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.

Photoinduced electron transfer in covalent ruthenium-anthraquinone dyads: relative importance of driving-force, solvent polarity, and donor-bridge energy gap.

PubMed

Hankache, Jihane; Wenger, Oliver S

2012-02-28

Four rigid rod-like molecules comprised of a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer, a 9,10-anthraquinone electron acceptor, and a molecular bridge connecting the two redox partners were synthesized and investigated by optical spectroscopic and electrochemical means. An attempt was made to assess the relative importance of driving-force, solvent polarity, and bridge variation on the rates of photoinduced electron transfer in these molecules. Expectedly, introduction of tert-butyl substituents in the bipyridine ligands of the ruthenium complex and a change in solvent from dichloromethane to acetonitrile lead to a significant acceleration of charge transfer rates. In dichloromethane, photoinduced electron transfer is not competitive with the inherent excited-state deactivation processes of the photosensitizer. In acetonitrile, an increase in driving-force by 0.2 eV through attachment of tert-butyl substituents to the bpy ancillary ligands causes an increase in electron transfer rates by an order of magnitude. Replacement of a p-xylene bridge by a p-dimethoxybenzene spacer entails an acceleration of charge transfer rates by a factor of 3.5. In the dyads from this study, the relative order of importance of individual influences on electron transfer rates is therefore as follows: solvent polarity ≥ driving-force > donor-bridge energy gap.

A small electron donor in cobalt complex electrolyte significantly improves efficiency in dye-sensitized solar cells

PubMed Central

Hao, Yan; Yang, Wenxing; Zhang, Lei; Jiang, Roger; Mijangos, Edgar; Saygili, Yasemin; Hammarström, Leif; Hagfeldt, Anders; Boschloo, Gerrit

2016-01-01

Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy—by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte—to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system. PMID:28000672

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

Dynamics and mechanism of UV-damaged DNA repair in indole-thymine dimer adduct: molecular origin of low repair quantum efficiency.

PubMed

Guo, Xunmin; Liu, Zheyun; Song, Qinhua; Wang, Lijuan; Zhong, Dongping

2015-02-26

Many biomimetic chemical systems for repair of UV-damaged DNA showed very low repair efficiency, and the molecular origin is still unknown. Here, we report our systematic characterization of the repair dynamics of a model compound of indole-thymine dimer adduct in three solvents with different polarity. By resolving all elementary steps including three electron-transfer processes and two bond-breaking and bond-formation dynamics with femtosecond resolution, we observed the slow electron injection in 580 ps in water, 4 ns in acetonitrile, and 1.38 ns in dioxane, the fast back electron transfer without repair in 120, 150, and 180 ps, and the slow bond splitting in 550 ps, 1.9 ns, and 4.5 ns, respectively. The dimer bond cleavage is clearly accelerated by the solvent polarity. By comparing with the biological repair machine photolyase with a slow back electron transfer (2.4 ns) and a fast bond cleavage (90 ps), the low repair efficiency in the biomimetic system is mainly determined by the fast back electron transfer and slow bond breakage. We also found that the model system exists in a dynamic heterogeneous C-clamped conformation, leading to a stretched dynamic behavior. In water, we even identified another stacked form with ultrafast cyclic electron transfer, significantly reducing the repair efficiency. Thus, the comparison of the repair efficiency in different solvents is complicated and should be cautious, and only the dynamics by resolving all elementary steps can finally determine the total repair efficiency. Finally, we use the Marcus electron-transfer theory to analyze all electron-transfer reactions and rationalize all observed electron-transfer dynamics.

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.

Single-molecule interfacial electron transfer dynamics in solar energy conversion

NASA Astrophysics Data System (ADS)

Dhital, Bharat

This dissertation work investigated the parameters affecting the interfacial electron transfer (ET) dynamics in dye-semiconductor nanoparticles (NPs) system by using single-molecule fluorescence spectroscopy and imaging combined with electrochemistry. The influence of the molecule-substrate electronic coupling, the molecular structure, binding geometry on the surface and the molecule-attachment surface chemistry on interfacial charge transfer processes was studied on zinc porphyrin-TiO2 NP systems. The fluorescence blinking measurement on TiO2 NP demonstrated that electronic coupling regulates dynamics of charge transfer processes at the interface depending on the conformation of molecule on the surface. Moreover, semiconductor surface charge induced electronic coupling of molecule which is electrostatically adsorbed on the semiconductor surface also predominantly alters the ET dynamics. Furthermore, interfacial electric field and electron accepting state density dependent ET dynamics has been dissected in zinc porphyrin-TiO2 NP system by observing the single-molecule fluorescence blinking dynamics and fluorescence lifetime with and without applied bias. The significant difference in fluorescence fluctuation and lifetime suggested the modulation of charge transfer dynamics at the interface with external electric field perturbation. Quasi-continuous distribution of fluorescence intensity with applied negative potential was attributed to the faster charge recombination due to reduced density of electron accepting states. The driving force and electron accepting state density ET dependent dynamics has also been probed in zinc porphyrin-TiO2 NP and zinc porphyrin-indium tin oxide (ITO) systems. Study of a molecule adsorbed on two different semiconductors (ITO and TiO2), with large difference in electron densities and distinct driving forces, allows us to observe the changes in rates of back electron transfer process reflected by the suppressed fluorescence blinking of molecule on ITO surface. Finally, the electric field effect on the interface properties has been probed by using surface-enhanced Raman spectroscopy and supported by density functional theory calculations in alizarin-TiO2 system. The perturbation, created by the external potential, has been observed to cause a shift and/or splitting interfacial bond vibrational mode, typical indicator of the coupling energy changes between alizarin and TiO2. Such splitting provides evidence for electric field-dependent electronic coupling changes that have a significant impact on the interfacial electron transfer dynamics.

Intramolecular electron-transfer rates in mixed-valence triarylamines: measurement by variable-temperature ESR spectroscopy and comparison with optical data.

PubMed

Lancaster, Kelly; Odom, Susan A; Jones, Simon C; Thayumanavan, S; Marder, Seth R; Brédas, Jean-Luc; Coropceanu, Veaceslav; Barlow, Stephen

2009-02-11

The electron spin resonance spectra of the radical cations of 4,4'-bis[di(4-methoxyphenyl)amino]tolane, E-4,4'-bis[di(4-methoxyphenyl)amino]stilbene, and E,E-1,4-bis{4-[di(4-methoxyphenyl)amino]styryl}benzene in dichloromethane exhibit five lines over a wide temperature range due to equivalent coupling to two 14N nuclei, indicating either delocalization between both nitrogen atoms or rapid intramolecular electron transfer on the electron spin resonance time scale. In contrast, those of the radical cations of 1,4-bis{4-[di(4-methoxyphenyl)amino]phenylethynyl}benzene and E,E-1,4-bis{4-[di(4-n-butoxyphenyl)amino]styryl}-2,5-dicyanobenzene exhibit line shapes that vary strongly with temperature, displaying five lines at room temperature and only three lines at ca. 190 K, indicative of slow electron transfer on the electron spin resonance time scale at low temperatures. The rates of intramolecular electron transfer in the latter compounds were obtained by simulation of the electron spin resonance spectra and display an Arrhenius temperature dependence. The activation barriers obtained from Arrhenius plots are significantly less than anticipated from Hush analyses of the intervalence bands when the diabatic electron-transfer distance, R, is equated to the N[symbol: see text]N distance. Comparison of optical and electron spin resonance data suggests that R is in fact only ca. 40% of the N[symbol: see text]N distance, while the Arrhenius prefactor indicates that the electron transfer falls in the adiabatic regime.

Bidirectional Photoinduced Electron Transfer in Ruthenium(II)-Tris-bipyridyl-Modified PpcA, a Multi-heme c -Type Cytochrome from Geobacter sulfurreducens

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

Kokhan, Oleksandr; Ponomarenko, Nina S.; Pokkuluri, P. Raj

PpcA, a tri-heme cytochrome c7 from Geobacter sulfurreducens was investigated as a model for photosensitizer-initiated electron transfer within a multi-heme "molecular wire" protein architecture. E. coli expression of PpcA was found to be tolerant of cysteine site-directed mutagenesis, demonstrated by the successful expression of natively folded proteins bearing cysteine mutations at a series of sites selected to vary characteristically with respect to the three -CXXCH- heme binding domains. A preliminary survey of 5 selected mutants found that the introduced cysteines can be readily covalently linked to a Ru(II)-(2,2'-bpy)2(4-bromomethyl-4’-methyl-2,2'-bpy) photosensitizer (where bpy = bipyridine), and that the linked constructs support bothmore » photo-oxidative and photo-reductive quenching of the photosensitizer excited-state, depending upon the initial heme redox state. For photo-oxidative electron transfer, apparent heme reduction risetimes were found to vary from 7 x 10-12 s to 5 x 10-8 s, depending upon the site of photosensitizer linking. The excited-state electron transfers are about 103-fold faster than any previously reported photosensitizer-redox protein covalently linked construct. Preliminary conformational analysis using molecular dynamics simulations shows that rates for electron transfer track both the distance and pathways for electron transfer. Two mutants with the fastest charge transfer rates, A23C and K29C, showed a significant role of specific paths for electron transfer. While K29C labeled mutant was expected to have approximately 0.8Å greater donor-acceptor distance, it showed 20-fold faster charge separation rate. Clear evidence for inter-heme electron transfer within the multi-heme protein is not detected within the lifetimes of the charge separated states. These results demonstrate an opportunity to develop multi-heme c-cytochromes for investigation of electron transfer in protein "molecular wires" and to serve as frameworks for metalloprotein designs that support multiple electron transfer redox chemistry.« less

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.

Feasibility study of electron transfer quantum well infrared photodetectors for spectral tuning in the long-wave infrared band

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

Jolley, Greg; Dehdashti Akhavan, Nima; Umana-Membreno, Gilberto

An electron transfer quantum well infrared photodetector (QWIP) consisting of repeating units of two coupled quantum wells (QWs) is capable of exhibiting a two color voltage dependent spectral response. However, significant electron transfer between the coupled QWs is required for spectral tuning, which may require the application of relatively high electric fields. Also, the band structure of coupled quantum wells is more complicated in comparison to a regular quantum well and, therefore, it is not always obvious if an electron transfer QWIP can be designed such that it meets specific performance characteristics. This paper presents a feasibility study of themore » electron transfer QWIP and its suitability for spectral tuning. Self consistent calculations have been performed of the bandstructure and the electric field that results from electron population within the quantum wells, from which the optical characteristics have been obtained. The band structure, spectral response, and the resonant final state energy locations have been compared with standard QWIPs. It is shown that spectral tuning in the long-wave infrared band can be achieved over a wide wavelength range of several microns while maintaining a relatively narrow spectral response FWHM. However, the total absorption strength is more limited in comparison to a standard QWIP, since the higher QW doping densities require much higher electric fields for electron transfer.« less

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; Arntsen, Christopher

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 molecules. 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 offer a word of cautionmore » for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer.« less

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

Role of Humic-Bound Iron as an Electron Transfer Agent in Dissimilatory Fe(III) Reduction

PubMed Central

Lovley, Derek R.; Blunt-Harris, Elizabeth L.

1999-01-01

The dissimilatory Fe(III) reducer Geobacter metallireducens reduced Fe(III) bound in humic substances, but the concentrations of Fe(III) in a wide range of highly purified humic substances were too low to account for a significant portion of the electron-accepting capacities of the humic substances. Furthermore, once reduced, the iron in humic substances could not transfer electrons to Fe(III) oxide. These results suggest that other electron-accepting moieties in humic substances, such as quinones, are the important electron-accepting and shuttling agents under Fe(III)-reducing conditions. PMID:10473447

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.

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 establishes the parameter by which the energetic efficiency of protein electron transfer is increased relative to the standard expectations, thus minimizing losses of energy to heat. Energetically efficient electron transfer occurs in a chain of conformationally quenched cofactors and is characterized by flattened free energy surfaces, reminiscent of the flat and rugged landscape at the stability basin of a folded protein.

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 establishes the parameter by which the energetic efficiency of protein electron transfer is increased relative to the standard expectations, thus minimizing losses of energy to heat. Energetically efficient electron transfer occurs in a chain of conformationally quenched cofactors and is characterized by flattened free energy surfaces, reminiscent of the flat and rugged landscape at the stability basin of a folded protein.

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

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

Observation of correlated electronic decay in expanding clusters triggered by near-infrared fields

PubMed Central

Schütte, B.; Arbeiter, M.; Fennel, T.; Jabbari, G.; Kuleff, A.I.; Vrakking, M.J.J.; Rouzée, A.

2015-01-01

When an excited atom is embedded into an environment, novel relaxation pathways can emerge that are absent for isolated atoms. A well-known example is interatomic Coulombic decay, where an excited atom relaxes by transferring its excess energy to another atom in the environment, leading to its ionization. Such processes have been observed in clusters ionized by extreme-ultraviolet and X-ray lasers. Here, we report on a correlated electronic decay process that occurs following nanoplasma formation and Rydberg atom generation in the ionization of clusters by intense, non-resonant infrared laser fields. Relaxation of the Rydberg states and transfer of the available electronic energy to adjacent electrons in Rydberg states or quasifree electrons in the expanding nanoplasma leaves a distinct signature in the electron kinetic energy spectrum. These so far unobserved electron-correlation-driven energy transfer processes may play a significant role in the response of any nano-scale system to intense laser light. PMID:26469997

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

PubMed

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

2018-03-28

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

Understanding the Role of Electron-driven Processes in Atmospheric Behaviour

NASA Astrophysics Data System (ADS)

Brunger, M. J.; Campbell, L.; Jones, D. B.; Cartwright, D. C.

2004-12-01

Electron-impact excitation plays a major role in emission from aurora and a less significant but nonetheless crucial role in the dayglow and nightglow. For some molecules, such as N2, O2 and NO, electron-impact excitation can be followed by radiative cascade through many different sets of energy levels, producing emission with a large number of lines. We review the application of our statistical equilibrium program to predict this rich spectrum of radiation, and we compare results we have obtained against available independent measurements. In addition, we also review the calculation of energy transfer rates from electrons to N2, O2 and NO in the thermosphere. Energy transfer from electrons to neutral gases and ions is one of the dominant electron cooling processes in the ionosphere, and the role of vibrationally excited N2 and O2 in this is particularly significant. The importance of the energy dependence and magnitude of the electron-impact vibrational cross sections in the calculation of these rates is assessed.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander; Hammes-Schiffer, Sharon

2015-11-17

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approachmore » in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (applications to molecular electrocatalysts).« less

Charge transfer in model peptides: obtaining Marcus parameters from molecular simulation.

PubMed

Heck, Alexander; Woiczikowski, P Benjamin; Kubař, Tomáš; Giese, Bernd; Elstner, Marcus; Steinbrecher, Thomas B

2012-02-23

Charge transfer within and between biomolecules remains a highly active field of biophysics. Due to the complexities of real systems, model compounds are a useful alternative to study the mechanistic fundamentals of charge transfer. In recent years, such model experiments have been underpinned by molecular simulation methods as well. In this work, we study electron hole transfer in helical model peptides by means of molecular dynamics simulations. A theoretical framework to extract Marcus parameters of charge transfer from simulations is presented. We find that the peptides form stable helical structures with sequence dependent small deviations from ideal PPII helices. We identify direct exposure of charged side chains to solvent as a cause of high reorganization energies, significantly larger than typical for electron transfer in proteins. This, together with small direct couplings, makes long-range superexchange electron transport in this system very slow. In good agreement with experiment, direct transfer between the terminal amino acid side chains can be dicounted in favor of a two-step hopping process if appropriate bridging groups exist. © 2012 American Chemical Society

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

PubMed

Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

2016-12-19

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center is more efficient than intermolecular electron transfer between the separate components.

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 variation in the electrochemical conditions under which mats were generated significantly impacted the relative abundances of mat members and mat metabolism.« less

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 variation in the electrochemical conditions under which mats were generated significantly impacted the relative abundances of mat members and mat metabolism.« less

Solvent electronic polarization effects on a charge transfer excitation studied by the mean-field QM/MM method

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

Nakano, Hiroshi; Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto 615-8245

2015-12-31

Electronic polarization effects of a medium can have a significant impact on a chemical reaction in condensed phases. We discuss the effects on the charge transfer excitation of a chromophore, N,N-dimethyl-4-nitroaniline, in various solvents using the mean-field QM/MM method with a polarizable force field. The results show that the explicit consideration of the solvent electronic polarization effects is important especially for a solvent with a low dielectric constant when we study the solvatochromism of the chromophore.

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.

[2.2]paracyclophane-bridged mixed-valence compounds: application of a generalized Mulliken-Hush three-level model.

PubMed

Amthor, Stephan; Lambert, Christoph

2006-01-26

A series of [2.2]paracylophane-bridged bis-triarylamine mixed-valence (MV) radical cations were analyzed by a generalized Mulliken-Hush (GMH) three-level model which takes two transitions into account: the intervalence charge transfer (IV-CT) band which is assigned to an optically induced hole transfer (HT) from one triarylamine unit to the second one and a second band associated with a triarylamine radical cation to bridge (in particular, the [2.2]paracyclophane bridge) hole transfer. From the GMH analysis, we conclude that the [2.2]paracyclophane moiety is not the limiting factor which governs the intramolecular charge transfer. AM1-CISD calculations reveal that both through-bond as well as through-space interactions of the [2.2]paracyclophane bridge play an important role for hole transfer processes. These electronic interactions are of course smaller than direct pi-conjugation, but from the order of magnitude of the couplings of the [2.2]paracyclophane MV species, we assume that this bridge is able to mediate significant through-space and through-bond interactions and that the cyclophane bridge acts more like an unsaturated spacer rather than a saturated one. From the exponential dependence of the electronic coupling V between the two triarylamine localized states on the distance r between the two redox centers, we infer that the hole transfer occurs via a superexchange mechanism. Our analysis reveals that even significantly longer pi-conjugated bridges should still mediate significant electronic interactions because the decay constant beta of a series of pi-conjugated MV species is small.

Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas

DOE PAGES

Hobbs, Richard G.; Putnam, William P.; Fallahi, Arya; ...

