfer flavoprotein:ubiquinone oxidoreductase (ETF-Q oxidoreductase) catalyses the re-oxidation of reduced electron-transfer flavoprotein (ETF) with ubiquinone-1 (Q-1) as the electron acceptor. A kinetic assay for the enzyme was devised in which glutaryl-CoA in the presence of glutaryl-CoA dehydrogenase was used to reduce ETFox. and the reduction of Q-1 was monitored at 275 nm. The partial reactions involved in the overall assay system were examined. Glutaryl-CoA dehydrogenase catalyses the rapid reduction of ETFox. to the anionic semiquinone (ETF.-), but reduces ETF.- to the fully reduced form (ETFhq) at a rate that is about 6-fold lower. ETF.-, but not ETFhq, is directly re-oxidized by Q-1 at a rate that, depending on the steady-state concentration of ETF.-, may contribute significantly to the overall reaction. ETF-Q oxidoreductase catalyses rapid disproportionation of ETF.- with an equilibrium constant of about 1.0 at pH 7.8. In the presence of Q-1 it also catalyses the re-oxidation of ETFhq at a rate that is faster than that of the overall reaction. Rapid-scan experiments indicated the formation of ETF.-, but its fractional concentration in the early stages of the re-oxidation of ETFhq is low. The data indicate that the re-oxidation of ETFhq proceeds at a rate that is adequate to account for the overall rate of electron transfer from glutaryl-CoA to Q-1. An unusual property of ETF-Q oxidoreductase seems to be that it not only catalyses the re-oxidation of the reduced forms of ETF but also facilitates the complete reduction of ETFox. to ETFhq by disproportionation of the radical. PMID:3593226

Analysis of shot noise suppression for electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratner, Daniel; Huang, Zhirong; Stupakov, Gennady

2011-06-24

Shot noise can affect the performance of free-electron lasers (FELs) by driving instabilities (e.g., the microbunching instability) or by competing with seeded density modulations. Recent papers have proposed suppressing shot noise to enhance FEL performance. In this paper we use a onedimensional (1D) model to calculate the noise amplification from an energy modulation (e.g., electron interactions from space charge or undulator radiation) followed by a dispersive section. We show that, for a broad class of interactions, selecting the correct dispersive strength suppresses shot noise across a wide range of frequencies. The final noise level depends on the beam’s energy spreadmore » and the properties of the interaction potential. As a result, we confirm and illustrate our analytical results with 1D simulations.« less

Analysis of Shot Noise Suppression for Electron Beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratner, Daniel; /Stanford U., Appl. Phys. Dept.; Huang, Zhirong

2012-05-07

Shot noise can affect the performance of free-electron lasers (FELs) by driving instabilities (e.g., the microbunching instability) or by competing with seeded density modulations. Recent papers have proposed suppressing shot noise to enhance FEL performance. In this paper we use a one-dimensional (1D) model to calculate the noise amplification from an energy modulation (e.g., electron interactions from space charge or undulator radiation) followed by a dispersive section. We show that, for a broad class of interactions, selecting the correct dispersive strength suppresses shot noise across a wide range of frequencies. The final noise level depends on the beam's energy spreadmore » and the properties of the interaction potential. We confirm and illustrate our analytical results with 1D simulations.« less

Electronic Transfer of School Records.

ERIC Educational Resources Information Center

Yeagley, Raymond

2001-01-01

Describes the electronic transfer of student records, notably the use of a Web-server named CHARLOTTE sponsored by the National Forum on Education Statistics and an Electronic Data Exchange system named SPEEDE/ExPRESS. (PKP)

Trap-state-dominated suppression of electron conduction in carbon nanotube thin-film transistors.

PubMed

Qian, Qingkai; Li, Guanhong; Jin, Yuanhao; Liu, Junku; Zou, Yuan; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2014-09-23

The often observed p-type conduction of single carbon nanotube field-effect transistors is usually attributed to the Schottky barriers at the metal contacts induced by the work function differences or by the doping effect of the oxygen adsorption when carbon nanotubes are exposed to air, which cause the asymmetry between electron and hole injections. However, for carbon nanotube thin-film transistors, our contrast experiments between oxygen doping and electrostatic doping demonstrate that the doping-generated transport barriers do not introduce any observable suppression of electron conduction, which is further evidenced by the perfect linear behavior of transfer characteristics with the channel length scaling. On the basis of the above observation, we conclude that the environmental adsorbates work by more than simply shifting the Fermi level of the CNTs; more importantly, these adsorbates cause a poor gate modulation efficiency of electron conduction due to the relatively large trap state density near the conduction band edge of the carbon nanotubes, for which we further propose quantitatively that the adsorbed oxygen-water redox couple is responsible.

31 CFR 208.3 - Payment by electronic funds transfer.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false Payment by electronic funds transfer... DISBURSEMENTS § 208.3 Payment by electronic funds transfer. Subject to § 208.4, and notwithstanding any other... electronic funds transfer. ...

31 CFR 208.3 - Payment by electronic funds transfer.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 2 2012-07-01 2012-07-01 false Payment by electronic funds transfer... DISBURSEMENTS § 208.3 Payment by electronic funds transfer. Subject to § 208.4, and notwithstanding any other... electronic funds transfer. ...

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

PubMed

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.

Ultrafast direct electron transfer at organic semiconductor and metal interfaces.

PubMed

Xiang, Bo; Li, Yingmin; Pham, C Huy; Paesani, Francesco; Xiong, Wei

2017-11-01

The ability to control direct electron transfer can facilitate the development of new molecular electronics, light-harvesting materials, and photocatalysis. However, control of direct electron transfer has been rarely reported, and the molecular conformation-electron dynamics relationships remain unclear. We describe direct electron transfer at buried interfaces between an organic polymer semiconductor film and a gold substrate by observing the first dynamical electric field-induced vibrational sum frequency generation (VSFG). In transient electric field-induced VSFG measurements on this system, we observe dynamical responses (<150 fs) that depend on photon energy and polarization, demonstrating that electrons are directly transferred from the Fermi level of gold to the lowest unoccupied molecular orbital of organic semiconductor. Transient spectra further reveal that, although the interfaces are prepared without deliberate alignment control, a subensemble of surface molecules can adopt conformations for direct electron transfer. Density functional theory calculations support the experimental results and ascribe the observed electron transfer to a flat-lying polymer configuration in which electronic orbitals are found to be delocalized across the interface. The present observation of direct electron transfer at complex interfaces and the insights gained into the relationship between molecular conformations and electron dynamics will have implications for implementing novel direct electron transfer in energy materials.

14 CFR 1274.931 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.931 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods July 2002 Payments under this...

14 CFR 1274.931 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.931 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods July 2002 Payments under this...

The influence of dielectric relaxation on intramolecular electron transfer

NASA Astrophysics Data System (ADS)

Heitele, H.; Michel-Beyerle, M. E.; Finckh, P.

1987-07-01

An unusually strong temperature dependence on the intramolecular electron-transfer rate has been observed for bridged donor-acceptor compounds in propylene glycol solution. In the frame of recent electron-transfer theories this effect reflects the influence of dielectric relaxation dynamics on electron transfer. With increasing dielectric relaxation time a smooth transition from non-adiabatic to solvent-controlled adiabatic behaviour is observed. The electron transfer rate in the solvent-controlled adiabatic limit is dominated by an inhomogeneous distribution of relaxation times.

Estimates of electronic coupling for excess electron transfer in DNA

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.

2005-07-01

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31G* and extended 6-31++G** basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack.

77 FR 40459 - Electronic Fund Transfers (Regulation E); Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-10

... Electronic Fund Transfers (Regulation E); Correction AGENCY: Bureau of Consumer Financial Protection. ACTION... published the Final Rule (77 FR 6194), which implements the Electronic Fund Transfer Act, and the official... Sec. 1005.3(a) in the interim final rule, Electronic Fund Transfers (Regulation E), published on...

14 CFR 1260.69 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS General Special Conditions § 1260.69 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods October 2000 (a) Payments under this grant will be made by the...

14 CFR 1260.69 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 14 Aeronautics and Space 5 2012-01-01 2012-01-01 false Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS General Special Conditions § 1260.69 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods October 2000 (a) Payments under this grant will be made by the...

14 CFR 1260.69 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Electronic funds transfer payment methods... COOPERATIVE AGREEMENTS General Special Conditions § 1260.69 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods October 2000 (a) Payments under this grant will be made by the...

Electron transfer from plastocyanin to photosystem I.

PubMed Central

Haehnel, W; Jansen, T; Gause, K; Klösgen, R B; Stahl, B; Michl, D; Huvermann, B; Karas, M; Herrmann, R G

1994-01-01

Mutant plastocyanins with Leu at position 10, 90 or 83 (Gly, Ala and Tyr respectively in wildtype) were constructed by site-specific mutagenesis of the spinach gene, and expressed in transgenic potato plants under the control of the authentic plastocyanin promoter, as well as in Escherichia coli as truncated precursor intermediates carrying the C-terminal 22 amino acid residues of the transit peptide, i.e. the thylakoid-targeting domain that acts as a bacterial export signal. The identity of the purified plastocyanins was verified by matrix-assisted laser desorption/ionization mass spectrometry. The formation of a complex between authentic or mutant spinach plastocyanin and isolated photosystem I and the electron transfer has been studied from the biphasic reduction kinetics of P700+ after excitation with laser flashes. The formation of the complex was abolished by the bulky hydrophobic group of Leu at the respective position of G10 or A90 which are part of the conserved flat hydrophobic surface around the copper ligand H87. The rate of electron transfer decreased by both mutations to < 20% of that found with wildtype plastocyanin. We conclude that the conserved flat surface of plastocyanin represents one of two crucial structural elements for both the docking at photosystem I and the efficient electron transfer via H87 to P700+. The Y83L mutant exhibited faster electron transfer to P700+ than did authentic plastocyanin. This proves that Y83 is not involved in electron transfer to P700 and suggests that electron transfer from cytochrome f and to P700 follows different routes in the plastocyanin molecule. Plastocyanin (Y83L) expressed in either E. coli or potato exhibited different isoelectric points and binding constants to photosystem I indicative of differences in the folding of the protein. The structure of the binding site at photosystem I and the mechanism of electron transfer are discussed. Images PMID:8131737

Structure of electron transfer flavoprotein-ubiquinone oxidoreductase and electron transfer to the mitochondrial ubiquinone pool

PubMed Central

Zhang, Jian; Frerman, Frank E.; Kim, Jung-Ja P.

2006-01-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a 4Fe4S flavoprotein located in the inner mitochondrial membrane. It catalyzes ubiquinone (UQ) reduction by ETF, linking oxidation of fatty acids and some amino acids to the mitochondrial respiratory chain. Deficiencies in ETF or ETF-QO result in multiple acyl-CoA dehydrogenase deficiency, a human metabolic disease. Crystal structures of ETF-QO with and without bound UQ were determined, and they are essentially identical. The molecule forms a single structural domain. Three functional regions bind FAD, the 4Fe4S cluster, and UQ and are closely packed and share structural elements, resulting in no discrete structural domains. The UQ-binding pocket consists mainly of hydrophobic residues, and UQ binding differs from that of other UQ-binding proteins. ETF-QO is a monotopic integral membrane protein. The putative membrane-binding surface contains an α-helix and a β-hairpin, forming a hydrophobic plateau. The UQ—flavin distance (8.5 Å) is shorter than the UQ—cluster distance (18.8 Å), and the very similar redox potentials of FAD and the cluster strongly suggest that the flavin, not the cluster, transfers electrons to UQ. Two possible electron transfer paths can be envisioned. First, electrons from the ETF flavin semiquinone may enter the ETF-QO flavin one by one, followed by rapid equilibration with the cluster. Alternatively, electrons may enter via the cluster, followed by equilibration between centers. In both cases, when ETF-QO is reduced to a two-electron reduced state (one electron at each redox center), the enzyme is primed to reduce UQ to ubiquinol via FAD. PMID:17050691

Structure of electron transfer flavoprotein-ubiquinone oxidoreductase and electron transfer to the mitochondrial ubiquinone pool.

PubMed

Zhang, Jian; Frerman, Frank E; Kim, Jung-Ja P

2006-10-31

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a 4Fe4S flavoprotein located in the inner mitochondrial membrane. It catalyzes ubiquinone (UQ) reduction by ETF, linking oxidation of fatty acids and some amino acids to the mitochondrial respiratory chain. Deficiencies in ETF or ETF-QO result in multiple acyl-CoA dehydrogenase deficiency, a human metabolic disease. Crystal structures of ETF-QO with and without bound UQ were determined, and they are essentially identical. The molecule forms a single structural domain. Three functional regions bind FAD, the 4Fe4S cluster, and UQ and are closely packed and share structural elements, resulting in no discrete structural domains. The UQ-binding pocket consists mainly of hydrophobic residues, and UQ binding differs from that of other UQ-binding proteins. ETF-QO is a monotopic integral membrane protein. The putative membrane-binding surface contains an alpha-helix and a beta-hairpin, forming a hydrophobic plateau. The UQ-flavin distance (8.5 A) is shorter than the UQ-cluster distance (18.8 A), and the very similar redox potentials of FAD and the cluster strongly suggest that the flavin, not the cluster, transfers electrons to UQ. Two possible electron transfer paths can be envisioned. First, electrons from the ETF flavin semiquinone may enter the ETF-QO flavin one by one, followed by rapid equilibration with the cluster. Alternatively, electrons may enter via the cluster, followed by equilibration between centers. In both cases, when ETF-QO is reduced to a two-electron reduced state (one electron at each redox center), the enzyme is primed to reduce UQ to ubiquinol via FAD.

Electron transfer between colloidal ZnO nanocrystals.

PubMed

Hayoun, Rebecca; Whitaker, Kelly M; Gamelin, Daniel R; Mayer, James M

2011-03-30

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.

Electron-transfer oxidation properties of DNA bases and DNA oligomers.

PubMed

Fukuzumi, Shunichi; Miyao, Hiroshi; Ohkubo, Kei; Suenobu, Tomoyoshi

2005-04-21

Kinetics for the thermal and photoinduced electron-transfer oxidation of a series of DNA bases with various oxidants having the known one-electron reduction potentials (E(red)) in an aqueous solution at 298 K were examined, and the resulting electron-transfer rate constants (k(et)) were evaluated in light of the free energy relationship of electron transfer to determine the one-electron oxidation potentials (E(ox)) of DNA bases and the intrinsic barrier of the electron transfer. Although the E(ox) value of GMP at pH 7 is the lowest (1.07 V vs SCE) among the four DNA bases, the highest E(ox) value (CMP) is only 0.19 V higher than that of GMP. The selective oxidation of GMP in the thermal electron-transfer oxidation of GMP results from a significant decrease in the pH dependent oxidation potential due to the deprotonation of GMP*+. The one-electron reduced species of the photosensitizer produced by photoinduced electron transfer are observed as the transient absorption spectra when the free energy change of electron transfer is negative. The rate constants of electron-transfer oxidation of the guanine moieties in DNA oligomers with Fe(bpy)3(3+) and Ru(bpy)3(3+) were also determined using DNA oligomers containing different guanine (G) sequences from 1 to 10 G. The rate constants of electron-transfer oxidation of the guanine moieties in single- and double-stranded DNA oligomers with Fe(bpy)3(2+) and Ru(bpy)3(3+) are dependent on the number of sequential guanine molecules as well as on pH.

Adoptively transferred immune T cells eradicate established tumors in spite of cancer-induced immune suppression

PubMed Central

Arina, Ainhoa; Schreiber, Karin; Binder, David C.; Karrison, Theodore; Liu, Rebecca B.; Schreiber, Hans

2014-01-01

Myeloid-derived CD11b+Gr1+ suppressor cells (MDSC) and tumor-associated macrophages (TAM) are considered a major obstacle for effective adoptive T cell therapy. Myeloid cells suppress naive T cell proliferation ex vivo and can prevent the generation of T cell responses in vivo. We find, however, that immune T cells adoptively transferred eradicate well-established tumors in the presence of MDSC and TAM which are strongly immunosuppressive ex vivo. These MDSC and TAM were comparable in levels and immunosuppression among different tumor models. Longitudinal microscopy of tumors in vivo revealed that after T cell transfer tumor vasculature and cancer cells disappeared simultaneously. During T-cell mediated tumor destruction, the tumor stroma contained abundant myeloid cells (mainly TAM) that retained their suppressive properties. Preimmunized but not naive mice resisted immune suppression caused by an unrelated tumor-burden supporting the idea that in vivo, myeloid immunosuppressive cells can suppress naive but not memory T cell responses. PMID:24367029

The iron-sulfur cluster of electron transfer flavoprotein-ubiquinone oxidoreductase is the electron acceptor for electron transfer flavoprotein.

PubMed

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

2008-08-26

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 and -30 mV for wild type to -11 and -19 mV, respectively. The N338A mutation decreased the potentials to -37 and -49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF 1e (-) 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.

The Iron-Sulfur Cluster of Electron Transfer Flavoprotein-Ubiquinone Oxidoreductase Is the Electron Acceptor for Electron Transfer Flavoprotein†

PubMed Central

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

2009-01-01

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 and -30 mV for wild type to -11 and -19 mV, respectively. The N338A mutation decreased the potentials to -37 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:9585549

Group transfer and electron transfer reactions of organometallic complexes

NASA Astrophysics Data System (ADS)

Atwood, Jim D.

During 1994, despite the disruptions, the authors have made progress in several aspects of their research on electron transfer reactions between organometallic complexes. This summary covers three areas that are relatively complete: (1) reactions between metal carbonyl anions and metal carbonyl halides, (2) reactions of hydrido- and alkyl-containing anions (RFe(CO)4(-) and RW(CO)5(-) with metal carbonyl cations; and (3) reactions of a seventeen-electron complex (Cp* Cr(CO)3*) with metal carbonyl derivatives. Two areas of examination that have just begun (possible carbene transfer and the possible role of metal carbonyl anions in carbon-hydrogen bond activation) will also be described.

Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Sotiriou, Georgios A.; Blattmann, Christoph O.; Deligiannakis, Yiannis

2015-12-01

Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon

The electron transfer flavoprotein: ubiquinone oxidoreductases.

PubMed

Watmough, Nicholas J; Frerman, Frank E

2010-12-01

Electron transfer flavoprotein: ubiqionone oxidoreductase (ETF-QO) is a component of the mitochondrial respiratory chain that together with electron transfer flavoprotein (ETF) forms a short pathway that transfers electrons from 11 different mitochondrial flavoprotein dehydrogenases to the ubiquinone pool. The X-ray structure of the pig liver enzyme has been solved in the presence and absence of a bound ubiquinone. This structure reveals ETF-QO to be a monotopic membrane protein with the cofactors, FAD and a [4Fe-4S](+1+2) cluster, organised to suggests that it is the flavin that serves as the immediate reductant of ubiquinone. ETF-QO is very highly conserved in evolution and the recombinant enzyme from the bacterium Rhodobacter sphaeroides has allowed the mutational analysis of a number of residues that the structure suggested are involved in modulating the reduction potential of the cofactors. These experiments, together with the spectroscopic measurement of the distances between the cofactors in solution have confirmed the intramolecular pathway of electron transfer from ETF to ubiquinone. This approach can be extended as the R. sphaeroides ETF-QO provides a template for investigating the mechanistic consequences of single amino acid substitutions of conserved residues that are associated with a mild and late onset variant of the metabolic disease multiple acyl-CoA dehydrogenase deficiency (MADD). Copyright © 2010 Elsevier B.V. All rights reserved.

Magnetization transfer contrast-suppressed imaging of amide proton transfer and relayed nuclear overhauser enhancement chemical exchange saturation transfer effects in the human brain at 7T.

PubMed

Xu, Xiang; Yadav, Nirbhay N; Zeng, Haifeng; Jones, Craig K; Zhou, Jinyuan; van Zijl, Peter C M; Xu, Jiadi

2016-01-01

To use the variable delay multipulse (VDMP) chemical exchange saturation transfer (CEST) approach to obtain clean amide proton transfer (APT) and relayed Nuclear Overhauser enhancement (rNOE) CEST images in the human brain by suppressing the conventional magnetization transfer contrast (MTC) and reducing the direct water saturation contribution. The VDMP CEST scheme consists of a train of RF pulses with a specific mixing time. The CEST signal with respect to the mixing time shows distinguishable characteristics for protons with different exchange rates. Exchange rate filtered CEST images are generated by subtracting images acquired at two mixing times at which the MTC signals are equal, while the APT and rNOE-CEST signals differ. Because the subtraction is performed at the same frequency offset for each voxel and the CEST signals are broad, no B0 correction is needed. MTC-suppressed APT and rNOE-CEST images of human brain were obtained using the VDMP method. The APT-CEST data show hyperintensity in gray matter versus white matter, whereas the rNOE-CEST images show negligible contrast between gray and white matter. The VDMP approach provides a simple and rapid way of recording MTC-suppressed APT-CEST and rNOE-CEST images without the need for B0 field correction. © 2015 Wiley Periodicals, Inc.

Using granular film to suppress charge leakage in a single-electron latch.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orlov, A. O.; Luo, X.; Yadavalli, K. K.

2008-01-01

A single-electron latch is a device that can be used as a building block for quantum-dot cellular automata circuits. It consists of three nanoscale metal 'dots' connected in series by tunnel junctions; charging of the dots is controlled by three electrostatic gates. One very important feature of a single-electron latch is its ability to store ('latch') information represented by the location of a single electron within the three dots. To obtain latching, the undesirable leakage of charge during the retention time must be suppressed. Previously, to achieve this goal, multiple tunnel junctions were used to connect the three dots. However,more » this method of charge leakage suppression requires an additional compensation of the background charges affecting each parasitic dot in the array of junctions. We report a single-electron latch where a granular metal film is used to fabricate the middle dot in the latch which concurrently acts as a charge leakage suppressor. This latch has no parasitic dots, therefore the background charge compensation procedure is greatly simplified. We discuss the origins of charge leakage suppression and possible applications of granular metal dots for various single-electron circuits.« less

Passive runaway electron suppression in tokamak disruptions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, H. M.; Helander, P.; Boozer, A. H.

2013-07-15

Runaway electrons created in disruptions pose a serious problem for tokamaks with large current. It would be desirable to have a runaway electron suppression method which is passive, i.e., a method that does not rely on an uncertain disruption prediction system. One option is to let the large electric field inherent in the disruption drive helical currents in the wall. This would create ergodic regions in the plasma and increase the runaway losses. Whether these regions appear at a suitable time and place to affect the formation of the runaway beam depends on disruption parameters, such as electron temperature andmore » density. We find that it is difficult to ergodize the central plasma before a beam of runaway current has formed. However, the ergodic outer region will make the Ohmic current profile contract, which can lead to instabilities that yield large runaway electron losses.« less

Coherent Electron Transfer at the Ag / Graphite Heterojunction Interface

NASA Astrophysics Data System (ADS)

Tan, Shijing; Dai, Yanan; Zhang, Shengmin; Liu, Liming; Zhao, Jin; Petek, Hrvoje

2018-03-01

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

A molecular shift register based on electron transfer

NASA Technical Reports Server (NTRS)

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.

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

PubMed Central

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

Real-time electron transfer in respiratory complex I

PubMed Central

Verkhovskaya, Marina L.; Belevich, Nikolai; Euro, Liliya; Wikström, Mårten; Verkhovsky, Michael I.

2008-01-01

Electron transfer in complex I from Escherichia coli was investigated by an ultrafast freeze-quench approach. The reaction of complex I with NADH was stopped in the time domain from 90 μs to 8 ms and analyzed by electron paramagnetic resonance (EPR) spectroscopy at low temperatures. The data show that after binding of the first molecule of NADH, two electrons move via the FMN cofactor to the iron–sulfur (Fe/S) centers N1a and N2 with an apparent time constant of ≈90 μs, implying that these two centers should have the highest redox potential in the enzyme. The rate of reduction of center N2 (the last center in the electron transfer sequence) is close to that predicted by electron transfer theory, which argues for the absence of coupled proton transfer or conformational changes during electron transfer from FMN to N2. After fast reduction of N1a and N2, we observe a slow, ≈1-ms component of reduction of other Fe/S clusters. Because all elementary electron transfer rates between clusters are several orders of magnitude higher than this observed rate, we conclude that the millisecond component is limited by a single process corresponding to dissociation of the oxidized NAD+ molecule from its binding site, where it prevents entry of the next NADH molecule. Despite the presence of approximately one ubiquinone per enzyme molecule, no transient semiquinone formation was observed, which has mechanistic implications, suggesting a high thermodynamic barrier for ubiquinone reduction to the semiquinone radical. Possible consequences of these findings for the proton translocation mechanism are discussed. PMID:18316732

Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

NASA Astrophysics Data System (ADS)

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.

14 CFR § 1260.69 - Electronic funds transfer payment methods.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 5 2014-01-01 2014-01-01 false Electronic funds transfer payment methods... GRANTS AND COOPERATIVE AGREEMENTS General Special Conditions § 1260.69 Electronic funds transfer payment methods. Electronic Funds Transfer Payment Methods October 2000 (a) Payments under this grant will be made...

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles.

PubMed

Tvrdy, Kevin; Frantsuzov, Pavel A; Kamat, Prashant V

2011-01-04

Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO(2), TiO(2), and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO(2)) were not the same as those which showed the highest photocurrent (TiO(2)). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency.

12 CFR 205.15 - Electronic fund transfer of government benefits.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 12 Banks and Banking 2 2011-01-01 2011-01-01 false Electronic fund transfer of government benefits. 205.15 Section 205.15 Banks and Banking FEDERAL RESERVE SYSTEM BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.15 Electronic fund transfer of government...

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

PubMed

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.

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

PubMed Central

Tvrdy, Kevin; Frantsuzov, Pavel A.; Kamat, Prashant V.

2011-01-01

Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO2, TiO2, and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO2) were not the same as those which showed the highest photocurrent (TiO2). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency. PMID:21149685

Anomalous single-electron transfer in common-gate quadruple-dot single-electron devices with asymmetric junction capacitances

NASA Astrophysics Data System (ADS)

Imai, Shigeru; Ito, Masato

2018-06-01

In this paper, anomalous single-electron transfer in common-gate quadruple-dot turnstile devices with asymmetric junction capacitances is revealed. That is, the islands have the same total number of excess electrons at high and low gate voltages of the swing that transfers a single electron. In another situation, two electrons enter the islands from the source and two electrons leave the islands for the source and drain during a gate voltage swing cycle. First, stability diagrams of the turnstile devices are presented. Then, sequences of single-electron tunneling events by gate voltage swings are investigated, which demonstrate the above-mentioned anomalous single-electron transfer between the source and the drain. The anomalous single-electron transfer can be understood by regarding the four islands as “three virtual islands and a virtual source or drain electrode of a virtual triple-dot device”. The anomalous behaviors of the four islands are explained by the normal behavior of the virtual islands transferring a single electron and the behavior of the virtual electrode.

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

NASA Astrophysics Data System (ADS)

Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

2017-12-01

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

Efficient Yttrium(III) Chloride-Treated TiO2 Electron Transfer Layers for Performance-Improved and Hysteresis-Less Perovskite Solar Cells.

PubMed

Li, Minghua; Huan, Yahuan; Yan, Xiaoqin; Kang, Zhuo; Guo, Yan; Li, Yong; Liao, Xinqin; Zhang, Ruxiao; Zhang, Yue

2018-01-10

Hybrid organic-inorganic metal halide perovskite solar cells have attracted widespread attention, owing to their high performance, and have undergone rapid development. In perovskite solar cells, the charge transfer layer plays an important role for separating and transferring photogenerated carriers. In this work, an efficient YCl 3 -treated TiO 2 electron transfer layer (ETL) is used to fabricate perovskite solar cells with enhanced photovoltaic performance and less hysteresis. The YCl 3 -treated TiO 2 layers bring about an upward shift of the conduction band minimum (E CBM ), which results in a better energy level alignment for photogenerated electron transfer and extraction from the perovskite into the TiO 2 layer. After optimization, perovskite solar cells based on the YCl 3 -treated TiO 2 layers achieve a maximum power conversion efficiency of about 19.99 % (19.29 % at forward scan) and a steady-state power output of about 19.6 %. Steady-state and time-resolved photoluminescence measurements and impedance spectroscopy are carried out to investigate the charge transfer and recombination dynamics between the perovskite and the TiO 2 electron transfer layer interface. The improved perovskite/TiO 2 ETL interface with YCl 3 treatment is found to separate and extract photogenerated charge rapidly and suppress recombination effectively, which leads to the improved performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical frequency shot-noise suppression in electron beams: Three-dimensional analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nause, A.; Dyunin, E.; Gover, A.

2010-05-15

A predicted effect of current shot-noise suppression at optical-frequencies in a drifting charged-particle-beam and the corresponding process of particles self-ordering are analyzed in a one-dimensional (1D) model and verified by three-dimensional numerical simulations. The analysis confirms the prediction of a 1D single mode Langmuir plasma wave model of longitudinal plasma oscillation in the beam, and it defines the regime of beam parameters in which this effect takes place. The suppression of relativistic beam shot noise can be utilized to enhance the coherence of free electron lasers and of any coherent radiation device using an electron beam.

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

PubMed Central

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

Extensive domain motion and electron transfer in the human electron transferring flavoprotein.medium chain Acyl-CoA dehydrogenase complex.

PubMed

Toogood, Helen S; van Thiel, Adam; Basran, Jaswir; Sutcliffe, Mike J; Scrutton, Nigel S; Leys, David

2004-07-30

The crystal structure of the human electron transferring flavoprotein (ETF).medium chain acyl-CoA dehydrogenase (MCAD) complex reveals a dual mode of protein-protein interaction, imparting both specificity and promiscuity in the interaction of ETF with a range of structurally distinct primary dehydrogenases. ETF partitions the functions of partner binding and electron transfer between (i) the recognition loop, which acts as a static anchor at the ETF.MCAD interface, and (ii) the highly mobile redox active FAD domain. Together, these enable the FAD domain of ETF to sample a range of conformations, some compatible with fast interprotein electron transfer. Disorders in amino acid or fatty acid catabolism can be attributed to mutations at the protein-protein interface. Crucially, complex formation triggers mobility of the FAD domain, an induced disorder that contrasts with general models of protein-protein interaction by induced fit mechanisms. The subsequent interfacial motion in the MCAD.ETF complex is the basis for the interaction of ETF with structurally diverse protein partners. Solution studies using ETF and MCAD with mutations at the protein-protein interface support this dynamic model and indicate ionic interactions between MCAD Glu(212) and ETF Arg alpha(249) are likely to transiently stabilize productive conformations of the FAD domain leading to enhanced electron transfer rates between both partners.

Proton-Coupled Electron Transfer in Artificial Photosynthetic Systems.

PubMed

Mora, S Jimena; Odella, Emmanuel; Moore, Gary F; Gust, Devens; Moore, Thomas A; Moore, Ana L

2018-02-20

Artificial photosynthetic constructs can in principle operate more efficiently than natural photosynthesis because they can be rationally designed to optimize solar energy conversion for meeting human demands rather than the multiple needs of an organism competing for growth and reproduction in a complex ecosystem. The artificial photosynthetic constructs described in this Account consist primarily of covalently linked synthetic chromophores, electron donors and acceptors, and proton donors and acceptors that carry out the light absorption, electron transfer, and proton-coupled electron transfer (PCET) processes characteristic of photosynthetic cells. PCET is the movement of an electron from one site to another accompanied by proton transfer. PCET and the transport of protons over tens of angstroms are important in all living cells because they are a fundamental link between redox processes and the establishment of transmembrane gradients of proton electrochemical potential, known as proton-motive force (PMF), which is the unifying concept in bioenergetics. We have chosen a benzimidazole phenol (BIP) system as a platform for the study of PCET because with appropriate substitutions it is possible to design assemblies in which one or multiple proton transfers can accompany oxidation of the phenol. In BIP, oxidation of the phenol increases its acidity by more than ten pK a units; thus, electrochemical oxidation of the phenol is associated with a proton transfer to the imidazole. This is an example of a PCET process involving transfer of one electron and one proton, known as electron-proton transfer (EPT). When the benzimidazole moiety of BIP is substituted at the 4-position with good proton acceptor groups such as aliphatic amines, experimental and theoretical results indicate that two proton transfers occur upon one-electron oxidation of the phenol. This phenomenon is described as a one-electron-two-proton transfer (E2PT) process and results in translocation of

Allotype suppression induced in the adoptive transfer system: the variables of the system and an apparent absence of a role for T cells.

PubMed

Lee, S K; Dresser, D W

1981-04-01

A study has been made of the variables concerned in allotype suppression of adult spleen cells in the adoptive transfer system. These are; SRBC (antigen) dose; the dose and timing of injection of anti-allotype serum IgG; the number of spleen cells transferred and whether these cells were taken from primed or unprimed donors. Adoptively transferred primed cells are considerably less susceptible to suppression by concomitantly injected anti-allotype serum IgG than are unprimed spleen cells. Injection of anti-allotype serum during the period after adoptive transfer, has shown that primed cells loose their susceptibility sooner (2 days) than the unprimed cells (4 days). Allotype heterozygous CBA spleen cells are less susceptible heterozygous CBA spleen cells are less susceptible to allotype suppression than either allotypically homozygous or heterozygous non-H-2k cells (H-2b,d, or s). Allotype suppression of the TI IgG response to DNP-Ficoll was measured 7 days after adoptive transfer of allotype-homozygous cells from both normal and nude CBA mice (unprimed). The results indicate that T cells do not play a role in the initiation of short-term allotype suppression in the adoptive transfer system.

Suppression of the sonic heat transfer limit in high-temperature heat pipes

NASA Astrophysics Data System (ADS)

Dobran, Flavio

1989-08-01

The design of high-performance heat pipes requires optimization of heat transfer surfaces and liquid and vapor flow channels to suppress the heat transfer operating limits. In the paper an analytical model of the vapor flow in high-temperature heat pipes is presented, showing that the axial heat transport capacity limited by the sonic heat transfer limit depends on the working fluid, vapor flow area, manner of liquid evaporation into the vapor core of the evaporator, and lengths of the evaporator and adiabatic regions. Limited comparisons of the model predictions with data of the sonic heat transfer limits are shown to be very reasonable, giving credibility to the proposed analytical approach to determine the effect of various parameters on the axial heat transport capacity. Large axial heat transfer rates can be achieved with large vapor flow cross-sectional areas, small lengths of evaporator and adiabatic regions or a vapor flow area increase in these regions, and liquid evaporation in the evaporator normal to the main flow.

The interaction of trimethylamine dehydrogenase and electron-transferring flavoprotein.

PubMed

Shi, Weiwei; Mersfelder, John; Hille, Russ

2005-05-27

The interaction between the physiological electron transfer partners trimethylamine dehydrogenase (TMADH) and electron-transferring flavoprotein (ETF) from Methylophilus methylotrophus has been examined with particular regard to the proposal that the former protein "imprints" a conformational change on the latter. The results indicate that the absorbance change previously attributed to changes in the environment of the FAD of ETF upon binding to TMADH is instead caused by electron transfer from partially reduced, as-isolated TMADH to ETF. Prior treatment of the as-isolated enzyme with the oxidant ferricenium essentially abolishes the observed spectral change. Further, when the semiquinone form of ETF is used instead of the oxidized form, the mirror image of the spectral change seen with as-isolated TMADH and oxidized ETF is observed. This is attributable to a small amount of electron transfer in the reverse of the physiological direction. Kinetic determination of the dissociation constant and limiting rate constant for electron transfer within the complex of (reduced) TMADH with (oxidized) ETF is reconfirmed and discussed in the context of a recently proposed model for the interaction between the two proteins that involves "structural imprinting" of ETF.

Improving Forest Wildfire Suppression Using Penetrating Reconnaissance And Real Time Data Transfer

NASA Astrophysics Data System (ADS)

Greer, Jerry D.

1990-02-01

The suppression of a wildfire is analogous to a combat action. Fires, like battles, spread fast and suppression forces must be highly mobile. The enemy, (in this case) the wildfire, is lethal in that it kills or destroys forces, equipment, and natural resources left in its path. The suppression action must be carried on day and night until the "enemy" is contained. Both air operations and ground forces are used. Just as in a combat situation, wildfire suppression forces need penetrating reconnaissance with real time data transfer. This paper presents a review of the current system of intelligence gathering on a wildfire where aerial observers, infrared detectors, and ground intelligence officers gather data and either radio or carry the data to the command center. It then attempts to show how some current military reconnaissance systems might be applied to wildfire control processes. The payoffs would include improved safety for both air and ground forces and faster containment of the wildfire which would reduce forest resources lost and decrease the total monetary cost of the containment action.

Modeling electron transfer in photosystem I.

PubMed

Makita, Hiroki; Hastings, Gary

2016-06-01

Nanosecond to millisecond time-resolved absorption spectroscopy has been used to study electron transfer processes in photosystem I particles from Synechocystis sp. PCC 6803 with eight different quinones incorporated into the A1 binding site, at both 298 and 77K. A detailed kinetic model was constructed and solved within the context of Marcus electron transfer theory, and it was found that all of the data could be well described only if the in situ midpoint potentials of the quinones fell in a tightly defined range. For photosystem I with phylloquinone incorporated into the A1 binding site all of the time-resolved optical data is best modeled when the in situ midpoint potential of phylloquinone on the A/B branch is -635/-690 mV, respectively. With the midpoint potential of the F(X) iron sulfur cluster set at -680 mV, this indicates that forward electron transfer from A(1)(-) to F(X) is slightly endergonic/exergonic on the A/B branch, respectively. Additionally, for forward electron transfer from A(1)(-) to F(X), on both the A and B branches the reorganization energy is close to 0.7 eV. Reorganization energies of 0.4 or 1.0 eV are not possible. For the eight different quinones incorporated, the same kinetic model was used, allowing us to establish in situ redox potentials for all of the incorporated quinones on both branches. A linear correlation was found between the in situ and in vitro midpoint potentials of the quinones on both branches. Copyright © 2016 Elsevier B.V. All rights reserved.

Extracellular electron transfer mechanisms between microorganisms and minerals.

PubMed

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

2016-10-01

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.

Reduction-Induced Suppression of Electron Flow (RISE) Is Relieved by Non-ATP-Consuming Electron Flow in Synechococcus elongatus PCC 7942.

PubMed

Shimakawa, Ginga; Shaku, Keiichiro; Miyake, Chikahiro

2018-01-01

Photosynthetic organisms oxidize P700 to suppress the production of reactive oxygen species (ROS) in photosystem I (PSI) in response to the lower efficiency of photosynthesis under high light and low CO 2 conditions. Previously, we found a positive relationship between reduction of plastoquinone (PQ) pool and oxidation of P700, which we named reduction-induced suppression of electron flow (RISE). In the RISE model, we proposed that the highly reduced state of the PQ pool suppresses Q-cycle turnover to oxidize P700 in PSI. Here, we tested whether RISE was relieved by the oxidation of the PQ pool, but not by the dissipation of the proton gradient (ΔpH) across the thylakoid membrane. Formation of ΔpH can also suppress electron flow to P700, because acidification on the luminal side of the thylakoid membrane lowers oxidation of reduced PQ in the cytochrome b 6 / f complex. We drove photosynthetic electron transport using H 2 O 2 -scavenging peroxidase reactions. Peroxidase reduces H 2 O 2 with electron donors regenerated along the photosynthetic electron transport system, thereby promoting the formation of ΔpH. Addition of H 2 O 2 to the cyanobacterium Synechococcus elongatus PCC 7942 under low CO 2 conditions induced photochemical quenching of chlorophyll fluorescence, enhanced NADPH fluorescence and reduced P700. Thus, peroxidase reactions relieved the RISE mechanism, indicating that P700 oxidation can be induced only by the reduction of PQ to suppress the production of ROS in PSI. Overall, our data suggest that RISE regulates the redox state of P700 in PSI in cooperation with ΔpH regulation.

A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

Shewanella secretes flavins that mediate extracellular electron transfer

PubMed Central

Marsili, Enrico; Baron, Daniel B.; Shikhare, Indraneel D.; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

2008-01-01

Bacteria able to transfer electrons to metals are key agents in biogeochemical metal cycling, subsurface bioremediation, and corrosion processes. More recently, these bacteria have gained attention as the transfer of electrons from the cell surface to conductive materials can be used in multiple applications. In this work, we adapted electrochemical techniques to probe intact biofilms of Shewanella oneidensis MR-1 and Shewanella sp. MR-4 grown by using a poised electrode as an electron acceptor. This approach detected redox-active molecules within biofilms, which were involved in electron transfer to the electrode. A combination of methods identified a mixture of riboflavin and riboflavin-5′-phosphate in supernatants from biofilm reactors, with riboflavin representing the dominant component during sustained incubations (>72 h). Removal of riboflavin from biofilms reduced the rate of electron transfer to electrodes by >70%, consistent with a role as a soluble redox shuttle carrying electrons from the cell surface to external acceptors. Differential pulse voltammetry and cyclic voltammetry revealed a layer of flavins adsorbed to electrodes, even after soluble components were removed, especially in older biofilms. Riboflavin adsorbed quickly to other surfaces of geochemical interest, such as Fe(III) and Mn(IV) oxy(hydr)oxides. This in situ demonstration of flavin production, and sequestration at surfaces, requires the paradigm of soluble redox shuttles in geochemistry to be adjusted to include binding and modification of surfaces. Moreover, the known ability of isoalloxazine rings to act as metal chelators, along with their electron shuttling capacity, suggests that extracellular respiration of minerals by Shewanella is more complex than originally conceived. PMID:18316736

Heterogeneous Electron-Transfer Dynamics through Dipole-Bridge Groups.

PubMed

Nieto-Pescador, Jesus; Abraham, Baxter; Li, Jingjing; Batarseh, Alberto; Bartynski, Robert A; Galoppini, Elena; Gundlach, Lars

2016-01-14

Heterogeneous electron transfer (HET) between photoexcited molecules and colloidal TiO 2 has been investigated for a set of Zn-porphyrin chromophores attached to the semiconductor via linkers that allow to change level alignment by 200 meV by reorientation of the dipole moment. These unique dye molecules have been studied by femtosecond transient absorption spectroscopy in solution and adsorbed on the TiO 2 colloidal film in vacuum. In solution energy transfer from the excited chromophore to the dipole group has been identified as a slow relaxation pathway competing with S 2 -S 1 internal conversion. On the film heterogeneous electron transfer occurred in 80 fs, much faster compared to all intramolecular pathways. Despite a difference of 200 meV in level alignment of the excited state with respect to the semiconductor conduction band, identical electron transfer times were measured for different linkers. The measurements are compared to a quantum-mechanical model that accounts for electronic-vibronic coupling and finite band width for the acceptor states. We conclude that HET occurs into a distribution of transition states that differs from regular surface states or bridge mediated states.

Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides

PubMed Central

Liu, Jian; McLuckey, Scott A.

2012-01-01

The effect of cation charge state on product partitioning in the gas-phase ion/ion electron transfer reactions of multiply protonated tryptic peptides, model peptides, and relatively large peptides with singly charged radical anions has been examined. In particular, partitioning into various competing channels, such as proton transfer (PT) versus electron transfer (ET), electron transfer with subsequent dissociation (ETD) versus electron transfer with no dissociation (ET,noD), and fragmentation of backbone bonds versus fragmentation of side chains, was measured quantitatively as a function of peptide charge state to allow insights to be drawn about the fundamental aspects of ion/ion reactions that lead to ETD. The ET channel increases relative to the PT channel, ETD increases relative to ET,noD, and fragmentation at backbone bonds increases relative to side-chain cleavages as cation charge state increases. The increase in ET versus PT with charge state is consistent with a Landau-Zener based curve-crossing model. An optimum charge state for ET is predicted by the model for the ground state-to-ground state reaction. However, when the population of excited product ion states is considered, it is possible that a decrease in ET efficiency as charge state increases will not be observed due to the possibility of the population of excited electronic states of the products. Several factors can contribute to the increase in ETD versus ET,noD and backbone cleavage versus side-chain losses. These factors include an increase in reaction exothermicity and charge state dependent differences in precursor and product ion structures, stabilities, and sites of protonation. PMID:23264749

Suppression of runaway electrons with a resonant magnetic perturbation in MST tokamak plasmas

NASA Astrophysics Data System (ADS)

Munaretto, Stefano; Chapman, B. E.; Almagri, A. F.; Cornille, B. S.; Dubois, A. M.; Goetz, J. A.; McCollam, K. J.; Sovinec, C. R.

2016-10-01

Runaway electrons generated in MST tokamak plasmas are now being probed with resonant magnetic perturbations (RMP's). An RMP with m =3 strongly suppresses the runaway electrons. Initial modeling of these plasmas with NIMROD shows the degradation of flux surfaces with an m =3 RMP, which may account for the runaway electron suppression. These MST tokamak plasmas have Bt =0.14 T, Ip =50kA, and q(a) =2.2, with a bulk electron density and temperature of 5x1017 m-3 and 150 eV. Runaway electrons are detected via x-ray emission. The RMP is produced by a poloidal array of 32 saddle coils at the narrow vertical insulated cut in MST's thick conducting shell. Each RMP has a single m but a broad n spectrum. A sufficiently strong m =3 RMP completely suppresses the runaway electrons, while a comparable m =1 RMP has little effect. The impact of the RMP's on the magnetic topology of these plasmas is being studied with the nonlinear MHD code, NIMROD. With an m =3 RMP, stochasticity is introduced in the outer third of the plasma. No such change is observed with the m =1 RMP. NIMROD also predicts regularly occurring sawtooth oscillations with a period comparable to MHD activity observed in the experiment. Work supported by USDOE.

Extracellular electron transfer mechanisms between microorganisms and minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Liang; Dong, Hailiang; Reguera, Gemma

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 andmore » nanomaterials.« less

Study of ring influence and electronic response to proton transfer reactions. Reaction electronic flux analysis.

PubMed

Herrera, Barbara

2011-05-01

In this article, a theoretical study of 1-5 proton transfers is presented. Two model systems which represent 1-5 proton transfer, 3-hidroxy-2-propenimine and salicyldenaniline have been studied as shown in Fig. 1. For this purpose, a DFT/B3LYP/6-311+G**, reaction force and reaction electronic flux analysis is made. The obtained results indicate that both proton transfers exhibit energetic and electronic differences emphasizing the role of the neighbor ring and the impact of conjugation on electronic properties.

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

Federal Register 2010, 2011, 2012, 2013, 2014

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...

Dosimetric impact of a CT metal artefact suppression algorithm for proton, electron and photon therapies

NASA Astrophysics Data System (ADS)

Wei, Jikun; Sandison, George A.; Hsi, Wen-Chien; Ringor, Michael; Lu, Xiaoyi

2006-10-01

Accurate dose calculation is essential to precision radiation treatment planning and this accuracy depends upon anatomic and tissue electron density information. Modern treatment planning inhomogeneity corrections use x-ray CT images and calibrated scales of tissue CT number to electron density to provide this information. The presence of metal in the volume scanned by an x-ray CT scanner causes metal induced image artefacts that influence CT numbers and thereby introduce errors in the radiation dose distribution calculated. This paper investigates the dosimetric improvement achieved by a previously proposed x-ray CT metal artefact suppression technique when the suppressed images of a patient with bilateral hip prostheses are used in commercial treatment planning systems for proton, electron or photon therapies. For all these beam types, this clinical image and treatment planning study reveals that the target may be severely underdosed if a metal artefact-contaminated image is used for dose calculations instead of the artefact suppressed one. Of the three beam types studied, the metal artefact suppression is most important for proton therapy dose calculations, intermediate for electron therapy and least important for x-ray therapy but still significant. The study of a water phantom having a metal rod simulating a hip prosthesis indicates that CT numbers generated after image processing for metal artefact suppression are accurate and thus dose calculations based on the metal artefact suppressed images will be of high fidelity.

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.

Electronic and Vibrational Coherence in Charge-Transfer Reactions

NASA Astrophysics Data System (ADS)

Scherer, Norbert

1996-03-01

The ultrafast dynamics associated with optically-induced intervalence charge-transfer reactions in solution and protein environments are reported. These studies include the Fe^(II)-Fe^(III) MMCT complex Prussian blue and the mixed valence dimer (CN)_5Ru^(II)CNRuRu^(III)(NH_3)_5. The protein systems include blue copper proteins and the bacterial photosynthetic reaction center. The experimental approaches include photon echo, wavelength-resolved pump-probe and anisotropy measurements performed with 12-16fs duration optical pulses. Complicated time-domain waveforms reflect the several different p[rocesses and time scales for relaxation of coherences (both electronic and vibrational) and populations within these systems. The photon echo and anisotropy results probe electronic coherence and dephasing prior to back electron transfer. Wavelength-resolved pump-probe results reveal vibrational modes coupled to the CT-coordinate as well as formation of new product states or vibrational cooling in the ground state following back electron transfer.

Screening of exciplex formation by distant electron transfer.

PubMed

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.

12 CFR 1005.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 12 Banks and Banking 8 2013-01-01 2013-01-01 false Electronic fund transfer service provider not... PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) General § 1005.14 Electronic fund transfer service provider not holding consumer's account. (a) Provider of electronic fund transfer service. A person that...

12 CFR 1005.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 12 Banks and Banking 8 2014-01-01 2014-01-01 false Electronic fund transfer service provider not... PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) General § 1005.14 Electronic fund transfer service provider not holding consumer's account. (a) Provider of electronic fund transfer service. A person that...

Radiatively-suppressed spherical accretion under relativistic radiative transfer

NASA Astrophysics Data System (ADS)

Fukue, Jun

2018-03-01

We numerically examine radiatively-suppressed relativistic spherical accretion flows on to a central object with mass M under Newtonian gravity and special relativity. We simultaneously solve both the relativistic radiative transfer equation and the relativistic hydrodynamical equations for spherically symmetric flows under the double iteration process in the case of the intermediate optical depth. We find that the accretion flow is suppressed, compared with the freefall case in the nonrelativistic regime. For example, in the case of accretion on to a luminous core with accretion luminosity L*, the freefall velocity v normalized by the speed of light c under the radiative force in the nonrelativistic regime is β (\\hat{r}) = v/c = -√{(1-Γ _*)/(\\hat{r}+1-Γ _*)}, where Γ* (≡ L*/LE, LE being the Eddington luminosity) is the Eddington parameter and \\hat{r} (= r/rS, rS being the Schwarzschild radius) the normalized radius, whereas the infall speed at the central core is ˜0.7β(1), irrespective of the mass-accretion rate. This is due to the relativistic effect; the comoving flux is enhanced by the advective flux. We briefly examine and discuss an isothermal case, where the emission takes place in the entire space.

Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

PubMed

Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

2014-11-01

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k 0 , approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

Electron transfer in biology

NASA Astrophysics Data System (ADS)

Williams, R. J. P.

Electron transfer is one of the key reactions of biology not just in catalysis of oxidation/reduction reactions but in the conversion of sources of energy such as light to usable form for chemical transformations. There are then two intriguing problems. What is the nature of the matrix in which electrons flow in a biological cell after the initial charge separation due for example to the absorption of light. Here we are examining biological structures similar to man's electronic wires and the construction must be of low resistance in what are apparently insulators - organic polymers. It has been found that the electronic conduction system is largely made from metallo-proteins associated with lipid membranes. We understand much about these biological wires today. The second problem concerns the conversion of the energy captured from the light into usable chemical form. The major synthetic step in the production of biological polymers, including proteins, DNA, RNA, polysaccharides and fats, is condensation, i.e. the removal of water in the formation of amides, esters and so on. Now these condensation reactions are driven in biology by using a drying agent in water, namely the anhydride, pyrophosphate, in a special compound ATP, adenosine triphosphate. The central problem is to discover exactly how the flow of electrons can be related to the synthesis of (bound) pyrophosphate. (In a thermodynamic sense pyrophosphate is a water soluble kinetically stable drying agent comparable with solid P2O5.) In the biological systems the connection between these different classes of reaction, electron transfer and condensation, is known to be via the production of an energized gradient of protons across the biological membrane which arises from the flow of electrons across the same membrane in the electron transport wires of biology. However we do not understand thoroughly the steps which lead from electron flow in a membrane to proton gradients in that membrane, i.e. electron

12 CFR 1005.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 12 Banks and Banking 8 2012-01-01 2012-01-01 false Electronic fund transfer service provider not... PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) § 1005.14 Electronic fund transfer service provider not holding consumer's account. (a) Provider of electronic fund transfer service. A person that provides an...

Is back-electron transfer process in Betaine-30 coherent?

NASA Astrophysics Data System (ADS)

Rafiq, Shahnawaz; Scholes, Gregory D.

2017-09-01

The possible role of coherent vibrational motion in ultrafast photo-induced electron transfer remains unclear despite considerable experimental and theoretical advances. We revisited this problem by tracking the back-electron transfer (bET) process in Betaine-30 with broadband pump-probe spectroscopy. Dephasing time constant of certain high-frequency vibrations as a function of solvent shows a trend similar to the ET rates. In the purview of Bixon-Jortner model, high-frequency quantum vibrations bridge the reactant-product energy gap by providing activationless vibronic channels. Such interaction reduces the effective coupling significantly and thereby the coherence effects are eliminated due to energy gap fluctuations, making the back-electron transfer incoherent.

Strong suppression of shot noise in a feedback-controlled single-electron transistor

NASA Astrophysics Data System (ADS)

Wagner, Timo; Strasberg, Philipp; Bayer, Johannes C.; Rugeramigabo, Eddy P.; Brandes, Tobias; Haug, Rolf J.

2017-03-01

Feedback control of quantum mechanical systems is rapidly attracting attention not only due to fundamental questions about quantum measurements, but also because of its novel applications in many fields in physics. Quantum control has been studied intensively in quantum optics but progress has recently been made in the control of solid-state qubits as well. In quantum transport only a few active and passive feedback experiments have been realized on the level of single electrons, although theoretical proposals exist. Here we demonstrate the suppression of shot noise in a single-electron transistor using an exclusively electronic closed-loop feedback to monitor and adjust the counting statistics. With increasing feedback response we observe a stronger suppression and faster freezing of charge current fluctuations. Our technique is analogous to the generation of squeezed light with in-loop photodetection as used in quantum optics. Sub-Poisson single-electron sources will pave the way for high-precision measurements in quantum transport similar to optical or optomechanical equivalents.

Interplay between structure, stoichiometry, and electron transfer dynamics in SILAR-based quantum dot-sensitized oxides.

PubMed

Wang, Hai; Barceló, Irene; Lana-Villarreal, Teresa; Gómez, Roberto; Bonn, Mischa; Cánovas, Enrique

2014-10-08

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor-acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

A simulation and optimisation procedure to model daily suppression resource transfers during a fire season in Colorado

Treesearch

Yu Wei; Erin J. Belval; Matthew P. Thompson; Dave E. Calkin; Crystal S. Stonesifer

2016-01-01

Sharing fire engines and crews between fire suppression dispatch zones may help improve the utilisation of fire suppression resources. Using the Resource Ordering and Status System, the Predictive Services’ Fire Potential Outlooks and the Rocky Mountain Region Preparedness Levels from 2010 to 2013, we tested a simulation and optimisation procedure to transfer crews and...

Electronic shift register memory based on molecular electron-transfer reactions

NASA Technical Reports Server (NTRS)

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.

ELECTRON TRANSFER MECHANISM AT THE SOLID-LIQUID INTERFACE OF PHYLLOSILICATES

EPA Science Inventory

Interfacial electron transfer processes on clay minerals have significant impact in natural environments and geochemical systems. Nitrobenzene was used as molecular probes to study the electron transfer mechanism at the solid-water interfaces of Fe-containing phyllosicates. For...

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

PubMed

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.

Electron Transfer Mechanisms of DNA Repair by Photolyase

NASA Astrophysics Data System (ADS)

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.

Sensitization of ultra-long-range excited-state electron transfer by energy transfer in a polymerized film

PubMed Central

Ito, Akitaka; Stewart, David J.; Fang, Zhen; Brennaman, M. Kyle; Meyer, Thomas J.

2012-01-01

Distance-dependent energy transfer occurs from the Metal-to-Ligand Charge Transfer (MLCT) excited state to an anthracene-acrylate derivative (Acr-An) incorporated into the polymer network of a semirigid poly(ethyleneglycol)dimethacrylate monolith. Following excitation, to Acr-An triplet energy transfer occurs followed by long-range, Acr-3An—Acr-An → Acr-An—Acr-3An, energy migration. With methyl viologen dication (MV2+) added as a trap, Acr-3An + MV2+ → Acr-An+ + MV+ electron transfer results in sensitized electron transfer quenching over a distance of approximately 90 Å. PMID:22949698

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

PubMed

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.

Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

NASA Astrophysics Data System (ADS)

Rogge, Paul C.; Chandrasena, Ravini U.; Cammarata, Antonio; Green, Robert J.; Shafer, Padraic; Lefler, Benjamin M.; Huon, Amanda; Arab, Arian; Arenholz, Elke; Lee, Ho Nyung; Lee, Tien-Lin; Nemšák, Slavomír; Rondinelli, James M.; Gray, Alexander X.; May, Steven J.

2018-01-01

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ˜5 -10 % in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.

Dynamics driving function: new insights from electron transferring flavoproteins and partner complexes.

PubMed

Toogood, Helen S; Leys, David; Scrutton, Nigel S

2007-11-01

Electron transferring flavoproteins (ETFs) are soluble heterodimeric FAD-containing proteins that function primarily as soluble electron carriers between various flavoprotein dehydrogenases. ETF is positioned at a key metabolic branch point, responsible for transferring electrons from up to 10 primary dehydrogenases to the membrane-bound respiratory chain. Clinical mutations of ETF result in the often fatal disease glutaric aciduria type II. Structural and biophysical studies of ETF in complex with partner proteins have shown that ETF partitions the functions of partner binding and electron transfer between (a) a 'recognition loop', which acts as a static anchor at the ETF-partner interface, and (b) a highly mobile redox-active FAD domain. Together, this enables the FAD domain of ETF to sample a range of conformations, some compatible with fast interprotein electron transfer. This 'conformational sampling' enables ETF to recognize structurally distinct partners, whilst also maintaining a degree of specificity. Complex formation triggers mobility of the FAD domain, an 'induced disorder' mechanism contrasting with the more generally accepted models of protein-protein interaction by induced fit mechanisms. We discuss the implications of the highly dynamic nature of ETFs in biological interprotein electron transfer. ETF complexes point to mechanisms of electron transfer in which 'dynamics drive function', a feature that is probably widespread in biology given the modular assembly and flexible nature of biological electron transfer systems.

Alternative ground states enable pathway switching in biological electron transfer

DOE PAGES

Abriata, Luciano A.; Alvarez-Paggi, Damian; Ledesma, Gabirela N.; ...

2012-10-10

Electron transfer is the simplest chemical reaction and constitutes the basis of a large variety of biological processes, such as photosynthesis and cellular respiration. Nature has evolved specific proteins and cofactors for these functions. The mechanisms optimizing biological electron transfer have been matter of intense debate, such as the role of the protein milieu between donor and acceptor sites. Here we propose a mechanism regulating long-range electron transfer in proteins. Specifically, we report a spectroscopic, electrochemical, and theoretical study on WT and single-mutant CuA redox centers from Thermus thermophilus, which shows that thermal fluctuations may populate two alternative ground-state electronicmore » wave functions optimized for electron entry and exit, respectively, through two different and nearly perpendicular pathways. In conclusion, these findings suggest a unique role for alternative or “invisible” electronic ground states in directional electron transfer. Moreover, it is shown that this energy gap and, therefore, the equilibrium between ground states can be fine-tuned by minor perturbations, suggesting alternative ways through which protein–protein interactions and membrane potential may optimize and regulate electron–proton energy transduction.« less

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

PubMed Central

Devaraj, Neal K.; Decreau, Richard A.; Ebina, Wataru; Collman, James P.; Chidsey, Christopher E. D.

2012-01-01

The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide–alkyne cycloaddition (a Sharpless “click” reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants from greater than 60,000 to 1 s−1 are obtained by varying the length and conjugation of the electron-transfer bridge and by varying the surrounding diluent thiols in the monolayer. Triazole and the triazole carbonyl linkages provide similar electronic coupling for electron transfer as esters. The ability to vary the rate of electron transfer to many different redox species over many orders of magnitude by using modular coupling chemistry provides a convenient way to study and control the delivery of electrons to multielectron redox catalysts and similar interfacial systems that require controlled delivery of electrons. PMID:16898751

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

Federal Register 2010, 2011, 2012, 2013, 2014

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...

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

Federal Register 2010, 2011, 2012, 2013, 2014

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...

75 FR 52485 - Electronic Funds Transfer of Depository Taxes; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-26

... DEPARTMENT OF THE TREASURY Internal Revenue Service 26 CFR Parts 1, 31, 40, and 301 [REG-153340-09] RIN 1545-BJ13 Electronic Funds Transfer of Depository Taxes; Correction AGENCY: Internal Revenue... to Federal tax deposits (FTDs) by Electronic Funds Transfer (EFT). FOR FURTHER INFORMATION CONTACT...

Effect of proton transfer on the electronic coupling in DNA

NASA Astrophysics Data System (ADS)

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

2006-06-01

The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, Vda, 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 Vda 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 Vda 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 Vda matrix elements are also analyzed.

Thermal transfer structures coupling electronics card(s) to coolant-cooled structure(s)

DOEpatents

David, Milnes P; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Parida, Pritish R; Schmidt, Roger R

2014-12-16

Cooling apparatuses and coolant-cooled electronic systems are provided which include thermal transfer structures configured to engage with a spring force one or more electronics cards with docking of the electronics card(s) within a respective socket(s) of the electronic system. A thermal transfer structure of the cooling apparatus includes a thermal spreader having a first thermal conduction surface, and a thermally conductive spring assembly coupled to the conduction surface of the thermal spreader and positioned and configured to reside between and physically couple a first surface of an electronics card to the first surface of the thermal spreader with docking of the electronics card within a socket of the electronic system. The thermal transfer structure is, in one embodiment, metallurgically bonded to a coolant-cooled structure and facilitates transfer of heat from the electronics card to coolant flowing through the coolant-cooled structure.

Single-Molecule Interfacial Electron Transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Wilson

Interfacial electron transfer (ET) plays an important role in many chemical and biological processes. Specifically, interfacial ET in TiO 2-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 andmore » TiO 2 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, solar

How does methylation suppress the electron-induced decomposition of 1-methyl-nitroimidazoles?

NASA Astrophysics Data System (ADS)

Kossoski, F.; Varella, M. T. do N.

2017-10-01

The efficient decomposition of nitroimidazoles (NIs) by low energy electrons is believed to underlie their radiosensitizing properties. Recent dissociative electron attachment (DEA) measurements showed that methylation at the N1 site unexpectedly suppresses the electron-induced reactions in 4(5)-NI. We report theoretical results that provide a clear interpretation of that astounding finding. Around 1.5 eV, DEA reactions into several fragments are initiated by a π* resonance, not considered in previous studies. The autoionization lifetime of this anion state, which limits the predissociation dynamics, is considerably shorter in the methylated species, thereby suppressing the DEA signals. On the other hand, the lifetime of the π* resonance located around 3 eV is less affected by methylation, which explains why DEA is still observed at these energies. Our results demonstrate how even a simple methylation can significantly modify the probabilities for DEA reactions, which may be significant for NI-based cancer therapy.

49 CFR 225.37 - Optical media transfer and electronic submission.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 4 2012-10-01 2012-10-01 false Optical media transfer and electronic submission..., AND INVESTIGATIONS § 225.37 Optical media transfer and electronic submission. (a) A railroad has the option of submitting the following reports, updates, and amendments by way of optical media (CD-ROM), or...

49 CFR 225.37 - Optical media transfer and electronic submission.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 4 2013-10-01 2013-10-01 false Optical media transfer and electronic submission..., AND INVESTIGATIONS § 225.37 Optical media transfer and electronic submission. (a) A railroad has the option of submitting the following reports, updates, and amendments by way of optical media (CD-ROM), or...

49 CFR 225.37 - Optical media transfer and electronic submission.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 4 2011-10-01 2011-10-01 false Optical media transfer and electronic submission..., AND INVESTIGATIONS § 225.37 Optical media transfer and electronic submission. (a) A railroad has the option of submitting the following reports, updates, and amendments by way of optical media (CD-ROM), or...

49 CFR 225.37 - Optical media transfer and electronic submission.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 4 2014-10-01 2014-10-01 false Optical media transfer and electronic submission..., AND INVESTIGATIONS § 225.37 Optical media transfer and electronic submission. (a) A railroad has the option of submitting the following reports, updates, and amendments by way of optical media (CD-ROM), or...

Theory of electron transfer and molecular state in DNA

NASA Astrophysics Data System (ADS)

Endres, Robert Gunter

2002-09-01

In this thesis, a mechanism for long-range electron transfer in DNA and a systematic search for high conductance DNA are developed. DNA is well known for containing the genetic code of all living species. On the other hand, there are some experimental indications that DNA can mediate effectively long-range electron transfer leading to the concept of chemistry at a distance. This can be important for DNA damage and healing. In the first part of the thesis, a possible mechanism for long-range electron transfer is introduced. The weak distance dependent electron transfer was experimentally observed using transition metal intercalators for donor and acceptor. In our model calculations, the transfer is mediated by the molecular analogue of a Kondo bound state well known from solid state physics of mixed-valence rare-earth compounds. We believe this is quite realistic, since localized d orbitals of the transition metal ions could function as an Anderson impurity embedded in a reservoir of rather delocalized molecular orbitals of the intercalator ligands and DNA pi orbitals. The effective Anderson model is solved with a physically intuitive variational ansatz as well as with the essentially exact DMRG method. The electronic transition matrix element, which is important because it contains the donor-acceptor distance dependence, is obtained with the Mulliken-Hush algorithm as well as from Born-Oppenheimer potential energy surfaces. Our possible explanation of long-range electron transfer is put in context to other more conventional mechanisms which also could lead to similar behavior. Another important issue of DNA is its possible use for nano-technology. Although DNA's mechanical properties are excellent, the question whether it can be conducting and be used for nano-wires is highly controversial. Experimentally, DNA shows conducting, semi-conducting and insulating properties. Motivated by these wide ranging experimental results on the conductivity of DNA, we have

Supramolecular networks with electron transfer in two dimensions

DOEpatents

Stupp, Samuel I.; Stoddart, J. Fraser; Shveyd, Alexander K.; Tayi, Alok S.; Sue, Chi-Hau; Narayanan, Ashwin

2016-09-13

Organic charge-transfer (CT) co-crystals in a crossed stack system are disclosed. The co-crystals exhibit bidirectional charge transfer interactions where one donor molecule shares electrons with two different acceptors, one acceptor face-to-face and the other edge-to-face. The assembly and charge transfer interaction results in a pleochroic material whereby the optical absorption continuously changes depending on the polarization angle of incident light.

Application of Electron-Transfer Theory to Several Systems of Biological Interest

DOE R&D Accomplishments Database

Marcus, R. A.; Sutin, N.

1985-03-23

Electron-transfer reaction rates are compared with theoretically calculated values for several reactions in the bacterial photosynthetic reaction center. A second aspect of the theory, the cross-relation, is illustrated using protein-protein electron transfers.

Dynamics of Interocular Suppression in Amblyopic Children during Electronically Monitored Occlusion Therapy: First Insight.

PubMed

Kehrein, Stephan; Kohnen, Thomas; Fronius, Maria

2016-06-01

Interocular suppression is assumed to be the mechanism leading to impaired visual acuity, especially in strabismic amblyopia. Little is known about the dynamics of suppression during treatment. The aim of our study was to assess the development of the depth of suppression and its relation to changes in visual acuity during electronically monitored occlusion treatment. In a prospective pilot study, 15 amblyopes (8 with and 7 without strabismus) aged 5 to 16 years (mean 10.24 years) were examined before initiation of patching and then every 3 to 6 weeks for 4 months. To quantify suppression, a red filter ladder (Sbisa bar) was used, attenuating the image of the dominant eye until the patients reported a binocular perception (diplopia, rivalry, color mixture) or a change in eye dominance. Acuity was assessed with crowded Landolt rings. Daily occlusion was recorded using occlusion dose monitors. The depth of interocular suppression showed a biphasic change: it increased significantly during the first month (P=0.02), while visual acuity improved (mean 0.14 log units ±0.13; P<0.01). During the following 3 months, median suppression decreased back to the initial values. This reduction in suppression was more pronounced in anisometropic patients without strabismus than in amblyopes with strabismus. The average visual acuity steadily improved (P<0.01) during the 4 months of treatment. Mean recorded patching dose rate was 3.91 h/d. The correlation between mean daily occlusion and suppression changes was not statistically significant. This first insight into the functional changes during electronically monitored patching suggests a complex relationship between visual acuity and interocular suppression that seems to be influenced by the presence of strabismus. Knowledge of the dynamics of interocular suppression is crucial for enhancing the outcome of occlusion treatment and also for the evaluation of its future role compared to emerging dichoptic treatments.