2017-09-19

Understanding plasmon-mediated electron emission and energy transfer on the nanometer length scale is critical to controlling light–matter interactions at nanoscale dimensions. In a high-resolution lithographic material, electron emission and energy transfer lead to chemical transformations. Here, we employ such chemical transformations in two different high-resolution electron-beam lithography resists, poly(methyl methacrylate) (PMMA) and hydrogen silsesquioxane (HSQ), to map local electron emission and energy transfer with nanometer resolution from plasmonic nanoantennas excited by femtosecond laser pulses. We observe exposure of the electron-beam resists (both PMMA and HSQ) in regions on the surface of nanoantennas where the local field is significantly enhanced. Exposuremore » in these regions is consistent with previously reported optical-field-controlled electron emission from plasmonic hotspots as well as earlier work on low-electron-energy scanning probe lithography. For HSQ, in addition to exposure in hotspots, we observe resist exposure at the centers of rod-shaped nanoantennas in addition to exposure in plasmonic hotspots. Optical field enhancement is minimized at the center of nanorods suggesting that exposure in these regions involves a different mechanism to that in plasmonic hotspots. Our simulations suggest that exposure at the center of nanorods results from the emission of hot electrons produced via plasmon decay in the nanorods. Our results provide a means to map both optical-field-controlled electron emission and hot-electron transfer from nanoparticles via chemical transformations produced locally in lithographic materials.« less

Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas

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

Hobbs, Richard G.; Putnam, William P.; Fallahi, Arya

Understanding plasmon-mediated electron emission and energy transfer on the nanometer length scale is critical to controlling light–matter interactions at nanoscale dimensions. In a high-resolution lithographic material, electron emission and energy transfer lead to chemical transformations. Here, we employ such chemical transformations in two different high-resolution electron-beam lithography resists, poly(methyl methacrylate) (PMMA) and hydrogen silsesquioxane (HSQ), to map local electron emission and energy transfer with nanometer resolution from plasmonic nanoantennas excited by femtosecond laser pulses. We observe exposure of the electron-beam resists (both PMMA and HSQ) in regions on the surface of nanoantennas where the local field is significantly enhanced. Exposuremore » in these regions is consistent with previously reported optical-field-controlled electron emission from plasmonic hotspots as well as earlier work on low-electron-energy scanning probe lithography. For HSQ, in addition to exposure in hotspots, we observe resist exposure at the centers of rod-shaped nanoantennas in addition to exposure in plasmonic hotspots. Optical field enhancement is minimized at the center of nanorods suggesting that exposure in these regions involves a different mechanism to that in plasmonic hotspots. Our simulations suggest that exposure at the center of nanorods results from the emission of hot electrons produced via plasmon decay in the nanorods. Our results provide a means to map both optical-field-controlled electron emission and hot-electron transfer from nanoparticles via chemical transformations produced locally in lithographic materials.« less

Surface modification of boron nitride nanosheets by polyelectrolytes via atom transfer radical polymerization

NASA Astrophysics Data System (ADS)

Wu, Yuanpeng; Guo, Meiling; Liu, Guanfei; Xue, Shishan; Xia, Yuanmeng; Liu, Dan; Lei, Weiwei

2018-04-01

In this study, the surface modification of boron nitride nanosheets (BNNSs) with poly 2-acrylamido-2-methyl- propanesulfonate (PAMPS) brushes is achieved through electron transfer atom transfer radical polymerization (ARGET ATRP). BNNSs surface was first modified with α-bromoisobutyryl bromide (BIBB) via hydroxyl groups, then PAMPS brushes were grown on the surface through ARGET ATRP. Polyelectrolyte brushes modified BNNSs were further characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses (TGA), x-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The concentraction of water-dispersion of BNNSs have been enhanced significantly by PAMPS and the high water-dispersible functional BNNSs/PAMPS composites are expected to have potential applications in biomedical and thermal management in electronics.

Dynamics of exciton transfer in coupled polymer chains.

PubMed

Zhang, Y L; Liu, X J; Sun, Z; An, Z

2013-05-07

The dynamics of singlet and triplet exciton transfer in coupled polymer chains are investigated within the Su-Schrieffer-Heeger+Pariser-Parr-Pople model including both electron-phonon (e-p) coupling and electron-electron (e-e) interactions, using a multi-configurational time-dependent Hartree-Fock dynamic method. In order to explain the processes involved, the effects of on-site and long-range e-e interactions on the locality of the singlet and triplet excitons are first investigated on an isolated chain. It is found that the locality of the singlet exciton decreases, while the locality of the triplet exciton increases with an increase in the on-site e-e interactions. On the other hand, an increase in the long-range e-e interaction results in a more localized singlet exciton and triplet exciton. In coupled polymer chains, we then quantitatively show the yields of singlet and triplet exciton transfer products under the same interchain coupling. It is found that the yield of singlet interchain excitons is much higher than that of triplet interchain excitons, that is to say, singlet exciton transfer is significantly easier than that for triplet excitons. This results from the fact that the singlet exciton is more delocalized than the triplet exciton. In addition, hopping of electrons with opposite spins between the coupled chains can facilitate the transfer of singlet excitons. The results are of great significance for understanding the photoelectric conversion process and developing high-power organic optoelectronic applications.

Cyclopropyl conjugation and ketyl anions: when do things begin to fall apart?

PubMed

Tanko, J M; Li, Xiangzhong; Chahma, M'hamed; Jackson, Woodward F; Spencer, Jared N

2007-04-11

Results pertaining to the electrochemical reduction of 1,2-diacetylcyclopropane (5), 1-acetyl-2-phenylcyclopropane (6), 1-acetyl-2-benzoylcyclopropane (7), and 1,2-dibenzoylcyclopropane (8) are reported. While 6*- exists as a discrete species, the barrier to ring opening is very small (<1 kcal/mol) and the rate constant for ring opening is >10(7) s(-1). For 7 and 8, the additional resonance stabilization afforded by the benzoyl moieties results in significantly lower rate constants for ring opening, on the order of 10(5)-10(6) s(-1). Electron transfer to 8 serves to initiate an unexpected vinylcyclopropane --> cyclopentene type rearrangement, which occurs via a radical ion chain mechanism. The results for reduction of 5 are less clear-cut: The experimental results suggest that the reduction is unexceptional, with a symmetry coefficient alpha

Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

PubMed

Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

2016-09-01

The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

Direct imaging of electron transfer and its influence on superconducting pairing at FeSe/SrTiO3 interface

PubMed Central

Zhao, Weiwei; Li, Mingda; Chang, Cui-Zu; Jiang, Jue; Wu, Lijun; Liu, Chaoxing; Moodera, Jagadeesh S.; Zhu, Yimei; Chan, Moses H. W.

2018-01-01

The exact mechanism responsible for the significant enhancement of the superconducting transition temperature (Tc) of monolayer iron selenide (FeSe) films on SrTiO3 (STO) over that of bulk FeSe is an open issue. We present the results of a coordinated study of electrical transport, low temperature electron energy-loss spectroscopy (EELS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) measurements on FeSe/STO films of different thicknesses. HAADF-STEM imaging together with EELS mapping across the FeSe/STO interface shows direct evidence of electrons transferred from STO to the FeSe layer. The transferred electrons were found to accumulate within the first two atomic layers of the FeSe films near the STO substrate. An additional Se layer is also resolved to reside between the FeSe film and the TiOx-terminated STO substrate. Our transport results found that a positive backgate applied from STO is particularly effective in enhancing Tc of the films while minimally changing the carrier density. This increase in Tc is due to the positive backgate that “pulls” the transferred electrons in FeSe films closer to the interface and thus enhances their coupling to interfacial phonons and also the electron-electron interaction within FeSe films. PMID:29556528

Direct imaging of electron transfer and its influence on superconducting pairing at FeSe/SrTiO 3 interface

DOE PAGES

Zhao, Weiwei; Li, Mingda; Chang, Cui -Zu; ...

2018-03-16

The exact mechanism responsible for the significant enhancement of the superconducting transition temperature (T c) of monolayer iron selenide (FeSe) films on SrTiO 3 (STO) over that of bulk FeSe is an open issue. We present the results of a coordinated study of electrical transport, low temperature electron energy-loss spectroscopy (EELS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) measurements on FeSe/STO films of different thicknesses. HAADF-STEM imaging together with EELS mapping across the FeSe/STO interface shows direct evidence of electrons transferred from STO to the FeSe layer. The transferred electrons were found to accumulate within the first twomore » atomic layers of the FeSe films near the STO substrate. An additional Se layer is also resolved to reside between the FeSe film and the TiO x-terminated STO substrate. Our transport results found that a positive backgate applied from STO is particularly effective in enhancing T c of the films while minimally changing the carrier density. Furthermore, this increase in T c is due to the positive backgate that “pulls” the transferred electrons in FeSe films closer to the interface and thus enhances their coupling to interfacial phonons and also the electron-electron interaction within FeSe films.« less

Design and engineering of a man-made diffusive electron-transport protein.

PubMed

Fry, Bryan A; Solomon, Lee A; Leslie Dutton, P; Moser, Christopher C

2016-05-01

Maquettes are man-made cofactor-binding oxidoreductases designed from first principles with minimal reference to natural protein sequences. Here we focus on water-soluble maquettes designed and engineered to perform diffusive electron transport of the kind typically carried out by cytochromes, ferredoxins and flavodoxins and other small proteins in photosynthetic and respiratory energy conversion and oxido-reductive metabolism. Our designs were tested by analysis of electron transfer between heme maquettes and the well-known natural electron transporter, cytochrome c. Electron-transfer kinetics were measured from seconds to milliseconds by stopped-flow, while sub-millisecond resolution was achieved through laser photolysis of the carbon monoxide maquette heme complex. These measurements demonstrate electron transfer from the maquette to cytochrome c, reproducing the timescales and charge complementarity modulation observed in natural systems. The ionic strength dependence of inter-protein electron transfer from 9.7×10(6) M(-1) s(-1) to 1.2×10(9) M(-1) s(-1) follows a simple Debye-Hückel model for attraction between +8 net charged oxidized cytochrome c and -19 net charged heme maquette, with no indication of significant protein dipole moment steering. Successfully recreating essential components of energy conversion and downstream metabolism in man-made proteins holds promise for in vivo clinical intervention and for the production of fuel or other industrial products. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. Copyright © 2015 Elsevier B.V. All rights reserved.

Atomic and electronic structure of trilayer graphene/SiC(0001): Evidence of Strong Dependence on Stacking Sequence and charge transfer.

PubMed

Pierucci, Debora; Brumme, Thomas; Girard, Jean-Christophe; Calandra, Matteo; Silly, Mathieu G; Sirotti, Fausto; Barbier, Antoine; Mauri, Francesco; Ouerghi, Abdelkarim

2016-09-15

The transport properties of few-layer graphene are the directly result of a peculiar band structure near the Dirac point. Here, for epitaxial graphene grown on SiC, we determine the effect of charge transfer from the SiC substrate on the local density of states (LDOS) of trilayer graphene using scaning tunneling microscopy/spectroscopy and angle resolved photoemission spectroscopy (ARPES). Different spectra are observed and are attributed to the existence of two stable polytypes of trilayer: Bernal (ABA) and rhomboedreal (ABC) staking. Their electronic properties strongly depend on the charge transfer from the substrate. We show that the LDOS of ABC stacking shows an additional peak located above the Dirac point in comparison with the LDOS of ABA stacking. The observed LDOS features, reflecting the underlying symmetry of the two polytypes, were reproduced by explicit calculations within density functional theory (DFT) including the charge transfer from the substrate. These findings demonstrate the pronounced effect of stacking order and charge transfer on the electronic structure of trilayer or few layer graphene. Our approach represents a significant step toward understand the electronic properties of graphene layer under electrical field.

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

PubMed

Trevethan, Thomas; Shluger, Alexander

2009-07-01

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

Communication: CDFT-CI couplings can be unreliable when there is fractional charge transfer

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

Mavros, Michael G.; Van Voorhis, Troy, E-mail: tvan@mit.edu

2015-12-21

Constrained density functional theory with configuration interaction (CDFT-CI) is a useful, low-cost tool for the computational prediction of electronic couplings between pseudo-diabatic constrained electronic states. Such couplings are of paramount importance in electron transfer theory and transition state theory, among other areas of chemistry. Unfortunately, CDFT-CI occasionally fails significantly, predicting a coupling that does not decay exponentially with distance and/or overestimating the expected coupling by an order of magnitude or more. In this communication, we show that the eigenvalues of the difference density matrix between the two constrained states can be used as an a priori metric to determine whenmore » CDFT-CI are likely to be reliable: when the eigenvalues are near 0 or ±1, transfer of a whole electron is occurring, and CDFT-CI can be trusted. We demonstrate the utility of this metric with several illustrative examples.« less

Communication: CDFT-CI couplings can be unreliable when there is fractional charge transfer

NASA Astrophysics Data System (ADS)

Mavros, Michael G.; Van Voorhis, Troy

2015-12-01

Constrained density functional theory with configuration interaction (CDFT-CI) is a useful, low-cost tool for the computational prediction of electronic couplings between pseudo-diabatic constrained electronic states. Such couplings are of paramount importance in electron transfer theory and transition state theory, among other areas of chemistry. Unfortunately, CDFT-CI occasionally fails significantly, predicting a coupling that does not decay exponentially with distance and/or overestimating the expected coupling by an order of magnitude or more. In this communication, we show that the eigenvalues of the difference density matrix between the two constrained states can be used as an a priori metric to determine when CDFT-CI are likely to be reliable: when the eigenvalues are near 0 or ±1, transfer of a whole electron is occurring, and CDFT-CI can be trusted. We demonstrate the utility of this metric with several illustrative examples.

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

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 maximize energy conservation. Bifurcating enzymes couple thermodynamically unfavorable reactions with thermodynamically favorable reactions in an overall spontaneous process. Here we show that the electron-transferring flavoprotein (Etf) enzyme family exhibits far greater diversity than previously recognized, and we provide a phylogenetic analysis that clearly delineates bifurcating versus nonbifurcating members of this family. Structural modeling of proteins within these groups reveals key differences between the bifurcating and nonbifurcating Etfs. PMID:28808132

Quantum electron tunneling in respiratory complex I.

PubMed

Hayashi, Tomoyuki; Stuchebrukhov, Alexei A

2011-05-12

We have simulated the atomistic details of electronic wiring of all Fe/S clusters in complex I, a key enzyme in the respiratory electron transport chain. The tunneling current theory of many-electron systems is applied to the broken-symmetry (BS) states of the protein at the ZINDO level. While the one-electron tunneling approximation is found to hold in electron tunneling between the antiferromagnetic binuclear and tetranuclear Fe/S clusters without major orbital or spin rearrangement of the core electrons, induced polarization of the core electrons contributes significantly to decrease the electron transfer rates to 19-56 %. Calculated tunneling energy is about 3 eV higher than Fermi level in the band gap of the protein, which supports that the mechanism of electron transfer is quantum mechanical tunneling, as in the rest of the electron transport chain. Resulting electron tunneling pathways consist of up to three key contributing protein residues between neighboring Fe/S clusters. A signature of the wave properties of electrons is observed as distinct quantum interferences when multiple tunneling pathways exist. In N6a-N6b, electron tunnels along different pathways depending on the involved BS states, suggesting possible fluctuations of the tunneling pathways driven by the local protein environment. The calculated distance dependence of the electron transfer rates with internal water molecules included is in good agreement with a reported phenomenological relation.

Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set

NASA Astrophysics Data System (ADS)

Oberhofer, Harald; Blumberger, Jochen

2010-12-01

We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT). Following the work of Wu and Van Voorhis [J. Chem. Phys. 125, 164105 (2006)], the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q-) anion. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The thermal average, ( {< {| {H_ab } |^2 } > } )^{1/2} = 6.7 {mH}, is significantly higher than the value obtained for the minimum energy structure, | {H_ab } | = 3.8 {mH}. While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q- in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.

Direct Laser Writing-Based Programmable Transfer Printing via Bioinspired Shape Memory Reversible Adhesive.

PubMed

Huang, Yin; Zheng, Ning; Cheng, Zhiqiang; Chen, Ying; Lu, Bingwei; Xie, Tao; Feng, Xue

2016-12-28

Flexible and stretchable electronics offer a wide range of unprecedented opportunities beyond conventional rigid electronics. Despite their vast promise, a significant bottleneck lies in the availability of a transfer printing technique to manufacture such devices in a highly controllable and scalable manner. Current technologies usually rely on manual stick-and-place and do not offer feasible mechanisms for precise and quantitative process control, especially when scalability is taken into account. Here, we demonstrate a spatioselective and programmable transfer strategy to print electronic microelements onto a soft substrate. The method takes advantage of automated direct laser writing to trigger localized heating of a micropatterned shape memory polymer adhesive stamp, allowing highly controlled and spatioselective switching of the interfacial adhesion. This, coupled to the proper tuning of the stamp properties, enables printing with perfect yield. The wide range adhesion switchability further allows printing of hybrid electronic elements, which is otherwise challenging given the complex interfacial manipulation involved. Our temperature-controlled transfer printing technique shows its critical importance and obvious advantages in the potential scale-up of device manufacturing. Our strategy opens a route to manufacturing flexible electronics with exceptional versatility and potential scalability.

Open-Circuit Voltage Losses in Selenium-Substituted Organic Photovoltaic Devices from Increased Density of Charge-Transfer States

DOE PAGES

Sulas, Dana B.; Yao, Kai; Intemann, Jeremy J.; ...

2015-09-12

Using an analysis based on Marcus theory, we characterize losses in open-circuit voltage (V OC) due to changes in charge-transfer state energy, electronic coupling, and spatial density of charge-transfer states in a series of polymer/fullerene solar cells. Here, we use a series of indacenodithiophene polymers and their selenium-substituted analogs as electron donor materials and fullerenes as the acceptors. By combining device measurements and spectroscopic studies (including subgap photocurrent, electroluminescence, and, importantly, time-resolved photoluminescence of the charge-transfer state) we are able to isolate the values for electronic coupling and the density of charge-transfer states (NCT), rather than the more commonly measuredmore » product of these values. We find values for NCT that are surprisingly large (~4.5 × 10 21–6.2 × 10 22 cm -3), and we find that a significant increase in N CT upon selenium substitution in donor polymers correlates with lower VOC for bulk heterojunction photovoltaic devices. The increase in N CT upon selenium substitution is also consistent with nanoscale morphological characterization. Using transmission electron microscopy, selected area electron diffraction, and grazing incidence wide-angle X-ray scattering, we find evidence of more intermixed polymer and fullerene domains in the selenophene blends, which have higher densities of polymer/fullerene interfacial charge-transfer states. Our results provide an important step toward understanding the spatial nature of charge-transfer states and their effect on the open-circuit voltage of polymer/fullerene solar cells« less

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.

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.

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.

Spontaneous modification of graphite anode by anthraquinone-2-sulfonic acid for microbial fuel cells.

PubMed

Tang, Xinhua; Li, Haoran; Du, Zhuwei; Ng, How Yong

2014-07-01

In this study, anthraquinone-2-sulfonic acid (AQS), an electron transfer mediator, was immobilized onto graphite felt surface via spontaneous reduction of the in situ generated AQS diazonium cations. Cyclic voltammetry (CV) and energy dispersive spectrometry (EDS) characterizations of AQS modified graphite demonstrated that AQS was covalently grafted onto the graphite surface. The modified graphite, with a surface AQS concentration of 5.37 ± 1.15 × 10(-9)mol/cm(2), exhibited good electrochemical activity and high stability. The midpoint potential of the modified graphite was about -0.248 V (vs. normal hydrogen electrode, NHE), indicating that electrons could be easily transferred from NADH in bacteria to the electrode. AQS modified anode in MFCs increased the maximum power density from 967 ± 33 mW/m(2) to 1872 ± 42 mW/m(2). These results demonstrated that covalently modified AQS functioned as an electron transfer mediator to facilitate extracellular electron transfer from bacteria to electrode and significantly enhanced the power production in MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Free energy functionals for polarization fluctuations: Pekar factor revisited

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

Dinpajooh, Mohammadhasan; Newton, Marshall D.; Matyushov, Dmitry V.

The separation of slow nuclear and fast electronic polarization in problems related to electron mobility in polarizable media was considered by Pekar 70 years ago. Within dielectric continuum models, this separation leads to the Pekar factor in the free energy of solvation by the nuclear degrees of freedom. The main qualitative prediction of Pekar’s perspective is a significant, by about a factor of two, drop of the nuclear solvation free energy compared to the total (electronic plus nuclear) free energy of solvation. The Pekar factor enters the solvent reorganization energy of electron transfer reactions and is a significant mechanistic parametermore » accounting for the solvent effect on electron transfer. Here, we study the separation of the fast and slow polarization modes in polar molecular liquids (polarizable dipolar liquids and polarizable water force fields) without relying on the continuum approximation. We derive the nonlocal free energy functional and use atomistic numerical simulations to obtain nonlocal, reciprocal space electronic and nuclear susceptibilities. A consistent transition to the continuum limit is introduced by extrapolating the results of finite-size numerical simulation to zero wavevector. The continuum nuclear susceptibility extracted from simulations is numerically close to the Pekar factor. However, we derive a new functionality involving the static and high-frequency dielectric constants. The main distinction of our approach from the traditional theories is found for the solvation free energy due to the nuclear polarization: the anticipated significant drop of its magnitude with increasing liquid polarizability does not occur. The reorganization energy of electron transfer is either nearly constant with increasing the solvent polarizability and the corresponding high-frequency dielectric constant (polarizable dipolar liquids) or actually noticeably increases (polarizable force fields of water).« less

Free energy functionals for polarization fluctuations: Pekar factor revisited

DOE PAGES

Dinpajooh, Mohammadhasan; Newton, Marshall D.; Matyushov, Dmitry V.

2017-02-13

The separation of slow nuclear and fast electronic polarization in problems related to electron mobility in polarizable media was considered by Pekar 70 years ago. Within dielectric continuum models, this separation leads to the Pekar factor in the free energy of solvation by the nuclear degrees of freedom. The main qualitative prediction of Pekar’s perspective is a significant, by about a factor of two, drop of the nuclear solvation free energy compared to the total (electronic plus nuclear) free energy of solvation. The Pekar factor enters the solvent reorganization energy of electron transfer reactions and is a significant mechanistic parametermore » accounting for the solvent effect on electron transfer. Here, we study the separation of the fast and slow polarization modes in polar molecular liquids (polarizable dipolar liquids and polarizable water force fields) without relying on the continuum approximation. We derive the nonlocal free energy functional and use atomistic numerical simulations to obtain nonlocal, reciprocal space electronic and nuclear susceptibilities. A consistent transition to the continuum limit is introduced by extrapolating the results of finite-size numerical simulation to zero wavevector. The continuum nuclear susceptibility extracted from simulations is numerically close to the Pekar factor. However, we derive a new functionality involving the static and high-frequency dielectric constants. The main distinction of our approach from the traditional theories is found for the solvation free energy due to the nuclear polarization: the anticipated significant drop of its magnitude with increasing liquid polarizability does not occur. The reorganization energy of electron transfer is either nearly constant with increasing the solvent polarizability and the corresponding high-frequency dielectric constant (polarizable dipolar liquids) or actually noticeably increases (polarizable force fields of water).« less

Free energy functionals for polarization fluctuations: Pekar factor revisited.

PubMed

Dinpajooh, Mohammadhasan; Newton, Marshall D; Matyushov, Dmitry V

2017-02-14

The separation of slow nuclear and fast electronic polarization in problems related to electron mobility in polarizable media was considered by Pekar 70 years ago. Within dielectric continuum models, this separation leads to the Pekar factor in the free energy of solvation by the nuclear degrees of freedom. The main qualitative prediction of Pekar's perspective is a significant, by about a factor of two, drop of the nuclear solvation free energy compared to the total (electronic plus nuclear) free energy of solvation. The Pekar factor enters the solvent reorganization energy of electron transfer reactions and is a significant mechanistic parameter accounting for the solvent effect on electron transfer. Here, we study the separation of the fast and slow polarization modes in polar molecular liquids (polarizable dipolar liquids and polarizable water force fields) without relying on the continuum approximation. We derive the nonlocal free energy functional and use atomistic numerical simulations to obtain nonlocal, reciprocal space electronic and nuclear susceptibilities. A consistent transition to the continuum limit is introduced by extrapolating the results of finite-size numerical simulation to zero wavevector. The continuum nuclear susceptibility extracted from the simulations is numerically close to the Pekar factor. However, we derive a new functionality involving the static and high-frequency dielectric constants. The main distinction of our approach from the traditional theories is found in the solvation free energy due to the nuclear polarization: the anticipated significant drop of its magnitude with increasing liquid polarizability does not occur. The reorganization energy of electron transfer is either nearly constant with increasing the solvent polarizability and the corresponding high-frequency dielectric constant (polarizable dipolar liquids) or actually noticeably increases (polarizable force fields of water).

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...

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...

Design and engineering of a man-made diffusive electron-transport protein

PubMed Central

Fry, Bryan A.; Solomon, Lee A.; Dutton, P. Leslie

2016-01-01

Maquettes are man-made cofactor-binding oxidoreductases designed from first principles with minimal reference to natural protein sequences. Here we focus on water-soluble maquettes designed and engineered to perform diffusive electron transport of the kind typically carried out by cytochromes, ferredoxins and flavodoxins and other small proteins in photosynthetic and respiratory energy conversion and oxido-reductive metabolism. Our designs were tested by analysis of electron transfer between heme maquettes and the well-known natural electron transporter, cytochrome c. Electron-transfer kinetics were measured from seconds to milliseconds by stopped-flow, while sub-millisecond resolution was achieved through laser photolysis of the carbon monoxide maquette heme complex. These measurements demonstrate electron transfer from the maquette to cytochrome c, reproducing the timescales and charge complementarity modulation observed in natural systems. The ionic strength dependence of inter-protein electron transfer from 9.7 × 106 M−1s−1 to 1.2 × 109 M−1s−1 follows a simple Debye-Hückel model for attraction between +8 net charged oxidized cytochrome c and −19 net charged heme maquette, with no indication of significant protein dipole moment steering. Successfully recreating essential components of energy conversion and downstream metabolism in man-made proteins holds promise for in vivo clinical intervention and for the production of fuel or other industrial products. PMID:26423266

Proton-Coupled Electron Transfer and a Tyrosine-Histidine Pair in a Photosystem II-Inspired β-Hairpin Maquette: Kinetics on the Picosecond Time Scale.

PubMed

Pagba, Cynthia V; McCaslin, Tyler G; Chi, San-Hui; Perry, Joseph W; Barry, Bridgette A

2016-02-25

Photosystem II (PSII) and ribonucleotide reductase employ oxidation and reduction of the tyrosine aromatic ring in radical transport pathways. Tyrosine-based reactions involve either proton-coupled electron transfer (PCET) or electron transfer (ET) alone, depending on the pH and the pKa of tyrosine's phenolic oxygen. In PSII, a subset of the PCET reactions are mediated by a tyrosine-histidine redox-driven proton relay, YD-His189. Peptide A is a PSII-inspired β-hairpin, which contains a single tyrosine (Y5) and histidine (H14). Previous electrochemical characterization indicated that Peptide A conducts a net PCET reaction between Y5 and H14, which have a cross-strand π-π interaction. The kinetic impact of H14 has not yet been explored. Here, we address this question through time-resolved absorption spectroscopy and 280-nm photolysis, which generates a neutral tyrosyl radical. The formation and decay of the neutral tyrosyl radical at 410 nm were monitored in Peptide A and its variant, Peptide C, in which H14 is replaced by cyclohexylalanine (Cha14). Significantly, both electron transfer (ET, pL 11, L = lyonium) and PCET (pL 9) were accelerated in Peptide A and C, compared to model tyrosinate or tyrosine at the same pL. Increased electronic coupling, mediated by the peptide backbone, can account for this rate acceleration. Deuterium exchange gave no significant solvent isotope effect in the peptides. At pL 9, but not at pL 11, the reaction rate decreased when H14 was mutated to Cha14. This decrease in rate is attributed to an increase in reorganization energy in the Cha14 mutant. The Y5-H14 mechanism in Peptide A is reminiscent of proton- and electron-transfer events involving YD-H189 in PSII. These results document a mechanism by which proton donors and acceptors can regulate the rate of PCET reactions.

Mutations in algal and cyanobacterial Photosystem I that independently affect the yield of initial charge separation in the two electron transfer cofactor branches.

PubMed

Badshah, Syed Lal; Sun, Junlei; Mula, Sam; Gorka, Mike; Baker, Patricia; Luthra, Rajiv; Lin, Su; van der Est, Art; Golbeck, John H; Redding, Kevin E

2018-01-01

In Photosystem I, light-induced electron transfer can occur in either of two symmetry-related branches of cofactors, each of which is composed of a pair of chlorophylls (ec2 A /ec3 A or ec2 B /ec3 B ) and a phylloquinone (PhQ A or PhQ B ). The axial ligand to the central Mg 2+ of the ec2 A and ec2 B chlorophylls is a water molecule that is also H-bonded to a nearby Asn residue. Here, we investigate the importance of this interaction for charge separation by converting each of the Asn residues to a Leu in the green alga, Chlamydomonas reinhardtii, and the cyanobacterium, Synechocystis sp. PCC6803, and studying the energy and electron transfer using time-resolved optical and EPR spectroscopy. Nanosecond transient absorbance measurements of the PhQ to F X electron transfer show that in both species, the PsaA-N604L mutation (near ec2 B ) results in a ~50% reduction in the amount of electron transfer in the B-branch, while the PsaB-N591L mutation (near ec2 A ) results in a ~70% reduction in the amount of electron transfer in the A-branch. A diminished quantum yield of P 700 + PhQ - is also observed in ultrafast optical experiments, but the lower yield does not appear to be a consequence of charge recombination in the nanosecond or microsecond timescales. The most significant finding is that the yield of electron transfer in the unaffected branch did not increase to compensate for the lower yield in the affected branch. Hence, each branch of the reaction center appears to operate independently of the other in carrying out light-induced charge separation. Copyright © 2017 Elsevier B.V. All rights reserved.

Space electronics technology summary

NASA Technical Reports Server (NTRS)

1976-01-01

An overview is given of current electronics R and D activities, potential future thrusts, and related NASA payoffs. Major increases in NASA mission return and significant concurrent reductions in mission cost appear possible through a focused, long range electronics technology program. The overview covers: guidance assessments, navigation and control, and sensing and data acquisition processing, storage, and transfer.

The central active site arginine in sulfite oxidizing enzymes alters kinetic properties by controlling electron transfer and redox interactions.

PubMed

Hsiao, Ju-Chun; McGrath, Aaron P; Kielmann, Linda; Kalimuthu, Palraj; Darain, Farzana; Bernhardt, Paul V; Harmer, Jeffrey; Lee, Mihwa; Meyers, Kimberley; Maher, Megan J; Kappler, Ulrike

2018-01-01

A central conserved arginine, first identified as a clinical mutation leading to sulfite oxidase deficiency, is essential for catalytic competency of sulfite oxidizing molybdoenzymes, but the molecular basis for its effects on turnover and substrate affinity have not been fully elucidated. We have used a bacterial sulfite dehydrogenase, SorT, which lacks an internal heme group, but transfers electrons to an external, electron accepting cytochrome, SorU, to investigate the molecular functions of this arginine residue (Arg78). Assay of the SorT Mo centre catalytic competency in the absence of SorU showed that substitutions in the central arginine (R78Q, R78K and R78M mutations) only moderately altered SorT catalytic properties, except for R78M which caused significant reduction in SorT activity. The substitutions also altered the Mo-centre redox potentials (Mo VI/V potential lowered by ca. 60-80mV). However, all Arg78 mutations significantly impaired the ability of SorT to transfer electrons to SorU, where activities were reduced 17 to 46-fold compared to SorT WT , precluding determination of kinetic parameters. This was accompanied by the observation of conformational changes in both the introduced Gln and Lys residues in the crystal structure of the enzymes. Taking into account data collected by others on related SOE mutations we propose that the formation and maintenance of an electron transfer complex between the Mo centre and electron accepting heme groups is the main function of the central arginine, and that the reduced turnover and increases in K Msulfite are caused by the inefficient operation of the oxidative half reaction of the catalytic cycle in enzymes carrying these mutations. Copyright © 2017 Elsevier B.V. All rights reserved.

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 production. We further discover a novel growth condition which enables the characterization of autotrophic (i.e., carbon-fixing) metabolism in Geobacter. Importantly, our systems-level modeling approach helped elucidate the key metabolic pathways and the energetic cost associated with extracellular electron transfer. This model can be applied to characterize and engineer the metabolism and electron transfer capabilities of Geobacter for biotechnological applications.« less

Biochar as an electron shuttle for reductive dechlorination of pentachlorophenol by Geobacter sulfurreducens

PubMed Central

Yu, Linpeng; Yuan, Yong; Tang, Jia; Wang, Yueqiang; Zhou, Shungui

2015-01-01

The reductive dechlorination of pentachlorophenol (PCP) by Geobacter sulfurreducens in the presence of different biochars was investigated to understand how biochars affect the bioreduction of environmental contaminants. The results indicated that biochars significantly accelerate electron transfer from cells to PCP, thus enhancing reductive dechlorination. The promotion effects of biochar (as high as 24-fold) in this process depend on its electron exchange capacity (EEC) and electrical conductivity (EC). A kinetic model revealed that the surface redox-active moieties (RAMs) and EC of biochar (900 °C) contributed to 56% and 41% of the biodegradation rate, respectively. This work demonstrates that biochars are efficient electron mediators for the dechlorination of PCP and that both the EC and RAMs of biochars play important roles in the electron transfer process. PMID:26592958

Probability of Two-Step Photoexcitation of Electron from Valence Band to Conduction Band through Doping Level in TiO2.

PubMed

Nishikawa, Masami; Shiroishi, Wataru; Honghao, Hou; Suizu, Hiroshi; Nagai, Hideyuki; Saito, Nobuo

2017-08-17

For an Ir-doped TiO 2 (Ir:TiO 2 ) photocatalyst, we examined the most dominant electron-transfer path for the visible-light-driven photocatalytic performance. The Ir:TiO 2 photocatalyst showed a much higher photocatalytic activity under visible-light irradiation than nondoped TiO 2 after grafting with the cocatalyst of Fe 3+ . For the Ir:TiO 2 photocatalyst, the two-step photoexcitation of an electron from the valence band to the conduction band through the Ir doping level occurred upon visible-light irradiation, as observed by electron spin resonance spectroscopy. The two-step photoexcitation through the doping level was found to be a more stable process with a lower recombination rate of hole-electron pairs than the two-step photoexcitation process through an oxygen vacancy. Once electrons are photoexcited to the conduction band by the two-step excitation, the electrons can easily transfer to the surface because the conduction band is a continuous electron path, whereas the electrons photoexcited at only the doping level could not easily transfer to the surface because of the discontinuity of this path. The observed two-step photoexcitation from the valence band to the conduction band through the doping level significantly contributes to the enhancement of the photocatalytic performance.

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

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.

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.

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.

Suppression of BRCA2 by Mutant Mitochondrial DNA in Prostate Cancer

DTIC Science & Technology

2011-05-01

Briefly, the electron transfer activities of complex I/III (NADH dehydrogenase/cytochrome bc1 complex: catalyzes the electron transfer from NADH to...ferricytochrome c) and complex II/III (succinate dehydrogenase/cytochrome bc1 complex: catalyzes the electron transfer from succinate to ferricytochrome...The electron transfer activity of complex IV (cytochrome c oxidase: catalyzes the final step of the respiratory chain by transferring electrons from

Chemical and quantum simulation of electron transfer through a polypeptide

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

Ungar, L.W.; Voth, G.A.; Newton, M.D.