Biotechnological Aspects of Microbial Extracellular Electron Transfer

PubMed Central

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

Bridge-mediated hopping or superexchange electron-transfer processes in bis(triarylamine) systems

NASA Astrophysics Data System (ADS)

Lambert, Christoph; Nöll, Gilbert; Schelter, Jürgen

2002-09-01

Hopping and superexchange are generally considered to be alternative electron-transfer mechanisms in molecular systems. In this work we used mixed-valence radical cations as model systems for the investigation of electron-transfer pathways. We show that substituents attached to a conjugated bridge connecting two triarylamine redox centres have a marked influence on the near-infrared absorption spectra of the corresponding cations. Spectral analysis, followed by evaluation of the electron-transfer parameters using the Generalized Mulliken-Hush theory and simulation of the potential energy surfaces, indicate that hopping and superexchange are not alternatives, but are both present in the radical cation with a dimethoxybenzene bridge. We found that the type of electron-transfer mechanism depends on the bridge-reorganization energy as well as on the bridge-state energy. Because superexchange and hopping follow different distance laws, our findings have implications for the design of new molecular and polymeric electron-transfer materials.

Femtosecond-level timing fluctuation suppression in atmospheric frequency transfer with passive phase conjunction correction.

PubMed

Sun, Fuyu; Hou, Dong; Zhang, Danian; Tian, Jie; Hu, Jianguo; Huang, Xianhe; Chen, Shijun

2017-09-04

We demonstrate femtosecond-level timing fluctuation suppression in indoor atmospheric comb-based frequency transfer with a passive phase conjunction correction technique. Timing fluctuations and Allan deviations are both measured to characterize the excess frequency instability incurred during the frequency transfer process. By transferring a 2 GHz microwave over a 52-m long free-space link in 5000 s, the total root-mean-square (RMS) timing fluctuation was measured to be about 280 fs with a fractional frequency instability on the order of 3 × 10 -13 at 1 s and 6 × 10 -17 at 1000 s. This atmospheric comb-based frequency transfer with passive phase conjunction correction can be used to build an atomic clock-based free-space frequency transmission link because its instability is less than that of a commercial Cs or H-master clock.

Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

PubMed Central

Farver, Ole; Kroneck, Peter M. H.; Zumft, Walter G.; Pecht, Israel

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. PMID:12802018

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

PubMed

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.

Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

PubMed

Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

2015-11-15

The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

A Review of the Suppression of Secondary Electron Emission from the Electrodes of Multistage Collectors

NASA Technical Reports Server (NTRS)

Dayton, James A., Jr.

1998-01-01

A review is presented of more than 20 years of research conducted at NASA Lewis Research Center on the suppression of secondary electron emission (SEE) for the enhancement of the efficiency of vacuum electron devices with multistage depressed collectors. This paper will include a description of measurement techniques, data from measurements of SEE on a variety of materials of engineering interest and methods of surface treatment for the suppression of SEE. In the course of this work the lowest secondary electron yield ever reported was achieved for ion textured graphite, and, in a parallel line of research, the highest yield was obtained for chemical vapor deposited thin diamond films.

The role of electron transfer in DNA building blocks: Evaluation of strand breaks and their implications

NASA Astrophysics Data System (ADS)

Almeida, Diogo Alexandre Fialho de

the first time collision induced site and bond selectivity breaking, where the electron is transferred into a given state of the acceptor molecule and the resulting fragmentation pathways are exclusive to the initial anionic state. Furthermore, the role of the potassium cation post collisionwas explored and indeed its presence is suggested to induce at least partial suppression of auto-detachment. The implications that ensue from this degradation are analysed in the light of the obtained fragmentation patterns.

12 CFR 205.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2010 CFR

2010-01-01

... consumer learns of the loss or theft; and extends the time periods for reporting unauthorized transfers or... 12 Banks and Banking 2 2010-01-01 2010-01-01 false Electronic fund transfer service provider not... GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.14 Electronic fund...

12 CFR 205.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2013 CFR

2013-01-01

... consumer learns of the loss or theft; and extends the time periods for reporting unauthorized transfers or... 12 Banks and Banking 2 2013-01-01 2013-01-01 false Electronic fund transfer service provider not... GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.14 Electronic fund...

12 CFR 205.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2014 CFR

2014-01-01

... consumer learns of the loss or theft; and extends the time periods for reporting unauthorized transfers or... 12 Banks and Banking 2 2014-01-01 2014-01-01 false Electronic fund transfer service provider not... GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.14 Electronic fund...

12 CFR 205.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2011 CFR

2011-01-01

... consumer learns of the loss or theft; and extends the time periods for reporting unauthorized transfers or... 12 Banks and Banking 2 2011-01-01 2011-01-01 false Electronic fund transfer service provider not... GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.14 Electronic fund...

12 CFR 205.14 - Electronic fund transfer service provider not holding consumer's account.

Code of Federal Regulations, 2012 CFR

2012-01-01

... consumer learns of the loss or theft; and extends the time periods for reporting unauthorized transfers or... 12 Banks and Banking 2 2012-01-01 2012-01-01 false Electronic fund transfer service provider not... GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.14 Electronic fund...

NONLINEAR AND FIBER OPTICS: Mutual suppression of the electron stimulated Raman scattering and four-wave parametric mixing

NASA Astrophysics Data System (ADS)

Malakyan, Yu P.

1990-04-01

A new effect is considered: self-induced suppression of electron stimulated Raman scattering involving generation of two new fields from the Stokes radiation as a result of four-wave mixing, interfering destructively with electron stimulated Raman scattering and suppressing it, which in turn suppresses the mixing process. The effect occurs in the steady-state case and not under transient conditions. The results account in a simple manner for the generation of the Stokes radiation in barium vapor as a result of different transitions, depending on the duration of the pump pulse.

Electronic energy transfer: Localized operator partitioning of electronic energy in composite quantum systems

NASA Astrophysics Data System (ADS)

Khan, Yaser; Brumer, Paul

2012-11-01

A Hamiltonian based approach using spatially localized projection operators is introduced to give precise meaning to the chemically intuitive idea of the electronic energy on a quantum subsystem. This definition facilitates the study of electronic energy transfer in arbitrarily coupled quantum systems. In particular, the decomposition scheme can be applied to molecular components that are strongly interacting (with significant orbital overlap) as well as to isolated fragments. The result defines a consistent electronic energy at all internuclear distances, including the case of separated fragments, and reduces to the well-known Förster and Dexter results in their respective limits. Numerical calculations of coherent energy and charge transfer dynamics in simple model systems are presented and the effect of collisionally induced decoherence is examined.

Electron Transfer Between Electrically Conductive Minerals and Quinones

NASA Astrophysics Data System (ADS)

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

Fast electron transfer through a single molecule natively structured redox protein

NASA Astrophysics Data System (ADS)

Della Pia, Eduardo Antonio; Chi, Qijin; MacDonald, J. Emyr; Ulstrup, Jens; Jones, D. Dafydd; Elliott, Martin

2012-10-01

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 conductance through single-molecules of the electron transfer protein cytochrome b562 in its native conformation, under pseudo-physiological conditions. This is achieved by thiol (SH) linker pairs at opposite ends of the molecule through protein engineering, resulting in defined covalent contact between a gold surface and a platinum-iridium STM tip. Two different orientations of the linkers were examined: a long-axis configuration (SH-LA) and a short-axis configuration (SH-SA). In each case, the molecular conductance could be `gated' through electrochemical control of the heme redox state. Reproducible and remarkably high conductance was observed in this relatively complex electron transfer system, with single-molecule conductance values peaking around 18 nS and 12 nS for the SH-SA and SH-LA cytochrome b562 molecules near zero electrochemical overpotential. This strongly points to the important role of the heme co-factor bound to the natively structured protein. We suggest that the two-step model of protein electron transfer in the STM geometry requires a multi-electron transfer to explain such a high conductance. The model also yields a low value for the reorganisation energy, implying that solvent reorganisation is largely absent.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 conductance through single-molecules of the electron transfer protein cytochrome b562 in its native conformation, under pseudo-physiological conditions. This is

Role of protein fluctuation correlations in electron transfer in photosynthetic complexes.

PubMed

Nesterov, Alexander I; Berman, Gennady P

2015-04-01

We consider the dependence of the electron transfer in photosynthetic complexes on correlation properties of random fluctuations of the protein environment. The electron subsystem is modeled by a finite network of connected electron (exciton) sites. The fluctuations of the protein environment are modeled by random telegraph processes, which act either collectively (correlated) or independently (uncorrelated) on the electron sites. We derived an exact closed system of first-order linear differential equations with constant coefficients, for the average density matrix elements and for their first moments. Under some conditions, we obtained analytic expressions for the electron transfer rates and found the range of parameters for their applicability by comparing with the exact numerical simulations. We also compared the correlated and uncorrelated regimes and demonstrated numerically that the uncorrelated fluctuations of the protein environment can, under some conditions, either increase or decrease the electron transfer rates.

Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

PubMed Central

Ha, Phuc T.; Lindemann, Stephen R.; Shi, Liang; Dohnalkova, Alice C.; Fredrickson, James K.; Madigan, Michael T.; Beyenal, Haluk

2017-01-01

Microbial phototrophs, key primary producers on Earth, use H2O, H2, H2S and other reduced inorganic compounds as electron donors. Here we describe a form of metabolism linking anoxygenic photosynthesis to anaerobic respiration that we call ‘syntrophic anaerobic photosynthesis'. We show that photoautotrophy in the green sulfur bacterium Prosthecochloris aestaurii can be driven by either electrons from a solid electrode or acetate oxidation via direct interspecies electron transfer from a heterotrophic partner bacterium, Geobacter sulfurreducens. Photosynthetic growth of P. aestuarii using reductant provided by either an electrode or syntrophy is robust and light-dependent. In contrast, P. aestuarii does not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer. Syntrophic anaerobic photosynthesis is therefore a carbon cycling process that could take place in anoxic environments. This process could be exploited for biotechnological applications, such as waste treatment and bioenergy production, using engineered phototrophic microbial communities. PMID:28067226

A molecularly based theory for electron transfer reorganization energy.

PubMed

Zhuang, Bilin; Wang, Zhen-Gang

2015-12-14

Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

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

PubMed Central

Westereng, Bjørge; Cannella, David; Wittrup Agger, Jane; Jørgensen, Henning; Larsen Andersen, Mogens; Eijsink, Vincent G.H.; Felby, Claus

2015-01-01

Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply 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 new light on how oxidative enzymes present in plant degraders may act in concert. PMID:26686263

On the physics of electron transfer (drift) in the substance: about the reason of “abnormal” fast transfer of electrons in the plasma of tokamak and at known Bohm’s diffusion

NASA Astrophysics Data System (ADS)

Boriev, I. A.

2018-03-01

An analysis of the problem of so-called “abnormal” fast transfer of electrons in tokamak plasma, which turned out much faster than the result of accepted calculation, is given. Such transfer of hot electrons leads to unexpectedly fast destruction of the inner tokamak wall with ejection of its matter in plasma volume, what violates a condition of plasma confinement for controlled thermonuclear fusion. It is shown, taking into account real physics of electron drift in the gas (plasma) and using the conservation law for momentum of electron transfer (drift), that the drift velocity of elastically scattered electrons should be significantly greater than that of accepted calculation. The reason is that the relaxation time of the momentum of electron transfer, to which the electron drift velocity is proportional, is significantly greater (from 16 up to 4 times) than the electron free path time. Therefore, generally accepted replacement of the relaxation time, which is unknown a priori, by the electron free path time, leads to significant (16 times for thermal electrons) underestimation of electron drift velocity (mobility). This result means, that transfer of elastically (and isotropically) scattered electrons in the gas phase should be so fast, and corresponds to multiplying coefficient (16), introduced by D. Bohm to explain the observed by him “abnormal” fast diffusion of electrons.

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

PubMed

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.

Electron attachment to molecules in a cluster environment: suppression and enhancement effects

NASA Astrophysics Data System (ADS)

Fabrikant, Ilya I.

2018-05-01

Cluster environments can strongly influence dissociative electron attachment (DEA) processes. These effects are important in many applications, particularly for surface chemistry, radiation damage, and atmospheric physics. We review several mechanisms for DEA suppression and enhancement due to cluster environments, particularly due to microhydration. Long-range electron-molecule and electron-cluster interactions play often a significant role in these effects and can be analysed by using theoretical models. Nevertheless many observations remain unexplained due to complexity of the physics and chemistry of interaction of DEA fragments with the cluster environment.

Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations.

PubMed

Qin, Haimei; Zhong, Xinxin; Si, Yubing; Zhang, Weiwei; Zhao, Yi

2011-04-14

The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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

2017-10-21

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.

Visualizing changes in electron distribution in coupled chains of cytochrome bc(1) by modifying barrier for electron transfer between the FeS cluster and heme c(1).

PubMed

Cieluch, Ewelina; Pietryga, Krzysztof; Sarewicz, Marcin; Osyczka, Artur

2010-02-01

Cytochrome c(1) of Rhodobacter (Rba.) species provides a series of mutants which change barriers for electron transfer through the cofactor chains of cytochrome bc(1) by modifying heme c(1) redox midpoint potential. Analysis of post-flash electron distribution in such systems can provide useful information about the contribution of individual reactions to the overall electron flow. In Rba. capsulatus, the non-functional low-potential forms of cytochrome c(1) which are devoid of the disulfide bond naturally present in this protein revert spontaneously by introducing a second-site suppression (mutation A181T) that brings the potential of heme c(1) back to the functionally high levels, yet maintains it some 100 mV lower from the native value. Here we report that the disulfide and the mutation A181T can coexist in one protein but the mutation exerts a dominant effect on the redox properties of heme c(1) and the potential remains at the same lower value as in the disulfide-free form. This establishes effective means to modify a barrier for electron transfer between the FeS cluster and heme c(1) without breaking disulfide. A comparison of the flash-induced electron transfers in native and mutated cytochrome bc(1) revealed significant differences in the post-flash equilibrium distribution of electrons only when the connection of the chains with the quinone pool was interrupted at the level of either of the catalytic sites by the use of specific inhibitors, antimycin or myxothiazol. In the non-inhibited system no such differences were observed. We explain the results using a kinetic model in which a shift in the equilibrium of one reaction influences the equilibrium of all remaining reactions in the cofactor chains. It follows a rather simple description in which the direction of electron flow through the coupled chains of cytochrome bc(1) exclusively depends on the rates of all reversible partial reactions, including the Q/QH2 exchange rate to/from the catalytic sites

Quantifying electron transfer reactions in biological systems: what interactions play the major role?

NASA Astrophysics Data System (ADS)

Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov'Yov, Ilia A.

2015-12-01

Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome-a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor.

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation

NASA Astrophysics Data System (ADS)

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.

Water-mediated electron transfer between protein redox centers.

PubMed

Migliore, Agostino; Corni, Stefano; Felice, Rosa Di; Molinari, Elisa

2007-04-12

Recent experimental and theoretical investigations show that water molecules between or near redox partners can significantly affect their electron-transfer (ET) properties. Here we study the effects of intervening water molecules on the electron self-exchange reaction of azurin (Az), by performing a conformational sampling on the water medium and by using a newly developed ab initio method to calculate transfer integrals between molecular redox sites. We show that the insertion of water molecules at the interface between the copper active sites of Az dimers slightly increases the overall ET rate, while some favorable water conformations can considerably enhance the ET kinetics. These features are traced back to the interplay of two competing factors: the electrostatic interaction between the water and protein subsystems (mainly opposing the ET process for the water arrangements drawn from MD simulations) and the effectiveness of water in mediating ET coupling pathways. Such an interplay provides a physical basis for the found absence of correlation between the electronic couplings derived through ab initio electronic structure calculations and the related quantities obtained through the Empirical Pathways (EP) method. In fact, the latter does not account for electrostatic effects on the transfer integrals. Thus, we conclude that the water-mediated electron tunneling is not controlled by the geometry of a single physical pathway. We discuss the results in terms of the interplay between different ET pathways controlled by the conformational changes of one of the water molecules via its electrostatic influence. Finally, we examine the dynamical effects of the interfacial water and check the validity of the Condon approximation.

Inner reorganization limiting electron transfer controlled hydrogen bonding: intra- vs. intermolecular effects.

PubMed

Martínez-González, Eduardo; Frontana, Carlos

2014-05-07

In this work, experimental evidence of the influence of the electron transfer kinetics during electron transfer controlled hydrogen bonding between anion radicals of metronidazole and ornidazole, derivatives of 5-nitro-imidazole, and 1,3-diethylurea as the hydrogen bond donor, is presented. Analysis of the variations of voltammetric EpIcvs. log KB[DH], where KB is the binding constant, allowed us to determine the values of the binding constant and also the electron transfer rate k, confirmed by experiments obtained at different scan rates. Electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level for metronidazole, including the solvent effect by the Cramer/Truhlar model, suggested that the minimum energy conformer is stabilized by intramolecular hydrogen bonding. In this structure, the inner reorganization energy, λi,j, contributes significantly (0.5 eV) to the total reorganization energy of electron transfer, thus leading to a diminishment of the experimental k.

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

DTIC Science & Technology

2016-07-08

AFRL-AFOSR-VA-TR-2016-0244 Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis Jahan Dawlaty UNIVERSITY OF SOUTHERN...TITLE AND SUBTITLE Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550...298 Back (Rev. 8/98) DISTRIBUTION A: Distribution approved for public release. Final Report: AFOSR YIP Grant FA9550-13-1-0128: Ultrafast Spectroscopy

Electron transfer and reaction mechanism of laccases.

PubMed

Jones, Stephen M; Solomon, Edward I

2015-03-01

Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme.

Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

DOE PAGES

Ha, Phuc T.; Lindemann, Stephen R.; Shi, Liang; ...

2017-01-09

Microbial phototrophs, key primary producers on Earth, use H 2O, H 2, H 2S and other reduced inorganic compounds as electron donors. Here we describe a form of metabolism linking anoxygenic photosynthesis to anaerobic respiration that we call ‘syntrophic anaerobic photosynthesis’. We show that photoautotrophy in the green sulfur bacterium Prosthecochloris aestaurii can be driven by either electrons from a solid electrode or acetate oxidation via direct interspecies electron transfer from a heterotrophic partner bacterium, Geobacter sulfurreducens. Photosynthetic growth of P. aestuarii using reductant provided by either an electrode or syntrophy is robust and light-dependent. In contrast, P. aestuarii doesmore » not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer. Syntrophic anaerobic photosynthesis is therefore a carbon cycling process that could take place in anoxic environments. Lastly, this process could be exploited for biotechnological applications, such as waste treatment and bioenergy production, using engineered phototrophic microbial communities.« less

Photosensitizing Electron Transfer Processes of Fullerenes, Carbon Nanotubes, and Carbon Nanohorns.

PubMed

Ito, Osamu

2017-03-01

In this account, studies on the photosensitizing electron transfer of nanocarbons, such as fullerenes, single-walled carbon nanotubes (SWCNTs), and carbon nanohorns (CNH), performed in our laboratory for about 15 years in the early 21st century have been briefly reviewed. These novel nanocarbons act as excellent electron acceptors, when they are linked to light-absorbing electron donors, such as porphyrins or phthalocyanines. For such molecule-nanocarbon hybrids, the direct confirmation of fast, transient, electron-transfer phenomena must be performed with time-resolved spectroscopic methods, such as transient absorption spectral measurements, in addition to fluorescence time-profile measurements in the wide-wavelength regions. Careful use of these methods affords useful information to understand photoinduced electron-transfer mechanisms. In addition, kinetic data obtained by these methods can assist in the construction of light-active devices, such as photovoltaic cells and solar H 2 -generation systems. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid electron transfer by the carbon matrix in natural pyrogenic carbon

PubMed Central

Sun, Tianran; Levin, Barnaby D. A.; Guzman, Juan J. L.; Enders, Akio; Muller, David A.; Angenent, Largus T.; Lehmann, Johannes

2017-01-01

Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria–carbon–mineral conductive network. PMID:28361882

ZnO-nanorods/graphene heterostructure: a direct electron transfer glucose biosensor

NASA Astrophysics Data System (ADS)

Zhao, Yu; Li, Wenbo; Pan, Lijia; Zhai, Dongyuan; Wang, Yu; Li, Lanlan; Cheng, Wen; Yin, Wei; Wang, Xinran; Xu, Jian-Bin; Shi, Yi

2016-08-01

ZnO-nanorods/graphene heterostructure was synthesized by hydrothermal growth of ZnO nanorods on chemically reduced graphene (CRG) film. The hybrid structure was demonstrated as a biosensor, where direct electron transfer between glucose oxidase (GOD) and electrode was observed. The charge transfer was attributed to the ZnO nanorod wiring between the redox center of GOD and electrode, and the ZnO/graphene heterostructure facilitated the transport of electrons on the hybride electrode. The glucose sensor based on the GOD-ZnO/CRG/Pt electrode had a high sensitivity of 17.64 μA mM-1, which is higher than most of the previously reported values for direct electron transfer based glucose biosensors. Moreover, this biosensor is linearly proportional to the concentration of glucose in the range of 0.2-1.6 mM. The study revealed that the band structure of electrode could affect the detection of direct electron transfer of GOD, which would be helpful for the design of the biosensor electrodes in the future.

ZnO-nanorods/graphene heterostructure: a direct electron transfer glucose biosensor

PubMed Central

Zhao, Yu; Li, Wenbo; Pan, Lijia; Zhai, Dongyuan; Wang, Yu; Li, Lanlan; Cheng, Wen; Yin, Wei; Wang, Xinran; Xu, Jian-Bin; Shi, Yi

2016-01-01

ZnO-nanorods/graphene heterostructure was synthesized by hydrothermal growth of ZnO nanorods on chemically reduced graphene (CRG) film. The hybrid structure was demonstrated as a biosensor, where direct electron transfer between glucose oxidase (GOD) and electrode was observed. The charge transfer was attributed to the ZnO nanorod wiring between the redox center of GOD and electrode, and the ZnO/graphene heterostructure facilitated the transport of electrons on the hybride electrode. The glucose sensor based on the GOD-ZnO/CRG/Pt electrode had a high sensitivity of 17.64 μA mM−1, which is higher than most of the previously reported values for direct electron transfer based glucose biosensors. Moreover, this biosensor is linearly proportional to the concentration of glucose in the range of 0.2–1.6 mM. The study revealed that the band structure of electrode could affect the detection of direct electron transfer of GOD, which would be helpful for the design of the biosensor electrodes in the future. PMID:27572675

The role of defects in Fe(II) – goethite electron transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrade de Notini, Luiza; Latta, Drew; Neumann, Anke

Despite accumulating experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemical calculations suggest that oxidation of sorbed Fe(II) is not energetically feasible unless defects are present. Here we used isotope specific 57Fe Mössbauer spectroscopy to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, we heated the mineral to try to anneal the goethite surface and ground goethite to try to create defects. We found that heating goethite results in less oxidation of sorbed Fe(II) by goethite. When goethite was re-ground after heating, electron transfer was partially restored. X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) ofmore » heated and ground goethite confirm that heating and grinding alter the surface structure of the goethite. We propose that the heating process annealed the surface and decreased the number of sites where electron transfer could occur. Our experimental findings suggest that surface defects play an important role in Fe(II)-goethite electron transfer as suggested by computational calculations. Our finding that defects influence heterogeneous Fe(II)-goethite electron transfer has important implications for Fe(II) driven recrystallization of Fe oxides, as well as X and Y.« less

Photocurrent generation by direct electron transfer using photosynthetic reaction centres

NASA Astrophysics Data System (ADS)

Mahmoudzadeh, A.; Saer, R.; Jun, D.; Mirvakili, S. M.; Takshi, A.; Iranpour, B.; Ouellet, E.; Lagally, E. T.; Madden, J. D. W.; Beatty, J. T.

2011-09-01

Photosynthetic reaction centres (RCs) convert light into separated charges with nearly perfect quantum efficiency, and have been used to generate photocurrent. Previous work has shown that electron tunnelling rates between redox centres in proteins depend exponentially on the tunnelling distance. In this work the RC from Rhodobacter sphaeroides was genetically modified with the aim of achieving the shortest tunnelling distances yet demonstrated between the RC's electron-accepting P site and underlying graphite and gold electrodes, and between the electron donor Q site and graphite electrodes. Opposite charges are carried to counter electrodes using mobile mediators, as in dye-sensitised solar cells. Native RCs are bound to graphite surfaces through N-(1-pyrene)iodoacetamide. Although the linker's length is only 4 Å, the electron transfer pathway between the Q electron donor site on the RC and the electrode surface is still too large for current to be significant. A mutant version with the electron acceptor P side close to the graphite surface produced currents of 15 nA cm-2 upon illumination. Direct binding of RCs to a gold surface is shown, resulting in currents of 5 nA cm-2. In both cases the current was unaffected by mediator concentration but increased with illumination, suggesting that direct electron transfer was achieved. The engineering of an RC to achieve direct electron transfer will help with long term efforts to demonstrate RC-based photovoltaic devices.

Charge transfer to ground-state ions produces free electrons

PubMed Central

You, D.; Fukuzawa, H.; Sakakibara, Y.; Takanashi, T.; Ito, Y.; Maliyar, G. G.; Motomura, K.; Nagaya, K.; Nishiyama, T.; Asa, K.; Sato, Y.; Saito, N.; Oura, M.; Schöffler, M.; Kastirke, G.; Hergenhahn, U.; Stumpf, V.; Gokhberg, K.; Kuleff, A. I.; Cederbaum, L. S.; Ueda, K

2017-01-01

Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne–Kr mixed clusters. PMID:28134238

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

PubMed

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.

Thermal-noise suppression in nano-scale Si field-effect transistors by feedback control based on single-electron detection

NASA Astrophysics Data System (ADS)

Chida, Kensaku; Nishiguchi, Katsuhiko; Yamahata, Gento; Tanaka, Hirotaka; Fujiwara, Akira

2015-08-01

We perform feedback (FB) control for suppressing thermal fluctuation in the number of electrons in a silicon single-electron (SE) device composed of a small transistor and capacitor. SEs enter and leave the capacitor via the transistor randomly at thermal equilibrium, which is monitored in real time using a high-charge-sensitivity detector. In order to suppress such random motion or thermal fluctuation of the electrons, SEs are injected and removed using the transistor according to the monitored change in the number of electrons in the capacitor, which is exactly the FB control. As a result, thermal fluctuation in the number of electrons in a SE device is suppressed by 60%, which corresponds to the so-called FB cooling from 300 to 110 K. Moreover, a thermodynamics analysis of this FB cooling reveals that entropy in the capacitor is reduced and the device is at non-equilibrium; i.e., the free energy of the device increases. Since this entropy reduction originates from information about the electrons' motion monitored by the detector, our results by the FB control represent one type of information-to-energy conversion.

Effects of G-Quadruplex Topology on Electronic Transfer Integrals

PubMed Central

Sun, Wenming; Varsano, Daniele; Di Felice, Rosa

2016-01-01

G-quadruplex is a quadruple helical form of nucleic acids that can appear in guanine-rich parts of the genome. The basic unit is the G-tetrad, a planar assembly of four guanines connected by eight hydrogen bonds. Its rich topology and its possible relevance as a drug target for a number of diseases have stimulated several structural studies. The superior stiffness and electronic π-π overlap between consecutive G-tetrads suggest exploitation for nanotechnologies. Here we inspect the intimate link between the structure and the electronic properties, with focus on charge transfer parameters. We show that the electronic couplings between stacked G-tetrads strongly depend on the three-dimensional atomic structure. Furthermore, we reveal a remarkable correlation with the topology: a topology characterized by the absence of syn-anti G-G sequences can better support electronic charge transfer. On the other hand, there is no obvious correlation of the electronic coupling with usual descriptors of the helix shape. We establish a procedure to maximize the correlation with a global helix shape descriptor. PMID:28335314

Electrochemical control over photoinduced electron transfer and trapping in CdSe-CdTe quantum-dot solids.

PubMed

Boehme, Simon C; Walvis, T Ardaan; Infante, Ivan; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Houtepen, Arjan J

2014-07-22

Understanding and controlling charge transfer between different kinds of colloidal quantum dots (QDs) is important for devices such as light-emitting diodes and solar cells and for thermoelectric applications. Here we study photoinduced electron transfer between CdTe and CdSe QDs in a QD film. We find that very efficient electron trapping in CdTe QDs obstructs electron transfer to CdSe QDs under most conditions. Only the use of thiol ligands results in somewhat slower electron trapping; in this case the competition between trapping and electron transfer results in a small fraction of electrons being transferred to CdSe. However, we demonstrate that electron trapping can be controlled and even avoided altogether by using the unique combination of electrochemistry and transient absorption spectroscopy. When the Fermi level is raised electrochemically, traps are filled with electrons and electron transfer from CdTe to CdSe QDs occurs with unity efficiency. These results show the great importance of knowing and controlling the Fermi level in QD films and open up the possibility of studying the density of trap states in QD films as well as the systematic investigation of the intrinsic electron transfer rates in donor-acceptor films.

Simulation-Based Approach to Determining Electron Transfer Rates Using Square-Wave Voltammetry.

PubMed

Dauphin-Ducharme, Philippe; Arroyo-Currás, Netzahualcóyotl; Kurnik, Martin; Ortega, Gabriel; Li, Hui; Plaxco, Kevin W

2017-05-09

The efficiency with which square-wave voltammetry differentiates faradic and charging currents makes it a particularly sensitive electroanalytical approach, as evidenced by its ability to measure nanomolar or even picomolar concentrations of electroactive analytes. Because of the relative complexity of the potential sweep it uses, however, the extraction of detailed kinetic and mechanistic information from square-wave data remains challenging. In response, we demonstrate here a numerical approach by which square-wave data can be used to determine electron transfer rates. Specifically, we have developed a numerical approach in which we model the height and the shape of voltammograms collected over a range of square-wave frequencies and amplitudes to simulated voltammograms as functions of the heterogeneous rate constant and the electron transfer coefficient. As validation of the approach, we have used it to determine electron transfer kinetics in both freely diffusing and diffusionless surface-tethered species, obtaining electron transfer kinetics in all cases in good agreement with values derived using non-square-wave methods.

Note: Self-biased voltage to suppress secondary electrons by a ZnO varistor in a compact pulsed neutron generator

NASA Astrophysics Data System (ADS)

Yang, Z.; Li, X.; Li, J.; Long, J. D.; Lan, C. H.; Wang, T.; Dong, P.; He, J. L.

2017-03-01

A large amount of back streaming electrons will bring about a part of current drain on power supply, cause sparking or high-voltage breakdowns, and affect the neutron yield and waveform for a compact sealed-tube pulsed neutron generator. A novel idea which uses a ZnO varistor to provide a constant self-biased voltage to suppress the secondary electrons is introduced. The I-V curve for the ZnO varistor was measured in the experiment. The effects of suppressing the secondary electrons were investigated using a ZnO varistor, linear resistors, and an independent power supply, respectively. The results show that the secondary electrons are suppressed effectively by the compact ZnO varistor, while not increasing the size and the component of the device. It is a promising design for compact sealed-tube neutron generators.

Experiments in DIII-D Toward Achieving Rapid Shutdown with Runaway Electron Suppression

NASA Astrophysics Data System (ADS)

Hollmann, E. M.

2009-11-01

For safe discharge shutdown in future large tokamaks in the event of an unavoidable disruption, it is important to develop rapid (˜ several ms)shutdown methods to avoid large runaway electron currents, which pose a serious threat to plasma facing components. Prevention of runaway current formation has been proposed by either increasing electron-electron collisionality with massive particle injection, or magnetically by using externally applied non-axisymmetric fields to increase radial diffusive losses of a runaway seed population. Experiments studying both approaches have been pursued in the DIII-D tokamak. For collisional suppression, three different rapid shutdown methods are being investigated: massive gas injection, massive shattered cryogenic pellet injection, and polystyrene shell pellet injection. First-of-kind demonstrations of fast shutdowns were produced by 3000 Torr-l (0.8-g) shattered D2 pellets and large, 10-mm diameter, 0.3-g polystyrene shell pellets filled with boron powder. The application of external magnetic perturbations shows promising preliminary results in suppressing seed runaway electrons, although lack of repeatability in the runaway seed term made these results challenging to interpret. Experiments have been performed to help understand how runaways form and are transported during rapid shutdown. These experiments confirm that the commonly used 0D loop voltage + Dreicer evaporation picture of runaway seed formation is not applicable here, with relativistic E > 0.5,MeV electrons forming before any external loop voltage appears. Present applications of 0D, 1D, and 2D models to the rapid shutdown and runaway confinement experiments, as well as preliminary extrapolations to ITER, will be discussed.

Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor.

PubMed

Zhang, Min; E, Wenbo; Ohkubo, Kei; Sanchez-Garcia, David; Yoon, Dae-Wi; Sessler, Jonathan L; Fukuzumi, Shunichi; Kadish, Karl M

2008-02-21

Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.

Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

PubMed

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.

Direct electron transfer of glucose oxidase on carbon nanotubes

NASA Astrophysics Data System (ADS)

Guiseppi-Elie, Anthony; Lei, Chenghong; Baughman, Ray H.

2002-10-01

In this report, exploitation of the unique properties of single-walled carbon nanotubes (SWNT) leads to the achievement of direct electron transfer with the redox active centres of adsorbed oxidoreductase enzymes. Flavin adenine dinucleotide (FAD), the redox active prosthetic group of flavoenzymes that catalyses important biological redox reactions and the flavoenzyme glucose oxidase (GOx), were both found to spontaneously adsorb onto carbon nanotube bundles. Both FAD and GOx were found to spontaneously adsorb to unannealed carbon nanotubes that were cast onto glassy carbon electrodes and to display quasi-reversible one-electron transfer. Similarly, GOx was found to spontaneously adsorb to annealed, single-walled carbon nanotube paper and to display quasi-reversible one-electron transfer. In particular, GOx immobilized in this way was shown, in the presence of glucose, to maintain its substrate-specific enzyme activity. It is believed that the tubular fibrils become positioned within tunnelling distance of the cofactors with little consequence to denaturation. The combination of SWNT with redox active enzymes would appear to offer an excellent and convenient platform for a fundamental understanding of biological redox reactions as well as the development of reagentless biosensors and nanobiosensors.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes.