1999-08-26

Quantum rate theory, molecular dynamics simulations, and semiempirical electronic structure calculations are used to fully investigate electron transfer mediated by a solvated polypeptide for the first time. Using a stationary-phase approximation, the nonadiabatic electron-transfer rate constant is calculated from the nuclear free energies and the electronic coupling between the initial and final states. The former are obtained from quantum path integral and classical molecular dynamics simulations; the latter are calculated using semiempirical electronic structure calculations and the generalized Mulliken-Hush method. Importantly, no parameters are fit to kinetic data. The simulated system consists of a solvated four-proline polypeptide with a tris(bipyridine)rutheniummore » donor group and an oxypentamminecobalt acceptor group. From the simulation data entropy and energy contributions to the free energies are distinguished. Quantum suppression of the barrier, including important solvent contributions, is demonstrated. Although free energy profiles along the reaction coordinate are nearly parabolic, pronounced departures from harmonic behavior are found for the separate energy and entropy functions. Harmonic models of the system are compared to simulation results in order to quantify anharmonic effects. Electronic structure calculations show that electronic coupling elements vary considerably with system conformation, even when the effective donor-acceptor separation remains roughly constant. The calculations indicate that electron transfer in a significant range of conformations linking the polypeptide to the acceptor may contribute to the overall rate constant. After correction for limitations of the solvent model, the simulations and calculations agree well with the experimental activation energy and Arrhenius prefactor.« less

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.

77 FR 6193 - Electronic Fund Transfers (Regulation E)

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-07

...'') \\6\\ For example, one study found that 52% of total worldwide transfers to India from Indians living... money to send. For instance, one study showed that small decreases in fees charged led to significant... contributed to downward market pressure on prices in some remittance markets.\\44\\ One study shows that the...

The Historian and Electronic Research: File Transfer Protocol (FTP).

ERIC Educational Resources Information Center

McCarthy, Michael J.

1993-01-01

Asserts that the Internet will become the academic communication medium for historians in the 1990s. Describes the "file transfer protocol" (FTP) access approach to the Internet and discusses its significant for historical research. Includes instructions for using FTP and a list of history-related FTP sites. (CFR)

Polarity inversion of bioanode for biocathodic reduction of aromatic pollutants.

PubMed

Yun, Hui; Liang, Bin; Kong, De-Yong; Cheng, Hao-Yi; Li, Zhi-Ling; Gu, Ya-Bing; Yin, Hua-Qun; Wang, Ai-Jie

2017-06-05

The enrichment of specific pollutant-reducing consortium is usually required prior to the startup of biocathode bioelectrochemical system (BES) and the whole process is time consuming. To rapidly establish a non-specific functional biocathode, direct polar inversion from bioanode to biocathode is proposed in this study. Based on the diverse reductases and electron transfer related proteins of anode-respiring bacteria (ARB), the acclimated electrochemically active biofilm (EAB) may catalyze reduction of different aromatic pollutants. Within approximately 12 d, the acclimated bioanodes were directly employed as biocathodes for nitroaromatic nitrobenzene (NB) and azo dye acid orange 7 (AO7) reduction. Our results indicated that the established biocathode significantly accelerated the reduction of NB to aniline (AN) and AO7 to discolored products compared with the abiotic cathode and open circuit controls. Several microbes possessing capabilities of nitroaromatic/azo dye reduction and bidirectional electron transfer were maintained or enriched in the biocathode communities. Cyclic voltammetry highlighted the decreased over-potentials and enhanced electron transfer of biocathode as well as demonstrated the ARB Geobacter containing cytochrome c involved in the backward electron transfer from electrode to NB. This study offers new insights into the rapid establishment and modularization of functional biocathodes for the potential treatment of complicated electron acceptors-coexisting wastewaters. Copyright © 2017 Elsevier B.V. All rights reserved.

Graphite from the University of Idaho Thermolyzed Asphalt Reaction (GUITAR): Fundamental Electrochemical Characterizations

NASA Astrophysics Data System (ADS)

Gyan, Isaiah Owusu

This dissertation details electrochemical characterization of GUITAR (Graphite from the University of Idaho Thermolyzed Asphalt Reaction), a new allotrope of carbon. Applications based on fundamental electrochemical properties of this material are also presented. The dissertation is presented in five chapters. Chapter one presents a summary of the discovery and physical characterizations of GUITAR and how its physical properties position it among carbon materials. In chapter two, fundamental electrochemical properties covering aqueous potential window and electron transfer kinetics with common dissolved redox couples are presented. This chapter highlights significant electrochemical differences between GUITAR and other sp2 carbon materials, notably, fast electron transfer across basal plane GUITAR, contrary to reports at basal planes of graphite and graphene electrodes. In chapter three, the concept of electron transfer facility is extended with biologically relevant molecules. GUITAR is shown to be suitable for biosensing with properties such as; facile electron transfer, low detection limit, high resistance to fouling and stability to anodic regeneration procedures. Chapter four presents further exploration of GUITAR's wide cathodic potential limits in other aqueous electrolytes and preliminary studies towards the exploitation of this property in the negative half of vanadium redox flow battery, where GUITAR-based electrodes are expected to increase coulombic efficiency and increase battery performance due to low hydrogen evolution. Chapter five concludes this dissertation with point-by-point presentation of significant discoveries that highlights GUITAR's uniqueness. This chapter also describes how the various fundamental electrochemical properties of GUITAR make it useful for various applications.

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. ...

48 CFR 18.124 - Electronic funds transfer.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 48 Federal Acquisition Regulations System 1 2011-10-01 2011-10-01 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...

48 CFR 18.124 - Electronic funds transfer.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 48 Federal Acquisition Regulations System 1 2013-10-01 2013-10-01 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...

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. ...

48 CFR 18.123 - Electronic funds transfer.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Electronic funds transfer. 18.123 Section 18.123 Federal Acquisition Regulations System FEDERAL ACQUISITION REGULATION... Electronic funds transfer. Electronic funds transfer payments may be waived for acquisitions to support...

48 CFR 18.124 - Electronic funds transfer.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 48 Federal Acquisition Regulations System 1 2012-10-01 2012-10-01 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...

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...

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.

Semiclassical study of quantum coherence and isotope effects in ultrafast electron transfer reactions coupled to a proton and a phonon bath.

PubMed

Venkataraman, Charulatha

2011-11-28

The linearized semiclassical initial value representation is employed to describe ultrafast electron transfer processes coupled to a phonon bath and weakly coupled to a proton mode. The goal of our theoretical investigation is to understand the influence of the proton on the electronic dynamics in various bath relaxation regimes. More specifically, we study the impact of the proton on coherences and analyze if the coupling to the proton is revealed in the form of an isotope effect. This will be important in distinguishing reactions in which the proton does not undergo significant rearrangement from those in which the electron transfer is accompanied by proton transfer. Unlike other methodologies widely employed to describe nonadiabatic electron transfer, this approach treats the electronic and nuclear degrees of freedom consistently. However, due to the linearized approximation, quantum interference effects are not captured accurately. Our study shows that at small phonon bath reorganization energies, coherent oscillations and isotope effect are observed in both slow and fast bath regimes. The coherences are more substantially damped by deuterium in comparison to the proton. Further, in contrast to the dynamics of the spin-boson model, the coherences are not long-lived. At large bath reorganization energies, the decay is incoherent in the slow and fast bath regimes. In this case, the extent of the isotope effect depends on the relative relaxation timescales of the proton mode and the phonon bath. The isotope effect is magnified for baths that relax on picosecond timescales in contrast to baths that relax in femtoseconds.

Single-particle studies of band alignment effects on electron transfer dynamics from semiconductor hetero-nanostructures to single-walled carbon nanotubes.

PubMed

Yuan, Chi-Tsu; Wang, Yong-Gang; Huang, Kuo-Yen; Chen, Ting-Yu; Yu, Pyng; Tang, Jau; Sitt, Amit; Banin, Uri; Millo, Oded

2012-01-24

We utilize single-molecule spectroscopy combined with time-correlated single-photon counting to probe the electron transfer (ET) rates from various types of semiconductor hetero-nanocrystals, having either type-I or type-II band alignment, to single-walled carbon nanotubes. A significantly larger ET rate was observed for type-II ZnSe/CdS dot-in-rod nanostructures as compared to type-I spherical CdSe/ZnS core/shell quantum dots and to CdSe/CdS dot-in-rod structures. Furthermore, such rapid ET dynamics can compete with both Auger and radiative recombination processes, with significance for effective photovoltaic operation. © 2011 American Chemical Society

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

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.

Modular electron transfer circuits for synthetic biology

PubMed Central

Agapakis, Christina M

2010-01-01

Electron transfer is central to a wide range of essential metabolic pathways, from photosynthesis to fermentation. The evolutionary diversity and conservation of proteins that transfer electrons makes these pathways a valuable platform for engineered metabolic circuits in synthetic biology. Rational engineering of electron transfer pathways containing hydrogenases has the potential to lead to industrial scale production of hydrogen as an alternative source of clean fuel and experimental assays for understanding the complex interactions of multiple electron transfer proteins in vivo. We designed and implemented a synthetic hydrogen metabolism circuit in Escherichia coli that creates an electron transfer pathway both orthogonal to and integrated within existing metabolism. The design of such modular electron transfer circuits allows for facile characterization of in vivo system parameters with applications toward further engineering for alternative energy production. PMID:21468209

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

Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.

PubMed

Sander, Michael; Hofstetter, Thomas B; Gorski, Christopher A

2015-05-19

Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes.

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.

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

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.

Boosting the efficiency of quantum dot sensitized solar cells through modulation of interfacial charge transfer.

PubMed

Kamat, Prashant V

2012-11-20

The demand for clean energy will require the design of nanostructure-based light-harvesting assemblies for the conversion of solar energy into chemical energy (solar fuels) and electrical energy (solar cells). Semiconductor nanocrystals serve as the building blocks for designing next generation solar cells, and metal chalcogenides (e.g., CdS, CdSe, PbS, and PbSe) are particularly useful for harnessing size-dependent optical and electronic properties in these nanostructures. This Account focuses on photoinduced electron transfer processes in quantum dot sensitized solar cells (QDSCs) and discusses strategies to overcome the limitations of various interfacial electron transfer processes. The heterojunction of two semiconductor nanocrystals with matched band energies (e.g., TiO(2) and CdSe) facilitates charge separation. The rate at which these separated charge carriers are driven toward opposing electrodes is a major factor that dictates the overall photocurrent generation efficiency. The hole transfer at the semiconductor remains a major bottleneck in QDSCs. For example, the rate constant for hole transfer is 2-3 orders of magnitude lower than the electron injection from excited CdSe into oxide (e.g., TiO(2)) semiconductor. Disparity between the electron and hole scavenging rate leads to further accumulation of holes within the CdSe QD and increases the rate of electron-hole recombination. To overcome the losses due to charge recombination processes at the interface, researchers need to accelerate electron and hole transport. The power conversion efficiency for liquid junction and solid state quantum dot solar cells, which is in the range of 5-6%, represents a significant advance toward effective utilization of nanomaterials for solar cells. The design of new semiconductor architectures could address many of the issues related to modulation of various charge transfer steps. With the resolution of those problems, the efficiencies of QDSCs could approach those of dye sensitized solar cells (DSSC) and organic photovoltaics.

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.

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...

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 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...

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.

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...

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...

How complete are immunization registries? The Philadelphia story.

PubMed

Kolasa, Maureen S; Chilkatowsky, Andrew P; Clarke, Kevin R; Lutz, James P

2006-01-01

To assess accuracy and completeness of Philadelphia, Pa, registry data among children served by providers in areas at risk for underimmunization. Philadelphia's Department of Public Health selected a simple random sample of 45 children age 19-35 months (or all children age 19-35 months if there were <45 children in the practice) from each of 30 private practices receiving government-funded vaccine and located in zip codes where children are at risk for underimmunization. Chart and registry data were compared with determine the proportion of children missing from the registry and assess differences in immunization coverage. Of 620 children reviewed, 567 (92%) were in the registry. Significant differences (P < .05) were observed in immunization coverage for 4 diphtheria-tetanus-acellular pertussis vaccinations, 3 polio vaccinations, 1 measles-mumps-rubella vaccination, and 3 Haemophilus influenzae type b vaccinations between the chart (80% coverage) and registry (62% coverage). Providers submitting electronic medical records or directly transferring electronic data to the registry had significantly more children in the registry and higher registry-reported immunization coverage than those whose data were entered from billing records or log forms. All practice types experienced difficulties in transferring complete data to the registry. Although 92% of study children were in the registry, immunization coverage was significantly lower when registry data were compared with chart data. Because electronic medical records and direct electronic data transfer resulted in more complete registry data, these methods should be encouraged in linking providers with immunization registries.

Sex-dependent accumulation and maternal transfer of Dechlorane Plus flame retardant in fish from an electronic waste recycling site in South China.

PubMed

Wu, Jiang-Ping; She, Ya-Zhe; Zhang, Ying; Peng, Ying; Mo, Ling; Luo, Xiao-Jun; Mai, Bi-Xian

2013-06-01

Knowledge is limited on sex-related accumulation and maternal transfer of Dechlorane Plus (DP) flame retardant in wildlife. In the present study, DP isomers were examined in liver and eggs of two fish species, northern snakehead and crucian carp, from an electronic waste recycling site in China. Hepatic ∑DP (sum of syn- and anti-DP) concentrations ranged 260-1920 ng/g lipid in northern snakehead and 340-1670 ng/g in crucian carp, with significantly higher levels in males relative to females. ∑DP concentrations ranged 4.6-310 ng/g lipid in the eggs, demonstrating their maternal transfer in the female fish. The mean eggs to liver concentration ratios (E/L ratios) were 0.03 and 0.03 in northern snakehead, and 0.26 and 0.25 in crucian carp, for syn- and anti-DP, respectively. A significantly negative correlation between the E/L ratios and the hepatic DP concentrations was observed, indicating a dose-dependent maternal transfer of DP isomers in the fish. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electron transfer capacity dependence of quinone-mediated Fe(III) reduction and current generation by Klebsiella pneumoniae L17.

PubMed

Li, Xiaomin; Liu, Liang; Liu, Tongxu; Yuan, Tian; Zhang, Wei; Li, Fangbai; Zhou, Shungui; Li, Yongtao

2013-06-01

Quinone groups in exogenous electron shuttles can accelerate extracellular electron transfer (EET) from bacteria to insoluble terminal electron acceptors, such as Fe(III) oxides and electrodes, which are important in biogeochemical redox processes and microbial electricity generation. However, the relationship between quinone-mediated EET performance and electron-shuttling properties of the quinones remains incompletely characterized. This study investigates the effects of a series of synthetic quinones (SQs) on goethite reduction and current generation by a fermenting bacterium Klebsiella pneumoniae L17. In addition, the voltammetric behavior and electron transfer capacities (ETCs) of SQ, including electron accepting (EAC) and donating (EDC) capacities, is also examined using electrochemical methods. The results showed that SQ can significantly increase both the Fe(III) reduction rates and current outputs of L17. Each tested SQ reversibly accepted and donated electrons as indicated by the cyclic voltammograms. The EAC and EDC results showed that Carmine and Alizarin had low relative capacities of electron transfer, whereas 9,10-anthraquinone-2,6-disulfonic acid (AQDS), 2-hydroxy-1,4-naphthoquinone (2-HNQ), and 5-hydroxy-1,4-naphthoquinone (5-HNQ) showed stronger relative ETC, and 9,10-anthraquinone-2-carboxylic acid (AQC) and 9,10-anthraquinone-2-sulfonic acid (AQS) had high relative ETC. Enhancement of microbial goethite reduction kinetics and current outputs by SQ had a good linear relationship with their ETC, indicating that the effectiveness of quinone-mediated EET may be strongly dependent on the ETC of the quinones. Therefore, the presence of quinone compounds and fermenting microorganisms may increase the diversity of microbial populations that contribute to element transformation in natural environments. Moreover, ETC determination of different SQ would help to evaluate their performance for microbial EET under anoxic conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Effects of Charge-Transfer Excitons on the Photophysics of Organic Semiconductors

NASA Astrophysics Data System (ADS)

Hestand, Nicholas J.

The field of organic electronics has received considerable attention over the past several years due to the promise of novel electronic materials that are cheap, flexible and light weight. While some devices based on organic materials have already emerged on the market (e.g. organic light emitting diodes), a deeper understanding of the excited states within the condensed phase is necessary both to improve current commercial products and to develop new materials for applications that are currently in the commercial pipeline (e.g. organic photovoltaics, wearable displays, and field effect transistors). To this end, a model for pi-conjugated molecular aggregates and crystals is developed and analyzed. The model considers two types of electronic excitations, namely Frenkel and charge-transfer excitons, both of which play a prominent role in determining the nature of the excited states within tightly-packed organic systems. The former consist of an electron-hole pair bound to the same molecule while in the later the electron and hole are located on different molecules. The model also considers the important nuclear reorganization that occurs when the system switches between electronic states. This is achieved using a Holstein-style Hamiltonian that includes linear vibronic coupling of the electronic states to the nuclear motion associated with the high frequency vinyl-stretching and ring-breathing modes. Analysis of the model reveals spectroscopic signatures of charge-transfer mediated J- and H-aggregation in systems where the photophysical properties are determined primarily by charge-transfer interactions. Importantly, such signatures are found to be sensitive to the relative phase of the intermolecular electron and hole transfer integrals, and the relative energy of the Frenkel and charge-transfer states. When the charge-transfer integrals are in phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits J-aggregate characteristics including a positive band curvature, a red shifted main absorption peak, and an increase in the ratio of the first two vibronic peaks relative to the monomer. On the other hand, when the charge-transfer integrals are out of phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits H-aggregate characteristics including a negative band curvature, a blue shifted main absorption peak, and a decrease in the ratio of the first two vibronic peaks relative to the monomer. Notably, these signatures are consistent with those exhibited by Coulombically coupled J- and H-aggregates. Additional signatures of charge-transfer J- and H-aggregation are also discovered, the most notable of which is the appearance of a second absorption band when the charge-transfer integrals are in phase and the charge-transfer and Frenkel excitons are near resonance. In such instances, the peak-to-peak spacing is found to be proportional to the sum of the electron and hole transfer integrals. Further analysis of the charge-transfer interactions within the context of an effective Frenkel exciton coupling reveals that the charge-transfer interactions interfere directly with the intermolecular Coulombic coupling. The interference can be either constructive or destructive resulting in either enhanced or suppressed J- or H- aggregate behavior relative to what is expected based on Coulombic coupling alone. Such interferences result in four new aggregate types, namely HH-, HJ-, JH-, and JJ-aggregates, where the first letter indicates the nature of the Coulombic coupling and the second indicates the nature of the charge-transfer coupling. Vibronic signatures of such aggregates are developed and provide a means by which to rapidly screen materials for certain electronic characteristics. Notably, a large total (Coulombic plus charge-transfer) exciton coupling is associated with an absorption spectrum in which the ratio of the first two vibronic peaks deviates significantly from that of the unaggregated monomer. Hence, strongly coupled, high exciton mobility aggregates can be readily distinguished from low mobility aggregates by the ratio of their first two vibronic peaks. (Abstract shortened by ProQuest.).