PubMed

Westlake, Brittany C; Brennaman, M Kyle; Concepcion, Javier J; Paul, Jared J; Bettis, Stephanie E; Hampton, Shaun D; Miller, Stephen A; Lebedeva, Natalia V; Forbes, Malcolm D E; Moran, Andrew M; Meyer, Thomas J; Papanikolas, John M

2011-05-24

The simultaneous, concerted transfer of electrons and protons--electron-proton transfer (EPT)--is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H(+) is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated (+)H ─ B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

Copper-Containing Nitrite Reductase Employing Proton-Coupled Spin-Exchanged Electron-Transfer and Multiproton Synchronized Transfer to Reduce Nitrite.

PubMed

Qin, Xin; Deng, Li; Hu, Caihong; Li, Li; Chen, Xiaohua

2017-10-20

The possible catalytic mechanism of the reduction of nitrite by copper-containing nitrite reductases (CuNiRs) is examined by using the M06 function according to two copper models, which include type-one copper (T1Cu) and type-two copper (T2Cu) sites. Examinations confirm that the protonation of two residues, His255 and Asp98, near the T2Cu site, can modulate the redox states of T1Cu and T2Cu, but cannot directly cause electron transfer from T1Cu to T2Cu. The electron hole remains at the T2Cu site when only one residue, His255 or Asp98, is protonated. However, the hole resides at the T1Cu site when both His255 and Asp98 are protonated. Then, the first protonation of nitrite takes place through indirect proton transfer from protonated His255 through the bridging H 2 O and Asp98 with three protons moving together, which cannot cause the cleavage of the HO-NO bond. Subsequently, the substrate is required to obtain another proton from reprotonated His255 through the bridging H 2 O. The reprotonation of nitrite induces the generation of nitric oxide (NO) and H 2 O at the T2Cu site through a special double-proton-coupled spin-exchanged electron-transfer mechanism with indirect proton transfer from His255 to the substrate, a beta-electron of T2Cu I shift to the NO cation, and the remaining alpha-electron changing spin direction at the same time. These results may provide useful information to better understand detailed proton-/electron-transfer reactions for the catalytic processes of CuNiR. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Promoting Interspecies Electron Transfer with Biochar

PubMed Central

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

Ab Initio Analysis of Auger-Assisted Electron Transfer.

PubMed

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.

Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

2017-09-01

The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

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

Federal Register 2010, 2011, 2012, 2013, 2014

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...

The dipole moment of the electron carrier adrenodoxin is not critical for redox partner interaction and electron transfer.

PubMed

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.

Experimental studies of fundamental issues in electron transfer through nanometer scale devices

NASA Astrophysics Data System (ADS)

Yamamoto, Hiromichi

Electron transfer reactions constitute many of the primary events in materials science, chemistry, physics, and biochemistry, e.g. the electron transport properties and photoexcited processes in solids and molecules, chemical reactions, corrosion, photosynthesis, respiration, and so forth. A self-assembled monolayer (SAM) film provides us with a unique environment not only to understand and manipulate the surface electronic properties of a solid, but also to control electron transfer processes at the interface. The first topic in this thesis describes the structure and electron tunneling characterization of alkanethiol SAMs on InP(100). Angle-resolved X-ray photoelectron spectroscopy was used to characterize the bonding of alkanethiols to n-InP surfaces and to measure the monolayer thickness. The results showed that the sulfur binds to In atoms on the surface, and provided film thicknesses of 6.4 A for C8H17SH, 11.1 A for C12H25SH, and 14.9 A for C16H 33SH, resulting in an average tilt angle of 55°. The analysis indicated that super-exchange coupling between the alkane chains plays an important role in defining electron tunneling barriers, especially for highly tilted chains. The second topic describes studies of cytochrome c bound to pure and mixed SAMs of o-terminated alkanethiol (terminated with pyridine, imidazole or nitrile groups) and alkanethiol on gold. Electrochemical methods are used to determine electron transfer rate constants of cytochrome c, and scanning tunneling microscopy to observe the cytochrome c on the SAM. Detailed analysis revealed direct association of the heme of cytochrome c with the terminal groups of the SAMs and a 'turning-over' of the electron transfer of cytochrome c from adiabatic to non-adiabatic regime. The third topic describes studies of oxidation and reduction of cytochrome c in solution through eleven different self-assembled monolayers (SAMs) on gold electrodes by cyclic voltammetry. Electron transfer rate constants of

Energy and Electron Transfer in Enhanced Two-Photon-Absorbing Systems with Triplet Cores

PubMed Central

Finikova, Olga S.; Troxler, Thomas; Senes, Alessandro; DeGrado, William F.; Hochstrasser, Robin M.; Vinogradov, Sergei A.

2008-01-01

Enhanced two-photon-absorbing (2PA) systems with triplet cores are currently under scrutiny for several biomedical applications, including photodynamic therapy (PDT) and two-photon microscopy of oxygen. The performance of so far developed molecules, however, is substantially below expected. In this study we take a detailed look at the processes occurring in these systems and propose ways to improve their performance. We focus on the interchromophore distance tuning as a means for optimization of two-photon sensors for oxygen. In these constructs, energy transfer from several 2PA chromophores is used to enhance the effective 2PA cross section of phosphorescent metalloporphyrins. Previous studies have indicated that intramolecular electron transfer (ET) can act as an effective quencher of phosphorescence, decreasing the overall sensor efficiency. We studied the interplay between 2PA, energy transfer, electron transfer, and phosphorescence emission using Rhodamine B-Pt tetrabenzoporphyrin (RhB-PtTBP) adducts as model compounds. 2PA cross sections (σ2) of tetrabenzoporphyrins (TBPs) are in the range of several tens of GM units (near 800 nm), making TBPs superior 2PA chromophores compared to regular porphyrins (σ2 values typically 1-2 GM). Relatively large 2PA cross sections of rhodamines (about 200 GM in 800-850 nm range) and their high photostabilities make them good candidates as 2PA antennae. Fluorescence of Rhodamine B (λfl = 590 nm, ϕfl = 0.5 in EtOH) overlaps with the Q-band of phosphorescent PtTBP (λabs = 615 nm, ϵ = 98 000 M-1 cm-1, ϕp ∼ 0.1), suggesting that a significant amplification of the 2PA-induced phosphorescence via fluorescence resonance energy transfer (FRET) might occur. However, most of the excitation energy in RhB-PtTBP assemblies is consumed in several intramolecular ET processes. By installing rigid nonconducting decaproline spacers (Pro10) between RhB and PtTBP, the intramolecular ETs were suppressed, while the chromophores were kept

Long-range electron transfer in a model for DNA

NASA Astrophysics Data System (ADS)

Endres, R. G.; Cox, D. L.

2001-03-01

Long-range electron transfer (ET) between well separated donor (D) and acceptor (A) sites through quantum mechanical tunneling is essential to many biological processes like respiration, photosynthesis and possibly DNA repair and damage. We are investigating the distance dependence of the electronic transition matrix element H_DA and hence of the electron transfer rate in a model for DNA. Fluorescence quenching in DNA at D-A distances of 40 Åand more suggests ET with an unusually high decay length β-1 of order 10 Å (S.O.Kelley and J.K.Barton, in:Metal Ions in Biological Systems), A.Sigel and H.Sigel, Eds., Marcel Dekker, New York, Vol.36, 1999. Assuming strong electron interactions on the D complex and suitable energetics, this could be explained by formation of a many electron Kondo boundstate. We obtain H_DA from the splitting between the two lowest adiabatic electronic eigenenergies, which constitute the potential energy surfaces (PES) of the nuclear motion in lowest order Born-Oppenheimer approximation. The PES are constructed by coupling D and A to local breathing modes and by making a semi-analytical variational ansatz for the adiabatic eigenstates. The results from the PES are compared with results from the Mulliken-Hush algorithm.

Structural insights into electron transfer in caa3-type cytochrome oxidase

PubMed Central

Lyons, Joseph A.; Aragão, David; Slattery, Orla; Pisliakov, Andrei V.; Soulimane, Tewfik; Caffrey, Martin

2012-01-01

Summary Paragraph Cytochrome c oxidase is a member of the heme copper oxidase superfamily (HCO)1. HCOs function as the terminal enzymes in the respiratory chain of mitochondria and aerobic prokaryotes, coupling molecular oxygen reduction to transmembrane proton pumping. Integral to the enzyme’s function is the transfer of electrons from cytochrome c to the oxidase via a transient association of the two proteins. Electron entry and exit are proposed to occur from the same site on cytochrome c2–4. Here we report the crystal structure of the caa3-type cytochrome oxidase from Thermus thermophilus, which has a covalently tethered cytochrome c domain. Crystals were grown in a bicontinuous mesophase using a synthetic short-chain monoacylglycerol as the hosting lipid. From the electron density map, at 2.36 Å resolution, a novel integral membrane subunit and a native glycoglycerophospholipid embedded in the complex were identified. Contrary to previous electron transfer mechanisms observed for soluble cytochrome c, the structure reveals the architecture of the electron transfer complex for the fused cupredoxin/cytochrome c domain which implicates different sites on cytochrome c for electron entry and exit. Support for an alternative to the classical proton gate characteristic of this HCO class is presented. PMID:22763450

Probe-based measurement of lateral single-electron transfer between individual molecules

PubMed Central

Steurer, Wolfram; Fatayer, Shadi; Gross, Leo; Meyer, Gerhard

2015-01-01

The field of molecular electronics aims at using single molecules as functional building blocks for electronics components, such as switches, rectifiers or transistors. A key challenge is to perform measurements with atomistic control over the alignment of the molecule and its contacting electrodes. Here we use atomic force microscopy to examine charge transfer between weakly coupled pentacene molecules on insulating films with single-electron sensitivity and control over the atomistic details. We show that, in addition to the imaging capability, the probe tip can be used to control the charge state of individual molecules and to detect charge transfers to/from the tip, as well as between individual molecules. Our approach represents a novel route for molecular charge transfer studies with a host of opportunities, especially in combination with single atom/molecule manipulation and nanopatterning techniques. PMID:26387533

An application protocol for CAD to CAD transfer of electronic information

NASA Technical Reports Server (NTRS)

Azu, Charles C., Jr.

1993-01-01

The exchange of Computer Aided Design (CAD) information between dissimilar CAD systems is a problem. This is especially true for transferring electronics CAD information such as multi-chip module (MCM), hybrid microcircuit assembly (HMA), and printed circuit board (PCB) designs. Currently, there exists several neutral data formats for transferring electronics CAD information. These include IGES, EDIF, and DXF formats. All these formats have limitations for use in exchanging electronic data. In an attempt to overcome these limitations, the Navy's MicroCIM program implemented a project to transfer hybrid microcircuit design information between dissimilar CAD systems. The IGES (Initial Graphics Exchange Specification) format is used since it is well established within the CAD industry. The goal of the project is to have a complete transfer of microelectronic CAD information, using IGES, without any data loss. An Application Protocol (AP) is being developed to specify how hybrid microcircuit CAD information will be represented by IGES entity constructs. The AP defines which IGES data items are appropriate for describing HMA geometry, connectivity, and processing as well as HMA material characteristics.

Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Karna, Shashi P.

2002-01-01

The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westlake, Brittany C.; Brennaman, Kyle M.; Concepcion, Javier J.

2011-05-24

The simultaneous, concerted transfer of electrons and protons—electron-proton transfer (EPT)—is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectralmore » measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H⁺ is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck–Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated ⁺H–B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.« less

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

PubMed

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.

Role of coherence and delocalization in photo-induced electron transfer at organic interfaces

NASA Astrophysics Data System (ADS)

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.

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

PubMed Central

Petrenko, Alexander; Stein, Matthias

2017-01-01

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron–sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from Density Functional Theory (DFT) calculations. The distal cubane FeS-cluster has a three-cysteine and one-histidine coordination [Fe4S4](His)(Cys)3 first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and an all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe4S4](Cys)4 case. The fast and efficient electron transfer from the distal iron–sulfur cluster is realized by a fine-tuned protein environment, which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering. PMID:28067774

Interplay between barrier width and height in electron tunneling: photoinduced electron transfer in porphyrin-based donor-bridge-acceptor systems.

PubMed

Pettersson, Karin; Wiberg, Joanna; Ljungdahl, Thomas; Mårtensson, Jerker; Albinsson, Bo

2006-01-12

The rate of electron tunneling in molecular donor-bridge-acceptor (D-B-A) systems is determined both by the tunneling barrier width and height, that is, both by the distance between the donor and acceptor as well as by the energy gap between the donor and bridge moieties. These factors are therefore important to control when designing functional electron transfer systems, such as constructs for photovoltaics, artificial photosynthesis, and molecular scale electronics. In this paper we have investigated a set of D-B-A systems in which the distance and the energy difference between the donor and bridge states (DeltaEDB) are systematically varied. Zinc(II) and gold(III) porphyrins were chosen as electron donor and acceptor because of their suitable driving force for photoinduced electron transfer (-0.9 eV in butyronitrile) and well-characterized photophysics. We have previously shown, in accordance with the superexchange mechanism for electron transfer, that the electron transfer rate is proportional to the inverse of DeltaEDB in a series of zinc/gold porphyrin D-B-A systems with bridges of constant edge to edge distance (19.6 A) and varying DeltaEDB (3900-17 600 cm(-1)). Here, we use the same donor and acceptor but the bridge is shortened or extended giving a set of oligo-p-phenyleneethynylene bridges (OPE) with four different edge to edge distances ranging from 12.7 to 33.4 A. These two sets of D-B-A systems-ZnP-RB-AuP+ and ZnP-nB-AuP+-have one bridge in common, and hence, for the first time both the distance and DeltaEDB dependence of electron transfer can be studied simultaneously in a systematic way.

Molecular control of pentacene/ZnO photoinduced charge transfer

NASA Astrophysics Data System (ADS)

Spalenka, Josef W.; Paoprasert, Peerasak; Franking, Ryan; Hamers, Robert J.; Gopalan, Padma; Evans, Paul G.

2011-03-01

Photoinduced charge transfer modifies the device properties of illuminated pentacene field effect transistors (FETs) incorporating ZnO quantum dots at the gate insulator/pentacene interface. The transferred charge is trapped on electronic states associated with the ZnO quantum dots, with a steady state population approximately proportional to the rate of organic-inorganic charge transfer. Trapped charge shifts the threshold voltage of the FETs, providing the means to evaluate the rate of organic/inorganic charge transfer and the effects of interface modification. Monolayers of the wide-gap alkane stearic acid and the conjugated oligomer terthiophene attached to the ZnO suppress or permit charge transfer, respectively.

Probing conformational dynamics by photoinduced electron transfer

NASA Astrophysics Data System (ADS)

Neuweiler, Hannes; Herten, Dirk P.; Marme, N.; Knemeyer, J. P.; Piestert, Oliver; Tinnefeld, Philip; Sauer, Marcus

2004-07-01

We demonstrate how photoinduced electron transfer (PET) reactions can be successfully applied to monitor conformational dynamics in individual biopolymers. Single-pair fluorescence resonance energy transfer (FRET) experiments are ideally suited to study conformational dynamics occurring on the nanometer scale, e.g. during protein folding or unfolding. In contrast, conformational dynamics with functional significance, for example occurring in enzymes at work, often appear on much smaller spatial scales of up to several Angströms. Our results demonstrate that selective PET-reactions between fluorophores and amino acids or DNA nucleotides represent a versatile tool to measure small-scale conformational dynamics in biopolymers on a wide range of time scales, extending from nanoseconds to seconds, at the single-molecule level under equilibrium conditions. That is, the monitoring of conformational dynamics of biopolymers with temporal resolutions comparable to those within reach using new techniques of molecular dynamic simulations. We present data about structural changes of single biomolecules like DNA hairpins and peptides by using quenching electron transfer reactions between guanosine or tryptophan residues in close proximity to fluorescent dyes. Furthermore, we demonstrate that the strong distance dependence of charge separation reactions on the sub-nanometer scale can be used to develop conformationally flexible PET-biosensors. These sensors enable the detection of specific target molecules in the sub-picomolar range and allow one to follow their molecular binding dynamics with temporal resolution.

Protein Conformational Dynamics Probed by Single-Molecule Electron Transfer

NASA Astrophysics Data System (ADS)

Yang, Haw; Luo, Guobin; Karnchanaphanurach, Pallop; Louie, Tai-Man; Rech, Ivan; Cova, Sergio; Xun, Luying; Xie, X. Sunney

2003-10-01

Electron transfer is used as a probe for angstrom-scale structural changes in single protein molecules. In a flavin reductase, the fluorescence of flavin is quenched by a nearby tyrosine residue by means of photo-induced electron transfer. By probing the fluorescence lifetime of the single flavin on a photon-by-photon basis, we were able to observe the variation of flavin-tyrosine distance over time. We could then determine the potential of mean force between the flavin and the tyrosine, and a correlation analysis revealed conformational fluctuation at multiple time scales spanning from hundreds of microseconds to seconds. This phenomenon suggests the existence of multiple interconverting conformers related to the fluctuating catalytic reactivity.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer.

PubMed

Tiwari, Vivek; Jonas, David M

2018-02-28

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

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer

NASA Astrophysics Data System (ADS)

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

Modeling time-coincident ultrafast electron transfer and solvation processes at molecule-semiconductor interfaces

NASA Astrophysics Data System (ADS)

Li, Lesheng; Giokas, Paul G.; Kanai, Yosuke; Moran, Andrew M.

2014-06-01

Kinetic models based on Fermi's Golden Rule are commonly employed to understand photoinduced electron transfer dynamics at molecule-semiconductor interfaces. Implicit in such second-order perturbative descriptions is the assumption that nuclear relaxation of the photoexcited electron donor is fast compared to electron injection into the semiconductor. This approximation breaks down in systems where electron transfer transitions occur on 100-fs time scale. Here, we present a fourth-order perturbative model that captures the interplay between time-coincident electron transfer and nuclear relaxation processes initiated by light absorption. The model consists of a fairly small number of parameters, which can be derived from standard spectroscopic measurements (e.g., linear absorbance, fluorescence) and/or first-principles electronic structure calculations. Insights provided by the model are illustrated for a two-level donor molecule coupled to both (i) a single acceptor level and (ii) a density of states (DOS) calculated for TiO2 using a first-principles electronic structure theory. These numerical calculations show that second-order kinetic theories fail to capture basic physical effects when the DOS exhibits narrow maxima near the energy of the molecular excited state. Overall, we conclude that the present fourth-order rate formula constitutes a rigorous and intuitive framework for understanding photoinduced electron transfer dynamics that occur on the 100-fs time scale.

Mathematical model of mass transfer at electron beam treatment

NASA Astrophysics Data System (ADS)

Konovalov, Sergey V.; Sarychev, Vladimir D.; Nevskii, Sergey A.; Kobzareva, Tatyana Yu.; Gromov, Victor E.; Semin, Alexander P.

2017-01-01

The paper proposes a model of convective mass transfer at electron beam treatment with beams in titanium alloys subjected to electro-explosion alloying by titanium diboride powder. The proposed model is based on the concept that treatment with concentrated flows of energy results in the initiation of vortices in the melted layer. The formation mechanism of these vortices rooted in the idea that the availability of temperature drop leads to the initiation of the thermo-capillary convection. For the melted layer of metal the equations of the convective heat transfer and boundary conditions in terms of the evaporated material are written. The finite element solution of these equations showed that electron-beam treatment results in the formation of multi-vortex structure that in developing captures all new areas of material. It leads to the fact that the strengthening particles are observed at the depth increasing many times the depth of their penetration according to the diffusion mechanism. The distribution of micro-hardness at depth and the thickness of strengthening zone determined from these data supported the view that proposed model of the convective mass transfer describes adequately the processes going on in the treatment with low-energy high-current electron beam.

Development of a Simple Electron Transfer and Polarization Model and Its Application to Biological Systems.

PubMed

Diller, David J

2017-01-10

Here we present a new method for point charge calculation which we call Q ET (charges by electron transfer). The intent of this work is to develop a method that can be useful for studying charge transfer in large biological systems. It is based on the intuitive framework of the Q EQ method with the key difference being that the Q ET method tracks all pairwise electron transfers by augmenting the Q EQ pseudoenergy function with a distance dependent cost function for each electron transfer. This approach solves the key limitation of the Q EQ method which is its handling of formally charged groups. First, we parametrize the Q ET method by fitting to electrostatic potentials calculated using ab initio quantum mechanics on over 11,000 small molecules. On an external test set of over 2500 small molecules the Q ET method achieves a mean absolute error of 1.37 kcal/mol/electron when compared to the ab initio electrostatic potentials. Second, we examine the conformational dependence of the charges on over 2700 tripeptides. With the tripeptide data set, we show that the conformational effects account for approximately 0.4 kcal/mol/electron on the electrostatic potentials. Third, we test the Q ET method for its ability to reproduce the effects of polarization and electron transfer on 1000 water clusters. For the water clusters, we show that the Q ET method captures about 50% of the polarization and electron transfer effects. Finally, we examine the effects of electron transfer and polarizability on the electrostatic interaction between p38 and 94 small molecule ligands. When used in conjunction with the Generalized-Born continuum solvent model, polarization and electron transfer with the Q ET model lead to an average change of 17 kcal/mol on the calculated electrostatic component of ΔG.

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

PubMed

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

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

PubMed

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.

Ultrafast Interlayer Electron Transfer in Incommensurate Transition Metal Dichalcogenide Homobilayers.

PubMed

Li, Yuanyuan; Cui, Qiannan; Ceballos, Frank; Lane, Samuel D; Qi, Zeming; Zhao, Hui

2017-11-08

Two-dimensional materials, such as graphene, transition metal dichalcogenides, and phosphorene, can be used to construct van der Waals multilayer structures. This approach has shown potentials to produce new materials that combine novel properties of the participating individual layers. One key requirement for effectively harnessing emergent properties of these materials is electronic connection of the involved atomic layers through efficient interlayer charge or energy transfer. Recently, ultrafast charge transfer on a time scale shorter than 100 fs has been observed in several van der Waals bilayer heterostructures formed by two different materials. However, information on the transfer between two atomic layers of the same type is rare. Because these homobilayers are essential elements in constructing multilayer structures with desired optoelectronic properties, efficient interlayer transfer is highly desired. Here we show that electron transfer between two monolayers of MoSe 2 occurs on a picosecond time scale. Even faster transfer was observed in homobilayers of WS 2 and WSe 2 . The samples were fabricated by manually stacking two exfoliated monolayer flakes. By adding a graphene layer as a fast carrier recombination channel for one of the two monolayers, the transfer of the photoexcited carriers from the populated to the drained monolayers was time-resolved by femtosecond transient absorption measurements. The observed efficient interlayer carrier transfer indicates that such homobilayers can be used in van der Waals multilayers to enhance their optical absorption without significantly compromising the interlayer transport performance. Our results also provide valuable information for understanding interlayer charge transfer in heterostructures.

Excited state electron transfer in systems with a well-defined geometry. [cyclophane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaufmann, K.J.

1980-12-01

The effect of temperature, dielectric strength and ligand on the structure of the mesopyropheophorbide cyclophanes will be studied. ESR, NMR, emission and absorption spectroscopy, as well as circular dichroism will be used. The changes in structure will be correlated with changes in the photochemical activity. Electron acceptors such as benzoquinone will be utilized to stabilize the charge separation. Charge separation in porphyrin quinone dimers will also be studied. It was found that electron transfer in the cyclophane system is relatively slow. This is presumably due to an orientation requirement for fast electron transfer. Solvent dielectric also is important in producingmore » a charge separation. Decreasing the temperature effects the yield of charge transfer, but not the kinetics.« less

Alternating electron and proton transfer steps in photosynthetic water oxidation

PubMed Central

Klauss, André; Haumann, Michael; Dau, Holger

2012-01-01

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel–production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese–calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S2 → S3 transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein–water interface is characterized by a high activation energy (Ea = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S0 → S1 transition are similar (τ, approximately 100 µs; Ea = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established. PMID:22988080

Alternating electron and proton transfer steps in photosynthetic water oxidation.

PubMed

Klauss, André; Haumann, Michael; Dau, Holger

2012-10-02

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

Triboelectric effect: A new perspective on electron transfer process

NASA Astrophysics Data System (ADS)

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.

Suppression of high-energy electrons generated in both disrupting and sustained MST tokamak plasmas

NASA Astrophysics Data System (ADS)

Pandya, M. D.; Chapman, B. E.; Munaretto, S.; Cornille, B. S.; McCollam, K. J.; Sovinec, C. R.; Dubois, A. M.; Almagri, A. F.; Goetz, J. A.

2017-10-01

High-energy electrons appearing during MST tokamak plasma disruptions are rapidly lost from the plasma due apparently to internal MHD activity. Work has just recently begun on generating and diagnosing disruptions in MST tokamak plasmas. Initial measurements show the characteristic drop in central temperature and density preceding a quench of the plasma current. This corresponds to a burst of dominantly n=1 MHD activity, which is accompanied by a short-lived burst of high-energy electrons. The short-lived nature of these electrons is suspected to be due to stochastic transport associated with the increased MHD. Earlier work shows that runaway electrons generated in low density, sustained plasmas are suppressed by a sufficiently large m=3 RMP in plasmas with q(a) <3. RMPs of various poloidal mode number can be generated with an array of saddle coils wound around the vertical insulated gap in MST's thick conducting shell. With an m=3 RMP, the degree of runaway suppression increases with RMP amplitude, while an m=1 RMP has little effect on the runaways. Nonlinear MHD modeling with NIMROD of these MST plasmas indicates increased stochasticity with an m=3 RMP, while no such increase in stochasticity is observed with an m=1 RMP. Work supported by US DOE.

Photoinduced electron transfer in a molecular dyad by nanosecond pump-pump-probe spectroscopy.

PubMed

Ha-Thi, M-H; Pham, V-T; Pino, T; Maslova, V; Quaranta, A; Lefumeux, C; Leibl, W; Aukauloo, A

2018-06-01

The design of robust and inexpensive molecular photocatalysts for the conversion of abundant stable molecules like H2O and CO2 into an energetic carrier is one of the major fundamental questions for scientists nowadays. The outstanding challenge is to couple single photoinduced charge separation events with the sequential accumulation of redox equivalents at the catalytic unit for performing multielectronic catalytic reactions. Herein, double excitation by nanosecond pump-pump-probe experiments was used to interrogate the photoinduced charge transfer and charge accumulation on a molecular dyad composed of a porphyrin chromophore and a ruthenium-based catalyst in the presence of a reversible electron acceptor. An accumulative charge transfer state is unattainable because of rapid reverse electron transfer to the photosensitizer upon the second excitation and the low driving force of the forward photodriven electron transfer reaction. Such a method allows the fundamental understanding of the relaxation mechanism after two sequential photon absorptions, deciphering the undesired electron transfer reactions that limit the charge accumulation efficiency. This study is a step toward the improvement of synthetic strategies of molecular photocatalysts for light-induced charge accumulation and more generally, for solar energy conversion.

Suppression of the Transit -Time Instability in Large-Area Electron Beam Diodes

NASA Astrophysics Data System (ADS)

Myers, Matthew C.; Friedman, Moshe; Swanekamp, Stephen B.; Chan, Lop-Yung; Ludeking, Larry; Sethian, John D.

2002-12-01

Experiment, theory, and simulation have shown that large-area electron-beam diodes are susceptible to the transit-time instability. The instability modulates the electron beam spatially and temporally, producing a wide spread in electron energy and momentum distributions. The result is gross inefficiency in beam generation and propagation. Simulations indicate that a periodic, slotted cathode structure that is loaded with resistive elements may be used to eliminate the instability. Such a cathode has been fielded on one of the two opposing 60 cm × 200 cm diodes on the NIKE KrF laser at the Naval Research Laboratory. These diodes typically deliver 600 kV, 500 kA, 250 ns electron beams to the laser cell in an external magnetic field of 0.2 T. We conclude that the slotted cathode suppressed the transit-time instability such that the RF power was reduced by a factor of 9 and that electron transmission efficiency into the laser gas was improved by more than 50%.

Radiationless Electronic Excitation Energy Transfer Between Monolayers of J-Aggregates

NASA Astrophysics Data System (ADS)

Chmereva, T. M.; Kucherenko, M. G.

2018-06-01

Radiationless electronic excitation energy transfer between monolayers of cyanine dye molecules forming J-aggregates by means of surface plasmons of the metal film of nanometer thickness inserted between the monolayers is theoretically investigated. A dependence of the rate of energy transfer on the geometrical and electrodynamic parameters of the system is established. It is demonstrated that the energy transfer between the monolayers is more effective in the presence of the metal film than in a nonconductive medium.

Photoinduced Electron Transfer and Hole Migration in Nanosized Helical Aromatic Oligoamide Foldamers.

PubMed

Li, Xuesong; Markandeya, Nagula; Jonusauskas, Gediminas; McClenaghan, Nathan D; Maurizot, Victor; Denisov, Sergey A; Huc, Ivan

2016-10-07

A series of photoactive triads have been synthesized and investigated in order to elucidate photoinduced electron transfer and hole migration mechanism across nanosized, rigid helical foldamers. The triads are comprised of a central helical oligoamide foldamer bridge with 9, 14, 18, 19, or 34 8-amino-2-quinolinecarboxylic acid repeat units, and of two chromophores, an N-terminal oligo(para-phenylenevinylene) electron donor and a C-terminal perylene bis-imide electron acceptor. Time-resolved fluorescence and transient absorption spectroscopic studies showed that, following photoexcitation of the electron acceptor, fast electron transfer occurs initially from the oligoquinoline bridge to the acceptor chromophore on the picosecond time scale. The oligo(para-phenylenevinylene) electron donor is oxidized after a time delay during which the hole migrates across the foldamer from the acceptor to the donor. The charge separated state that is finally generated was found to be remarkably long-lived (>80 μs). While the initial charge injection rate is largely invariant for all foldamer lengths (ca. 60 ps), the subsequent hole transfer to the donor varies from 1 × 10 9 s -1 for the longest sequence to 17 × 10 9 s -1 for the shortest. In all cases, charge transfer is very fast considering the foldamer length. Detailed analysis of the process in different media and at varying temperatures is consistent with a hopping mechanism of hole transport through the foldamer helix, with individual hops occurring on the subpicosecond time scale (k ET = 2.5 × 10 12 s -1 in CH 2 Cl 2 ). This work demonstrates the possibility of fast long-range hole transfer over 300 Å (through bonds) across a synthetic modular bridge, an achievement that had been previously observed principally with DNA structures.

Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

PubMed

Mukherjee, Tamal; Ito, Naoki; Gould, Ian R

2011-03-17

The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

New electron-energy transfer rates for vibrational excitation of O2

NASA Astrophysics Data System (ADS)

Jones, D. B.; Campbell, L.; Bottema, M. J.; Brunger, M. J.

2003-09-01

We report on our computation of electron-energy transfer rates for vibrational excitation of O2. This work was necessitated by inadequacies in the electron-impact cross section databases employed in previous studies and, in one case, an inaccurate approximate formulation to the rate equation. Both these inadequacies led to incorrect energy transfer rates being published in the literature. We also demonstrate the importance of using cross sections that encompass an energy range that is extended enough to appropriately describe the environment under investigation.

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

PubMed

Bollella, Paolo; Gorton, Lo; Antiochia, Riccarda

2018-04-24

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.

Fabrication and single-electron-transfer operation of a triple-dot single-electron transistor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jo, Mingyu, E-mail: mingyujo@eis.hokudai.ac.jp; Uchida, Takafumi; Tsurumaki-Fukuchi, Atsushi

2015-12-07

A triple-dot single-electron transistor was fabricated on silicon-on-insulator wafer using pattern-dependent oxidation. A specially designed one-dimensional silicon wire having small constrictions at both ends was converted to a triple-dot single-electron transistor by means of pattern-dependent oxidation. The fabrication of the center dot involved quantum size effects and stress-induced band gap reduction, whereas that of the two side dots involved thickness modulation because of the complex edge structure of two-dimensional silicon. Single-electron turnstile operation was confirmed at 8 K when a 100-mV, 1-MHz square wave was applied. Monte Carlo simulations indicated that such a device with inhomogeneous tunnel and gate capacitances canmore » exhibit single-electron transfer.« less

Ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine and N-acetyltryptophan in aqueous solution: proton-coupled electron transfer versus electron transfer.

PubMed

Zhang, Ying; Yuan, Shuwei; Lu, Rong; Yu, Anchi

2013-06-20

We studied the ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine (AcTyr) and N-acetyltryptophan (AcTrp) in aqueous solution with femtosecond transient absorption spectroscopy. We found that the charge-transfer rate between Atto655 and AcTyr is about 240 times smaller than that between Atto655 and AcTrp. The pH value and D2O dependences of the excited-state decay kinetics of Atto655 in the presence of AcTyr and AcTrp reveal that the quenching of Atto655 fluorescence by AcTyr in aqueous solution is via a proton-coupled electron-transfer (PCET) process and that the quenching of Atto655 fluorescence by AcTrp in aqueous solution is via an electron-transfer process. With the version of the semiclassical Marcus ET theory, we derived that the electronic coupling constant for the PCET reaction between Atto655 and AcTyr in aqueous solution is 8.3 cm(-1), indicating that the PCET reaction between Atto655 and AcTyr in aqueous solution is nonadiabatic.

Direct Observation of Excimer-Mediated Intramolecular Electron Transfer in a Cofacially-Stacked Perylene Bisimide Pair.

PubMed

Sung, Jooyoung; Nowak-Król, Agnieszka; Schlosser, Felix; Fimmel, Benjamin; Kim, Woojae; Kim, Dongho; Würthner, Frank

2016-07-27

We have elucidated excimer-mediated intramolecular electron transfer in cofacially stacked PBIs tethered by two phenylene-butadiynylene loops. The electron transfer between energetically equivalent PBIs is revealed by the simultaneous observation of the PBI radical anion and cation bands in the transient absorption spectra. The fluorescence decay time of the excimer states is in good agreement with the rise time of PBI radical bands in transient absorption spectra suggesting that the electron transfer dynamics proceed via the excimer state. We can conclude that the excimer state effectuates the efficient charge transfer in the cofacially stacked PBI dimer.

Potential for direct interspecies electron transfer in methanogenic wastewater digester aggregates.