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...

12 CFR 1005.3 - Coverage.

Code of Federal Regulations, 2014 CFR

2014-01-01

...-time electronic fund transfer from a consumer's account. The consumer must authorize the transfer. (ii... one-time electronic fund transfer (in providing a check to a merchant or other payee for the MICR... transfer. A consumer authorizes a one-time electronic fund transfer from his or her account to pay the fee...

A modeling approach to direct interspecies electron transfer process in anaerobic transformation of ethanol to methane.

PubMed

Liu, Yiwen; Zhang, Yaobin; Zhao, Zhiqiang; Ngo, Huu Hao; Guo, Wenshan; Zhou, Junliang; Peng, Lai; Ni, Bing-Jie

2017-01-01

Recent studies have shown that direct interspecies electron transfer (DIET) plays an important part in contributing to methane production from anaerobic digestion. However, so far anaerobic digestion models that have been proposed only consider two pathways for methane production, namely, acetoclastic methanogenesis and hydrogenotrophic methanogenesis, via indirect interspecies hydrogen transfer, which lacks an effective way for incorporating DIET into this paradigm. In this work, a new mathematical model is specifically developed to describe DIET process in anaerobic digestion through introducing extracellular electron transfer as a new pathway for methane production, taking anaerobic transformation of ethanol to methane as an example. The developed model was able to successfully predict experimental data on methane dynamics under different experimental conditions, supporting the validity of the developed model. Modeling predictions clearly demonstrated that DIET plays an important role in contributing to overall methane production (up to 33 %) and conductive material (i.e., carbon cloth) addition would significantly promote DIET through increasing ethanol conversion rate and methane production rate. The model developed in this work will potentially enhance our current understanding on syntrophic metabolism via DIET.

Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li 2CuO 2

DOE PAGES

Johnston, Steve; Monney, Claude; Bisogni, Valentina; ...

2016-02-17

Strongly correlated insulators are broadly divided into two classes: Mott–Hubbard insulators, where the insulating gap is driven by the Coulomb repulsion U on the transition-metal cation, and charge-transfer insulators, where the gap is driven by the charge-transfer energy Δ between the cation and the ligand anions. The relative magnitudes of U and Δ determine which class a material belongs to, and subsequently the nature of its low-energy excitations. These energy scales are typically understood through the local chemistry of the active ions. Here we show that the situation is more complex in the low-dimensional charge-transfer insulator Li 2CuO 2, wheremore » Δ has a large non-electronic component. Combining resonant inelastic X-ray scattering with detailed modelling, we determine how the elementary lattice, charge, spin and orbital excitations are entangled in this material. This results in a large lattice-driven renormalization of Δ, which significantly reshapes the fundamental electronic properties of Li 2CuO 2.« less

Fragment charge difference method for estimating donor-acceptor electronic coupling: Application to DNA π-stacks

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.; Rösch, Notker

2002-09-01

The purpose of this communication is two-fold. We introduce the fragment charge difference (FCD) method to estimate the electron transfer matrix element HDA between a donor D and an acceptor A, and we apply this method to several aspects of hole transfer electronic couplings in π-stacks of DNA, including systems with several donor-acceptor sites. Within the two-state model, our scheme can be simplified to recover a convenient estimate of the electron transfer matrix element HDA=(1-Δq2)1/2(E2-E1)/2 based on the vertical excitation energy E2-E1 and the charge difference Δq between donor and acceptor. For systems with strong charge separation, Δq≳0.95, one should resort to the FCD method. As favorable feature, we demonstrate the stability of the FCD approach for systems which require an approach beyond the two-state model. On the basis of ab initio calculations of various DNA related systems, we compared three approaches for estimating the electronic coupling: the minimum splitting method, the generalized Mulliken-Hush (GMH) scheme, and the FCD approach. We studied the sensitivity of FCD and GMH couplings to the donor-acceptor energy gap and found both schemes to be quite robust; they are applicable also in cases where donor and acceptor states are off resonance. In the application to π-stacks of DNA, we demonstrated for the Watson-Crick pair dimer [(GC),(GC)] how structural changes considerably affect the coupling strength of electron hole transfer. For models of three Watson-Crick pairs, we showed that the two-state model significantly overestimates the hole transfer coupling whereas simultaneous treatment of several states leads to satisfactory results.

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

Defining the origins of electron transfer at screen-printed graphene-like and graphite electrodes: MoO2 nanowire fabrication on edge plane sites reveals electrochemical insights.

PubMed

Rowley-Neale, Samuel J; Brownson, Dale A C; Banks, Craig E

2016-08-18

Molybdenum (di)oxide (MoO2) nanowires are fabricated onto graphene-like and graphite screen-printed electrodes (SPEs) for the first time, revealing crucial insights into the electrochemical properties of carbon/graphitic based materials. Distinctive patterns observed in the electrochemical process of nanowire decoration show that electron transfer occurs predominantly on edge plane sites when utilising SPEs fabricated/comprised of graphitic materials. Nanowire fabrication along the edge plane sites (and on edge plane like-sites/defects) of graphene/graphite is confirmed with Cyclic Voltammetry, Scanning Electron Microscopy (SEM) and Raman Spectroscopy. Comparison of the heterogeneous electron transfer (HET) rate constants (k°) at unmodified and nanowire coated SPEs show a reduction in the electrochemical reactivity of SPEs when the edge plane sites are effectively blocked/coated with MoO2. Throughout the process, the basal plane sites of the graphene/graphite electrodes remain relatively uncovered; except when the available edge plane sites have been utilised, in which case MoO2 deposition grows from the edge sites covering the entire surface of the electrode. This work clearly illustrates the distinct electron transfer properties of edge and basal plane sites on graphitic materials, indicating favourable electrochemical reactivity at the edge planes in contrast to limited reactivity at the basal plane sites. In addition to providing fundamental insights into the electron transfer properties of graphite and graphene-like SPEs, the reported simple, scalable, and cost effective formation of unique and intriguing MoO2 nanowires realised herein is of significant interest for use in both academic and commercial applications.

Real-Time Risk Prediction on the Wards: A Feasibility Study.

PubMed

Kang, Michael A; Churpek, Matthew M; Zadravecz, Frank J; Adhikari, Richa; Twu, Nicole M; Edelson, Dana P

2016-08-01

Failure to detect clinical deterioration in the hospital is common and associated with poor patient outcomes and increased healthcare costs. Our objective was to evaluate the feasibility and accuracy of real-time risk stratification using the electronic Cardiac Arrest Risk Triage score, an electronic health record-based early warning score. We conducted a prospective black-box validation study. Data were transmitted via HL7 feed in real time to an integration engine and database server wherein the scores were calculated and stored without visualization for clinical providers. The high-risk threshold was set a priori. Timing and sensitivity of electronic Cardiac Arrest Risk Triage score activation were compared with standard-of-care Rapid Response Team activation for patients who experienced a ward cardiac arrest or ICU transfer. Three general care wards at an academic medical center. A total of 3,889 adult inpatients. The system generated 5,925 segments during 5,751 admissions. The area under the receiver operating characteristic curve for electronic Cardiac Arrest Risk Triage score was 0.88 for cardiac arrest and 0.80 for ICU transfer, consistent with previously published derivation results. During the study period, eight of 10 patients with a cardiac arrest had high-risk electronic Cardiac Arrest Risk Triage scores, whereas the Rapid Response Team was activated on two of these patients (p < 0.05). Furthermore, electronic Cardiac Arrest Risk Triage score identified 52% (n = 201) of the ICU transfers compared with 34% (n = 129) by the current system (p < 0.001). Patients met the high-risk electronic Cardiac Arrest Risk Triage score threshold a median of 30 hours prior to cardiac arrest or ICU transfer versus 1.7 hours for standard Rapid Response Team activation. Electronic Cardiac Arrest Risk Triage score identified significantly more cardiac arrests and ICU transfers than standard Rapid Response Team activation and did so many hours in advance.

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

Rapid Characterization of Bacterial Electrogenicity Using a Single-Sheet Paper-Based Electrofluidic Array

PubMed Central

Gao, Yang; Hassett, Daniel J.; Choi, Seokheun

2017-01-01

Electrogenicity, or bacterial electron transfer capacity, is an important application which offers environmentally sustainable advances in the fields of biofuels, wastewater treatment, bioremediation, desalination, and biosensing. Significant boosts in this technology can be achieved with the growth of synthetic biology that manipulates microbial electron transfer pathways, thereby potentially significantly improving their electrogenic potential. There is currently a need for a high-throughput, rapid, and highly sensitive test array to evaluate the electrogenic properties of newly discovered and/or genetically engineered bacterial species. In this work, we report a single-sheet, paper-based electrofluidic (incorporating both electronic and fluidic structure) screening platform for rapid, sensitive, and potentially high-throughput characterization of bacterial electrogenicity. This novel screening array uses (i) a commercially available wax printer for hydrophobic wax patterning on a single sheet of paper and (ii) water-dispersed electrically conducting polymer mixture, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate, for full integration of electronic and fluidic components into the paper substrate. The engineered 3-D, microporous, hydrophilic, and conductive paper structure provides a large surface area for efficient electron transfer. This results in rapid and sensitive power assessment of electrogenic bacteria from a microliter sample volume. We validated the effectiveness of the sensor array using hypothesis-driven genetically modified Pseudomonas aeruginosa mutant strains. Within 20 min, we observed that the sensor platform successfully measured the electricity-generating capacities of five isogenic mutants of P. aeruginosa while distinguishing their differences from genetically unmodified bacteria. PMID:28798914

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces.

PubMed

Gross, Benjamin J; El-Naggar, Mohamed Y

2015-06-01

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe an experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces

NASA Astrophysics Data System (ADS)

Gross, Benjamin J.; El-Naggar, Mohamed Y.

2015-06-01

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe an experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.

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 embarked on a theoretical effort to ascertain what conditions might induce such remarkable behavior. We use a combination of an ab initio density functional theory method and a parameterized Huckel-Slater-Koster model. Our focus here is to examine whether any likely DNA structures or environments can yield reduced activation gaps to conduction or enhanced electronic overlaps. In particular, we study a hypothetical stretched ribbon structure, A-, and B-form DNA, and the effects of counterions and humidity. Unlike solids, DNA and other molecules are considered soft condensed matter. Hence, we study the influence of vibrations upon the electronic structure of DNA. We calculate parameters for charge transfer rates between adjacent bases. We find good agreement between our estimated rates and recent experimental data assuming that torsional vibrations limit the charge transfer most significantly.

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...

Changes to Workflow and Process Measures in the PICU During Transition From Semi to Full Electronic Health Record.

PubMed

Salib, Mina; Hoffmann, Raymond G; Dasgupta, Mahua; Zimmerman, Haydee; Hanson, Sheila

2015-10-01

Studies showing the changes in workflow during transition from semi to full electronic medical records are lacking. This objective study is to identify the changes in workflow in the PICU during transition from semi to full electronic health record. Prospective observational study. Children's Hospital of Wisconsin Institutional Review Board waived the need for approval so this study was institutional review board exempt. This study measured clinical workflow variables at a 72-bed PICU during different phases of transition to a full electronic health record, which occurred on November 4, 2012. Phases of electronic health record transition were defined as follows: pre-electronic health record (baseline data prior to transition to full electronic health record), transition phase (3 wk after electronic health record), and stabilization (6 mo after electronic health record). Data were analyzed for the three phases using Mann-Whitney U test with a two-sided p value of less than 0.05 considered significant. Seventy-two bed PICU. All patients in the PICU were included during the study periods. Five hundred and sixty-four patients with 2,355 patient days were evaluated in the three phases. Duration of rounds decreased from a median of 9 minutes per patient pre--electronic health record to 7 minutes per patient post electronic health record. Time to final note decreased from 2.06 days pre--electronic health record to 0.5 days post electronic health record. Time to first medication administration after admission also decreased from 33 minutes pre--electronic health record and 7 minutes post electronic health record. Time to Time to medication reconciliation was significantly higher pre-electronic health record than post electronic health record and percent of medication reconciliation completion was significantly lower pre--electronic health record than post electronic health record and percent of medication reconciliation completion was significantly higher pre--electronic health record than. There was no significant change in time between placement of discharge order and physical transfer from the unit [corrected].changes clinical workflow in a PICU with decreased duration of rounds, time to final note, time to medication administration, and time to medication reconciliation completion. There was no change in the duration from medical to physical transfer.

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.

Photosynthetic Membranes of Synechocystis or Plants Convert Sunlight to Photocurrent through Different Pathways due to Different Architectures.

PubMed

Pinhassi, Roy I; Kallmann, Dan; Saper, Gadiel; Larom, Shirley; Linkov, Artyom; Boulouis, Alix; Schöttler, Mark-Aurel; Bock, Ralph; Rothschild, Avner; Adir, Noam; Schuster, Gadi

2015-01-01

Thylakoid membranes contain the redox active complexes catalyzing the light-dependent reactions of photosynthesis in cyanobacteria, algae and plants. Crude thylakoid membranes or purified photosystems from different organisms have previously been utilized for generation of electrical power and/or fuels. Here we investigate the electron transferability from thylakoid preparations from plants or the cyanobacterium Synechocystis. We show that upon illumination, crude Synechocystis thylakoids can reduce cytochrome c. In addition, this crude preparation can transfer electrons to a graphite electrode, producing an unmediated photocurrent of 15 μA/cm2. Photocurrent could be obtained in the presence of the PSII inhibitor DCMU, indicating that the source of electrons is QA, the primary Photosystem II acceptor. In contrast, thylakoids purified from plants could not reduce cyt c, nor produced a photocurrent in the photocell in the presence of DCMU. The production of significant photocurrent (100 μA/cm2) from plant thylakoids required the addition of the soluble electron mediator DCBQ. Furthermore, we demonstrate that use of crude thylakoids from the D1-K238E mutant in Synechocystis resulted in improved electron transferability, increasing the direct photocurrent to 35 μA/cm2. Applying the analogous mutation to tobacco plants did not achieve an equivalent effect. While electron abstraction from crude thylakoids of cyanobacteria or plants is feasible, we conclude that the site of the abstraction of the electrons from the thylakoids, the architecture of the thylakoid preparations influence the site of the electron abstraction, as well as the transfer pathway to the electrode. This dictates the use of different strategies for production of sustainable electrical current from photosynthetic thylakoid membranes of cyanobacteria or higher plants.

Apparatus and method of direct water cooling several parallel circuit cards each containing several chip packages

DOEpatents

Cipolla, Thomas M [Katonah, NY; Colgan, Evan George [Chestnut Ridge, NY; Coteus, Paul W [Yorktown Heights, NY; Hall, Shawn Anthony [Pleasantville, NY; Tian, Shurong [Mount Kisco, NY

2011-12-20

A cooling apparatus, system and like method for an electronic device includes a plurality of heat producing electronic devices affixed to a wiring substrate. A plurality of heat transfer assemblies each include heat spreaders and thermally communicate with the heat producing electronic devices for transferring heat from the heat producing electronic devices to the heat transfer assemblies. The plurality of heat producing electronic devices and respective heat transfer assemblies are positioned on the wiring substrate having the regions overlapping. A heat conduit thermally communicates with the heat transfer assemblies. The heat conduit circulates thermally conductive fluid therethrough in a closed loop for transferring heat to the fluid from the heat transfer assemblies via the heat spreader. A thermally conductive support structure supports the heat conduit and thermally communicates with the heat transfer assemblies via the heat spreader transferring heat to the fluid of the heat conduit from the support structure.

An Approach for Externalization of Expert Tacit Knowledge Using a Query Management System in an E-Learning Environment

ERIC Educational Resources Information Center

Khan, Abdul Azeez; Khader, Sheik Abdul

2014-01-01

E-learning or electronic learning platforms facilitate delivery of the knowledge spectrum to the learning community through information and communication technologies. The transfer of knowledge takes place from experts to learners, and externalization of the knowledge transfer is significant. In the e-learning environment, the learners seek…

Photosynthetic antenna-reaction center mimicry with a covalently linked monostyryl boron-dipyrromethene-aza-boron-dipyrromethene-C60 triad.

PubMed

Shi, Wen-Jing; El-Khouly, Mohamed E; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K P

2013-08-19

An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP-ADP and ADP-C60 , and the triad BDP-ADP-C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

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

Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

DOE PAGES

Fujihashi, Yuta; Fleming, Graham R.; Ishizaki, Akihito

2015-03-11

Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. Here in this work, we address a dimer which produces little beating of electronic origin in the absencemore » of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.« less

Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

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

Fujihashi, Yuta; Ishizaki, Akihito, E-mail: ishizaki@ims.ac.jp; Fleming, Graham R.

2015-06-07

Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence ofmore » vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.« less

The effect of twisted D–D–π–A configuration on electron transfer and photo-physics characteristics

NASA Astrophysics Data System (ADS)

Liu, Yunpeng; Li, Yuanzuo; Song, Peng; Ma, Fengcai; Yang, Yanhui

2018-05-01

Two D-D-π-A organic dyes (M45, M46) with dithieno[3,2-b:2‧,3‧-d]pyrrole (DTP) units as election donors in two perpendicular directions, were investigated using density functional theory (DFT) and time-dependent DFT. The ground-state geometries, the absorption, the electronic structures, the charge density difference and molecular electrostatic potential were obtained. To simulate a more realistic performance, all calculations were based on gas condition and dichloromethane solvent. Photoelectric parameters were evaluated by the following factors: the light harvesting efficiency, electron injection driving force, the excited lifetime and vertical dipole moment. Meanwhile, the polarisability and hyperpolarisability were investigated to further explain the relationship between non-linear optical properties and efficiency. The direction of the DTP obviously affects the twisted degree of molecule, forming a better coplanarity on the donor 2 of M45, which results in stronger charge transfer interactions. Furthermore, M45 possesses significant advantages in geometric structure, absorption band and intramolecular charge transfer mechanism. These critical parameters supported the higher performance of M45 in comparison with M46. Moreover, four dyes were designed by the substitution of donor 2, which further verify the influence of the twisted donor 2 on electron transfer and photoelectric properties of D-D-π-A configuration.

The mitochondrial electron transfer flavoprotein complex is essential for survival of Arabidopsis in extended darkness.

PubMed

Ishizaki, Kimitsune; Schauer, Nicolas; Larson, Tony R; Graham, Ian A; Fernie, Alisdair R; Leaver, Christopher J

2006-09-01

In mammals, the electron transfer flavoprotein (ETF) is a heterodimeric protein composed of two subunits, alpha and beta, that is responsible for the oxidation of at least nine mitochondrial matrix flavoprotein dehydrogenases. Electrons accepted by ETF are further transferred to the main respiratory chain via the ETF ubiquinone oxide reductase (ETFQO). Sequence analysis of the unique Arabidopsis homologues of two subunits of ETF revealed their high similarity to both subunits of the mammalian ETF. Yeast two-hybrid experiments showed that the Arabidopsis ETFalpha and ETFbeta can form a heteromeric protein. Isolation and characterization of two independent T-DNA insertional Arabidopsis mutants of the ETFbeta gene revealed accelerated senescence and early death compared to wild-type during extended darkness. Furthermore in contrast to wild-type, the etfb mutants demonstrated a significant accumulation of several amino acids, isovaleryl CoA and phytanoyl CoA during dark-induced carbohydrate deprivation. These phenotypic characteristics of etfb mutants are broadly similar to those that we observed previously in Arabidopsis etfqo mutants, suggesting functional association between ETF and ETFQO in Arabidopsis, and confirming the essential roles of the ETF/ETFQO electron transfer complex in the catabolism of leucine and involvement in the chlorophyll degradation pathway activated during dark-induced carbohydrate deprivation.

Light-Induced Conversion of Chemical Permeability to Enhance Electron and Molecular Transfer in Nanoscale Assemblies

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

Balgley, Renata; de Ruiter, Graham; Evmenenko, Guennadi

In this paper, we demonstrate how photochemically enhancing the permeability of metal–organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)3][PF6]2; M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0–13.4 nm). UV-irradiation (λ = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic (nBu4NBF4) and inorganic (NiCl2) salts inside themore » assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive π-conjugation of its individual organic components.« less

Alteration of intracellular protein expressions as a key mechanism of the deterioration of bacterial denitrification caused by copper oxide nanoparticles.

PubMed

Su, Yinglong; Zheng, Xiong; Chen, Yinguang; Li, Mu; Liu, Kun

2015-10-28

The increasing production and utilization of copper oxide nanoparticles (CuO NPs) result in the releases into the environment. However, the influence of CuO NPs on bacterial denitrification, one of the most important pathways to transform nitrate to dinitrogen in environment, has seldom been studied. Here we reported that CuO NPs caused a significant alteration of key protein expressions of a model denitrifier, Paracoccus denitrificans, leading to severe inhibition to denitrification. Total nitrogen removal efficiency was decreased from 98.3% to 62.1% with the increase of CuO NPs from 0.05 to 0.25 mg/L. Cellular morphology and integrity studies indicated that nanoparticles entered the cells. The proteomic bioinformatics analysis showed that CuO NPs caused regulation of proteins involved in nitrogen metabolism, electron transfer and substance transport. The down-regulation of GtsB protein (responsible for glucose transport) decreased the production of NADH (electron donor for denitrification). Also, the expressions of key electron-transfer proteins (including NADH dehydrogenase and cytochrome) were suppressed by CuO NPs, which adversely affected electrons transfer for denitrification. Further investigation revealed that CuO NPs significantly inhibited the expressions and catalytic activities of nitrate reductase and nitrite reductase. These results provided a fundamental understanding of the negative influences of CuO NPs on bacterial denitrification.

Alteration of intracellular protein expressions as a key mechanism of the deterioration of bacterial denitrification caused by copper oxide nanoparticles

PubMed Central

Su, Yinglong; Zheng, Xiong; Chen, Yinguang; Li, Mu; Liu, Kun

2015-01-01

The increasing production and utilization of copper oxide nanoparticles (CuO NPs) result in the releases into the environment. However, the influence of CuO NPs on bacterial denitrification, one of the most important pathways to transform nitrate to dinitrogen in environment, has seldom been studied. Here we reported that CuO NPs caused a significant alteration of key protein expressions of a model denitrifier, Paracoccus denitrificans, leading to severe inhibition to denitrification. Total nitrogen removal efficiency was decreased from 98.3% to 62.1% with the increase of CuO NPs from 0.05 to 0.25 mg/L. Cellular morphology and integrity studies indicated that nanoparticles entered the cells. The proteomic bioinformatics analysis showed that CuO NPs caused regulation of proteins involved in nitrogen metabolism, electron transfer and substance transport. The down-regulation of GtsB protein (responsible for glucose transport) decreased the production of NADH (electron donor for denitrification). Also, the expressions of key electron-transfer proteins (including NADH dehydrogenase and cytochrome) were suppressed by CuO NPs, which adversely affected electrons transfer for denitrification. Further investigation revealed that CuO NPs significantly inhibited the expressions and catalytic activities of nitrate reductase and nitrite reductase. These results provided a fundamental understanding of the negative influences of CuO NPs on bacterial denitrification. PMID:26508362

Marcus equation

DOE R&D Accomplishments Database

1998-09-21

In the late 1950s to early 1960s Rudolph A. Marcus developed a theory for treating the rates of outer-sphere electron-transfer reactions. Outer-sphere reactions are reactions in which an electron is transferred from a donor to an acceptor without any chemical bonds being made or broken. (Electron-transfer reactions in which bonds are made or broken are referred to as inner-sphere reactions.) Marcus derived several very useful expressions, one of which has come to be known as the Marcus cross-relation or, more simply, as the Marcus equation. It is widely used for correlating and predicting electron-transfer rates. For his contributions to the understanding of electron-transfer reactions, Marcus received the 1992 Nobel Prize in Chemistry. This paper discusses the development and use of the Marcus equation. Topics include self-exchange reactions; net electron-transfer reactions; Marcus cross-relation; and proton, hydride, atom and group transfers.

Control of Electron Flow Direction in Photoexcited Cycloplatinated Complex Containing Conjugated Polymer-Single Walled Carbon Nanotube Hybrids.

PubMed

Xiong, Wenjuan; Du, Lili; Lo, Kin Cheung; Shi, Haiting; Takaya, Tomohisa; Iwata, Koichi; Chan, Wai Kin; Phillips, David Lee

2018-06-25

Conjugated polymers incorporated with cycloplatinated complexes (P1-Pt and P2-Pt) were used as dispersants for single walled carbon nanotubes (SWCNTs). Significant changes in the UV-vis absorption spectra were observed after the formation of the polymer/SWCNT hybrids. Molecular dynamics (MD) simulations revealed the presence of a strong interaction between the cycloplatinated complex moieties and the SWCNT surface. The photoinduced electron transfer processes in these hybrids were strongly dependent on the type of the comonomer unit. Upon photoexcitation, the excited P1-Pt donates electrons to the SWCNT, while P2-Pt accepts electrons from the photoexcited SWCNT. These observations were supported by results from Raman and femtosecond time-resolved transient absorption spectroscopy experiments. The strong electronic interaction between the Pt complexes and the SWCNT gives rise to a new hybrid system that has a controllable photo-induced electron transfer flow, which are important in regulating the charge transport processes SWCNT-based optoelectronic devices.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

The influence of the distance between the donor-acceptor groups of polymethine dyes on their photovoltaic properties

NASA Astrophysics Data System (ADS)

Seliverstova, E.; Ibrayev, N.

2018-01-01

Spectral-luminescent and photovoltaic properties of polymethine dyes of various structures are studied. It is shown that an increase in the length of the methylene chain between the active chromophores leads to a red-wave shift of the absorption and fluorescence spectra. Significant changes in the absorptivity and lifetime of fluorescence do not occur in this case. The best photovoltaic parameters have cells sensitized with shorter dye molecules. It is shown, that for a longer dye the resistance associated with electron recombination on the TiO2/electrolyte surface is much higher than the electron transfer resistance in the semiconductor, which reduces the efficiency of electron transfer in the solar cell, sensitized with longer dye molecules.

Transition-density-fragment interaction combined with transfer integral approach for excitation-energy transfer via charge-transfer states

NASA Astrophysics Data System (ADS)

Fujimoto, Kazuhiro J.

2012-07-01

A transition-density-fragment interaction (TDFI) combined with a transfer integral (TI) method is proposed. The TDFI method was previously developed for describing electronic Coulomb interaction, which was applied to excitation-energy transfer (EET) [K. J. Fujimoto and S. Hayashi, J. Am. Chem. Soc. 131, 14152 (2009)] and exciton-coupled circular dichroism spectra [K. J. Fujimoto, J. Chem. Phys. 133, 124101 (2010)]. In the present study, the TDFI method is extended to the exchange interaction, and hence it is combined with the TI method for applying to the EET via charge-transfer (CT) states. In this scheme, the overlap correction is also taken into account. To check the TDFI-TI accuracy, several test calculations are performed to an ethylene dimer. As a result, the TDFI-TI method gives a much improved description of the electronic coupling, compared with the previous TDFI method. Based on the successful description of the electronic coupling, the decomposition analysis is also performed with the TDFI-TI method. The present analysis clearly shows a large contribution from the Coulomb interaction in most of the cases, and a significant influence of the CT states at the small separation. In addition, the exchange interaction is found to be small in this system. The present approach is useful for analyzing and understanding the mechanism of EET.

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

PubMed

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

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

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.

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer.

PubMed

Lynch, Michael S; Slenkamp, Karla M; Khalil, Munira

2012-06-28

Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ∼57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs.

Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy.

PubMed

Ghosh, Hirendra N; Verma, Sandeep; Nibbering, Erik T J

2011-02-10

Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

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.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, R.; Calvin, M.

1984-01-24

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces

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

Gross, Benjamin J.; El-Naggar, Mohamed Y., E-mail: mnaggar@usc.edu; Molecular and Computational Biology Section, Department of Biological Sciences, University of Southern California, Los Angeles, California 90089-0484

2015-06-15

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe anmore » experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.« less

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

Extracellular Enzymes Facilitate Electron Uptake in Biocorrosion and Bioelectrosynthesis

PubMed Central

Deutzmann, Jörg S.; Sahin, Merve

2015-01-01

ABSTRACT Direct, mediator-free transfer of electrons between a microbial cell and a solid phase in its surrounding environment has been suggested to be a widespread and ecologically significant process. The high rates of microbial electron uptake observed during microbially influenced corrosion of iron [Fe(0)] and during microbial electrosynthesis have been considered support for a direct electron uptake in these microbial processes. However, the underlying molecular mechanisms of direct electron uptake are unknown. We investigated the electron uptake characteristics of the Fe(0)-corroding and electromethanogenic archaeon Methanococcus maripaludis and discovered that free, surface-associated redox enzymes, such as hydrogenases and presumably formate dehydrogenases, are sufficient to mediate an apparent direct electron uptake. In genetic and biochemical experiments, we showed that these enzymes, which are released from cells during routine culturing, catalyze the formation of H2 or formate when sorbed to an appropriate redox-active surface. These low-molecular-weight products are rapidly consumed by M. maripaludis cells when present, thereby preventing their accumulation to any appreciable or even detectable level. Rates of H2 and formate formation by cell-free spent culture medium were sufficient to explain the observed rates of methane formation from Fe(0) and cathode-derived electrons by wild-type M. maripaludis as well as by a mutant strain carrying deletions in all catabolic hydrogenases. Our data collectively show that cell-derived free enzymes can mimic direct extracellular electron transfer during Fe(0) corrosion and microbial electrosynthesis and may represent an ecologically important but so far overlooked mechanism in biological electron transfer. PMID:25900658

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.

Parallel Large-scale Semidefinite Programming for Strong Electron Correlation: Using Correlation and Entanglement in the Design of Efficient Energy-Transfer Mechanisms

DTIC Science & Technology

2014-09-24

which nature uses strong electron correlation for efficient energy transfer, particularly in photosynthesis and bioluminescence, (ii) providing an...strong electron correlation for efficient energy transfer, particularly in photosynthesis and bioluminescence, (ii) providing an innovative paradigm...efficient energy transfer, particularly in photosynthesis and bioluminescence, (ii) providing an innovative paradigm for energy transfer in photovoltaic

Size and Temperature Dependence of Electron Transfer between CdSe Quantum Dots and a TiO 2 Nanobelt

DOE PAGES

Tafen, De Nyago; Prezhdo, Oleg V.

2015-02-24

Understanding charge transfer reactions between quantum dots (QD) and metal oxides is fundamental for improving photocatalytic, photovoltaic and electronic devices. The complexity of these processes makes it difficult to find an optimum QD size with rapid charge injection and low recombination. We combine time-domain density functional theory with nonadiabatic molecular dynamics to investigate the size and temperature dependence of the experimentally studied electron transfer and charge recombination at CdSe QD-TiO 2 nanobelt (NB) interfaces. The electron injection rate shows strong dependence on the QD size, increasing for small QDs. The rate exhibits Arrhenius temperature dependence, with the activation energy ofmore » the order of millielectronvolts. The charge recombination process occurs due to coupling of the electronic subsystem to vibrational modes of the TiO 2 NB. Inelastic electron-phonon scattering happens on a picosecond time scale, with strong dependence on the QD size. Our simulations demonstrate that the electron-hole recombination rate decreases significantly as the QD size increases, in excellent agreement with experiments. The temperature dependence of the charge recombination rates can be successfully modeled within the framework of the Marcus theory through optimization of the electronic coupling and the reorganization energy. Our simulations indicate that by varying the QD size, one can modulate the photoinduced charge separation and charge recombination, fundamental aspects of the design principles for high efficiency devices.« less

Electron Tunneling in Lithium Ammonia Solutions Probed by Frequency-Dependent Electron-Spin Relaxation Studies

PubMed Central

Maeda, Kiminori; Lodge, Matthew T.J.; Harmer, Jeffrey; Freed, Jack H.; Edwards, Peter P.

2012-01-01

Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T1) and spin-spin (T2) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multi-exponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1–10)×10−12 s over a temperature range 230–290K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a timescale of ca. 10−13 s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multi-frequency EPR measurements to interrogate the microscopic nature and dynamics of ultra fast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer. PMID:22568866

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.

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

Effect of anode polarization on biofilm formation and electron transfer in Shewanella oneidensis/graphite felt microbial fuel cells.

PubMed

Pinto, David; Coradin, Thibaud; Laberty-Robert, Christel

2018-04-01

In microbial fuel cells, electricity generation is assumed by bacterial degradation of low-grade organics generating electrons that are transferred to an electrode. The nature and efficiency of the electron transfer from the bacteria to the electrodes are determined by several chemical, physical and biological parameters. Specifically, the application of a specific potential at the bioanode has been shown to stimulate the formation of an electro-active biofilm, but the underlying mechanisms remain poorly understood. In this study, we have investigated the effect of an applied potential on the formation and electroactivity of biofilms established by Shewanella oneidensis bacteria on graphite felt electrodes in single- and double-chamber reactor configurations in oxic conditions. Using amperometry, cyclic voltammetry, and OCP/Power/Polarization curves techniques, we showed that a potential ranging between -0.3V and +0.5V (vs. Ag/AgCl/KCl sat.) and its converse application to a couple of electrodes leads to different electrochemical behaviors, anodic currents and biofilm architectures. For example, when the bacteria were confined in the anodic compartment of a double-chamber cell, a negative applied potential (-0.3V) at the bioanode favors a mediated electron transfer correlated with the progressive formation of a biofilm that fills the felt porosity and bridges the graphite fibers. In contrast, a positive applied potential (+0.3V) at the bioanode stimulates a direct electron transfer resulting in the fast-bacterial colonization of the fibers only. These results provide significant insight for the understanding of the complex bacteria-electrode interactions in microbial fuel cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors.

PubMed

Rosokha, Sergiy V; Lü, Jian-Ming; Newton, Marshall D; Kochi, Jay K

2005-05-25

Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

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.

An experimental study of OH(A2Σ+) + H2: Electronic quenching, rotational energy transfer, and collisional depolarization

NASA Astrophysics Data System (ADS)

Brouard, M.; Lawlor, J.; McCrudden, G.; Perkins, T.; Seamons, S. A.; Stevenson, P.; Chadwick, H.; Aoiz, F. J.

2017-06-01

Zeeman quantum beat spectroscopy has been used to determine the thermal (300 K) rate constants for electronic quenching, rotational energy transfer, and collisional depolarization of OH(A2Σ+) by H2. Cross sections for both the collisional disorientation and collisional disalignment of the angular momentum in the OH(A2Σ+) radical are reported. The experimental results for OH(A2Σ+) + H2 are compared to previous work on the OH(A2Σ+) + He and Ar systems. Further comparisons are also made to the OH(A2Σ+) + Kr system, which has been shown to display significant non-adiabatic dynamics. The OH(A2Σ+) + H2 experimental data reveal that collisions that survive the electronic quenching process are highly depolarizing, reflecting the deep potential energy wells that exist on the excited electronic state surface.

Dynamics of Polarons in Organic Conjugated Polymers with Side Radicals.

PubMed

Liu, J J; Wei, Z J; Zhang, Y L; Meng, Y; Di, B

2017-03-16

Based on the one-dimensional tight-binding Su-Schrieffer-Heeger (SSH) model, and using the molecular dynamics method, we discuss the dynamics of electron and hole polarons propagating along a polymer chain, as a function of the distance between side radicals and the magnitude of the transfer integrals between the main chain and the side radicals. We first discuss the average velocities of electron and hole polarons as a function of the distance between side radicals. It is found that the average velocities of the electron polarons remain almost unchanged, while the average velocities of hole polarons decrease significantly when the radical distance is comparable to the polaron width. Second, we have found that the average velocities of electron polarons decrease with increasing transfer integral, but the average velocities of hole polarons increase. These results may provide a theoretical basis for understanding carriers transport properties in polymers chain with side radicals.