PubMed

Morita, Masahiko; Malvankar, Nikhil S; Franks, Ashley E; Summers, Zarath M; Giloteaux, Ludovic; Rotaru, Amelia E; Rotaru, Camelia; Lovley, Derek R

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 conductivities 3-fold higher than the conductivities previously reported for dual-species aggregates of Geobacter species in which the two species appeared to exchange electrons via interspecies electron transfer. The temperature dependence response of the aggregate conductance was characteristic of the organic metallic-like conductance previously described for the conductive pili of Geobacter sulfurreducens and was inconsistent with electron conduction through minerals. Studies in which aggregates were incubated with high concentrations of potential electron donors demonstrated that the aggregates had no significant capacity for conversion of hydrogen to methane. The aggregates converted formate to methane but at rates too low to account for the rates at which that the aggregates syntrophically metabolized ethanol, an important component of the reactor influent. Geobacter species comprised 25% of 16S rRNA gene sequences recovered from the aggregates, suggesting that Geobacter species may have contributed to some but probably not all of the aggregate conductivity. Microorganisms most closely related to the acetate-utilizing Methanosaeta concilii accounted for more than 90% of the sequences that could be assigned to methane producers, consistent with the poor capacity for hydrogen and formate utilization. These results demonstrate for the first time that methanogenic wastewater aggregates can be electrically conductive and suggest that direct interspecies electron transfer could be an important mechanism for electron exchange in some methanogenic systems.

Heat shock suppresses mating and sperm transfer in the rice leaf folder Cnaphalocrocis medinalis.

PubMed

Liao, H J; Qian, Q; Liu, X D

2014-06-01

Temperature is a key environmental factor in determining the population size of Cnaphalocrocis medinalis in summer. High temperatures inhibit survival, development and fecundity of this insect. However, biological responses of female and male adults to heat shock, and physiological mechanism of high temperature suppressing population development are still ambiguous. We experimentally tested the impact of heat shock (5 h day-1) on biological traits, spermatogenesis and sperm transfer of adults of C. medinalis. The result showed that heat exposure to 39 and 40 °C for 5 h reduced longevity and copulation frequency of adults, and hatchability of eggs. Immediate survival rate of males was lower than that of females after 3 days of exposure to 41 °C. The oviposition period, copulation frequency, fecundity of adults and hatchability of eggs were significantly lower when male adults were exposed to 40 or 41 °C for 3 days. Heat shock decreased frequency and success rate of mating when males were exposed, and it also resulted in postponement of mating behaviour and prolongation of mating duration as both the female and male adults were exposed. Heat shock did not affect spermatogenesis, but significantly inhibited sperms maturation. Moreover, males could not ejaculate sperm into females during copulation when these male moths received heat shock. Heat shock remarkably suppressed mating behaviour and sperm transfer, which led to a dramatic decline of rice leaf folder populations.

Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rury, Aaron S., E-mail: arury@usc.edu; Sorenson, Shayne; Dawlaty, Jahan M.

2016-03-14

Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone,more » we find sub-cm{sup −1} oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.« less

Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

NASA Astrophysics Data System (ADS)

Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

2016-03-01

Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

Adoptively transferred TRAIL+ T cells suppress GVHD and augment antitumor activity

PubMed Central

Ghosh, Arnab; Dogan, Yildirim; Moroz, Maxim; Holland, Amanda M.; Yim, Nury L.; Rao, Uttam K.; Young, Lauren F.; Tannenbaum, Daniel; Masih, Durva; Velardi, Enrico; Tsai, Jennifer J.; Jenq, Robert R.; Penack, Olaf; Hanash, Alan M.; Smith, Odette M.; Piersanti, Kelly; Lezcano, Cecilia; Murphy, George F.; Liu, Chen; Palomba, M. Lia; Sauer, Martin G.; Sadelain, Michel; Ponomarev, Vladimir; van den Brink, Marcel R.M.

2013-01-01

Current strategies to suppress graft-versus-host disease (GVHD) also compromise graft-versus-tumor (GVT) responses. Furthermore, most experimental strategies to separate GVHD and GVT responses merely spare GVT function without actually enhancing it. We have previously shown that endogenously expressed TNF-related apoptosis-inducing ligand (TRAIL) is required for optimal GVT activity against certain malignancies in recipients of allogeneic hematopoietic stem cell transplantation (allo-HSCT). In order to model a donor-derived cellular therapy, we genetically engineered T cells to overexpress TRAIL and adoptively transferred donor-type unsorted TRAIL+ T cells into mouse models of allo-HSCT. We found that murine TRAIL+ T cells induced apoptosis of alloreactive T cells, thereby reducing GVHD in a DR5-dependent manner. Furthermore, murine TRAIL+ T cells mediated enhanced in vitro and in vivo antilymphoma GVT response. Moreover, human TRAIL+ T cells mediated enhanced in vitro cytotoxicity against both human leukemia cell lines and against freshly isolated chronic lymphocytic leukemia (CLL) cells. Finally, as a model of off-the-shelf, donor-unrestricted antitumor cellular therapy, in vitro–generated TRAIL+ precursor T cells from third-party donors also mediated enhanced GVT response in the absence of GVHD. These data indicate that TRAIL-overexpressing donor T cells could potentially enhance the curative potential of allo-HSCT by increasing GVT response and suppressing GVHD. PMID:23676461

Mechanisms of transport and electron transfer at conductive polymer/liquid interfaces

NASA Astrophysics Data System (ADS)

Ratcliff, Erin

Organic semiconductors (OSCs) have incredible prospects for next-generation, flexible electronic devices including bioelectronics, thermoelectrics, opto-electronics, and energy storage and conversion devices. Yet many fundamental challenges still exist. First, solution processing prohibits definitive control over microstructure, which is fundamental for controlling electrical, ionic, and thermal transport properties. Second, OSCs generally suffer from poor electrical conductivities due to a combination of low carriers and low mobility. Third, polymeric semiconductors have potential-dependent, dynamically evolving electronic and chemical states, leading to complex interfacial charge transfer properties in contact with liquids. This talk will focus on the use of alternative synthetic strategies of oxidative chemical vapor deposition and electrochemical deposition to control physical, electronic, and chemical structure. We couple our synthetic efforts with energy-, time-, and spatially resolved spectroelectrochemical and microscopy techniques to understand the critical interfacial chemistry-microstructure-property relationships: first at the macroscale, and then moving towards the nanoscale. In particular, approaches to better understand electron transfer events at polymer/liquid interfaces as a function of: 1.) chemical composition; 2.) electronic density of states (DOS); and 3.) crystallinity and microstructure will be discussed.

Tip-Enhanced Photoinduced Electron Transfer and Ionization on Vertical Silicon Nanowires.

PubMed

Chen, Xiaoming; Wang, Tao; Lin, Leimiao; Wo, Fangjie; Liu, Yaqin; Liang, Xiao; Ye, Hui; Wu, Jianmin

2018-05-02

Nanostructured semiconductors are one of the most potent candidates for matrix-free laser desorption/ionization mass spectrometric (LDI-MS) analysis of low-molecular-weight molecules. Herein, the enhanced photoinduced electron transfer and LDI on the tip of a vertical silicon nanowire (SiNW) array were investigated. Theoretical simulation and LDI detection of indigo and isatin molecules in negative ion mode revealed that the electric field can be enhanced on the tip end of SiNWs, thereby promoting the energy and electron transfer to the analytes adsorbed on the tip of SiNWs. On the basis of this finding, a tip-contact sampling method coupled with LDI-MS detection was established. In this strategy, the tip of SiNWs can be regarded as microextraction heads for the sampling of molecules when they come in contact with analytes. Impression of skin, tissue, and pericarp on the vertical SiNW array can effectively transfer endogenous metabolites or exogenous substances onto the tip. Upon laser irradiation, the adsorbed molecules on the SiNW tip can be efficiently ionized and detected in negative ion mode because of the tip-enhanced electron transfer and LDI effect. We believe this work may significantly expand the application of LDI-MS in various fields.

Regulation of electron transfer processes affects phototrophic mat structure and activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan

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 mV Ag/AgCl [cathodic (CAT) mat system] and +300 mV Ag/AgCl [anodic (AN)more » 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. In conclusion, these data suggested that

Regulation of electron transfer processes affects phototrophic mat structure and activity

DOE PAGES

Ha, Phuc T.; Renslow, Ryan S.; Atci, Erhan; ...

2015-09-03

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 mV Ag/AgCl [cathodic (CAT) mat system] and +300 mV Ag/AgCl [anodic (AN)more » 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. In conclusion, these data suggested that

Human METTL20 Methylates Lysine Residues Adjacent to the Recognition Loop of the Electron Transfer Flavoprotein in Mitochondria*

PubMed Central

Rhein, Virginie F.; Carroll, Joe; He, Jiuya; Ding, Shujing; Fearnley, Ian M.; Walker, John E.

2014-01-01

In mammalian mitochondria, protein methylation is a relatively uncommon post-transcriptional modification, and the extent of the mitochondrial protein methylome, the modifying methyltransferases, and their substrates have been little studied. As shown here, the β-subunit of the electron transfer flavoprotein (ETF) is one such methylated protein. The ETF is a heterodimer of α- and β-subunits. Lysine residues 199 and 202 of mature ETFβ are almost completely trimethylated in bovine heart mitochondria, whereas ETFα is not methylated. The enzyme responsible for the modifications was identified as methyltransferase-like protein 20 (METTL20). In human 143B cells, the methylation of ETFβ is less extensive and is diminished further by suppression of METTL20. Tagged METTL20 expressed in HEK293T cells specifically associates with the ETF and promotes the trimethylation of ETFβ lysine residues 199 and 202. ETF serves as a mobile electron carrier linking dehydrogenases involved in fatty acid oxidation and one-carbon metabolism to the membrane-associated ubiquinone pool. The methylated residues in ETFβ are immediately adjacent to a protein loop that recognizes and binds to the dehydrogenases. Suppression of trimethylation of ETFβ in mouse C2C12 cells oxidizing palmitate as an energy source reduced the consumption of oxygen by the cells. These experiments suggest that the oxidation of fatty acids in mitochondria and the passage of electrons via the ETF may be controlled by modulating the protein-protein interactions between the reduced dehydrogenases and the β-subunit of the ETF by trimethylation of lysine residues. METTL20 is the first lysine methyltransferase to be found to be associated with mitochondria. PMID:25023281

Human METTL20 methylates lysine residues adjacent to the recognition loop of the electron transfer flavoprotein in mitochondria.

PubMed

Rhein, Virginie F; Carroll, Joe; He, Jiuya; Ding, Shujing; Fearnley, Ian M; Walker, John E

2014-08-29

In mammalian mitochondria, protein methylation is a relatively uncommon post-transcriptional modification, and the extent of the mitochondrial protein methylome, the modifying methyltransferases, and their substrates have been little studied. As shown here, the β-subunit of the electron transfer flavoprotein (ETF) is one such methylated protein. The ETF is a heterodimer of α- and β-subunits. Lysine residues 199 and 202 of mature ETFβ are almost completely trimethylated in bovine heart mitochondria, whereas ETFα is not methylated. The enzyme responsible for the modifications was identified as methyltransferase-like protein 20 (METTL20). In human 143B cells, the methylation of ETFβ is less extensive and is diminished further by suppression of METTL20. Tagged METTL20 expressed in HEK293T cells specifically associates with the ETF and promotes the trimethylation of ETFβ lysine residues 199 and 202. ETF serves as a mobile electron carrier linking dehydrogenases involved in fatty acid oxidation and one-carbon metabolism to the membrane-associated ubiquinone pool. The methylated residues in ETFβ are immediately adjacent to a protein loop that recognizes and binds to the dehydrogenases. Suppression of trimethylation of ETFβ in mouse C2C12 cells oxidizing palmitate as an energy source reduced the consumption of oxygen by the cells. These experiments suggest that the oxidation of fatty acids in mitochondria and the passage of electrons via the ETF may be controlled by modulating the protein-protein interactions between the reduced dehydrogenases and the β-subunit of the ETF by trimethylation of lysine residues. METTL20 is the first lysine methyltransferase to be found to be associated with mitochondria. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Long-range electron transfer in porphyrin-containing [2]-rotaxanes: tuning the rate by metal cation coordination.

PubMed

Andersson, Mikael; Linke, Myriam; Chambron, Jean-Claude; Davidsson, Jan; Heitz, Valérie; Hammarström, Leif; Sauvage, Jean-Pierre

2002-04-24

A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP*+-AuP* charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2x10(10) x s(-1) were obtained over a 15-17 A edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced superexchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)22+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron- and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2+ (k = 5.1x10(9) x s(-1)) that proceeded in competition with electron

Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot.

PubMed

Waskasi, Morteza M; Kodis, Gerdenis; Moore, Ana L; Moore, Thomas A; Gust, Devens; Matyushov, Dmitry V

2016-07-27

The Marcus theory of electron transfer predicts a bell-shaped dependence of the reaction rate on the reaction free energy. The top of the "inverted parabola" corresponds to zero activation barrier when the electron-transfer reorganization energy and the reaction free energy add up to zero. Although this point has traditionally been reached by altering the chemical structures of donors and acceptors, the theory suggests that it can also be reached by varying other parameters of the system including temperature. We find here dramatic evidence of this phenomenon from experiments on a fullerene-porphyrin dyad. Following photoinduced electron transfer, the rate of charge recombination shows a bell-shaped dependence on the inverse temperature, first increasing with cooling and then decreasing at still lower temperatures. This non-Arrhenius rate law is a result of a strong, approximately hyperbolic temperature variation of the reorganization energy and the reaction free energy. Our results provide potentially the cleanest confirmation of the Marcus energy gap law so far since no modification of the chemical structure is involved.

Novel Architectures for Achieving Direct Electron Transfer in Enzymatic Biofuel Cells

NASA Astrophysics Data System (ADS)

Blaik, Rita A.

Enzymatic biofuel cells are a promising source of alternative energy for small device applications, but still face the challenge of achieving direct electron transfer with high enzyme concentrations in a simple system. In this dissertation, methods of constructing electrodes consisting of enzymes attached to nanoparticle-enhanced substrates that serve as high surface area templates are evaluated. In the first method described, glucose oxidase is covalently attached to gold nanoparticles that are assembled onto genetically engineered M13 bacteriophage. The resulting anodes achieve a high peak current per area and a significant improvement in enzyme surface coverage. In the second system, fructose dehydrogenase, a membrane-bound enzyme that has the natural ability to achieve direct electron transfer, is immobilized into a matrix consisting of binders and carbon nanotubes to extend the lifetime of the anode. For the cathode, bilirubin oxidase is immobilized in a carbon nanotube and sol-gel matrix to achieve direct electron transfer. Finally, a full fuel cell consisting of both an anode and cathode is constructed and evaluated with each system described.

Distance dependence in photo-induced intramolecular electron transfer

NASA Astrophysics Data System (ADS)

Larsson, Sven; Volosov, Andrey

1986-09-01

The distance dependence of the rate of photo-induced electron transfer reactions is studied. A quantum mechanical method CNDO/S is applied to a series of molecules recently investigated by Hush et al. experimentally. The calculations show a large interaction through the saturated bridge which connects the two chromophores. The electronic matrix element HAB decreases a factor 10 in about 4 Å. There is also a decrease of the rate due to less exothermicity for the longer molecule. The results are in fair agreement with the experimental results.

Hardwiring microbes via direct interspecies electron transfer: mechanisms and applications.

PubMed

Cheng, Qiwen; Call, Douglas F

2016-08-10

Multicellular microbial communities are important catalysts in engineered systems designed to treat wastewater, remediate contaminated sediments, and produce energy from biomass. Understanding the interspecies interactions within them is therefore essential to design effective processes. The flow of electrons within these communities is especially important in the determination of reaction possibilities (thermodynamics) and rates (kinetics). Conventional models of electron transfer incorporate the diffusion of metabolites generated by one organism and consumed by a second, frequently referred to as mediated interspecies electron transfer (MIET). Evidence has emerged in the last decade that another method, called direct interspecies electron transfer (DIET), may occur between organisms or in conjunction with electrically conductive materials. Recent research has suggested that DIET can be stimulated in engineered systems to improve desired treatment goals and energy recovery in systems such as anaerobic digesters and microbial electrochemical technologies. In this review, we summarize the latest understanding of DIET mechanisms, the associated microorganisms, and the underlying thermodynamics. We also critically examine approaches to stimulate DIET in engineered systems and assess their effectiveness. We find that in most cases attempts to promote DIET in mixed culture systems do not yield the improvements expected based on defined culture studies. Uncertainties of other processes that may be co-occurring in real systems, such as contaminant sorption and biofilm promotion, need to be further investigated. We conclude by identifying areas of future research related to DIET and its application in biological treatment processes.

ACTIVE SUPPRESSION OF IMMUNOGLOBULIN ALLOTYPE SYNTHESIS

PubMed Central

Herzenberg, Leonore A.; Chan, Eva L.; Ravitch, Myrnice M.; Riblet, Roy J.; Herzenberg, Leonard A.

1973-01-01

Thymus-derived cells (T cells) that actively suppress production of IgG2a immunoglobulins carrying the Ig-1b allotype have been found in adult (SJL x BALB/c)F1 mice exposed to anti-Ig-1b early in life. The suppression is specific for Ig-1b. The allelic product, Ig-1a, is unaffected. Spleen, lymph node, bone marrow, or thymus cells from suppressed mice suppress production of Ig-1b by syngeneic spleen cells from normal F1 mice. When a mixture of suppressed and normal cells is transferred into lethally irradiated BALB/c mice, there is a short burst of Ig-1b production after which Ig-1b levels in the recipient fall rapidly below detectability. Pretreatment of the cells from the suppressed mice with antiserum specific for T cells (anti-Thy-1b) plus complement before mixture destroys the suppressing activity. Similar results with suppressor cells were obtained in vitro using Mishell-Dutton cultures. Mixture of spleen cells from suppressed animals with sheep erythrocyte (SRBC)-primed syngeneic normal spleen before culture suppresses Ig-1b plaque-forming cell (PFC) formation while leaving Ig-1a PFC unaffected. Treatment of the suppressed spleen with anti-Thy-1b before transfer removes the suppressing activity. PMID:4541122

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

PubMed

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.

Theoretical study of electronic transfer current rate at dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

AL-Agealy, Hadi J. M.; AlMaadhede, Taif Saad; Hassooni, Mohsin A.; Sadoon, Abbas K.; Ashweik, Ahmed M.; Mahdi, Hind Abdlmajeed; Ghadhban, Rawnaq Qays

2018-05-01

In this research, we present a theoretical study of electronic transfer kinetics rate in N719/TiO2 and N719/ZnO dye-sensitized solar cells (DSSC) systems using a simple model depending on the postulate of quantum mechanics theory. The evaluation of the electronic transition current rate in DSSC systems are function of many parameters such that; the reorientation transition energies ΛSe m D y e , the transition coupling parameter ℂT(0), potential exponential effect e-(E/C-EF ) kBT , unit cell volume VSem, and temperature T. Furthermore, the analysis of electronic transfer current rate in N719/TiO2 and N719/ZnO systems show that the rate upon dye-sensitization solar cell increases with increases of transition coupling parameter, decreasing potential that building at interface a results of different material in this devices and increasing with reorientation transition energy. On the other hand, we can find the electronic transfer behavior is dependent of the dye absorption spectrum and mainly depending on the reorientation of transition energy. The replacement of the solvents in both DSSC system caused increasing of current rates dramatically depending on polarity of solvent in subset devices. This change in current rate of electron transfer were attributed to much more available of recombination sites introduced by the solvents medium. The electronic transfer current dynamics are shown to occurs in N719/TiO2 system faster many time compare to ocuures at N719/ZnO system, this indicate that TiO2 a is a good and active material compare with ZnO to using in dye sensitized solar cell devices. In contrast, the large current rate in N719/TiO2 comparing to ZnO of N719/ZnO systems indicate that using TiO2 with N719 dye lead to increasing the efficiency of DSSC.

Experimental insights on the electron transfer and energy transfer processes between Ce{sup 3+}-Yb{sup 3+} and Ce{sup 3+}-Tb{sup 3+} in borate glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sontakke, Atul D., E-mail: sontakke.atul.55a@st.kyoto-u.ac.jp; Katayama, Yumiko; Tanabe, Setsuhisa

2015-03-30

A facile method to describe the electron transfer and energy transfer processes among lanthanide ions is presented based on the temperature dependent donor luminescence decay kinetics. The electron transfer process in Ce{sup 3+}-Yb{sup 3+} exhibits a steady rise with temperature, whereas the Ce{sup 3+}-Tb{sup 3+} energy transfer remains nearly unaffected. This feature has been investigated using the rate equation modeling and a methodology for the quantitative estimation of interaction parameters is presented. Moreover, the overall consequences of electron transfer and energy transfer process on donor-acceptor luminescence behavior, quantum efficiency, and donor luminescence decay kinetics are discussed in borate glass host.more » The results in this study propose a straight forward approach to distinguish the electron transfer and energy transfer processes between lanthanide ions in dielectric hosts, which is highly advantageous in view of the recent developments on lanthanide doped materials for spectral conversion, persistent luminescence, and related applications.« less

Increased electron temperature turbulence during suppression of edge localized mode by resonant magnetic perturbations in the DIII-D tokamak

NASA Astrophysics Data System (ADS)

Sung, C.; Wang, G.; Rhodes, T. L.; Smith, S. P.; Osborne, T. H.; Ono, M.; McKee, G. R.; Yan, Z.; Groebner, R. J.; Davis, E. M.; Zeng, L.; Peebles, W. A.; Evans, T. E.

2017-11-01

The first observation of increased electron temperature turbulence during edge localized mode (ELM) suppression by resonant magnetic perturbations (RMPs) is presented. These are long wavelength fluctuations (kθρs ≤ 0.2, where kθ = poloidal wavenumber and ρs = ion sound gyroradius) observed during H-mode plasmas on the DIII-D. This increase occurs only after ELMs are suppressed and are not observed during the initial RMP application. The T˜ e/Te increases ( >60%) are coincident with changes in normalized density and electron temperature gradients in the region from the top of the pedestal outward to the upper portion of the steep edge gradient. Density turbulence (kθρs ≤ 0.4) in this location was also observed to increase only after ELM suppression. These results are significant since they indicate that increased gradient-driven turbulent transport is one possible mechanism to regulate and maintain ELM-free H-mode operation. Investigation of linear stability of drift wave instabilities using the CGYRO code [Candy et al., J. Comput. Phys. 324, 73 (2016)] shows that the dominant mode moves closer to the electron mode branch from the ion mode branch only after ELMs are suppressed, correlated with the increased turbulence. The increased turbulence during ELM suppression, rather than with the initial RMP application, indicates that the often observed RMP induced "density pump-out" cannot be attributed to long wavelength edge turbulence level changes.

Evidence that Additions of Grignard Reagents to Aliphatic Aldehydes Do Not Involve Single-Electron-Transfer Processes.

PubMed

Otte, Douglas A L; Woerpel, K A

2015-08-07

Addition of allylmagnesium reagents to an aliphatic aldehyde bearing a radical clock gave only addition products and no evidence of ring-opened products that would suggest single-electron-transfer reactions. The analogous Barbier reaction also did not provide evidence for a single-electron-transfer mechanism in the addition step. Other Grignard reagents (methyl-, vinyl-, t-Bu-, and triphenylmethylmagnesium halides) also do not appear to add to an alkyl aldehyde by a single-electron-transfer mechanism.

Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives.

PubMed

Driscoll, Eric; Sorenson, Shayne; Dawlaty, Jahan M

2015-06-04

Concerted motion of electrons and protons in the excited state is pertinent to a wide range of chemical phenomena, including those relevant for solar-to-fuel light harvesting. The excited state dynamics of small proton-bearing molecules are expected to serve as models for better understanding such phenomena. In particular, for designing the next generation of multielectron and multiproton redox catalysts, understanding the dynamics of more than one proton in the excited state is important. Toward this goal, we have measured the ultrafast dynamics of intramolecular excited state proton transfer in a recently synthesized dye with two equivalent transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a wide bandwidth in the visible range. The measurement shows that the signal which is characteristic of proton transfer emerges within ∼710 fs. To identify whether both protons were transferred in the excited state, we have measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer time in that molecule was ∼427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported by the ultrafast observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals in the Franck-Condon region. The calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer is

Covalent Electron Transfer Theory of Superconductivity

DTIC Science & Technology

1992-06-19

carriers. This situation is analogous to a vacuum diode without space charge, where each electron emitted from the cathode arrives at the anode before...Generic MO energy level diagram for a do cation in an oxygen octahedral complex. 89 53 Band model approximation of the MO states of a Cu perovskite ...C2) CuO4 complex. 94 57 p-type 3d 2,2-2p a Cu2+-O-Cu3+ covalent transfer in I 80-deg perovskite bond 95 geometry for d9 - d8(low-spin). xi LIST OF

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeda, Kouta; Matsumura, Hirotoshi; Ishida, Takuya

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

Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor

NASA Astrophysics Data System (ADS)

Kumar, Vinay; Kashyap, D. M. Nikhila; Hebbar, Suraj; Swetha, R.; Prasad, Sujay; Kamala, T.; Srikanta, S. S.; Krishnaswamy, P. R.; Bhat, Navakanta

2017-02-01

Direct Electron Transfer biosensors, facilitating direct communication between the biomolecule of interest and electrode surface, are preferable compared to enzymatic and mediator based sensors. Although hemoglobin (Hb) contains four redox active iron centres, direct detection is not possible due to inaccessibility of iron centres and formation of dimers, blocking electron transfer. Through the coordination of iron with aza-heterocyclic receptors - pyridine and imidazole - we report a cost effective, highly sensitive and simple electrochemical Hb sensor using cyclic voltammetry and chronoamperometry. The receptor can be either in the form of liquid micro-droplet mixed with blood or dry chemistry embedded in paper membrane on top of screen printed carbon electrodes. We demonstrate excellent linearity and robustness against interference using clinical samples. A truly point of care technology is demonstrated by integrating disposable test strips with handheld reader, enabling finger prick to result in less than a minute.

Modeling biofilms with dual extracellular electron transfer mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Renslow, Ryan S.; Babauta, Jerome T.; Kuprat, Andrew P.

2013-11-28

Electrochemically active biofilms have a unique form of respiration in which they utilize solid external materials as their terminal electron acceptor for metabolism. Currently, two primary mechanisms have been identified for long-range extracellular electron transfer (EET): a diffusion- and a conduction-based mechanism. Evidence in the literature suggests that some biofilms, particularly Shewanella oneidensis, produce components requisite for both mechanisms. In this study, a generic model is presented that incorporates both diffusion- and conduction-based mechanisms and allows electrochemically active biofilms to utilize both simultaneously. The model was applied to Shewanella oneidensis and Geobacter sulfurreducens biofilms using experimentally generated data found themore » literature. Our simulation results showed that 1) biofilms having both mechanisms available, especially if they can interact, may have metabolic advantage over biofilms that can use only a single mechanism; 2) the thickness of Geobacter sulfurreducens biofilms is likely not limited by conductivity; 3) accurate intrabiofilm diffusion coefficient values are critical for current generation predictions; and 4) the local biofilm potential and redox potential are two distinct measurements and cannot be assumed to have identical values. Finally, we determined that cyclic and squarewave voltammetry are currently not good tools to determine the specific percentage of extracellular electron transfer mechanisms used by biofilms. The developed model will be a critical tool in designing experiments to explain EET mechanisms.« less

Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

PubMed

Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Weinstein, Julia A

2015-04-21

The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and

27 CFR 19.524 - Payment of tax by electronic fund transfer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... under this part and parts 26 and 27 of this chapter, shall use a commercial bank in making payment by... shall direct the taxpayer's bank to make an electronic fund transfer in the amount of the taxpayment to... bank early enough for the transfer to be made to the Treasury Account by no later than the close of...

Time-resolved measurement of intramolecular photoinduced electron transfer processes in perylene diimides (Conference Presentation)

NASA Astrophysics Data System (ADS)

Döring, Robin Carl; Baal, Eduard; Sundermeyer, Jörg; Chatterjee, Sangam

2017-02-01

Perylene-3,4,9,10-tetracarboxylic acid (PTCDA) and respective derivatives (e.g. perylene diimide - PDI) are widely used as dyes but also for device applications such as organic field effect transistors or in organic photovoltaics. Due to their intrinsically high quantum efficiencies they are also used as spectroscopic standards. One major drawback of these materials is their low solubility in organic solvents which can be addressed by long alkyl substitutions. When introducing a tertiary amine into the molecule a mechanism known as photoinduced electron transfer (PET) can occur. Here, following an optically excited HOMO-LUMO transition of the core, an electron from the electron lone pair of the amine is transferred to the HOMO of the perylene core. Hence, radiative recombination is disallowed and photoluminescence effectively quenched. Here, we perform a systematic study of the distance dependence of the PET by introducing alkyle groups as spacer units between PDI core and the tertiary amine. Dynamics of the PET are extracted from ultrafast time-resolved photoluminescence measurement data. A rate equation model, simulating a three level system, reveals rate constant of the back electron transfer, otherwise not accessible with our experimental methods. Assuming a Marcus model of electron transfer, electronic coupling strength between the electronic states involved in the respective transitions can be calculated. In addition to the distance dependence, the effects of protonation and methylation of the the tertiary amine units are studied.

"Sticky electrons" transport and interfacial transfer of electrons in the dye-sensitized solar cell.

PubMed

Peter, Laurence

2009-11-17

Dye-sensitized solar cells (DSCs, also known as Gratzel cells) mimic the photosynthetic process by using a sensitizer dye to harvest light energy to generate electrical power. Several functional features of these photochemical devices are unusual, and DSC research offers a rewarding arena in which to test new ideas, new materials, and new methodologies. Indeed, one of the most attractive chemical features of the DSC is that the basic concept can be used to construct a range of devices, replacing individual components with alternative materials. Despite two decades of increasing research activity, however, many aspects of the behavior of electrons in the DSC remain puzzling. In this Account, we highlight current understanding of the processes involved in the functioning of the DSC, with particular emphasis on what happens to the electrons in the mesoporous film following the injection step. The collection of photoinjected electrons appears to involve a random walk process in which electrons move through the network of interconnected titanium dioxide nanoparticles while undergoing frequent trapping and detrapping. During their passage to the cell contact, electrons may be lost by transfer to tri-iodide species in the redox electrolyte that permeates the mesoporous film. Competition between electron collection and back electron transfer determines the performance of a DSC: ideally, all injected electrons should be collected without loss. This Account then goes on to survey recent experimental and theoretical progress in the field, placing particular emphasis on issues that need to be resolved before we can gain a clear picture of how the DSC works. Several important questions about the behavior of "sticky" electrons, those that undergo multiple trapping and detrapping, in the DSC remain unanswered. The most fundamental of these concerns is the nature of the electron traps that appear to dominate the time-dependent photocurrent and photovoltage response of DSCs. The

Hyphal formation of Candida albicans is controlled by electron transfer system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Toshihiko; Ogasawara, Ayako; Mikami, Takeshi

2006-09-15

Most Candida albicans cells cultured in RPMI1640 medium at 37 deg. C grow in hyphal form in aerobic conditions, but they grow in yeast form in anaerobic conditions. The hyphal growth of C. albicans was inhibited in glucose-deficient conditions. Malonic acid, an inhibitor of succinate dehydrogenase, enhanced the yeast proliferation of C. albicans, indicating that the hyphal-formation signal was derived from the glycolysis system and the signal was transmitted to the electron transfer system via the citric acid cycle. Thenoyl trifluoro acetone (TTFA), an inhibitor of the signal transmission between complex II and Co Q, significantly inhibited the hyphal growthmore » of C. albicans. Antimycin, KCN, and oligomycin, inhibitors of complex III, IV, and V, respectively, did not inhibit the hyphal growth of C. albicans. The production of mRNAs for the hyphal formation signal was completely inhibited in anaerobic conditions. These results indicate that the electron transfer system functions upstream of the RAS1 signal pathway and activates the expression of the hyphal formation signal. Since the electron transfer system is inactivated in anaerobic conditions, C. albicans grew in yeast form in this condition.« less

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

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via 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 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using 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 is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Sub-Poissonian light and photocurrent shot-noise suppression in closed opto-electronic loop

NASA Technical Reports Server (NTRS)

Masalov, A. V.; Putilin, A. A.; Vasilyev, Michael V.

1994-01-01

We examine experimentally photocurrent noise reduction in the opto-electronic closed loop. Photocurrent noise density 12.5 dB below the shot-noise was observed. So large suppression was not reached in previous experiments and cannot be explained in terms of an ordinary sub-Poissonian light in the loop. We propose the concept of anticorrelation state for the description of light in the loop.

76 FR 67153 - Federal Acquisition Regulation; Submission for OMB Review; Payment by Electronic Fund Transfer

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-31

...; Submission for OMB Review; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD), General... collection requirement concerning payment by electronic fund transfer. A notice was published in the Federal... technological collection techniques or other forms of information technology. DATES: Submit comments on or...

Direct Interspecies Electron Transfer in Anaerobic Digestion: A Review.

PubMed

Dubé, Charles-David; Guiot, Serge R

2015-01-01

Direct interspecies electrons transfer (DIET) is a syntrophic metabolism in which free electrons flow from one cell to another without being shuttled by reduced molecules such as molecular hydrogen or formate. As more and more microorganisms show a capacity for electron exchange, either to export or import them, it becomes obvious that DIET is a syntrophic metabolism that is much more present in nature than previously thought. This article reviews literature related to DIET, specifically in reference to anaerobic digestion. Anaerobic granular sludge, a biofilm, is a specialized microenvironment where syntrophic bacterial and archaeal organisms grow together in close proximity. Exoelectrogenic bacteria degrading organic substrates or intermediates need an electron sink and electrotrophic methanogens represent perfect partners to assimilate those electrons and produce methane. The granule extracellular polymeric substances by making the biofilm matrix more conductive, play a role as electrons carrier in DIET.

Suppressing the image smear of the vibration modulation transfer function for remote-sensing optical cameras.

PubMed

Li, Jin; Liu, Zilong; Liu, Si

2017-02-20

In on-board photographing processes of satellite cameras, the platform vibration can generate image motion, distortion, and smear, which seriously affect the image quality and image positioning. In this paper, we create a mathematical model of a vibrating modulate transfer function (VMTF) for a remote-sensing camera. The total MTF of a camera is reduced by the VMTF, which means the image quality is degraded. In order to avoid the degeneration of the total MTF caused by vibrations, we use an Mn-20Cu-5Ni-2Fe (M2052) manganese copper alloy material to fabricate a vibration-isolation mechanism (VIM). The VIM can transform platform vibration energy into irreversible thermal energy with its internal twin crystals structure. Our experiment shows the M2052 manganese copper alloy material is good enough to suppress image motion below 125 Hz, which is the vibration frequency of satellite platforms. The camera optical system has a higher MTF after suppressing the vibration of the M2052 material than before.