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.

Time-Domain Ab Initio Analysis of Excitation Dynamics in a Quantum Dot/Polymer Hybrid: Atomistic Description Rationalizes Experiment.

PubMed

Long, Run; Prezhdo, Oleg V

2015-07-08

Hybrid organic/inorganic polymer/quantum dot (QD) solar cells are an attractive alternative to the traditional cells. The original, simple models postulate that one-dimensional polymers have continuous energy levels, while zero-dimensional QDs exhibit atom-like electronic structure. A realistic, atomistic viewpoint provides an alternative description. Electronic states in polymers are molecule-like: finite in size and discrete in energy. QDs are composed of many atoms and have high, bulk-like densities of states. We employ ab initio time-domain simulation to model the experimentally observed ultrafast photoinduced dynamics in a QD/polymer hybrid and show that an atomistic description is essential for understanding the time-resolved experimental data. Both electron and hole transfers across the interface exhibit subpicosecond time scales. The interfacial processes are fast due to strong electronic donor-acceptor, as evidenced by the densities of the photoexcited states which are delocalized between the donor and the acceptor. The nonadiabatic charge-phonon coupling is also strong, especially in the polymer, resulting in rapid energy losses. The electron transfer from the polymer is notably faster than the hole transfer from the QD, due to a significantly higher density of acceptor states. The stronger molecule-like electronic and charge-phonon coupling in the polymer rationalizes why the electron-hole recombination inside the polymer is several orders of magnitude faster than in the QD. As a result, experiments exhibit multiple transfer times for the long-lived hole inside the QD, ranging from subpicoseconds to nanoseconds. In contrast, transfer of the short-lived electron inside the polymer does not occur beyond the first picosecond. The energy lost by the hole on its transit into the polymer is accommodated by polymer's high-frequency vibrations. The energy lost by the electron injected into the QD is accommodated primarily by much lower-frequency collective and QD modes. The electron dynamics is exponential, whereas evolution of the injected hole through the low density manifold of states of the polymer is highly nonexponential. The time scale of the electron-hole recombination at the interface is intermediate between those in pristine polymer and QD and is closer to that in the polymer. The detailed atomistic insights into the photoinduced charge and energy dynamics at the polymer/QD interface provide valuable guidelines for optimization of solar light harvesting and photovoltaic efficiency in modern nanoscale materials.

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.

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.

Uphill energy transfer from long-wavelength absorbing chlorophylls to PS II in Ostreobium sp. is functional in carbon assimilation.

PubMed

Wilhelm, Christian; Jakob, Torsten

2006-03-01

From the algal genus Ostrobium two species are known which express a chlorophyll antenna absorbing between 710 and 725 nm to a different extent. In a comparative study with these two species it is shown that quanta absorbed by this long wavelength antenna can be transferred to PS II leading to significant PS II-related electron transfer. It is documented that under monochromatic far red light illumination growth continues with rather high efficiency. The data show that the uphill-energy transfer to PS II reduces the quantum yield under white light significantly. It is discussed that this strategy of energy conversion might play a role in special environments where far red light is the predominant energy source.

Electron transfer kinetics on natural crystals of MoS2 and graphite.

PubMed

Velický, Matěj; Bissett, Mark A; Toth, Peter S; Patten, Hollie V; Worrall, Stephen D; Rodgers, Andrew N J; Hill, Ernie W; Kinloch, Ian A; Novoselov, Konstantin S; Georgiou, Thanasis; Britnell, Liam; Dryfe, Robert A W

2015-07-21

Here, we evaluate the electrochemical performance of sparsely studied natural crystals of molybdenite and graphite, which have increasingly been used for fabrication of next generation monolayer molybdenum disulphide and graphene energy storage devices. Heterogeneous electron transfer kinetics of several redox mediators, including Fe(CN)6(3-/4-), Ru(NH3)6(3+/2+) and IrCl6(2-/3-) are determined using voltammetry in a micro-droplet cell. The kinetics on both materials are studied as a function of surface defectiveness, surface ageing, applied potential and illumination. We find that the basal planes of both natural MoS2 and graphite show significant electroactivity, but a large decrease in electron transfer kinetics is observed on atmosphere-aged surfaces in comparison to in situ freshly cleaved surfaces of both materials. This is attributed to surface oxidation and adsorption of airborne contaminants at the surface exposed to an ambient environment. In contrast to semimetallic graphite, the electrode kinetics on semiconducting MoS2 are strongly dependent on the surface illumination and applied potential. Furthermore, while visibly present defects/cracks do not significantly affect the response of graphite, the kinetics on MoS2 systematically accelerate with small increase in disorder. These findings have direct implications for use of MoS2 and graphene/graphite as electrode materials in electrochemistry-related applications.

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.

Food Antioxidants: Chemical Insights at the Molecular Level.

PubMed

Galano, Annia; Mazzone, Gloria; Alvarez-Diduk, Ruslán; Marino, Tiziana; Alvarez-Idaboy, J Raúl; Russo, Nino

2016-01-01

In this review, we briefly summarize the reliability of the density functional theory (DFT)-based methods to accurately predict the main antioxidant properties and the reaction mechanisms involved in the free radical-scavenging reactions of chemical compounds present in food. The analyzed properties are the bond dissociation energies, in particular those involving OH bonds, electron transfer enthalpies, adiabatic ionization potentials, and proton affinities. The reaction mechanisms are hydrogen-atom transfer, proton-coupled electron transfer, radical adduct formation, single electron transfer, sequential electron proton transfer, proton-loss electron transfer, and proton-loss hydrogen-atom transfer. Furthermore, the chelating ability of these compounds and its role in decreasing or inhibiting the oxidative stress induced by Fe(III) and Cu(II) are considered. Comparisons between theoretical and experimental data confirm that modern theoretical tools are not only able to explain controversial experimental facts but also to predict chemical behavior.

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.

Molecular level energy and electron transfer processes at nanocrystalline titanium dioxide interfaces

NASA Astrophysics Data System (ADS)

Farzad, Fereshteh

This thesis describes photo-induced molecular electron and energy transfer processes occurring at nanocrystalline semiconductor interfaces. The Introductory Chapter provides background and describes how these materials may be useful for solar energy conversion. In Chapter 2, results describing excitation of Ru(deeb)(bpy)2 2+, bis(2,2'-bipyridine)(2,2'-bipyridine-4,4 '-diethylester)ruthenium(II) hexafluorophosphate, bound to nanocrystalline TiO2 thin films, immersed in an acetonitrile bath are presented. The data indicates that light excitation forms predominately long-lived metal-to-ligand charge-transfer, MLCT, excited states under these conditions. Modeling of the data as a function of irradiance has been accomplished assuming parallel unimolecular and bimolecular excited state deactivation processes. The quantum yield for excited state formation depends on the excitation irradiance, consistent with triplet-triplet annihilation processes that occur with k > 1 x 108 s-1. Chapter 3 extends the work described in Chapter 2 to LiClO4 acetonitrile solutions. Li+ addition results in a red shift in the MLCT absorption and photoluminescence, PL, and a concentration dependent quenching of the PL intensity on TiO2. The Li+ induced spectroscopic changes were found to be reversible by varying the electrolyte composition. A second-order kinetic model quantified charge recombination transients. A model is proposed wherein Li+ ion adsorption stabilizes TiO2 acceptor states resulting in energetically more favorable interfacial electron transfer. The photophysical and photoelectrochemical properties of porous nanocrystalline anatase TiO2 electrodes modified with Ru(deeb)(bpy)2 2+, Os(deeb)(bpy)22+, and mixtures of both are described in Chapters 4 and 5. In regenerative solar cells with 0.5 M LiI/0.05 M I2 acetonitrile electrolyte, both compounds efficiently inject electrons into TiO2 producing monochromatic incident photon-to-current efficiencies (IPCE), IPCE (460 nm) = 0.70 + 0.05 for Ru(dcb)(bpy)2 2+/TiO2 and 0. 10 + 0.05 for Os(dcb)(bpy)2 2+/TiO2. Os(dcb)(bpy)22+ extends the spectral sensitivity of the TiO2 material beyond 700 rim. Application of a negative bias to the derivatized TiO2 surfaces results in inefficient interfacial electron transfer and no significant photocurrent. Instead, lateral energy transfer cross the nanocrystalline TiO2 surface from Ru(dcb)(bpy)22+* to Os(dcb)(bpy) 22+ is observed. The energy transfer process can be switched off with a positive applied bias ten times with no significant deterioration. The results demonstrate control of molecular excited states at nanostructured interfaces.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, Roland; Calvin, Melvin

1984-01-01

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

Electronic levels and charge distribution near the interface of nickel

NASA Technical Reports Server (NTRS)

Waber, J. T.

1982-01-01

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

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.

Tattoo-Paper Transfer as a Versatile Platform for All-Printed Organic Edible Electronics.

PubMed

Bonacchini, Giorgio E; Bossio, Caterina; Greco, Francesco; Mattoli, Virgilio; Kim, Yun-Hi; Lanzani, Guglielmo; Caironi, Mario

2018-04-01

The use of natural or bioinspired materials to develop edible electronic devices is a potentially disruptive technology that can boost point-of-care testing. The technology exploits devices that can be safely ingested, along with pills or even food, and operated from within the gastrointestinal tract. Ingestible electronics can potentially target a significant number of biomedical applications, both as therapeutic and diagnostic tool, and this technology may also impact the food industry, by providing ingestible or food-compatible electronic tags that can "smart" track goods and monitor their quality along the distribution chain. Temporary tattoo-paper is hereby proposed as a simple and versatile platform for the integration of electronics onto food and pharmaceutical capsules. In particular, the fabrication of all-printed organic field-effect transistors on untreated commercial tattoo-paper, and their subsequent transfer and operation on edible substrates with a complex nonplanar geometry is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement of Charge Transportation in Si Quantum Dot-Sensitized Solar Cells Using Vanadium Doped TiO2.

PubMed

Seo, Hyunwoong; Ichida, Daiki; Hashimoto, Shinji; Itagaki, Naho; Koga, Kazunori; Shiratani, Masaharu; Nam, Sang-Hun; Boo, Jin-Hyo

2016-05-01

The multiple exciton generation characteristics of quantum dots have been expected to enhance the performance of photochemical solar cells. In previous work, we first introduced Si quantum dot for sensitized solar cells. The Si quantum dots were fabricated by multi-hollow discharge plasma chemical vapor deposition, and were characterized optically and morphologically. The Si quantum dot-sensitized solar cells had poor performance due to significant electron loss by charge recombination. Although the large Si particle size resulted in the exposure of a large TiO2 surface area, there was a limit to ho much the particle size could be decreased due to the reduced absorbance of small particles. Therefore, this work focused on decreasing the internal impedance to improve charge transfer. TiO2 was electronically modified by doping with vanadium, which can improve electron transfer in the TiO2 network, and which is stable in the redox electrolyte. Photogenerated electrons can more easily arrive at the conductive electrode due to the decreased internal impedance. The dark photovoltaic properties confirmed the reduction of charge recombination, and the photon-to-current conversion efficiency reflected the improved electron transfer. Impedance analysis confirmed a decrease in internal impedance and an increased electron lifetime. Consequently, these improvements by vanadium doping enhanced the overall performance of Si quantum dot-sensitized solar cells.

The Effects of the SUN Project on Teacher Knowledge and Self-Efficacy Regarding Biological Energy Transfer Are Significant and Long-Lasting: Results of a Randomized Controlled Trial

PubMed Central

Batiza, Ann Finney; Gruhl, Mary; Zhang, Bo; Harrington, Tom; Roberts, Marisa; LaFlamme, Donna; Haasch, Mary Anne; Knopp, Jonathan; Vogt, Gina; Goodsell, David; Hagedorn, Eric; Marcey, David; Hoelzer, Mark; Nelson, Dave

2013-01-01

Biological energy flow has been notoriously difficult to teach. Our approach to this topic relies on abiotic and biotic examples of the energy released by moving electrons in thermodynamically spontaneous reactions. A series of analogical model-building experiences was supported with common language and representations including manipulatives. These materials were designed to help learners understand why electrons move in a hydrogen explosion and hydrogen fuel cell, so they could ultimately understand the rationale for energy transfer in the mitochondrion and the chloroplast. High school biology teachers attended a 2-wk Students Understanding eNergy (SUN) workshop during a randomized controlled trial. These treatment group teachers then took hydrogen fuel cells, manipulatives, and other materials into their regular biology classrooms. In this paper, we report significant gains in teacher knowledge and self-efficacy regarding biological energy transfer in the treatment group versus randomized controls. Significant effects on treatment group teacher knowledge and self-efficacy were found not only post–SUN workshop but even 1 yr later. Teacher knowledge was measured with both a multiple-choice exam and a drawing with a written explanation. Teacher confidence in their ability to teach biological energy transfer was measured by a modified form of the Science Teaching Efficacy Belief Instrument, In-Service A. Professional development implications regarding this topic are discussed. PMID:23737635

The effects of the SUN project on teacher knowledge and self-efficacy regarding biological energy transfer are significant and long-lasting: results of a randomized controlled trial.

PubMed

Batiza, Ann Finney; Gruhl, Mary; Zhang, Bo; Harrington, Tom; Roberts, Marisa; LaFlamme, Donna; Haasch, Mary Anne; Knopp, Jonathan; Vogt, Gina; Goodsell, David; Hagedorn, Eric; Marcey, David; Hoelzer, Mark; Nelson, Dave

2013-06-01

Biological energy flow has been notoriously difficult to teach. Our approach to this topic relies on abiotic and biotic examples of the energy released by moving electrons in thermodynamically spontaneous reactions. A series of analogical model-building experiences was supported with common language and representations including manipulatives. These materials were designed to help learners understand why electrons move in a hydrogen explosion and hydrogen fuel cell, so they could ultimately understand the rationale for energy transfer in the mitochondrion and the chloroplast. High school biology teachers attended a 2-wk Students Understanding eNergy (SUN) workshop during a randomized controlled trial. These treatment group teachers then took hydrogen fuel cells, manipulatives, and other materials into their regular biology classrooms. In this paper, we report significant gains in teacher knowledge and self-efficacy regarding biological energy transfer in the treatment group versus randomized controls. Significant effects on treatment group teacher knowledge and self-efficacy were found not only post-SUN workshop but even 1 yr later. Teacher knowledge was measured with both a multiple-choice exam and a drawing with a written explanation. Teacher confidence in their ability to teach biological energy transfer was measured by a modified form of the Science Teaching Efficacy Belief Instrument, In-Service A. Professional development implications regarding this topic are discussed.

Biomimetic Interfacial Electron-Induced Electrochemiluminesence.

PubMed

Pu, Guiqiang; Zhang, Dongxu; Mao, Xiang; Zhang, Zhen; Wang, Huan; Ning, Xingming; Lu, Xiaoquan

2018-04-17

We provide here, for the first time, a new interfacial electron-induced electrochemiluminescence (IEIECL) system, realizing bionic construction of bioluminescence (BL) by exploiting electrochemiluminescence (ECL) and ITIES (the interface between two immiscible electrolyte solutions). Significantly, the superiority of the IEIECL system is embodied with the solution of the two bottlenecks encountered in the conventional ECL innovation: that are (a) the applications of hydrophobic luminophores in more commonly used aqueous solution are inhibited tremendously due to the poor inherent solubility and the instability of radicals and (b) the analytes, insoluble in water, are hard to be discovered in an aqueous system because of too little content. More productive IEIECL radiation, analogous to BL, originates from the triplet excited state porphyrin in comparison to the homogeneous ECL. The mechanism of IEIECL, as well as the interaction mechanism between IEIECL and charge transfer (comprising electron transfer (ET), ion transfer (IT), and facilitated ion transfer (FIT)) at the ITIES, are explored in detail. Finally, we emphasize the actual application potential of the IEIECL system with the detection of cytochrome c (Cyt c); it is a key biomolecule in the electron transport chain in the process of biological oxidation and is also an intermediate species in apoptosis. Potentially, the IEIECL system permits ones to explore the lifetime and diffusion path of free radicals, as well as imparting a possibility for the construction of a bionic sensor.

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.

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.

X.400: The Standard for Message Handling Systems.

ERIC Educational Resources Information Center

Swain, Leigh; Tallim, Paula

1990-01-01

Profiles X.400, the Open Systems Interconnection (OSI) Application layer standard that supports interpersonal electronic mail services, facsimile transfer, electronic data interchange, electronic funds transfer, electronic publishing, and electronic invoicing. Also discussed are an electronic directory to support message handling, compatibility…

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.

Copper vertical micro dendrite fin arrays and their superior boiling heat transfer capability

NASA Astrophysics Data System (ADS)

Wang, Ya-Qiao; Lyu, Shu-Shen; Luo, Jia-Li; Luo, Zhi-Yong; Fu, Yuan-Xiang; Heng, Yi; Zhang, Jian-Hui; Mo, Dong-Chuan

2017-11-01

Micro pin fin arrays have been widely used in electronic cooling, micro reactors, catalyst support, and wettability modification and so on, and a facile way to produce better micro pin fin arrays is demanded. Herein, a simple electrochemical method has been developed to fabricate copper vertical micro dendrite fin arrays (Cu-VMDFA) with controllable shapes, number density and height. High copper sulphate concentration is one key point to make the dendrite stand vertically. Besides, the applied current should rise at an appropriate rate to ensure the copper dendrite can grow vertically on its own. The Cu-VMDFA can significantly enhance the heat transfer coefficient by approximately twice compared to the plain copper surface. The Cu-VMDFA may be widely used in boiling heat transfer areas such as nuclear power plants, electronic cooling, heat exchangers, and so on.