Photoinduced charge-transfer electronic excitation of tetracyanoethylene/tetramethylethylene complex in dichloromethane

NASA Astrophysics Data System (ADS)

Xu, Long-Kun; Bi, Ting-Jun; Ming, Mei-Jun; Wang, Jing-Bo; Li, Xiang-Yuan

2017-07-01

Based on the previous work on nonequilibrium solvation model by the authors, Intermolecular charge-transfer electronic excitation of tetracyanoethylene (TCE)/tetramethylethylene (TME) π -stacked complex in dichloromethane (DCM) has been investigated. For weak interaction correction, dispersion corrected functional DFT-D3 is adopted for geometry optimization. In order to identify the excitation metric, dipole moment components of each Cartesian direction, atomic charge, charge separation and Δr index are analyzed for TCE/TME complex. Calculation shows that the calculated excitation energy is dependent on the functional choice, when conjuncted with suitable time-dependent density functional, the modified nonequilibrium expression gives satisfied results for intermolecular charge-transfer electronic excitation.

Interdomain electron transfer in cellobiose dehydrogenase is governed by surface electrostatics.

PubMed

Kadek, Alan; Kavan, Daniel; Marcoux, Julien; Stojko, Johann; Felice, Alfons K G; Cianférani, Sarah; Ludwig, Roland; Halada, Petr; Man, Petr

2017-02-01

Cellobiose dehydrogenase (CDH) is a fungal extracellular oxidoreductase which fuels lytic polysaccharide monooxygenase with electrons during cellulose degradation. Interdomain electron transfer between the flavin and cytochrome domain in CDH, preceding the electron flow to lytic polysaccharide monooxygenase, is known to be pH dependent, but the exact mechanism of this regulation has not been experimentally proven so far. To investigate the structural aspects underlying the domain interaction in CDH, hydrogen/deuterium exchange (HDX-MS) with improved proteolytic setup (combination of nepenthesin-1 with rhizopuspepsin), native mass spectrometry with ion mobility and electrostatics calculations were used. HDX-MS revealed pH-dependent changes in solvent accessibility and hydrogen bonding at the interdomain interface. Electrostatics calculations identified these differences to result from charge neutralization by protonation and together with ion mobility pointed at higher electrostatic repulsion between CDH domains at neutral pH. In addition, we uncovered extensive O-glycosylation in the linker region and identified the long-unknown exact cleavage point in papain-mediated domain separation. Transition of CDH between its inactive (open) and interdomain electron transfer-capable (closed) state is shown to be governed by changes in the protein surface electrostatics at the domain interface. Our study confirms that the interdomain electrostatic repulsion is the key factor modulating the functioning of CDH. The results presented in this paper provide experimental evidence for the role of charge repulsion in the interdomain electron transfer in cellobiose dehydrogenases, which is relevant for exploiting their biotechnological potential in biosensors and biofuel cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Covalent electron transfer chemistry of graphene with diazonium salts.

PubMed

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.

The impact of symmetric modes on intramolecular electron transfer: A semi-classical approach

NASA Astrophysics Data System (ADS)

Coropceanu, Veaceslav; Boldyrev, Sergei I.; Risko, Chad; Brédas, Jean-Luc

2006-07-01

We have generalized the Hush equations developed for the analysis of intervalence charge-transfer bands by including into the model the interaction with symmetric vibrations. Our results indicate that in symmetric class-II systems the maximum of the intervalence charge-transfer band is equal to the reorganization energy λ related to the antisymmetric vibrations as is the case in the conventional Hush model. In contrast, the corresponding transition dipole moment and the activation barrier for thermal electron transfer, in addition to their dependence on λ, also depend on the reorganization energy L related to symmetric vibrational modes. We show that the interaction with symmetric vibrational modes reduces the activation barrier and that the thermal electron-transfer rates derived on the basis of a Hush-type analysis of the optical data are generally underestimated.

Exosome-mediated miR-146a transfer suppresses type I interferon response and facilitates EV71 infection

PubMed Central

Fu, Yuxuan; Zhang, Li; Zhang, Fang; Tang, Ting; Zhou, Qi; Feng, Chunhong; Jin, Yu

2017-01-01

Exosomes can transfer genetic materials between cells. Their roles in viral infections are beginning to be appreciated. Researches have shown that exosomes released from virus-infected cells contain a variety of viral and host cellular factors that are able to modulate recipient’s cellular response and result in productive infection of the recipient host. Here, we showed that EV71 infection resulted in upregulated exosome secretion and differential packaging of the viral genomic RNA and miR-146a into exosomes. We provided evidence showing that miR-146a was preferentially enriched in exosomes while the viral RNA was not in infected cells. Moreover, the exosomes contained replication-competent EV71 RNA in complex with miR-146a, Ago2, and GW182 and could mediate EV71 transmission independent of virus-specific receptor. The exosomal viral RNA could be transferred to and replicate in a new target cell while the exosomal miR-146a suppressed type I interferon response in the target cell, thus facilitating the viral replication. Additionally, we found that the IFN-stimulated gene factors (ISGs), BST-2/tetherin, were involved in regulating EV71-induced upregulation of exosome secretion. Importantly, in vivo study showed that exosomal viral RNA exhibited differential tissue accumulation as compared to the free virus particles. Together, our findings provide evidence that exosomes secreted by EV71-infected cells selectively packaged high level miR-146a that can be functionally transferred to and facilitate exosomal EV71 RNA to replicate in the recipient cells by suppressing type I interferon response. PMID:28910400

Theory for electron transfer from a mixed-valence dimer with paramagnetic sites to a mononuclear acceptor

NASA Astrophysics Data System (ADS)

Bominaar, E. L.; Achim, C.; Borshch, S. A.

1999-06-01

Polynuclear transition-metal complexes, such as Fe-S clusters, are the prosthetic groups in a large number of metalloproteins and serve as temporary electron storage units in a number of important redox-based biological processes. Polynuclearity distinguishes clusters from mononuclear centers and confers upon them unique properties, such as spin ordering and the presence of thermally accessible excited spin states in clusters with paramagnetic sites, and fractional valencies in clusters of the mixed-valence type. In an earlier study we presented an effective-mode (EM) analysis of electron transfer from a binuclear mixed-valence donor with paramagnetic sites to a mononuclear acceptor which revealed that the cluster-specific attributes have an important impact on the kinetics of long-range electron transfer. In the present study, the validity of these results is tested in the framework of more detailed theories which we have termed the multimode semiclassical (SC) model and the quantum-mechanical (QM) model. It is found that the qualitative trends in the rate constant are the same in all treatments and that the semiclassical models provide a good approximation of the more rigorous quantum-mechanical description of electron transfer under physiologically relevant conditions. In particular, the present results corroborate the importance of electron transfer via excited spin states in reactions with a low driving force and justify the use of semiclassical theory in cases in which the QM model is computationally too demanding. We consider cases in which either one or two donor sites of a dimer are electronically coupled to the acceptor. In the case of multiconnectivity, the rate constant for electron transfer from a valence-delocalized (class-III) donor is nonadditive with respect to transfer from individual metal sites of the donor and undergoes an order-of-magnitude change by reversing the sign of the intradimer metal-metal resonance parameter (β). In the case of

31 CFR 208.3 - Payment by electronic funds transfer.

Code of Federal Regulations, 2010 CFR

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...

Three-dimensional representations of photo-induced electron transfer rates in pyrene-(CH2)n-N,N'-dimethylaniline systems obtained by three electron transfer theories.

PubMed

Rujkorakarn, Rong; Tanaka, Fumio

2009-01-01

The observed rates of photo-induced electron transfer (ET) from N,N'-dimethylaniline (DMA) to the excited pyrene (Py) in confined systems of pyrene-(CH(2))(n)-N,N'- dimethylaniline (PnD: n=1-3) were studied by molecular dynamic simulation (MD) and three kinds of electron transfer theories. ET parameters contained in Marcus theory (M theory), Bixon and Jortner theory (BJ theory) and Kakitani and Mataga theory (KM theory) were determined so as to fit the calculated fluorescence intensities with those obtained by the observed ET rates, according to a non-linear least squares method. Three-dimensional profiles of logarithm of calculated ET rates depending on two of three ET parameters, R, epsilon(0) and -DeltaG degrees were systematically examined with best-fit ET parameters of P1D. Bell shape dependencies of ET rate were predicted on R and on epsilon(0), and on -DeltaG degrees as well, by M theory and KM theory. The profiles of logarithm of ET rate calculated by BJ theory exhibited oscillatory dependencies not only on -DeltaG degrees , but also on R and on epsilon(0). Relationship between ET state and charge transfer complex was discussed with BJ theory.

Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

PubMed

Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

2009-04-02

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Ultrafast Electron Transfer Kinetics in the LM Dimer of Bacterial Photosynthetic Reaction Center from Rhodobacter sphaeroides.

PubMed

Sun, Chang; Carey, Anne-Marie; Gao, Bing-Rong; Wraight, Colin A; Woodbury, Neal W; Lin, Su

2016-06-23

It has become increasingly clear that dynamics plays a major role in the function of many protein systems. One system that has proven particularly facile for studying the effects of dynamics on protein-mediated chemistry is the bacterial photosynthetic reaction center from Rhodobacter sphaeroides. Previous experimental and computational analysis have suggested that the dynamics of the protein matrix surrounding the primary quinone acceptor, QA, may be particularly important in electron transfer involving this cofactor. One can substantially increase the flexibility of this region by removing one of the reaction center subunits, the H-subunit. Even with this large change in structure, photoinduced electron transfer to the quinone still takes place. To evaluate the effect of H-subunit removal on electron transfer to QA, we have compared the kinetics of electron transfer and associated spectral evolution for the LM dimer with that of the intact reaction center complex on picosecond to millisecond time scales. The transient absorption spectra associated with all measured electron transfer reactions are similar, with the exception of a broadening in the QX transition and a blue-shift in the QY transition bands of the special pair of bacteriochlorophylls (P) in the LM dimer. The kinetics of the electron transfer reactions not involving quinones are unaffected. There is, however, a 4-fold decrease in the electron transfer rate from the reduced bacteriopheophytin to QA in the LM dimer compared to the intact reaction center and a similar decrease in the recombination rate of the resulting charge-separated state (P(+)QA(-)). These results are consistent with the concept that the removal of the H-subunit results in increased flexibility in the region around the quinone and an associated shift in the reorganization energy associated with charge separation and recombination.

On generalized Mulliken-Hush approach of electronic transfer: Inclusion of non-zero off-diagonal diabatic dipole moment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kryachko, E.S.

1999-06-03

The electronic coupling between the initial and final diabatic states is the major factor that determines the rate of electron transfer. A general formula for the adiabatic-to-diabatic mixing angle in terms of the electronic dipole moments is derived within a two-state model. It expresses the electronic coupling determining the rate of electronic transfer in terms of the off-diagonal diabatic dipole moment.

Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

NASA Astrophysics Data System (ADS)

Zhang, Yan; Hao, Huilian; Wang, Linlin

2016-12-01

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 (k0) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k0 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. k0 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.

Correlating electronic and vibrational motions in charge transfer systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khalil, Munira

2014-06-27

The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

Optical determination of charge transfer times from indoline dyes to ZnO in solid state dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Meyenburg, I.; Hofeditz, N.; Ruess, R.; Rudolph, M.; Schlettwein, D.; Heimbrodt, W.

2018-05-01

We studied the electron transfer at the interface of organic-inorganic hybrids consisting of indoline derivatives (D149 and D131) on ZnO substrates using a new optical method. We revealed the electron transfer times from the excited dye, e.g. the excitons formed in the dye aggregates to the ZnO substrate by analyzing the photoluminescence transients of the excitons after femtosecond excitation and applying kinetic model calculations. We reveal the changes of the electron transfer times by applying electrical bias. Pushing the Fermi energy of the ZnO substrate towards the excited dye level the transfer time gets longer and eventually the electron transfer is suppressed. The level alignment between the excited dye state and the ZnO Fermi-level is estimated. The excited state of D131 is about 100 meV higher than the respective state of D149 compared to the ZnO conduction band. This leads to shorter electron transfer times and eventually to higher quantum efficiencies of the solar cells.

Electron Transfer Dissociation of iTRAQ Labeled Peptide Ions

PubMed Central

Han, Hongling; Pappin, Darryl J.; Ross, Philip L; McLuckey, Scott A.

2009-01-01

Triply and doubly charged iTRAQ (isobaric tagging for relative and absolute quantitation) labeled peptide cations from a tryptic peptide mixture of bovine carbonic anhydrase II were subjected to electron transfer ion/ion reactions to investigate the effect of charge bearing modifications associated with iTRAQ on the fragmentation pattern. It was noted that electron transfer dissociation (ETD) of triply charged or activated ETD (ETD + supplemental collisional activation of intact electron transfer species) of doubly charged iTRAQ tagged peptide ions yielded extensive sequence information, in analogy with ETD of unmodified peptide ions. That is, addition of the fixed charge iTRAQ tag showed relatively little deleterious effect on the ETD performance of the modified peptides. ETD of the triply charged iTRAQ labeled peptide ions followed by collision-induced dissociation (CID) of the product ion at m/z 162 yielded the reporter ion at m/z 116, which is the reporter ion used for quantitation via CID of the same precursor ions. The reporter ion formed via the two-step activation process is expected to provide quantitative information similar to that directly produced from CID. A 103 Da neutral loss species observed in the ETD spectra of all the triply and doubly charged iTRAQ labeled peptide ions is unique to the 116 Da iTRAQ reagent, which implies that this process also has potential for quantitation of peptides/proteins. Therefore, ETD with or without supplemental collisional activation, depending on the precursor ion charge state, has the potential to directly identify and quantify the peptides/proteins simultaneously using existing iTRAQ reagents. PMID:18646790

Enhanced Ionization of Embedded Clusters by Electron-Transfer-Mediated Decay in Helium Nanodroplets.

PubMed

LaForge, A C; Stumpf, V; Gokhberg, K; von Vangerow, J; Stienkemeier, F; Kryzhevoi, N V; O'Keeffe, P; Ciavardini, A; Krishnan, S R; Coreno, M; Prince, K C; Richter, R; Moshammer, R; Pfeifer, T; Cederbaum, L S; Mudrich, M

2016-05-20

We report the observation of electron-transfer-mediated decay (ETMD) involving magnesium (Mg) clusters embedded in helium (He) nanodroplets. ETMD is initiated by the ionization of He followed by removal of two electrons from the Mg clusters of which one is transferred to the He ion while the other electron is emitted into the continuum. The process is shown to be the dominant ionization mechanism for embedded clusters for photon energies above the ionization potential of He. For Mg clusters larger than five atoms we observe stable doubly ionized clusters. Thus, ETMD provides an efficient pathway to the formation of doubly ionized cold species in doped nanodroplets.

Electron Transfer Mechanism in Gold Surface Modified with Self-Assembly Monolayers from First Principles

NASA Astrophysics Data System (ADS)

Lima, Filipe C. D. A.; Iost, Rodrigo M.; Crespilho, Frank N.; Caldas, Marília J.; Calzolari, Arrigo; Petrilli, Helena M.

2013-03-01

We report the investigation of electron tunneling mechanism of peptide ferrocenyl-glycylcystamine self-assembled monolayers (SAMs) onto Au (111) electrode surfaces. Recent experimental investigations showed that electron transfer in peptides can occur across long distances by separating the donor from the acceptor. This mechanism can be further fostered by the presence of electron donor terminations of Fc terminal units on SAMs but the charge transfer mechanism is still not clear. We study the interaction of the peptide ferrocenyl-glycylcystamine on the Au (111) from first principles calculations to evaluate the electron transfer mechanism. For this purpose, we used the Kohn Sham (KS) scheme for the Density Functional Theory (DFT) as implemented in the Quantum-ESPRESSO suit of codes, using Vandebilt ultrasoft pseudopotentials and GGA-PBE exchange correlation functional to evaluate the ground-state atomic and electronic structure of the system. The analysis of KS orbital at the Fermi Energy showed high electronic density localized in Fc molecules and the observation of a minor contribution from the solvent and counter ion. Based on the results, we infer evidences of electron tunneling mechanism from the molecule to the Au(111). We acknowledge FAPESP for grant support. Also, LCCA/USP, RICE and CENAPAD for computational resources.

Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

NASA Astrophysics Data System (ADS)

Larsson, Sven; Volosov, Andrey

1987-12-01

Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

A redox beginning: Which came first phosphoryl, acyl, or electron transfer ?. [Abstract only

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

Thermodynamic and kinetic information available on the synthesis of prebiotic monomers and polymers will be examined in order to illuminate the prebiotic plausibility of polymer syntheses based on (a) phosphoryl transfer that yields phosphodiester polymers, (b) acyl transfer that gives polyamides, and (c) electron transfer that produces polydisulfide or poly(thio)ester polymers. New experimental results on the oxidative polymerization of 2,3-dimercaptopropanol by ferric ions on the surface of ferric hydroxide oxide will be discussed as a chemical model of polymerization by electron transfer. This redox polymerization that yields polymers with a polydisulfide backbone was found to give oligomers up to the 15-mer from 1 mM of 2,3-dimercaptopropanol after one day at 25 C. High pressure liquid chromatography (HPLC) analysis of the oligomers was carried out on an Alltech OH-100 column eluted with acetonitrile-water.

Unusual Internal Electron Transfer in Conjugated Radical Polymers.

PubMed

Li, Fei; Gore, Danielle N; Wang, Shaoyang; Lutkenhaus, Jodie L

2017-08-07

Nitroxide-containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy transfer between two vacuum-gapped metal plates: Coulomb fluctuations and electron tunneling

NASA Astrophysics Data System (ADS)

Zhang, Zu-Quan; Lü, Jing-Tao; Wang, Jian-Sheng

2018-05-01

Recent experimental measurements for near-field radiative heat transfer between two bodies have been able to approach the gap distance within 2 nm , where the contributions of Coulomb fluctuation and electron tunneling are comparable. Using the nonequilibrium Green's function method in the G0W0 approximation, based on a tight-binding model, we obtain for the energy current a Caroli formula from the Meir-Wingreen formula in the local equilibrium approximation. Also, the Caroli formula is consistent with the evanescent part of the heat transfer from the theory of fluctuational electrodynamics. We go beyond the local equilibrium approximation to study the energy transfer in the crossover region from electron tunneling to Coulomb fluctuation based on a numerical calculation.

Tuning of Hemes b Equilibrium Redox Potential Is Not Required for Cross-Membrane Electron Transfer.

PubMed

Pintscher, Sebastian; Kuleta, Patryk; Cieluch, Ewelina; Borek, Arkadiusz; Sarewicz, Marcin; Osyczka, Artur

2016-03-25

In biological energy conversion, cross-membrane electron transfer often involves an assembly of two hemesb The hemes display a large difference in redox midpoint potentials (ΔEm_b), which in several proteins is assumed to facilitate cross-membrane electron transfer and overcome a barrier of membrane potential. Here we challenge this assumption reporting on hemebligand mutants of cytochromebc1in which, for the first time in transmembrane cytochrome, one natural histidine has been replaced by lysine without loss of the native low spin type of heme iron. With these mutants we show that ΔEm_b can be markedly increased, and the redox potential of one of the hemes can stay above the level of quinone pool, or ΔEm_b can be markedly decreased to the point that two hemes are almost isopotential, yet the enzyme retains catalytically competent electron transfer between quinone binding sites and remains functionalin vivo This reveals that cytochromebc1can accommodate large changes in ΔEm_b without hampering catalysis, as long as these changes do not impose overly endergonic steps on downhill electron transfer from substrate to product. We propose that hemesbin this cytochrome and in other membranous cytochromesbact as electronic connectors for the catalytic sites with no fine tuning in ΔEm_b required for efficient cross-membrane electron transfer. We link this concept with a natural flexibility in occurrence of several thermodynamic configurations of the direction of electron flow and the direction of the gradient of potential in relation to the vector of the electric membrane potential. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Multiple sites of retardation of electron transfer in Photosystem II after hydrolysis of phosphatidylglycerol.

PubMed

Kim, Eun-Ha; Razeghifard, Reza; Anderson, Jan M; Chow, Wah Soon

2007-01-01

Phosphatidylglycerol (PG), containing the unique fatty acid Delta3, trans-16:1-hexadecenoic acid, is a minor but ubiquitous lipid component of thylakoid membranes of chloroplasts and cyanobacteria. We investigated its role in electron transfers and structural organization of Photosystem II (PSII) by treating Arabidopsis thaliana thylakoids with phospholipase A(2) to decrease the PG content. Phospholipase A(2) treatment of thylakoids (a) inhibited electron transfer from the primary quinone acceptor Q(A) to the secondary quinone acceptor Q(B), (b) retarded electron transfer from the manganese cluster to the redox-active tyrosine Z, (c) decreased the extent of flash-induced oxidation of tyrosine Z and dark-stable tyrosine D in parallel, and (d) inhibited PSII reaction centres such that electron flow to silicomolybdate in continuous light was inhibited. In addition, phospholipase A(2) treatment of thylakoids caused the partial dissociation of (a) PSII supercomplexes into PSII dimers that do not have the complete light-harvesting complex of PSII (LHCII); (b) PSII dimers into monomers; and (c) trimers of LHCII into monomers. Thus, removal of PG by phospholipase A(2) brings about profound structural changes in PSII, leading to inhibition/retardation of electron transfer on the donor side, in the reaction centre, and on the acceptor side. Our results broaden the simple view of the predominant effect being on the Q(B)-binding site.

Constraint-Based Modeling of Carbon Fixation and the Energetics of Electron Transfer in Geobacter metallireducens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feist, AM; Nagarajan, H; Rotaru, AE

2014-04-24

Geobacter species are of great interest for environmental and biotechnology applications as they can carry out direct electron transfer to insoluble metals or other microorganisms and have the ability to assimilate inorganic carbon. Here, we report on the capability and key enabling metabolic machinery of Geobacter metallireducens GS-15 to carry out CO2 fixation and direct electron transfer to iron. An updated metabolic reconstruction was generated, growth screens on targeted conditions of interest were performed, and constraint-based analysis was utilized to characterize and evaluate critical pathways and reactions in G. metallireducens. The novel capability of G. metallireducens to grow autotrophically withmore » formate and Fe(III) was predicted and subsequently validated in vivo. Additionally, the energetic cost of transferring electrons to an external electron acceptor was determined through analysis of growth experiments carried out using three different electron acceptors (Fe(III), nitrate, and fumarate) by systematically isolating and examining different parts of the electron transport chain. The updated reconstruction will serve as a knowledgebase for understanding and engineering Geobacter and similar species. Author Summary The ability of microorganisms to exchange electrons directly with their environment has large implications for our knowledge of industrial and environmental processes. For decades, it has been known that microbes can use electrodes as electron acceptors in microbial fuel cell settings. Geobacter metallireducens has been one of the model organisms for characterizing microbe-electrode interactions as well as environmental processes such as bioremediation. Here, we significantly expand the knowledge of metabolism and energetics of this model organism by employing constraint-based metabolic modeling. Through this analysis, we build the metabolic pathways necessary for carbon fixation, a desirable property for industrial chemical

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

NASA Astrophysics Data System (ADS)

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.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

36 CFR § 1235.44 - What general transfer requirements apply to electronic records?

Code of Federal Regulations, 2013 CFR

2013-07-01

... requirements apply to electronic records? § 1235.44 Section § 1235.44 Parks, Forests, and Public Property NATIONAL ARCHIVES AND RECORDS ADMINISTRATION RECORDS MANAGEMENT TRANSFER OF RECORDS TO THE NATIONAL... requirements apply to electronic records? (a) Each agency must retain a copy of permanent electronic records...

Transverse momentum and centrality dependence of high-pT nonphotonic electron suppression in Au+Au collisions at sqrt[s NN]=200 GeV.

PubMed

Abelev, B I; Aggarwal, M M; Ahammed, Z; Anderson, B D; Arkhipkin, D; Averichev, G S; Bai, Y; Balewski, J; Barannikova, O; Barnby, L S; Baudot, J; Baumgart, S; Belaga, V V; Bellingeri-Laurikainen, A; Bellwied, R; Benedosso, F; Betts, R R; Bhardwaj, S; Bhasin, A; Bhati, A K; Bichsel, H; Bielcik, J; Bielcikova, J; Bland, L C; Blyth, S-L; Bombara, M; Bonner, B E; Botje, M; Bouchet, J; Brandin, A V; Bravar, A; Burton, T P; Bystersky, M; Cadman, R V; Cai, X Z; Caines, H; Calderón de la Barca Sánchez, M; Callner, J; Catu, O; Cebra, D; Chajecki, Z; Chaloupka, P; Chattopadhyay, S; Chen, H F; Chen, J H; Chen, J Y; Cheng, J; Cherney, M; Chikanian, A; Christie, W; Chung, S U; Coffin, J P; Cormier, T M; Cosentino, M R; Cramer, J G; Crawford, H J; Das, D; Dash, S; Daugherity, M; de Moura, M M; Dedovich, T G; Dephillips, M; Derevschikov, A A; Didenko, L; Dietel, T; Djawotho, P; Dogra, S M; Dong, X; Drachenberg, J L; Draper, J E; Du, F; Dunin, V B; Dunlop, J C; Dutta Mazumdar, M R; Eckardt, V; Edwards, W R; Efimov, L G; Emelianov, V; Engelage, J; Eppley, G; Erazmus, B; Estienne, M; Fachini, P; Fatemi, R; Fedorisin, J; Feng, A; Filip, P; Finch, E; Fine, V; Fisyak, Y; Fu, J; Gagliardi, C A; Gaillard, L; Ganti, M S; Garcia-Solis, E; Ghazikhanian, V; Ghosh, P; Gorbunov, Y G; Gos, H; Grebenyuk, O; Grosnick, D; Guertin, S M; Guimaraes, K S F F; Gupta, N; Haag, B; Hallman, T J; Hamed, A; Harris, J W; He, W; Heinz, M; Henry, T W; Heppelmann, S; Hippolyte, B; Hirsch, A; Hjort, E; Hoffman, A M; Hoffmann, G W; Hofman, D; Hollis, R; Horner, M J; Huang, H Z; Hughes, E W; Humanic, T J; Igo, G; Iordanova, A; Jacobs, P; Jacobs, W W; Jakl, P; Jia, F; Jones, P G; Judd, E G; Kabana, S; Kang, K; Kapitan, J; Kaplan, M; Keane, D; Kechechyan, A; Kettler, D; Khodyrev, V Yu; Kim, B C; Kiryluk, J; Kisiel, A; Kislov, E M; Klein, S R; Knospe, A G; Kocoloski, A; Koetke, D D; Kollegger, T; Kopytine, M; Kotchenda, L; Kouchpil, V; Kowalik, K L; Kravtsov, P; Kravtsov, V I; Krueger, K; Kuhn, C; Kulikov, A I; Kumar, A; Kurnadi, P; Kuznetsov, A A; Lamont, M A C; Landgraf, J M; Lange, S; Lapointe, S; Laue, F; Lauret, J; Lebedev, A; Lednicky, R; Lee, C-H; Lehocka, S; LeVine, M J; Li, C; Li, Q; Li, Y; Lin, G; Lin, X; Lindenbaum, S J; Lisa, M A; Liu, F; Liu, H; Liu, J; Liu, L; Ljubicic, T; Llope, W J; Longacre, R S; Love, W A; Lu, Y; Ludlam, T; Lynn, D; Ma, G L; Ma, J G; Ma, Y G; Magestro, D; Mahapatra, D P; Majka, R; Mangotra, L K; Manweiler, R; Margetis, S; Markert, C; Martin, L; Matis, H S; Matulenko, Yu A; McClain, C J; McShane, T S; Melnick, Yu; Meschanin, A; Millane, J; Miller, M L; Minaev, N G; Mioduszewski, S; Mironov, C; Mischke, A; Mitchell, J; Mohanty, B; Morozov, D A; Munhoz, M G; Nandi, B K; Nattrass, C; Nayak, T K; Nelson, J M; Nepali, N S; Netrakanti, P K; Nogach, L V; Nurushev, S B; Odyniec, G; Ogawa, A; Okorokov, V; Oldenburg, M; Olson, D; Pachr, M; Pal, S K; Panebratsev, Y; Pavlinov, A I; Pawlak, T; Peitzmann, T; Perevoztchikov, V; Perkins, C; Peryt, W; Phatak, S C; Planinic, M; Pluta, J; Poljak, N; Porile, N; Poskanzer, A M; Potekhin, M; Potrebenikova, E; Potukuchi, B V K S; Prindle, D; Pruneau, C; Putschke, J; Qattan, I A; Raniwala, R; Raniwala, S; Ray, R L; Relyea, D; Ridiger, A; Ritter, H G; Roberts, J B; Rogachevskiy, O V; Romero, J L; Rose, A; Roy, C; Ruan, L; Russcher, M J; Sahoo, R; Sakrejda, I; Sakuma, T; Salur, S; Sandweiss, J; Sarsour, M; Sazhin, P S; Schambach, J; Scharenberg, R P; Schmitz, N; Seger, J; Selyuzhenkov, I; Seyboth, P; Shabetai, A; Shahaliev, E; Shao, M; Sharma, M; Shen, W Q; Shimanskiy, S S; Sichtermann, E P; Simon, F; Singaraju, R N; Smirnov, N; Snellings, R; Sorensen, P; Sowinski, J; Speltz, J; Spinka, H M; Srivastava, B; Stadnik, A; Stanislaus, T D S; Staszak, D; Stock, R; Strikhanov, M; Stringfellow, B; Suaide, A A P; Suarez, M C; Subba, N L; Sumbera, M; Sun, X M; Sun, Z; Surrow, B; Symons, T J M; Szanto de Toledo, A; Takahashi, J; Tang, A H; Tarnowsky, T; Thomas, J H; Timmins, A R; Timoshenko, S; Tokarev, M; Trainor, T A; Trentalange, S; Tribble, R E; Tsai, O D; Ulery, J; Ullrich, T; Underwood, D G; Van Buren, G; van der Kolk, N; van Leeuwen, M; Vander Molen, A M; Varma, R; Vasilevski, I M; Vasiliev, A N; Vernet, R; Vigdor, S E; Viyogi, Y P; Vokal, S; Voloshin, S A; Waggoner, W T; Wang, F; Wang, G; Wang, J S; Wang, X L; Wang, Y; Watson, J W; Webb, J C; Westfall, G D; Wetzler, A; Whitten, C; Wieman, H; Wissink, S W; Witt, R; Wu, J; Wu, Y; Xu, N; Xu, Q H; Xu, Z; Yepes, P; Yoo, I-K; Yue, Q; Yurevich, V I; Zhan, W; Zhang, H; Zhang, W M; Zhang, Y; Zhang, Z P; Zhao, Y; Zhong, C; Zhou, J; Zoulkarneev, R; Zoulkarneeva, Y; Zubarev, A N; Zuo, J X

2007-05-11

The STAR collaboration at the BNL Relativistic Heavy-Ion Collider (RHIC) reports measurements of the inclusive yield of nonphotonic electrons, which arise dominantly from semileptonic decays of heavy flavor mesons, over a broad range of transverse momenta (1.2electron yield exhibits an unexpectedly large suppression in central Au+Au collisions at high p(T), suggesting substantial heavy-quark energy loss at RHIC. The centrality and p(T) dependences of the suppression provide constraints on theoretical models of suppression.

Preparation of high performance NBR/HNTs nanocomposites using an electron transferring interaction method

NASA Astrophysics Data System (ADS)

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.

Quantitative Probes of Electron-Phonon Coupling in an Organic Charge-Transfer Material

NASA Astrophysics Data System (ADS)

Rury, Aaron; Sorenson, Shayne; Driscoll, Eric; Dawlaty, Jahan

While organic charge transfer (CT) materials may provide alternatives to inorganic materials in electronics and photonics applications, properties central to applications remain understudied in these organic materials. Specifically, electron-phonon coupling plays a pivotal role in electronic applications yet this coupling in CT materials remains difficult to directly characterize. To better understand the suitability of organic CT materials for electronic applications, we have devised an experimental technique that can directly assess electron-phonon coupling in a model organic CT material. Upon non-resonant interaction with an ultrafast laser pulse, we show that coherent excitation of Raman-active lattice vibrations of quinhydrone, a 1:1 co-crystal of the hydroquinone and p-benzoquinone, modulates the energies of electronic transitions probed by a white light pulse. Using a well-established theoretical framework of vibrational quantum beat spectra across the probe bandwidth, we quantitatively extract the parameters describing these electronic transitions to characterize electron-phonon coupling in this material. In conjunction with temperature-dependent resonance Raman measurements, we assess the hypothesis that several sharp transitions in the near-IR correspond to previously unknown excitonic states of this material. These results and their interpretation set the foundation for further elucidation of the one of the most important parameters in the application of organic charge-transfer materials to electronics and photonics.

A new semiclassical decoupling scheme for electronic transitions in molecular collisions - Application to vibrational-to-electronic energy transfer

NASA Technical Reports Server (NTRS)

Lee, H.-W.; Lam, K. S.; Devries, P. L.; George, T. F.

1980-01-01

A new semiclassical decoupling scheme (the trajectory-based decoupling scheme) is introduced in a computational study of vibrational-to-electronic energy transfer for a simple model system that simulates collinear atom-diatom collisions. The probability of energy transfer (P) is calculated quasiclassically using the new scheme as well as quantum mechanically as a function of the atomic electronic-energy separation (lambda), with overall good agreement between the two sets of results. Classical mechanics with the new decoupling scheme is found to be capable of predicting resonance behavior whereas an earlier decoupling scheme (the coordinate-based decoupling scheme) failed. Interference effects are not exhibited in P vs lambda results.

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

PubMed Central

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin-ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

2015-01-01

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined. PMID:25727920

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

DOE PAGES

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; ...

2015-03-02

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

Experimental and Theoretical Demonstrations for the Mechanism behind Enhanced Microbial Electron Transfer by CNT Network

NASA Astrophysics Data System (ADS)

Liu, Xian-Wei; Chen, Jie-Jie; Huang, Yu-Xi; Sun, Xue-Fei; Sheng, Guo-Ping; Li, Dao-Bo; Xiong, Lu; Zhang, Yuan-Yuan; Zhao, Feng; Yu, Han-Qing

2014-01-01

Bioelectrochemical systems (BESs) share the principle of the microbially catalyzed anodic substrate oxidation. Creating an electrode interface to promote extracellular electron transfer from microbes to electrode and understanding such mechanisms are crucial for engineering BESs. In this study, significantly promoted electron transfer and a 10-times increase in current generation in a BES were achieved by the utilization of carbon nanotube (CNT) network, compared with carbon paper. The mechanisms for the enhanced current generation with the CNT network were elucidated with both experimental approach and molecular dynamic simulations. The fabricated CNT network was found to be able to substantially enhance the interaction between the c-type cytochromes and solid electron acceptor, indicating that the direct electron transfer from outer-membrane decaheme c-type cytochromes to electrode might occur. The results obtained in this study will benefit for the optimized design of new materials to target the outer membrane proteins for enhanced electron exchanges.

Cross-linking of the electron-transfer flavoprotein to electron-transfer flavoprotein-ubiquinone oxidoreductase with heterobifunctional reagents.

PubMed Central

Steenkamp, D J

1988-01-01

The mitochondrial electron-transfer flavoprotein (ETF) is a heterodimer containing only one FAD. In previous work on the structure-function relationships of ETF, its interaction with the general acyl-CoA dehydrogenase (GAD) was studied by chemical cross-linking with heterobifunctional reagents [D. J. Steenkamp (1987) Biochem. J. 243, 519-524]. GAD whose lysine residues were substituted with 3-(2-pyridyldithio)propionyl groups was preferentially cross-linked to the small subunit of ETF, the lysine residues of which had been substituted with 4-mercaptobutyramidine (MBA) groups. This work was extended to the interaction of ETF with ETF-ubiquinone oxidoreductase (ETF-Q ox). ETF-Q ox was partially inactivated by modification with N-succinimidyl 3-(2-pyridyldithio)propionate to introduce pyridyl disulphide structures. A similar modification of ETF caused a large increase in the apparent Michaelis constant of ETF-Q ox for modified ETF owing to the loss of positive charge on some critical lysines of ETF. When ETF-Q ox was modified with 2-iminothiolane to introduce 4-mercaptobutyramidine groups, only a minor effect on the activity of the enzyme was observed. To retain the positive charges on the lysine residues of ETF, pyridyl disulphide structures were introduced by treating ETF with 2-iminothiolane in the presence of 2,2'-dithiodipyridyl. The electron-transfer activity of the resultant ETF preparation containing 4-(2-pyridyldithio)butyramidine (PDBA) groups was only slightly affected. When ETF-Q ox substituted with MBA groups was mixed with ETF bearing PDBA groups, at least 70% of the cross-links formed between the two proteins were between the small subunit of ETF and ETF-Q ox. ETF-Q ox, therefore, interacts predominantly with the same subunit of ETF as GAD. Variables which affect the selectivity of ETF-Q ox cross-linking to the subunits of ETF are considered. Images Fig. 4. Fig. 5. Fig. 6. PMID:3145738

Constraint-based modeling of carbon fixation and the energetics of electron transfer in Geobacter metallireducens.

PubMed

Feist, Adam M; Nagarajan, Harish; Rotaru, Amelia-Elena; Tremblay, Pier-Luc; Zhang, Tian; Nevin, Kelly P; Lovley, Derek R; Zengler, Karsten

2014-04-01

Geobacter species are of great interest for environmental and biotechnology applications as they can carry out direct electron transfer to insoluble metals or other microorganisms and have the ability to assimilate inorganic carbon. Here, we report on the capability and key enabling metabolic machinery of Geobacter metallireducens GS-15 to carry out CO2 fixation and direct electron transfer to iron. An updated metabolic reconstruction was generated, growth screens on targeted conditions of interest were performed, and constraint-based analysis was utilized to characterize and evaluate critical pathways and reactions in G. metallireducens. The novel capability of G. metallireducens to grow autotrophically with formate and Fe(III) was predicted and subsequently validated in vivo. Additionally, the energetic cost of transferring electrons to an external electron acceptor was determined through analysis of growth experiments carried out using three different electron acceptors (Fe(III), nitrate, and fumarate) by systematically isolating and examining different parts of the electron transport chain. The updated reconstruction will serve as a knowledgebase for understanding and engineering Geobacter and similar species.

Solvent dynamics and electron transfer reactions

NASA Astrophysics Data System (ADS)

Rasaiah, Jayendran C.; Zhu, Jianjun

1994-02-01

Recent experimental and theoretical studies of the influence of solvent dynamics on electron transfer (ET) reactions are discussed. It is seen that the survival probabilities of the reactants and products can be obtained as the solution to an integral equation using experimental or simulation data on the solvation dynamics. The theory developed for ET between thermally equilibrated reactants in solution, in which the ligand vibrations were treated classically, is extended to include quantum effects on the inner-shell ligand vibration and electron transfer from a nonequilibrium initial state prepared, for example, by laser excitation. This leads to a slight modification of the integral equation which is easily solved on a personal computer to provide results that can be directly compared with experiment. Analytic approximations to the solutions of the integral equation, ranging from a single exponential to multiexponential time dependence of the survival probabilities are discussed. The rate constant for the single exponential decay of the reactants interpolates between the thermal equilibrium rate constant kie (that is independent of solvent dynamics) and a diffusion controlled rate constant kid (determined by solvent dynamics) and also between the wide (A=0) and narrow (A=1) window limits dominated by inner-sphere ligand vibration and outer-sphere solvent reorganization respectively. The explicit dependence of the integral equation solutions on solvation dynamics S(t), the free energy of reaction ΔG0, the total reorganization energy λ and its partitioning between ligand vibration λq and solvent polarization fluctuations λ0, and the nature of the initial state should be useful in the analysis and design of ET experiments in different solvents.

31 CFR 208.3 - Payment by electronic funds transfer.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 2 2013-07-01 2013-07-01 false Payment by electronic funds transfer. 208.3 Section 208.3 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued... provision of law, effective January 2, 1999, all Federal payments made by an agency shall be made by...

31 CFR 208.3 - Payment by electronic funds transfer.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance: Treasury 2 2014-07-01 2014-07-01 false Payment by electronic funds transfer. 208.3 Section 208.3 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued... provision of law, effective January 2, 1999, all Federal payments made by an agency shall be made by...

Visible-light-induced two-electron-transfer photoreductions on CdS: Effects of morphology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiragami, Tsutomu; Pac, Chyongjin; Yanagida, Shozo

1990-01-25

Freshly prepared CdS suspensions (CdS-O) consisting of quantized particles and their loose aggregation catalyze photoreductions of aromatic ketones and olefins in methanol under visible light irradiation using triethylamine as sacrificial electron donor, yielding alcohols and dihydro compounds, respectively, which are more selective than photocatalysis of commercially available crystalline CdS (Aldrich) (CdS-Ald). Deuterium incorporation experiments in photolysis of dimethyl maleate in methanol-O-D revealed that CdS-O catalyzes sequential two-electron-transfer photoreduction, affording dideuterated dimethyl succinate, while CdS-Ald induces both photoreduction and photoisomerization through disproportionation between one-electron-transfer-reduction intermediates, yielding much trideuterated dimethyl succinate and monodeuterated dimethyl fumarate and maleate.

Photoinduced electron transfer at the tetrapyrrole-TiO2 interface: Effect of the energy alignment

NASA Astrophysics Data System (ADS)

Nieto-Pescador, Jesus S.

Photoinduced electron transfer is a ubiquitous process behind several physical, chemical, and biological processes. Its potential applications, ranging from solar cell technologies to photodynamic cancer therapy, require a thorough understanding of the basics of the reaction. This dissertation addresses open questions for a particular case of electron transfer processes: Heterogeneous Electron Transfer (HET). In this process, an electron is transferred between a localized donor and a multitude of delocalized acceptor states. HET between photoexcited tetrapyrroles and colloidal TiO2 has been investigated using femtosecond transient absorption spectroscopy. Specifically, this work explores the not well-understood influence of the availability of states on the HET reaction. This problem is addressed by measuring electron injection times as a function of the energy difference between the LUMO and the conduction band of TiO2. The change in the energy alignment was done using two experimental strategies. The first one employs a recently synthesized phlorin with two different excited states above the conduction band of TiO2. This molecule allows comparing HET rates from two different excited states. The second strategy measures the electron injection rates after exciting the same electronic state of a set of specially designed porphyrins. The novelty of the approach is that the difference in energy alignment is attained by the introduction of dipole groups within the bridge group of the molecule. This strategy generates a difference in energy alignment of up to 200 meV. The reported measurements were carried in a high vacuum environment with an apparatus capable of resolving sub 30 fs processes. Disentanglement of the electron transfer processes was done, after careful study of the relaxation dynamics of the molecules in solution, by monitoring the decay of the excited state absorption and the rise of the cation spectral signatures. Within our time resolution, our results

First principles design of a core bioenergetic transmembrane electron-transfer protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goparaju, Geetha; Fry, Bryan A.; Chobot, Sarah E.

Here we describe the design, Escherichia coli expression and characterization of a simplified, adaptable and functionally transparent single chain 4-α-helix transmembrane protein frame that binds multiple heme and light activatable porphyrins. Such man-made cofactor-binding oxidoreductases, designed from first principles with minimal reference to natural protein sequences, are known as maquettes. This design is an adaptable frame aiming to uncover core engineering principles governing bioenergetic transmembrane electron-transfer function and recapitulate protein archetypes proposed to represent the origins of photosynthesis. This article is part of a Special Issue entitled Biodesign for Bioenergetics — the design and engineering of electronic transfer cofactors, proteinsmore » and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson.« less

Suppression of electron spin decoherence in Rabi oscillations induced by an inhomogeneous microwave field

NASA Astrophysics Data System (ADS)

Saiko, A. P.; Fedaruk, R.; Markevich, S. A.

2018-05-01

The decay of Rabi oscillations provides direct information about coherence of electron spins. When observed in EPR experiments, it is often shortened by spatial inhomogeneity of the microwave field amplitude in a bulk sample. In order to suppress this undesired loss of coherence, we propose an additional dressing of spin states by a weak longitudinal continuous radiofrequency field. The Gaussian, cosine and linear distributions of the microwave amplitude is analyzed. Our calculations of the Rabi oscillations between the doubly dressed spin states show that for all these distributions the maximum suppression of the inhomogeneity-induced decoherence is achieved at the so-called Rabi resonance when the radio-field frequency is in resonance with the Rabi frequency of spins in the microwave field. The manifestations of such suppression in the published EPR experiments with the bichromatic driving are discussed. The realization of the Rabi resonance using the radiofrequency field could open new possibilities for separating the contributions of relaxation mechanisms from those due to the inhomogeneous driving in spin decoherence.

Photoemission into water adsorbed on metals: Probing dissociative electron transfer using theory

NASA Astrophysics Data System (ADS)

Zhang, Yu; Whitten, J. L.

The photoinduced dissociation of water adsorbed on a silver nanoparticle is explored using theory to probe reaction pathways that produce hydrogen. Ab initio configuration theory is used to describe the systems. A formulation that allows excited electronic states embedded in a near continuum of lower energy states to be calculated accurately is described. Electron attachment of a photoemitted electron to adsorbed water can lead to the formation of H2 at a very low energy barrier with oxygen remaining on the Ag surface. A large energy barrier to form H2 plus adsorbed O is found for the ground state. The excited state has a much smaller barrier to OH stretch; however, to dissociate, the system must cross over from the excited state to the ground state potential energy surface. The cross over point is near the transition state for a ground state process. A characteristic feature of the excited state potential curve is an increase in energy in the early stages of OH stretch as the charge transfer state evolves from a state with considerable Rydberg character to one that has a typical OH antibonding molecular orbital. Another pathway releases a H atom leaving OH on the surface. Effects due to doping of a Ag nanoparticle with a K electron donor atom are compared with those caused by a Fermi level shift due to an applied potential. Results are also reported for electron transfer to a solvated lithium ion, Li(H2O) 6+, near the surface of a silver particle. A steering mechanism is found that involves the interaction of a hydridic hydrogen formed after electron transfer with an acidic hydrogen of a second solvated water molecule.

Verification of the electron/proton coupled mechanism for phenolic H-atom transfer using a triplet π,π ∗ carbonyl

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Oshima, Juro; Hidaka, Motohiko

2009-06-01

Evidence for the coupled electron/proton transfer mechanism of the phenolic H-atom transfer between triplet π,π ∗ 3,3'-carbonylbis(7-diethylaminocoumarin) and phenol derivatives is obtained by using laser photolysis techniques. It was confirmed that the quenching rate constants of triplet CBC by phenols having positive Hammett constants do not follow the Rehm-Weller equation for electron transfer while those by phenols with negative Hammett constants do it. From the viewpoint of thermodynamic parameters for electron transfer, the crucial factors for phenolic H-atom transfer to π,π ∗ triplet are discussed.

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

NASA Astrophysics Data System (ADS)

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.

Microbial interspecies electron transfer via electric currents through conductive minerals

PubMed Central

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

77 FR 10373 - Greenhouse Gas Reporting Program: Electronics Manufacturing: Revisions to Heat Transfer Fluid...

Federal Register 2010, 2011, 2012, 2013, 2014

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... related to the electronics manufacturing source category. DATES: This rule will be effective on March 23...

Oxidation of the FAD cofactor to the 8-formyl-derivative in human electron-transferring flavoprotein

PubMed Central

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

Enhanced interfacial electron transfer of inverted perovskite solar cells by introduction of CoSe into the electron-transporting-layer

NASA Astrophysics Data System (ADS)

Chen, Shanshan; Yang, Songwang; Sun, Hong; Zhang, Lu; Peng, Jiajun; Liang, Ziqi; Wang, Zhong-Sheng

2017-06-01

To improve the electron transfer at the interface between the perovskite film and the electron-transporting-material (ETM) layer, CoSe doped [6,6]-phenyl C61-butyric acid methyl ester (PCBM) is employed as the ETM layer for the inverted planar perovskite solar cell with NiO as the hole-transporting-material layer. Introduction of CoSe (5.8 wt%) into the PCBM layer improves the conductivity of the ETM layer and decreases the photoluminescence intensity, thus enhancing the interfacial electron extraction and reducing the electron transfer resistance at the perovskite/ETM interface. As a consequence, the power conversion efficiency is enhanced from 11.43% to 14.91% by 30% due to the noted increases in short-circuit current density from 17.95 mA cm-2 to 19.85 mA cm-2 and fill factor from 0.60 to 0.70. This work provides a new strategy to improve the performance of inverted perovskite solar cells.

Electronic Delocalization, Vibrational Dynamics and Energy Transfer in Organic Chromophores

DOE PAGES

Nelson, Tammie Renee; Fernandez Alberti, Sebastian; Roitberg, Adrian; ...

2017-06-12

The efficiency of materials developed for solar energy and technological applications depends on the interplay between molecular architecture and light-induced electronic energy redistribution. The spatial localization of electronic excitations is very sensitive to molecular distortions. Vibrational nuclear motions can couple to electronic dynamics driving changes in localization. The electronic energy transfer among multiple chromophores arises from several distinct mechanisms that can give rise to experimentally measured signals. Atomistic simulations of coupled electron-vibrational dynamics can help uncover the nuclear motions directing energy flow. Through careful analysis of excited state wave function evolution and a useful fragmenting of multichromophore systems, through-bond transportmore » and exciton hopping (through-space) mechanisms can be distinguished. Such insights are crucial in the interpretation of fluorescence anisotropy measurements and can aid materials design. Finally, this Perspective highlights the interconnected vibrational and electronic motions at the foundation of nonadiabatic dynamics where nuclear motions, including torsional rotations and bond vibrations, drive electronic transitions.« less

Structure and Electronic Spectra of Purine-Methyl Viologen Charge Transfer Complexes

PubMed Central

Jalilov, Almaz S.; Patwardhan, Sameer; Singh, Arunoday; Simeon, Tomekia; Sarjeant, Amy A.; Schatz, George C.; Lewis, Frederick D.

2014-01-01

The structure and properties of the electron donor-acceptor complexes formed between methyl viologen (MV) and purine nucleosides and nucleotides in water and the solid state have been investigated using a combination of experimental and theoretical methods. Solution studies were performed using UV-vis and 1H NMR spectroscopy. Theoretical calculations were performed within the framework of density functional theory (DFT). Energy decomposition analysis indicates that dispersion and induction (charge-transfer) interactions dominate the total binding energy, whereas electrostatic interactions are largely repulsive. The appearance of charge transfer bands in the absorption spectra of the complexes are well described by time-dependent (TD) DFT and are further explained in terms of the redox properties of purine monomers and solvation effects. Crystal structures are reported for complexes of methyl viologen with the purines 2′-deoxyguanosine 3′-monophosphate GMP (DAD′DAD′ type) and 7-deazaguanosine zG (DAD′ADAD′ type). Comparison of the structures determined in the solid state and by theoretical methods in solution provides valuable insights into the nature of charge-transfer interactions involving purine bases as electron donors. PMID:24294996

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

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

PubMed

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.

Using the plasmon linewidth to calculate the time and efficiency of electron transfer between gold nanorods and graphene.

PubMed

Hoggard, Anneli; Wang, Lin-Yung; Ma, Lulu; Fang, Ying; You, Ge; Olson, Jana; Liu, Zheng; Chang, Wei-Shun; Ajayan, Pulickel M; Link, Stephan

2013-12-23

We present a quantitative analysis of the electron transfer between single gold nanorods and monolayer graphene under no electrical bias. Using single-particle dark-field scattering and photoluminescence spectroscopy to access the homogeneous linewidth, we observe broadening of the surface plasmon resonance for gold nanorods on graphene compared to nanorods on a quartz substrate. Because of the absence of spectral plasmon shifts, dielectric interactions between the gold nanorods and graphene are not important and we instead assign the plasmon damping to charge transfer between plasmon-generated hot electrons and the graphene that acts as an efficient acceptor. Analysis of the plasmon linewidth yields an average electron transfer time of 160 ± 30 fs, which is otherwise difficult to measure directly in the time domain with single-particle sensitivity. In comparison to intrinsic hot electron decay and radiative relaxation, we furthermore calculate from the plasmon linewidth that charge transfer between the gold nanorods and the graphene support occurs with an efficiency of ∼10%. Our results are important for future applications of light harvesting with metal nanoparticle plasmons and efficient hot electron acceptors as well as for understanding hot electron transfer in plasmon-assisted chemical reactions.

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

PubMed Central

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

Tuning electronic properties of graphene nanoflake polyaromatic hydrocarbon through molecular charge-transfer interactions

NASA Astrophysics Data System (ADS)

Sharma, Vaishali; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

2018-05-01

By means of first principles calculation we have tuned the electronic properties of graphene nanoflake polyaromatic hydrocarbon via molecular charge transfer. Acceptor/donor Tetracyanoquinodimethane (TCNQ) and Tetrathiafulvalene (TTF) organic molecules are adsorbed on polyaromatic hydrocarbons (PAH) in order to introduce the charge transfer. The substrate's n- or p- type nature depends on the accepting/donating behavior of dopant molecules. Two different classes of PAH (extended form of triangulene) namely Bow-tie graphene nanoflake (BTGNF) and triangular zigzag graphene nanoflake (TZGNF). It is revealed that all the TCNQ and TTF modified graphene nanoflakes exhibit significant changes in HOMO-LUMO gap in range from 0.58 eV to 0.64 eV and 0.01 eV to 0.05 eV respectively. The adsorption energies are in the range of -0.05 kcal/mol to -2.6 kcal/mol. The change in work function is also calculated and discussed, the maximum charge transfer is for TCNQ adsorbed BTGNF. These alluring findings in the tuning of electronic properties will be advantageous for promoting graphene nanoflake polyaromatic hydrocarbon for their applications in electronic devices.

Zn induced in-gap electronic states in La214 probed by uniform magnetic susceptibility: relevance to the suppression of superconducting T c

NASA Astrophysics Data System (ADS)

Islam, R. S.; Naqib, S. H.

2018-02-01

Substitution of isovalent non-magnetic defects, such as Zn, in the CuO2 plane strongly modifies the magnetic properties of strongly electron correlated hole doped cuprate superconductors. The reason for enhanced uniform magnetic susceptibility, χ, in Zn substituted cuprates is debatable. Generally the defect induced magnetic behavior has been analyzed mainly in terms of two somewhat contrasting scenarios. The first one is due to independent localized moments appearing in the vicinity of Zn arising because of the strong electronic/magnetic correlations present in the host compound and the second one is due to transfer of quasiparticle (QP) spectral weight and creation of weakly localized low-energy electronic states associated with each Zn atom in place of an in-plane Cu. If the second scenario is correct, one should expect a direct correspondence between Zn induced suppression of the superconducting transition temperature, T c, and the extent of the enhanced magnetic susceptibility at low temperature. In this case, the low-T enhancement of χ would be due to weakly localized QP states at low energy and these electronic states will be precluded from taking part in Cooper pairing. We explore this second possibility by analyzing the χ(T) data for La2-x Sr x Cu1-y Zn y O4 with different hole contents, p (=x), and Zn concentrations (y) in this paper. The results of our analysis support this scenario.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements

NASA Astrophysics Data System (ADS)

Cave, Robert J.; Newton, Marshall D.

1996-01-01

A new method for the calculation of the electronic coupling matrix element for electron transfer processes is introduced and results for several systems are presented. The method can be applied to ground and excited state systems and can be used in cases where several states interact strongly. Within the set of states chosen it is a non-perturbative treatment, and can be implemented using quantities obtained solely in terms of the adiabatic states. Several applications based on quantum chemical calculations are briefly presented. Finally, since quantities for adiabatic states are the only input to the method, it can also be used with purely experimental data to estimate electron transfer matrix elements.

Electron transfer mediators accelerated the microbiologically influence corrosion against carbon steel by nitrate reducing Pseudomonas aeruginosa biofilm.

PubMed

Jia, Ru; Yang, Dongqing; Xu, Dake; Gu, Tingyue

2017-12-01

Electron transfer is a rate-limiting step in microbiologically influenced corrosion (MIC) caused by microbes that utilize extracellular electrons. Cross-cell wall electron transfer is necessary to transport the electrons released from extracellular iron oxidation into the cytoplasm of cells. Electron transfer mediators were found to accelerate the MIC caused by sulfate reducing bacteria. However, there is no publication in the literature showing the effect of electron transfer mediators on MIC caused by nitrate reducing bacteria (NRB). This work demonstrated that the corrosion of anaerobic Pseudomonas aeruginosa (PAO1) grown as a nitrate reducing bacterium biofilm on C1018 carbon steel was enhanced by two electron transfer mediators, riboflavin and flavin adenine dinucleotide (FAD) separately during a 7-day incubation period. The addition of either 10ppm (w/w) (26.6μM) riboflavin or 10ppm (12.7μM) FAD did not increase planktonic cell counts, but they increased the maximum pit depth on carbon steel coupons considerably from 17.5μm to 24.4μm and 25.0μm, respectively. Riboflavin and FAD also increased the specific weight loss of carbon steel from 2.06mg/cm 2 to 2.34mg/cm 2 and 2.61mg/cm 2 , respectively. Linear polarization resistance, electrochemical impedance spectroscopy and potentiodynamic polarization curves all corroborated the pitting and weight loss data. Copyright © 2017 Elsevier B.V. All rights reserved.

Sandwiched confinement of quantum dots in graphene matrix for efficient electron transfer and photocurrent production

PubMed Central

Zhu, Nan; Zheng, Kaibo; Karki, Khadga J.; Abdellah, Mohamed; Zhu, Qiushi; Carlson, Stefan; Haase, Dörthe; Žídek, Karel; Ulstrup, Jens; Canton, Sophie E.; Pullerits, Tõnu; Chi, Qijin

2015-01-01

Quantum dots (QDs) and graphene are both promising materials for the development of new-generation optoelectronic devices. Towards this end, synergic assembly of these two building blocks is a key step but remains a challenge. Here, we show a one-step strategy for organizing QDs in a graphene matrix via interfacial self-assembly, leading to the formation of sandwiched hybrid QD-graphene nanofilms. We have explored structural features, electron transfer kinetics and photocurrent generation capacity of such hybrid nanofilms using a wide variety of advanced techniques. Graphene nanosheets interlink QDs and significantly improve electronic coupling, resulting in fast electron transfer from photoexcited QDs to graphene with a rate constant of 1.3 × 109 s−1. Efficient electron transfer dramatically enhances photocurrent generation in a liquid-junction QD-sensitized solar cell where the hybrid nanofilm acts as a photoanode. We thereby demonstrate a cost-effective method to construct large-area QD-graphene hybrid nanofilms with straightforward scale-up potential for optoelectronic applications. PMID:25996307

Sandwiched confinement of quantum dots in graphene matrix for efficient electron transfer and photocurrent production

NASA Astrophysics Data System (ADS)

Zhu, Nan; Zheng, Kaibo; Karki, Khadga J.; Abdellah, Mohamed; Zhu, Qiushi; Carlson, Stefan; Haase, Dörthe; Žídek, Karel; Ulstrup, Jens; Canton, Sophie E.; Pullerits, Tõnu; Chi, Qijin

2015-05-01

Quantum dots (QDs) and graphene are both promising materials for the development of new-generation optoelectronic devices. Towards this end, synergic assembly of these two building blocks is a key step but remains a challenge. Here, we show a one-step strategy for organizing QDs in a graphene matrix via interfacial self-assembly, leading to the formation of sandwiched hybrid QD-graphene nanofilms. We have explored structural features, electron transfer kinetics and photocurrent generation capacity of such hybrid nanofilms using a wide variety of advanced techniques. Graphene nanosheets interlink QDs and significantly improve electronic coupling, resulting in fast electron transfer from photoexcited QDs to graphene with a rate constant of 1.3 × 109 s-1. Efficient electron transfer dramatically enhances photocurrent generation in a liquid-junction QD-sensitized solar cell where the hybrid nanofilm acts as a photoanode. We thereby demonstrate a cost-effective method to construct large-area QD-graphene hybrid nanofilms with straightforward scale-up potential for optoelectronic applications.

Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu Jianjun; Wang Jianji; Stell, George

2006-10-28

The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying themore » solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.« less

Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

NASA Astrophysics Data System (ADS)

Zhu, Jianjun; Wang, Jianji; Stell, George

2006-10-01

The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying the solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.

Few-femtosecond-resolution characterization and suppression of excess timing jitter and drift in indoor atmospheric frequency comb transfer.

PubMed

Kang, Jinho; Shin, Junho; Kim, Chur; Jung, Kwangyun; Park, Suhyeon; Kim, Jungwon

2014-10-20

We characterize the timing jitter spectral density of the time-of-flight (TOF) in the indoor atmospheric transfer of optical pulse train over 10 decades of Fourier frequency range (10 μHz - 100 kHz) with sub-100-as resolution using a balanced optical cross-correlator (BOC). Based on the well-known theory for atmospheric transfer of a laser beam, we could fit the measured timing jitter power spectral density to the theory and analyze it with a fairly good agreement from 20 mHz to 10 Hz Fourier frequency range. Moreover, we demonstrate that the BOC-based timing stabilization method can suppress the excess fluctuations in timing from >200 fs (rms) to 2.6 fs (rms) maintained over 130 hours when an optical pulse train is transferred over a 76.2-m long free-space beam path in laboratory environment. The demonstrated stabilization result corresponds to 4 × 10(-20) overlapping Allan deviation at 117,000 s averaging time.

Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF–TCNQ as an Example

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Changwon; Atalla, Viktor; Smith, Sean

Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor–acceptor molecules, tetrathiafulvalene–tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, onemore » can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. In conclusion, our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.« less

Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF–TCNQ as an Example

DOE PAGES

Park, Changwon; Atalla, Viktor; Smith, Sean; ...

2017-06-16

Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor–acceptor molecules, tetrathiafulvalene–tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, onemore » can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. In conclusion, our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.« less

Role of the photosynthetic electron transfer chain in electrogenic activity of cyanobacteria.

PubMed

Pisciotta, John M; Zou, Yongjin; Baskakov, Ilia V

2011-07-01

Certain anaerobic bacteria, termed electrogens, produce an electric current when electrons from oxidized organic molecules are deposited to extracellular metal oxide acceptors. In these heterotrophic "metal breathers", the respiratory electron transport chain (R-ETC) works in concert with membrane-bound cytochrome oxidases to transfer electrons to the extracellular acceptors. The diversity of bacteria able to generate an electric current appears more widespread than previously thought, and aerobic phototrophs, including cyanobacteria, possess electrogenic activity. However, unlike heterotrophs, cyanobacteria electrogenic activity is light dependent, which suggests that a novel pathway could exist. To elucidate the electrogenic mechanism of cyanobacteria, the current studies used site-specific inhibitors to target components of the photosynthetic electron transport chain (P-ETC) and cytochrome oxidases. Here, we show that (1) P-ETC and, particularly, water photolysed by photosystem II (PSII) is the source of electrons discharged to the environment by illuminated cyanobacteria, and (2) water-derived electrons are transmitted from PSII to extracellular electron acceptors via plastoquinone and cytochrome bd quinol oxidase. Two cyanobacterial genera (Lyngbya and Nostoc) displayed very similar electrogenic responses when treated with P-ETC site-specific inhibitors, suggesting a conserved electrogenic pathway. We propose that in cyanobacteria, electrogenic activity may represent a form of overflow metabolism to protect cells under high-intensity light. This study offers insight into electron transfer between phototrophic microorganisms and the environment and expands our knowledge into biologically based mechanisms for harnessing solar energy.

Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems.

PubMed

Hwang, Sang-Yeon; Kim, Jaewook; Kim, Woo Youn

2018-04-04

In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to π-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole- and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase π stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.

Fabrication of nanowire electronics on nonconventional substrates by water-assisted transfer printing method

NASA Astrophysics Data System (ADS)

Lee, Chi Hwan; Kim, Dong Rip; Zheng, Xiaolin

2015-06-01

We report a simple, versatile, and wafer-scale water-assisted transfer printing method (WTP) that enables the transfer of nanowire devices onto diverse nonconventional substrates that were not easily accessible before, such as paper, plastics, tapes, glass, polydimethylsiloxane (PDMS), aluminum foil, and ultrathin polymer substrates. The WTP method relies on the phenomenon of water penetrating into the interface between Ni and SiO2. The transfer yield is nearly 100%, and the transferred devices, including NW resistors, diodes, and field effect transistors, maintain their original geometries and electronic properties with high fidelity.

Allotype suppression in an adoptive transfer system in adult mice: the specificity and feedback effects of a monoclonal IgG3 anti-(Igh-1b) allotype antibody.

PubMed Central

Curling, E M; Dresser, D W

1984-01-01

Using an adoptive transfer system in mice, an allotype-specific suppression has been induced by a monoclonal IgG3 anti-Igh-1b (Hyb 5.7) reagent. Suppression was specific for IgG2a (Igh-1b) and led to a compensatory increase of the Igh-1a response in irradiated mice reconstituted with allotype heterozygous (Igha/b) spleen cells. Suppression, which was not antigen-specific, lasted for at least 1 month after anti-allotype treatment. PMID:6365744

Hybrid fusions show that inter-monomer electron transfer robustly supports cytochrome bc{sub 1} function in vivo

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ekiert, Robert; Czapla, Monika; Sarewicz, Marcin

2014-08-22

Highlights: • We used hybrid fusion bc{sub 1} complex to test inter-monomer electron transfer in vivo. • Cross-inactivated complexes were able to sustain photoheterotrophic growth. • Inter-monomer electron transfer supports catalytic cycle in vivo. • bc{sub 1} dimer is functional even when cytochrome b subunits come from different species. - Abstract: Electronic connection between Q{sub o} and Q{sub i} quinone catalytic sites of dimeric cytochrome bc{sub 1} is a central feature of the energy-conserving Q cycle. While both the intra- and inter-monomer electron transfers were shown to connect the sites in the enzyme, mechanistic and physiological significance of the lattermore » remains unclear. Here, using a series of mutated hybrid cytochrome bc{sub 1}-like complexes, we show that inter-monomer electron transfer robustly sustains the function of the enzyme in vivo, even when the two subunits in a dimer come from different species. This indicates that minimal requirement for bioenergetic efficiency is to provide a chain of cofactors for uncompromised electron flux between the catalytic sites, while the details of protein scaffold are secondary.« less

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer.

PubMed

Duan, Hong-Guang; Prokhorenko, Valentyn I; Cogdell, Richard J; Ashraf, Khuram; Stevens, Amy L; Thorwart, Michael; Miller, R J Dwayne

2017-08-08

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales [Formula: see text]100 fs. Today's understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes.

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer

NASA Astrophysics Data System (ADS)

Duan, Hong-Guang; Prokhorenko, Valentyn I.; Cogdell, Richard J.; Ashraf, Khuram; Stevens, Amy L.; Thorwart, Michael; Miller, R. J. Dwayne

2017-08-01

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales <<100 fs. Today’s understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes.

Electron transfer dynamics and yield from gold nanoparticle to different semiconductors induced by plasmon band excitation

NASA Astrophysics Data System (ADS)

Du, L. C.; Xi, W. D.; Zhang, J. B.; Matsuzaki, H.; Furube, A.

2018-06-01

Photoinduced electron transfer from gold nanoparticles (NPs) to semiconductor under plasmon excitation is an important phenomenon in photocatalysis and solar cell applications. Femtosecond plasmon-induced electron transfer from gold NPs to the conduction band of different semiconductor like TiO2, SnO2, and ZnO was monitored at 3440 nm upon optical excitation of the surface plasmon band of gold NPs. It was found that electron injection was completed within 240 fs and the electron injection yield reached 10-30% under 570 nm excitation. It means TiO2 is not the only proper semiconductor as electron acceptors in such gold/semiconductor nanoparticle systems.

"Super-Reducing" Photocatalysis: Consecutive Energy and Electron Transfers with Polycyclic Aromatic Hydrocarbons.

PubMed

Brasholz, Malte

2017-08-21

Donation welcome: Recent developments in visible-light photocatalysis allow the utilization of increasingly negative reduction potentials. Successive energy and electron transfer with polycyclic aromatic hydrocarbons enables the catalytic formation of strongly reducing arene radical anions, classical stoichiometric reagents for one-electron reduction in organic synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

12 CFR 205.15 - Electronic fund transfer of government benefits.

Code of Federal Regulations, 2010 CFR

2010-01-01

...) Account balance. The means by which the consumer may obtain information concerning the account balance... history or other account information, under paragraph (c) of this section, in which the error is first... consumer for use in initiating an electronic fund transfer of government benefits from an account, other...

Substrate specificity and interferences of a direct-electron-transfer-based glucose biosensor.

PubMed

Felice, Alfons K G; Sygmund, Christoph; Harreither, Wolfgang; Kittl, Roman; Gorton, Lo; Ludwig, Roland

2013-05-01

Electrochemical sensors for glucose monitoring employ different signal transduction strategies for electron transfer from the biorecognition element to the electrode surface. We present a biosensor that employs direct electron transfer and evaluate its response to various interfering substances known to affect glucose biosensors. The enzyme cellobiose dehydrogenase (CDH) was adsorbed on the surface of a carbon working electrode and covalently bound by cross linking. The response of CDH-modified electrodes to glucose and possible interfering compounds was measured by flow-injection analysis, linear sweep, and chronoamperometry. Chronoamperometry showed initial swelling/wetting of the electrode. After stabilization, the signal was stable and a sensitivity of 0.21 µA mM-1 cm-2 was obtained. To investigate the influence of the interfering substances on the biorecognition element, the simplest possible sensor architecture was used. The biosensor showed little (<5% signal deviation) or no response to various reported electroactive or otherwise interfering substances. Direct electron transfer from the biorecognition element to the electrode is a new principle applied to glucose biosensors, which can be operated at a low polarization potential of -100 mV versus silver/silver chloride. The reduction of interferences by electrochemically active substances is an attractive feature of this promising technology for the development of continuous glucose biosensors. © 2013 Diabetes Technology Society.

Probing the coupling between proton and electron transfer in Photosystem II core complexes containing a 3-fluorotyrosine

PubMed Central

Rappaport, Fabrice; Boussac, Alain; Force, Dee Ann; Peloquin, Jeffrey; Brynda, Marcin; Sugiura, Miwa; Un, Sun; Britt, R. David; Diner, Bruce A.

2009-01-01

The catalytic cycle of numerous enzymes involves the coupling between proton transfer and electron transfer. Yet, the understanding of this coordinated transfer in biological systems remains limited, likely because its characterization relies on the controlled but experimentally challenging modifications of the free energy changes associated with either the electron or proton transfer. We have performed such a study here in Photosystem II. The driving force for electron transfer from TyrZ to P680•+ has been decreased by ~ 80 meV by mutating the axial ligand of P680, and that for proton transfer upon oxidation of TyrZ by substituting a 3-fluorotyrosine (3F-TyrZ) for TyrZ. In Mn-depleted Photosystem II, the dependence upon pH of the oxidation rates of TyrZ and 3F-TyrZ were found to be similar. However, in the pH range where the phenolic hydroxyl of TyrZ is involved in a H-bond with a proton acceptor, the activation energy of the oxidation of 3F-TyrZ is decreased by 110 meV, a value which correlates with the in vitro finding of a 90 meV stabilization energy to the phenolate form of 3F-Tyr when compared to Tyr (Seyedsayamdost et al., 2006, JACS 128:1569–79). Thus, when the phenol of YZ acts as a H-bond-donor, its oxidation by P680•+ is controlled by its prior deprotonation. This contrasts with the situation prevailing at lower pH, where the proton acceptor is protonated and therefore unavailable, in which the oxidation-induced proton transfer from the phenolic hydroxyl of TyrZ has been proposed to occur concertedly with the electron transfer to P680•+. This suggests a switch between a concerted proton/electron transfer at pHs < 7.5 to a sequential one at pHs > 7.5 and illustrates the roles of the H-bond and of the likely salt-bridge existing between the phenolate and the nearby proton acceptor in determining the coupling between proton and electron transfer. PMID:19265377

Real-Time Quantum Dynamics of Long-Range Electronic Excitation Transfer in Plasmonic Nanoantennas.

PubMed

Ilawe, Niranjan V; Oviedo, M Belén; Wong, Bryan M

2017-08-08

Using large-scale, real-time, quantum dynamics calculations, we present a detailed analysis of electronic excitation transfer (EET) mechanisms in a multiparticle plasmonic nanoantenna system. Specifically, we utilize real-time, time-dependent, density functional tight binding (RT-TDDFTB) to provide a quantum-mechanical description (at an electronic/atomistic level of detail) for characterizing and analyzing these systems, without recourse to classical approximations. We also demonstrate highly long-range electronic couplings in these complex systems and find that the range of these couplings is more than twice the conventional cutoff limit considered by Förster resonance energy transfer (FRET)-based approaches. Furthermore, we attribute these unusually long-ranged electronic couplings to the coherent oscillations of conduction electrons in plasmonic nanoparticles. This long-range nature of plasmonic interactions has important ramifications for EET; in particular, we show that the commonly used "nearest-neighbor" FRET model is inadequate for accurately characterizing EET even in simple plasmonic antenna systems. These findings provide a real-time, quantum-mechanical perspective for understanding EET mechanisms and provide guidance in enhancing plasmonic properties in artificial light-harvesting systems.

Nanosecond-timescale spin transfer using individual electrons in a quadruple-quantum-dot device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baart, T. A.; Jovanovic, N.; Vandersypen, L. M. K.

2016-07-25

The ability to coherently transport electron-spin states between different sites of gate-defined semiconductor quantum dots is an essential ingredient for a quantum-dot-based quantum computer. Previous shuttles using electrostatic gating were too slow to move an electron within the spin dephasing time across an array. Here, we report a nanosecond-timescale spin transfer of individual electrons across a quadruple-quantum-dot device. Utilizing enhanced relaxation rates at a so-called hot spot, we can upper bound the shuttle time to at most 150 ns. While actual shuttle times are likely shorter, 150 ns is already fast enough to preserve spin coherence in, e.g., silicon based quantum dots.more » This work therefore realizes an important prerequisite for coherent spin transfer in quantum dot arrays.« less

Electron-transfer mediator for a NAD-glucose dehydrogenase-based glucose sensor.

PubMed

Kim, Dong-Min; Kim, Min-yeong; Reddy, Sanapalli S; Cho, Jaegeol; Cho, Chul-ho; Jung, Suntae; Shim, Yoon-Bo

2013-12-03

A new electron-transfer mediator, 5-[2,5-di (thiophen-2-yl)-1H-pyrrol-1-yl]-1,10-phenanthroline iron(III) chloride (FePhenTPy) oriented to the nicotinamide adenine dinucleotide-dependent-glucose dehydrogenase (NAD-GDH) system was synthesized through a Paal-Knorr condensation reaction. The structure of the mediator was confirmed by Fourier-transform infrared spectroscopy, proton and carbon nucler magnetic resonance spectroscopy, and mass spectroscopy, and its electron-transfer characteristic for a glucose sensor was investigated using voltammetry and impedance spectroscopy. A disposable amperometric glucose sensor with NAD-GDH was constructed with FePhenTPy as an electron-transfer mediator on a screen printed carbon electrode (SPCE) and its performance was evaluated, where the addition of reduces graphene oxide (RGO) to the mediator showed the enhanced sensor performance. The experimental parameters to affect the analytical performance and the stability of the proposed glucose sensor were optimized, and the sensor exhibited a dynamic range between 30 mg/dL and 600 mg/dL with the detection limit of 12.02 ± 0.6 mg/dL. In the real sample experiments, the interference effects by acetaminophen, ascorbic acid, dopamine, uric acid, caffeine, and other monosaccharides (fructose, lactose, mannose, and xylose) were completely avoided through coating the sensor surface with the Nafion film containing lead(IV) acetate. The reliability of proposed glucose sensor was evaluated by the determination of glucose in artificial blood and human whole blood samples.

Extracting electron transfer coupling elements from constrained density functional theory

NASA Astrophysics Data System (ADS)

Wu, Qin; Van Voorhis, Troy

2006-10-01

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives Hab≈17kcal /mol, which qualitatively disagrees with experimental results, the Hab calculated from constrained DFT is about 3kcal /mol and the generated ground state has a barrier height of 1.70kcal/mol, successfully predicting (Q-TTF-Q)- to be a class II mixed-valence compound.

Ultrafast Spectroscopy Reveals Electron-Transfer Cascade That Improves Hydrogen Evolution with Carbon Nitride Photocatalysts.

PubMed

Corp, Kathryn L; Schlenker, Cody W

2017-06-14

Solar hydrogen generation from water represents a compelling component of a future sustainable energy portfolio. Recently, chemically robust heptazine-based polymers known as graphitic carbon nitrides (g-C 3 N 4 ) have emerged as promising photocatalysts for hydrogen evolution using visible light while withstanding harsh chemical environments. However, since g-C 3 N 4 electron-transfer dynamics are poorly understood, rational design rules for improving activity remain unclear. Here, we use visible and near-infrared femtosecond transient absorption (TA) spectroscopy to reveal an electron-transfer cascade that correlates with a near-doubling in photocatalytic activity from 2050 to 3810 μmol h -1 g -1 when we infuse a suspension of bulk g-C 3 N 4 with 10% mass loading of chemically exfoliated carbon nitride. TA spectroscopy indicates that exfoliated carbon nitride quenches photogenerated electrons on g-C 3 N 4 at rates approaching the molecular diffusion limit. The TA signal for photogenerated electrons on g-C 3 N 4 decays with a time constant of 1/k e ' = 660 ps in the mixture versus 1/k e = 4.1 ns in g-C 3 N 4 alone. Our TA measurements suggest that the charge generation efficiency in g-C 3 N 4 is greater than 65%. Exfoliated carbon nitride, which liberates only trace hydrogen levels when photoexcited directly, does not appear to independently sustain appreciable long-lived charge generation. Thus, the activity enhancement in the two-component infusion evidently results from a cooperative effect in which charge is generated on g-C 3 N 4 , followed by electron transfer to exfoliated carbon nitride containing photocatalytic chain terminations. This correlation between electron transfer and photocatalytic activity provides new insight into structural modifications for controlling charge separation dynamics and activity of carbon-based photocatalysts.

The electron transfer system of syntrophically grown Desulfovibrio vulgaris

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walker, C.B.; He, Z.; Yang, Z.K.

2009-05-01

Interspecies hydrogen transfer between organisms producing and consuming hydrogen promotes the decomposition of organic matter in most anoxic environments. Although syntrophic couplings between hydrogen producers and consumers are a major feature of the carbon cycle, mechanisms for energy recovery at the extremely low free energies of reactions typical of these anaerobic communities have not been established. In this study, comparative transcriptional analysis of a model sulfate-reducing microbe, Desulfovibrio vulgaris Hildenborough, suggested the use of alternative electron transfer systems dependent upon growth modality. During syntrophic growth on lactate with a hydrogenotrophic methanogen, D. vulgaris up-regulated numerous genes involved in electron transfermore » and energy generation when compared with sulfate-limited monocultures. In particular, genes coding for the putative membrane-bound Coo hydrogenase, two periplasmic hydrogenases (Hyd and Hyn) and the well-characterized high-molecular weight cytochrome (Hmc) were among the most highly expressed and up-regulated. Additionally, a predicted operon coding for genes involved in lactate transport and oxidation exhibited up-regulation, further suggesting an alternative pathway for electrons derived from lactate oxidation during syntrophic growth. Mutations in a subset of genes coding for Coo, Hmc, Hyd and Hyn impaired or severely limited syntrophic growth but had little affect on growth via sulfate-respiration. These results demonstrate that syntrophic growth and sulfate-respiration use largely independent energy generation pathways and imply that understanding of microbial processes sustaining nutrient cycling must consider lifestyles not captured in pure culture.« less

The Electron Transfer System of Syntrophically Grown Desulfovibrio vulgaris

DOE Office of Scientific and Technical Information (OSTI.GOV)

PBD; ENIGMA; GTL

2009-06-22

Interspecies hydrogen transfer between organisms producing and consuming hydrogen promotes the decomposition of organic matter in most anoxic environments. Although syntrophic couplings between hydrogen producers and consumers are a major feature of the carbon cycle, mechanisms for energy recovery at the extremely low free energies of reactions typical of these anaerobic communities have not been established. In this study, comparative transcriptional analysis of a model sulfate-reducing microbe, Desulfovibrio vulgaris Hildenborough, suggested the use of alternative electron transfer systems dependent upon growth modality. During syntrophic growth on lactate with a hydrogenotrophic methanogen, D. vulgaris up-regulated numerous genes involved in electron transfermore » and energy generation when compared with sulfate-limited monocultures. In particular, genes coding for the putative membrane-bound Coo hydrogenase, two periplasmic hydrogenases (Hyd and Hyn) and the well-characterized high-molecular weight cytochrome (Hmc) were among the most highly expressed and up-regulated. Additionally, a predicted operon coding for genes involved in lactate transport and oxidation exhibited up-regulation, further suggesting an alternative pathway for electrons derived from lactate oxidation during syntrophic growth. Mutations in a subset of genes coding for Coo, Hmc, Hyd and Hyn impaired or severely limited syntrophic growth but had little affect on growth via sulfate-respiration. These results demonstrate that syntrophic growth and sulfate-respiration use largely independent energy generation pathways and imply that understanding of microbial processes sustaining nutrient cycling must consider lifestyles not captured in pure culture.« less

Electric-field-driven electron-transfer in mixed-valence molecules.

PubMed

Blair, Enrique P; Corcelli, Steven A; Lent, Craig S

2016-07-07

Molecular quantum-dot cellular automata is a computing paradigm in which digital information is encoded by the charge configuration of a mixed-valence molecule. General-purpose computing can be achieved by arranging these compounds on a substrate and exploiting intermolecular Coulombic coupling. The operation of such a device relies on nonequilibrium electron transfer (ET), whereby the time-varying electric field of one molecule induces an ET event in a neighboring molecule. The magnitude of the electric fields can be quite large because of close spatial proximity, and the induced ET rate is a measure of the nonequilibrium response of the molecule. We calculate the electric-field-driven ET rate for a model mixed-valence compound. The mixed-valence molecule is regarded as a two-state electronic system coupled to a molecular vibrational mode, which is, in turn, coupled to a thermal environment. Both the electronic and vibrational degrees-of-freedom are treated quantum mechanically, and the dissipative vibrational-bath interaction is modeled with the Lindblad equation. This approach captures both tunneling and nonadiabatic dynamics. Relationships between microscopic molecular properties and the driven ET rate are explored for two time-dependent applied fields: an abruptly switched field and a linearly ramped field. In both cases, the driven ET rate is only weakly temperature dependent. When the model is applied using parameters appropriate to a specific mixed-valence molecule, diferrocenylacetylene, terahertz-range ET transfer rates are predicted.

Electric-field-driven electron-transfer in mixed-valence molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blair, Enrique P., E-mail: enrique-blair@baylor.edu; Corcelli, Steven A., E-mail: scorcell@nd.edu; Lent, Craig S., E-mail: lent@nd.edu

2016-07-07

Molecular quantum-dot cellular automata is a computing paradigm in which digital information is encoded by the charge configuration of a mixed-valence molecule. General-purpose computing can be achieved by arranging these compounds on a substrate and exploiting intermolecular Coulombic coupling. The operation of such a device relies on nonequilibrium electron transfer (ET), whereby the time-varying electric field of one molecule induces an ET event in a neighboring molecule. The magnitude of the electric fields can be quite large because of close spatial proximity, and the induced ET rate is a measure of the nonequilibrium response of the molecule. We calculate themore » electric-field-driven ET rate for a model mixed-valence compound. The mixed-valence molecule is regarded as a two-state electronic system coupled to a molecular vibrational mode, which is, in turn, coupled to a thermal environment. Both the electronic and vibrational degrees-of-freedom are treated quantum mechanically, and the dissipative vibrational-bath interaction is modeled with the Lindblad equation. This approach captures both tunneling and nonadiabatic dynamics. Relationships between microscopic molecular properties and the driven ET rate are explored for two time-dependent applied fields: an abruptly switched field and a linearly ramped field. In both cases, the driven ET rate is only weakly temperature dependent. When the model is applied using parameters appropriate to a specific mixed-valence molecule, diferrocenylacetylene, terahertz-range ET transfer rates are predicted.« less

Parallel electron force balance and the L-H transition

DOE PAGES

Stoltzfus-Dueck, T.

2016-05-23

In one popular paradigm for the L-H transition, energy transfer to the mean flows directly depletes turbulence fluctuation energy, resulting in suppression of the turbulence and a corresponding transport bifurcation. To quantitatively evaluate this mechanism, one must remember that electron parallel force balance couples nonzonal velocity fluctuations with electron pressure fluctuations on rapid timescales, comparable with the electron transit time. For this reason, energy in the nonzonal velocity stays in a fairly fixed ratio to the free energy in electron density fluctuations, at least for frequency scales much slower than electron transit. Furthermore, in order for direct depletion of themore » energy in turbulent fluctuations to cause the L-H transition, energy transfer via Reynolds stress must therefore drain enough energy to significantly reduce the sum of the free energy in nonzonal velocities and electron pressure fluctuations. At low k⊥, the electron thermal free energy is much larger than the energy in nonzonal velocities, posing a stark challenge for this model of the L-H transition.« less

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

PubMed

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.

Redox Modulation of Flavin and Tyrosine Determines Photoinduced Proton-coupled Electron Transfer and Photoactivation of BLUF Photoreceptors

PubMed Central

Mathes, Tilo; van Stokkum, Ivo H. M.; Stierl, Manuela; Kennis, John T. M.

2012-01-01

Photoinduced electron transfer in biological systems, especially in proteins, is a highly intriguing matter. Its mechanistic details cannot be addressed by structural data obtained by crystallography alone because this provides only static information on a given redox system. In combination with transient spectroscopy and site-directed manipulation of the protein, however, a dynamic molecular picture of the ET process may be obtained. In BLUF (blue light sensors using FAD) photoreceptors, proton-coupled electron transfer between a tyrosine and the flavin cofactor is the key reaction to switch from a dark-adapted to a light-adapted state, which corresponds to the biological signaling state. Particularly puzzling is the fact that, although the various naturally occurring BLUF domains show little difference in the amino acid composition of the flavin binding pocket, the reaction rates of the forward reaction differ quite largely from a few ps up to several hundred ps. In this study, we modified the redox potential of the flavin/tyrosine redox pair by site-directed mutagenesis close to the flavin C2 carbonyl and fluorination of the tyrosine, respectively. We provide information on how changes in the redox potential of either reaction partner significantly influence photoinduced proton-coupled electron transfer. The altered redox potentials allowed us furthermore to experimentally describe an excited state charge transfer intermediately prior to electron transfer in the BLUF photocycle. Additionally, we show that the electron transfer rate directly correlates with the quantum yield of signaling state formation. PMID:22833672

Rudolph A. Marcus and His Theory of Electron Transfer Reactions

Science.gov Websites

early 1950s and soon discovered ... a strong experimental program at Brookhaven on electron-transfer experimental work provided the first verification of several of the predictions of his theory. This, in turn Marcus theory, namely, experimental evidence for the so-called "inverted region" where rates

Microhydration Prevents Fragmentation of Uracil and Thymine by Low-Energy Electrons.

PubMed

Kočišek, J; Pysanenko, A; Fárník, M; Fedor, J

2016-09-01

When ionizing radiation passes biological matter, a large number of secondary electrons with very low energies (<3 eV) is produced. It is known that such electrons cause an efficient fragmentation of isolated nucleobases via dissociative electron attachment. We present an experimental study of the electron attachment to microhydrated nucleobases. Our novel approach allows significant control over the hydration of molecules studied in the molecular beam. We directly show for the first time that the presence of a few water molecules suppresses the dissociative channel and leads exclusively to formation of intact molecular and hydrated anions. The suppression of fragmentation is ascribed to caging-like effects and fast energy transfer to the solvent. This is in contrast with theoretical prediction that microhydration strongly enhances the fragmentation of nucleobases. The current observation impacts mechanisms of reductive DNA strand breaks proposed to date on the basis of gas-phase experiments.

Reaction Dynamics of Proton-Coupled Electron Transfer from Reduced ZnO Nanocrystals.

PubMed

Braten, Miles N; Gamelin, Daniel R; Mayer, James M

2015-10-27

The creation of systems that efficiently interconvert chemical and electrical energies will be aided by understanding proton-coupled electron transfers at solution-semiconductor interfaces. Steps in developing that understanding are described here through kinetic studies of reactions of photoreduced colloidal zinc oxide (ZnO) nanocrystals (NCs) with the nitroxyl radical TEMPO. These reactions proceed by proton-coupled electron transfer (PCET) to give the hydroxylamine TEMPOH. They occur on the submillisecond to seconds time scale, as monitored by stopped-flow optical spectroscopy. Under conditions of excess TEMPO, the reactions are multiexponential in character. One of the contributors to this multiexponential kinetics may be a distribution of reactive proton sites. A graphical overlay method shows the reaction to be first order in [TEMPO]. Different electron concentrations in otherwise identical NC samples were achieved by three different methods: differing photolysis times, premixing with an unphotolyzed sample, or prereaction with TEMPO. The reaction velocities were consistently higher for NCs with higher numbers of electrons. For instance, NCs with an average of 2.6 e(-)/NC reacted faster than otherwise identical samples containing ≤1 e(-)/NC. Surprisingly, NC samples with the same average number of electrons but prepared in different ways often had different reaction profiles. These results show that properties beyond electron content determine PCET reactivity of the particles.

Electron impact excitation of SO2 - Differential, integral, and momentum transfer cross sections

NASA Technical Reports Server (NTRS)

Vuskovic, L.; Trajmar, S.

1982-01-01

Electron impact excitation of the electronic states of SO2 was investigated. Differential, integral, and inelastic momentum transfer cross sections were obtained by normalizing the relative measurements to the elastic cross sections. The cross sections are given for seven spectral ranges of the energy-loss spectra extending from the lowest electronic state to near the first ionization limit. Most of the regions represent the overlap of several electronic transitions. No measurements for these cross sections have been reported previously.

Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids.

PubMed

DeVine, Jessalyn A; Labib, Marena; Harries, Megan E; Rached, Rouba Abdel Malak; Issa, Joseph; Wishart, James F; Castner, Edward W

2015-08-27

Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime.

Extracellular Electron Transfer and Survival Strategies in Acid Mine Drainage Impacted Soils

NASA Astrophysics Data System (ADS)

Gorby, Y. A.; Senko, J.

2011-12-01

Acid mine drainage (AMD) is a prominent and increasing problem in the greater Appalachian region of the United States and throughout the world. Recognition of the importance of extracellular electron transfer (EET) in microbial communities has provided a fertile research environment for multidisciplinary collaborations to emerge and effectively address complex questions with important environmental implications. Our research focuses on the components, strategies and mechanisms of EET in soil systems impacted by AMD and extends to other biogeochemical systems typified by steep redox gradients. Organisms within acid mine drainage use Fe(II) as their primary electron donor and couple Fe(II) oxidation to the reduction of oxygen as the terminal electron acceptor. Biogenic minerals formed by this process completely encase microbes in think deposits that would seem to limit diffusion of both Fe(II) and O2 for access by the organisms. We have developed methods for catalytically removing biogenic minerals revealing microorganisms and a fine network of filamentous extracellular material. Here we present a status report of our efforts to characterize the molecular and electronic properties of these filaments and to address the hypothesis that at least some of these filaments are electrically conductive microbial nanowires that facilitate electron transfer reactions within this complex biogeochemical system.

Electrochemical performance and microbial community profiles in microbial fuel cells in relation to electron transfer mechanisms.

PubMed

Uria, Naroa; Ferrera, Isabel; Mas, Jordi

2017-10-18

Microbial fuel cells (MFCs) operating with complex microbial communities have been extensively reported in the past, and are commonly used in applications such as wastewater treatment, bioremediation or in-situ powering of environmental sensors. However, our knowledge on how the composition of the microbial community and the different types of electron transfer to the anode affect the performance of these bioelectrochemical systems is far from complete. To fill this gap of knowledge, we designed a set of three MFCs with different constrains limiting direct and mediated electron transfer to the anode. The results obtained indicate that MFCs with a naked anode on which a biofilm was allowed unrestricted development (MFC-A) had the most diverse archaeal and bacterial community, and offered the best performance. In this MFC both, direct and mediated electron transfer, occurred simultaneously, but direct electron transfer was the predominant mechanism. Microbial fuel cells in which the anode was enclosed in a dialysis membrane and biofilm was not allowed to develop (MFC-D), had a much lower power output (about 60% lower), and a prevalence of dissolved redox species that acted as putative electron shuttles. In the anolyte of this MFC, Arcobacter and Methanosaeta were the prevalent bacteria and archaea respectively. In the third MFC, in which the anode had been covered by a cation selective nafion membrane (MFC-N), power output decreased a further 5% (95% less than MFC-A). In this MFC, conventional organic electron shuttles could not operate and the low power output obtained was presumably attributed to fermentation end-products produced by some of the organisms present in the anolyte, probably Pseudomonas or Methanosaeta. Electron transfer mechanisms have an impact on the development of different microbial communities and in turn on MFC performance. Although a stable current was achieved in all cases, direct electron transfer MFC showed the best performance concluding

GPU-accelerated computation of electron transfer.

PubMed

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.

36 CFR 1235.50 - What specifications and standards for transfer apply to electronic records?

Code of Federal Regulations, 2014 CFR

2014-07-01

... Property NATIONAL ARCHIVES AND RECORDS ADMINISTRATION RECORDS MANAGEMENT TRANSFER OF REC- ORDS TO THE... Records Administration, Electronic/Special Media Records Services Division (NWME), 8601 Adelphi Road... and Records Administration, Electronic/Special Media Records Services Division (NWME), 8601 Adelphi...

Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reslan, Randa; Lopata, Kenneth A.; Arntsen, Christopher D.

2012-12-14

We use time-dependent density functional theory and time-dependent ZINDO (a semi-empirical method) to study transfer of an extra electron between a pair of pentacene dimers. A measure of the electronic transfer integral is computed in a dynamic picture via the vertical excitation energy from a delocalized anionic ground state. With increasing dimer separation, this dynamical measurement of charge transfer is shown to be significantly larger than the commonly used static approximation (i.e., LUMO+1 - LUMO of the neutral dimer, or HOMO - LUMO of the charged dimer), up to an order of magnitude higher at 6 Å. These results offermore » a word of caution for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer.« less

Studying electron transfer through alkanethiol self-assembled monolayers on a hanging mercury drop electrode using potentiometric measurements.

PubMed

Cohen-Atiya, Meirav; Mandler, Daniel

2006-10-14

A new approach based on measuring the change of the open-circuit potential (OCP) of a hanging mercury drop electrode (HMDE), modified with alkanethiols of different chain length conducted in a solution containing a mixture of Ru(NH3)6(2+) and Ru(NH3)6(3+) is used for studying electron transfer across the monolayer. Following the time dependence of the OCP allowed the extraction of the kinetic parameters, such as the charge transfer resistance (R(ct)) and the electron transfer rate constant (k(et)), for different alkanethiol monolayers. An electron tunneling coefficient, beta, of 0.9 A(-1) was calculated for the monolayers on Hg.

Enhanced electron transfer and silver-releasing suppression in Ag-AgBr/titanium-doped Al2O3 suspensions with visible-light irradiation.

PubMed

Zhou, Xuefeng; Hu, Chun; Hu, Xuexiang; Peng, Tianwei

2012-06-15

Ag-AgBr was deposited onto mesoporous alumina (MA) and titanium-doped MA by a deposition-precipitation method. The photocatalytic activity and the dissolution of Ag(+) from different catalysts were investigated during the photodegradation of 2-chlorophenol (2-CP) and phenol in ultrapure water and tap water with visible-light irradiation. With the increase in doped titanium, the Ag(+) dissolution decreased with a decrease in the photocatalytic activity. Ag-AgBr/MA-Ti1 was considered the better catalyst for practical applications because its Ag(+) dissolution was minimal (0.4 mg L(-1) in ultrapure water and 5 μg L(-1) in tap water), although its photoactivity was slightly less than that of Ag-AgBr/MA. The dissolution of Ag(+) was related to a charge-transfer process based on the study of cyclic voltammetry analyses under a variety of experimental conditions. The results suggested that several types of anions in the water, including CO(3)(2-), SO(4)(2-), and Cl(-), could act as electron donors that trap the photogenerated holes on Ag nanoparticles to facilitate electron circulation; this would decrease the release of Ag(+). Our studies indicated that the catalyst had a higher activity and stability in water purification. Copyright © 2012. Published by Elsevier B.V.

Electron transfer properties of peat organic matter: from electrochemical analysis to redox processes in peatlands

NASA Astrophysics Data System (ADS)

Sander, Michael; Getzinger, Gordon; Walpen, Nicolas

2017-04-01

Peat organic matter contains redox-active functional groups that can accept and/or donate electrons from and to biotic and abiotic reaction partners present in peatlands. Several studies have provided evidence that electron accepting quinone moieties in the peat organic matter may act as terminal electron acceptors for anaerobic microbial respiration. This respiration pathway may competitively suppress methanogenesis and thereby lead to excess carbon dioxide to methane formation in peatlands. Electron donating phenolic moieties in peat organic matter have long been considered to inhibit microbial and enzymatic activities in peatlands, thereby contributing to carbon stabilization and accumulation in these systems. Phenols are expected to be comparatively stable in anoxic parts of the peats as phenoloxidases, a class of enzymes capable of oxidatively degrading phenols, require molecular oxygen as co-substrate. Despite the general recognition of the importance of redox-active moieties in peat organic matter, the abundance, redox properties and reactivities of these moieties remain poorly studied and understood, in large part due to analytical challenges. This contribution will, in a first part, summarize recent advances in our research group on the analytical chemistry of redox-active moieties in peat organic matter. We will show how mediated electrochemical analysis can be used to quantify the capacities of electron accepting and donating moieties in both dissolved and particulate peat organic matter. We will link these capacities to the physicochemical properties of peat organic matter and provide evidence for quinones and phenols as major electron accepting and donating moieties, respectively. The second part of this contribution will highlight how these electroanalytical techniques can be utilized to advance a more fundamental understanding of electron transfer processes involving peat organic matter. These processes include the redox cycling (i.e., repeated

Electronic coupling between Watson-Crick pairs for hole transfer and transport in desoxyribonucleic acid

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.; Jortner, Joshua; Bixon, M.; Rösch, Notker

2001-04-01

Electronic matrix elements for hole transfer between Watson-Crick pairs in desoxyribonucleic acid (DNA) of regular structure, calculated at the Hartree-Fock level, are compared with the corresponding intrastrand and interstrand matrix elements estimated for models comprised of just two nucleobases. The hole transfer matrix element of the GAG trimer duplex is calculated to be larger than that of the GTG duplex. "Through-space" interaction between two guanines in the trimer duplexes is comparable with the coupling through an intervening Watson-Crick pair. The gross features of bridge specificity and directional asymmetry of the electronic matrix elements for hole transfer between purine nucleobases in superstructures of dimer and trimer duplexes have been discussed on the basis of the quantum chemical calculations. These results have also been analyzed with a semiempirical superexchange model for the electronic coupling in DNA duplexes of donor (nuclobases)-acceptor, which incorporates adjacent base-base electronic couplings and empirical energy gaps corrected for solvation effects; this perturbation-theory-based model interpretation allows a theoretical evaluation of experimental observables, i.e., the absolute values of donor-acceptor electronic couplings, their distance dependence, and the reduction factors for the intrastrand hole hopping or trapping rates upon increasing the size of the nucleobases bridge. The quantum chemical results point towards some limitations of the perturbation-theory-based modeling.

CymA and Exogenous Flavins Improve Extracellular Electron Transfer and Couple It to Cell Growth in Mtr-Expressing Escherichia coli

DOE PAGES

Jensen, Heather M.; TerAvest, Michaela A.; Kokish, Mark G.; ...

2016-03-22

Introducing extracellular electron transfer pathways into heterologous organisms offers the opportunity to explore fundamental biogeochemical processes and to biologically alter redox states of exogenous metals for various applications. While expression of the MtrCAB electron nanoconduit from Shewanella oneidensis MR-1 permits extracellular electron transfer in Escherichia coli, the low electron flux and absence of growth in these cells limits their practicality for such applications. In this paper, we investigate how the rate of electron transfer to extracellular Fe(III) and cell survival in engineered E. coli are affected by mimicking different features of the S. oneidensis pathway: the number of electron nanoconduits,more » the link between the quinol pool and MtrA, and the presence of flavin-dependent electron transfer. While increasing the number of pathways does not significantly improve the extracellular electron transfer rate or cell survival, using the native inner membrane component, CymA, significantly improves the reduction rate of extracellular acceptors and increases cell viability. Strikingly, introducing both CymA and riboflavin to Mtr-expressing E. coli also allowed these cells to couple metal reduction to growth, which is the first time an increase in biomass of an engineered E. coli has been observed under Fe 2O 3 (s) reducing conditions. Overall and finally, this work provides engineered E. coli strains for modulating extracellular metal reduction and elucidates critical factors for engineering extracellular electron transfer in heterologous organisms.« less

CymA and Exogenous Flavins Improve Extracellular Electron Transfer and Couple It to Cell Growth in Mtr-Expressing Escherichia coli

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jensen, Heather M.; TerAvest, Michaela A.; Kokish, Mark G.

Introducing extracellular electron transfer pathways into heterologous organisms offers the opportunity to explore fundamental biogeochemical processes and to biologically alter redox states of exogenous metals for various applications. While expression of the MtrCAB electron nanoconduit from Shewanella oneidensis MR-1 permits extracellular electron transfer in Escherichia coli, the low electron flux and absence of growth in these cells limits their practicality for such applications. In this paper, we investigate how the rate of electron transfer to extracellular Fe(III) and cell survival in engineered E. coli are affected by mimicking different features of the S. oneidensis pathway: the number of electron nanoconduits,more » the link between the quinol pool and MtrA, and the presence of flavin-dependent electron transfer. While increasing the number of pathways does not significantly improve the extracellular electron transfer rate or cell survival, using the native inner membrane component, CymA, significantly improves the reduction rate of extracellular acceptors and increases cell viability. Strikingly, introducing both CymA and riboflavin to Mtr-expressing E. coli also allowed these cells to couple metal reduction to growth, which is the first time an increase in biomass of an engineered E. coli has been observed under Fe 2O 3 (s) reducing conditions. Overall and finally, this work provides engineered E. coli strains for modulating extracellular metal reduction and elucidates critical factors for engineering extracellular electron transfer in heterologous organisms.« less

Co-adsorption of water and oxygen on GaN: Effects of charge transfer and formation of electron depletion layer.

PubMed

Wang, Qi; Puntambekar, Ajinkya; Chakrapani, Vidhya

2017-09-14

Species from ambient atmosphere such as water and oxygen are known to affect electronic and optical properties of GaN, but the underlying mechanism is not clearly known. In this work, we show through careful measurement of electrical resistivity and photoluminescence intensity under various adsorbates that the presence of oxygen or water vapor alone is not sufficient to induce electron transfer to these species. Rather, the presence of both water and oxygen is necessary to induce electron transfer from GaN that leads to the formation of an electron depletion region on the surface. Exposure to acidic gases decreases n-type conductivity due to increased electron transfer from GaN, while basic gases increase n-type conductivity and PL intensity due to reduced charge transfer from GaN. These changes in the electrical and optical properties, as explained using a new electrochemical framework based on the phenomenon of surface transfer doping, suggest that gases interact with the semiconductor surface through electrochemical reactions occurring in an adsorbed water layer present on the surface.

Robust and stretchable indium gallium zinc oxide-based electronic textiles formed by cilia-assisted transfer printing