Chemical and charge transfer studies on interfaces of a conjugated polymer and ITO

NASA Astrophysics Data System (ADS)

David, Tanya M. S.; Arasho, Wondwosson; Smith, O'Neil; Hong, Kunlun; Bonner, Carl; Sun, Sam-Shajing

2017-08-01

Conjugated oligomers and polymers are very attractive for potential future plastic electronic and opto-electronic device applications such as plastic photo detectors and solar cells, thermoelectric devices, field effect transistors, and light emitting diodes. Understanding and optimizing charge transport between an active polymer layer and conductive substrate is critical to the optimization of polymer based electronic and opto-electronic devices. This study focused on the design, synthesis, self-assembly, and electron transfers and transports of a phosphonic acid end-functionalized polyphenylenevinylene (PPV) that was covalently attached and self-assembled onto an Indium Tin Oxide (ITO) substrate. This study demonstrated how atomic force microscopy (AFM) can be an effective characterization technique in conjunction with conventional electron transfer methods, including cyclic voltammetry (CV), towards determining electron transfer rates in polymer and polymer/conductor interface systems. This study found that the electron transfer rates of covalently attached and self-assembled films were much faster than the spin coated films. The knowledge from this study can be very useful for designing potential polymer based electronic and opto-electronic thin film devices.

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.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization.

PubMed

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-12-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 (3-/4-) as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization

NASA Astrophysics Data System (ADS)

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-06-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 3-/4- as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

The Critical Role of Arabidopsis Electron-Transfer Flavoprotein:Ubiquinone Oxidoreductase during Dark-Induced StarvationW⃞

PubMed Central

Ishizaki, Kimitsune; Larson, Tony R.; Schauer, Nicolas; Fernie, Alisdair R.; Graham, Ian A.; Leaver, Christopher J.

2005-01-01

In mammals, electron-transfer flavoprotein:ubiquinone oxidoreductase (ETFQO) and electron-transfer flavoprotein (ETF) are functionally associated, and ETF accepts electrons from at least nine mitochondrial matrix flavoprotein dehydrogenases and transfers them to ubiquinone in the inner mitochondrial membrane. In addition, the mammalian ETF/ETFQO system plays a key role in β-oxidation of fatty acids and catabolism of amino acids and choline. By contrast, nothing is known of the function of ETF and ETFQO in plants. Sequence analysis of the unique Arabidopsis thaliana homologue of ETFQO revealed high similarity to the mammalian ETFQO protein. Moreover, green fluorescent protein cellular localization experiments suggested a mitochondrial location for this protein. RNA gel blot analysis revealed that Arabidopsis ETFQO transcripts accumulated in long-term dark-treated leaves. Analysis of three independent insertional mutants of Arabidopsis ETFQO revealed a dramatic reduction in their ability to withstand extended darkness, resulting in senescence and death within 10 d after transfer, whereas wild-type plants remained viable for at least 15 d. Metabolite profiling of dark-treated leaves of the wild type and mutants revealed a dramatic decline in sugar levels. In contrast with the wild type, the mutants demonstrated a significant accumulation of several amino acids, an intermediate of Leu catabolism, and, strikingly, high-level accumulation of phytanoyl-CoA. These data demonstrate the involvement of a mitochondrial protein, ETFQO, in the catabolism of Leu and potentially of other amino acids in higher plants and also imply a novel role for this protein in the chlorophyll degradation pathway activated during dark-induced senescence and sugar starvation. PMID:16055629

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Mauck, Catherine M; Krzyaniak, Matthew D; Wasielewski, Michael R

2017-06-15

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA • -mPD-ANI-NDI, where BDPA • is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA • -mPD +• -ANI-NDI -• in which the mPD +• -ANI-NDI -• radical ion pair is spin coupled to the BDPA • stable radical. BDPA • -mPD +• -ANI-NDI -• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3 (mPD +• -ANI-NDI -• ) is in equilibrium with the 3 *NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA • over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

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.

Evidence for protein conformational change at a Au(110)/protein interface

NASA Astrophysics Data System (ADS)

Messiha, H. L.; Smith, C. I.; Scrutton, N. S.; Weightman, P.

2008-07-01

Evidence is presented that reflection anisotropy spectroscopy (RAS) can provide real-time measurements of conformational change in proteins induced by electron transfer reactions. A bacterial electron transferring flavoprotein (ETF) has been modified so as to adsorb on an Au(110) electrode and enable reversible electron transfer to the protein cofactor in the absence of mediators. Reversible changes are observed in the RAS of this protein that are interpreted as arising from conformational changes accompanying the transfer of electrons.

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.

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

Protein's electronic polarization contributes significantly to its catalytic function

NASA Astrophysics Data System (ADS)

Xiang, Yun; Duan, Lili; Zhang, John Z. H.

2011-05-01

Ab initio quantum mechanical/molecular mechanical method is combined with the polarized protein-specific charge to study the chemical reactions catalyzed by protein enzymes. Significant improvement in the accuracy and efficiency of free-energy simulation is demonstrated by calculating the free-energy profile of the primary proton transfer reaction in triosephosphate isomerase. Quantitative agreement with experimental results is achieved. Our simulation results indicate that electronic polarization makes important contribution to enzyme catalysis by lowering the energy barrier by as much as 3 kcal/mol.

Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

NASA Astrophysics Data System (ADS)

Skourtis, Spiros S.; Prytkova, Tatiana; Beratan, David N.

2007-12-01

This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH--containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH-, upon photo-excitation of FADH- with 350-450 nm light. We compute the lowest singlet excited states of FADH- in DNA photolyase using INDO/S configuration interaction, time-dependent density-functional, and time-dependent Hartree-Fock methods. The calculations identify the lowest singlet excited state of FADH- that is populated after photo-excitation and that acts as the electron donor. For this donor state we compute conformationally-averaged tunneling matrix elements to empty electron-acceptor states of a thymine dimer bound to photolyase. The conformational averaging involves different FADH--thymine dimer confromations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. The tunneling matrix element computations use INDO/S-level Green's function, energy splitting, and Generalized Mulliken-Hush methods. These calculations indicate that photo-excitation of FADH- causes a π→π* charge-transfer transition that shifts electron density to the side of the flavin isoalloxazine ring that is adjacent to the docked thymine dimer. This shift in electron density enhances the FADH--to-dimer electronic coupling, thus inducing rapid electron transfer.

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.

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 transfer to AuP+ and was followed by a quantitative energy transfer to give the 3ZnP state (k = 1.5x10(9) x s(-1)).

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.

Sensory methods and electronic nose as innovative tools for the evaluation of the aroma transfer properties of food plastic bags.

PubMed

Torri, Luisa; Piochi, Maria

2016-07-01

Despite the key role of the sensory quality for food acceptance, the aroma transfer properties of food packaging materials have not yet been studied using sensory approaches. This research investigated the suitability of sensory and electronic nose methods to evaluate the aroma transfer properties of plastic materials that come in contact with food. Four (W, X, Y, and Z) commercial freezer bags (polyethylene) for domestic uses were compared. The degree of the aroma transfer through the materials was estimated as the sensory contamination of an odor absorber food (bread) by an odor releaser food (onion), separated by the bags and stored under frozen conditions. Bread samples were analyzed by means of an electronic nose, and 42 assessors used three different sensory methods (triangle, scoring, and partial sorted Napping tests). From the triangle test, none of the plastic bags acted as a complete aroma barrier, showing a sensory contamination of bread stored in all four materials. Partial sorting Napping results clearly described the sensory contamination of bread as "onion flavor", due to the aroma transfer from the odor releaser food to the odor absorber food through the plastic bag. Scoring tests showed significant (p<0.0001) differences of aroma transfer properties among the plastic bags, revealing the highest aroma permeation for W (3.1±0.1), the lowest aroma transfer for X and Y (2.0±0.1), and intermediate aroma transfer properties for Z (2.6±0.1). Electronic nose data were in good agreement with the sensory responses, and a high correlation with the scoring data was observed (R 2 =0.988). The presented approaches had suitable results to provide meaningful information on the aroma transfer properties of freezer plastic bags, and could advantageously be applied in the future for analyzing other finished food containers (e.g. plastic trays, boxes, etc.) or packaging materials of a different nature (multilayer plastic films, biodegradable materials, composites, etc.). Copyright © 2016 Elsevier Ltd. All rights reserved.

12 CFR 1005.6 - Liability of consumer for unauthorized transfers.

Code of Federal Regulations, 2012 CFR

2012-01-01

... transfers. 1005.6 Section 1005.6 Banks and Banking BUREAU OF CONSUMER FINANCIAL PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) § 1005.6 Liability of consumer for unauthorized transfers. (a) Conditions for..., for an unauthorized electronic fund transfer involving the consumer's account only if the financial...

Stabilization of non-productive conformations underpins rapid electron transfer to electron-transferring flavoprotein.

PubMed

Toogood, Helen S; van Thiel, Adam; Scrutton, Nigel S; Leys, David

2005-08-26

Crystal structures of protein complexes with electron-transferring flavoprotein (ETF) have revealed a dual protein-protein interface with one region serving as anchor while the ETF FAD domain samples available space within the complex. We show that mutation of the conserved Glu-165beta in human ETF leads to drastically modulated rates of interprotein electron transfer with both medium chain acyl-CoA dehydrogenase and dimethylglycine dehydrogenase. The crystal structure of free E165betaA ETF is essentially identical to that of wild-type ETF, but the crystal structure of the E165betaA ETF.medium chain acyl-CoA dehydrogenase complex reveals clear electron density for the FAD domain in a position optimal for fast interprotein electron transfer. Based on our observations, we present a dynamic multistate model for conformational sampling that for the wild-type ETF. medium chain acyl-CoA dehydrogenase complex involves random motion between three distinct positions for the ETF FAD domain. ETF Glu-165beta plays a key role in stabilizing positions incompatible with fast interprotein electron transfer, thus ensuring high rates of complex dissociation.

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...

31 CFR 208.4 - Waivers.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) Payment by electronic funds transfer is not required in the following cases: (1) Where an individual: (i... are not required to be made by electronic funds transfer, unless and until such payments become... waiver request with Treasury certifying that payment by electronic funds transfer would impose a hardship...

12 CFR 1005.7 - Initial disclosures.

Code of Federal Regulations, 2012 CFR

2012-01-01

... disclosures required by this section at the time a consumer contracts for an electronic fund transfer service or before the first electronic fund transfer is made involving the consumer's account. (b) Content of... Banks and Banking BUREAU OF CONSUMER FINANCIAL PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E...

Solvent effects on the oxidation (electron transfer) reaction of [Fe(CN) 6] 4- by [Co(NH 3) 5pz] 3+

NASA Astrophysics Data System (ADS)

Muriel, F.; Jiménez, R.; López, M.; Prado-Gotor, R.; Sánchez, F.

2004-03-01

Solvent effects on the title reaction were studied in different reaction media constituted by water and organic cosolvents (methanol, tert-butyl alcohol, ethyleneglycol and glucose) at 298.2 K. The results are considered in light of the Marcus-Hush approach for electron transfer reactions. Variations of the electron transfer rate constant are shown to be mainly due to changes in the reaction free energy. On the other hand the energies of the MMCT band, corresponding to the optical electron transfer within the ion pair [Fe(CN) 6] 4-/[Co(NH 3) 5pz] 3+, in the different reaction media, have been obtained. The activation free energies of the thermal electron transfer process have been calculated from the band ( Eop) data, and compared with those obtained from the kinetic study. Quantitative agreement is found between the two series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from static (optical) measurements.

Electronic doping of transition metal oxide perovskites

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

Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz; Rondinelli, James M.

2016-05-23

CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

Photoemission of Energetic Hot Electrons Produced via Up-Conversion in Doped Quantum Dots.

PubMed

Dong, Yitong; Parobek, David; Rossi, Daniel; Son, Dong Hee

2016-11-09

The benefits of the hot electrons from semiconductor nanostructures in photocatalysis or photovoltaics result from their higher energy compared to that of the band-edge electrons facilitating the electron-transfer process. The production of high-energy hot electrons usually requires short-wavelength UV or intense multiphoton visible excitation. Here, we show that highly energetic hot electrons capable of above-threshold ionization are produced via exciton-to-hot-carrier up-conversion in Mn-doped quantum dots under weak band gap excitation (∼10 W/cm 2 ) achievable with the concentrated solar radiation. The energy of hot electrons is as high as ∼0.4 eV above the vacuum level, much greater than those observed in other semiconductor or plasmonic metal nanostructures, which are capable of performing energetically and kinetically more-challenging electron transfer. Furthermore, the prospect of generating solvated electron is unique for the energetic hot electrons from up-conversion, which can open a new door for long-range electron transfer beyond short-range interfacial electron transfer.

Charge-density analysis of a protein structure at subatomic resolution: the human aldose reductase case.

PubMed

Guillot, Benoît; Jelsch, Christian; Podjarny, Alberto; Lecomte, Claude

2008-05-01

The valence electron density of the protein human aldose reductase was analyzed at 0.66 angstroms resolution. The methodological developments in the software MoPro to adapt standard charge-density techniques from small molecules to macromolecular structures are described. The deformation electron density visible in initial residual Fourier difference maps was significantly enhanced after high-order refinement. The protein structure was refined after transfer of the experimental library multipolar atom model (ELMAM). The effects on the crystallographic statistics, on the atomic thermal displacement parameters and on the structure stereochemistry are analyzed. Constrained refinements of the transferred valence populations Pval and multipoles Plm were performed against the X-ray diffraction data on a selected substructure of the protein with low thermal motion. The resulting charge densities are of good quality, especially for chemical groups with many copies present in the polypeptide chain. To check the effect of the starting point on the result of the constrained multipolar refinement, the same charge-density refinement strategy was applied but using an initial neutral spherical atom model, i.e. without transfer from the ELMAM library. The best starting point for a protein multipolar refinement is the structure with the electron density transferred from the database. This can be assessed by the crystallographic statistical indices, including Rfree, and the quality of the static deformation electron-density maps, notably on the oxygen electron lone pairs. The analysis of the main-chain bond lengths suggests that stereochemical dictionaries would benefit from a revision based on recently determined unrestrained atomic resolution protein structures.

Charge transfer from TiO2 into adsorbed benzene diazonium compounds

NASA Astrophysics Data System (ADS)

Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

2004-08-01

Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

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.

12 CFR 1005.6 - Liability of consumer for unauthorized transfers.

Code of Federal Regulations, 2014 CFR

2014-01-01

... transfers. 1005.6 Section 1005.6 Banks and Banking BUREAU OF CONSUMER FINANCIAL PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) General § 1005.6 Liability of consumer for unauthorized transfers. (a) Conditions... this section, for an unauthorized electronic fund transfer involving the consumer's account only if the...

12 CFR 1005.6 - Liability of consumer for unauthorized transfers.

Code of Federal Regulations, 2013 CFR

2013-01-01

... transfers. 1005.6 Section 1005.6 Banks and Banking BUREAU OF CONSUMER FINANCIAL PROTECTION ELECTRONIC FUND TRANSFERS (REGULATION E) General § 1005.6 Liability of consumer for unauthorized transfers. (a) Conditions... this section, for an unauthorized electronic fund transfer involving the consumer's account only if the...

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...

Fraction of Electrons Consumed in Electron Acceptor Reduction and Hydrogen Thresholds as Indicators of Halorespiratory Physiology

PubMed Central

Löffler, Frank E.; Tiedje, James M.; Sanford, Robert A.

1999-01-01

Measurements of the hydrogen consumption threshold and the tracking of electrons transferred to the chlorinated electron acceptor (fe) reliably detected chlororespiratory physiology in both mixed cultures and pure cultures capable of using tetrachloroethene, cis-1,2-dichloroethene, vinyl chloride, 2-chlorophenol, 3-chlorobenzoate, 3-chloro-4-hydroxybenzoate, or 1,2-dichloropropane as an electron acceptor. Hydrogen was consumed to significantly lower threshold concentrations of less than 0.4 ppmv compared with the values obtained for the same cultures without a chlorinated compound as an electron acceptor. The fe values ranged from 0.63 to 0.7, values which are in good agreement with theoretical calculations based on the thermodynamics of reductive dechlorination as the terminal electron-accepting process. In contrast, a mixed methanogenic culture that cometabolized 3-chlorophenol exhibited a significantly lower fe value, 0.012. PMID:10473415

Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc1 complex

NASA Astrophysics Data System (ADS)

Martin, Daniel R.; Matyushov, Dmitry V.

2015-04-01

Cross-membrane electron transport between cofactors localized in proteins of mitochondrial respiration and bacterial photosynthesis is the source of all biological energy. The statistics and dynamics of nuclear fluctuations in these protein/membrane/water heterogeneous systems are critical for their energetic efficiency. The results of 13 μs of atomistic molecular dynamics simulations of the membrane-bound bc1 bacterial complex are analyzed here. The reaction is affected by a broad spectrum of nuclear modes, with the slowest dynamics in the range of time-scales ˜0.1-1.6 μs contributing half of the reaction reorganization energy. Two reorganization energies are required to describe protein electron transfer due to dynamical arrest of protein conformations on the observation window. This mechanistic distinction allows significant lowering of activation barriers for reactions in proteins.

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.

Phylogenetic analysis of proteins associated in the four major energy metabolism systems: photosynthesis, aerobic respiration, denitrification, and sulfur respiration.

PubMed

Tomiki, Takeshi; Saitou, Naruya

2004-08-01

The four electron transfer energy metabolism systems, photosynthesis, aerobic respiration, denitrification, and sulfur respiration, are thought to be evolutionarily related because of the similarity of electron transfer patterns and the existence of some homologous proteins. How these systems have evolved is elusive. We therefore conducted a comprehensive homology search using PSI-BLAST, and phylogenetic analyses were conducted for the three homologous groups (groups 1-3) based on multiple alignments of domains defined in the Pfam database. There are five electron transfer types important for catalytic reaction in group 1, and many proteins bind molybdenum. Deletions of two domains led to loss of the function of binding molybdenum and ferredoxin, and these deletions seem to be critical for the electron transfer pattern changes in group 1. Two types of electron transfer were found in group 2, and all its member proteins bind siroheme and ferredoxin. Insertion of the pyridine nucleotide disulfide oxidoreductase domain seemed to be the critical point for the electron transfer pattern change in this group. The proteins belonging to group 3 are all flavin enzymes, and they bind flavin adenine dinucleotide (FAD) or flavin mononucleotide (FMN). Types of electron transfer in this group are divergent, but there are two common characteristics. NAD(P)H works as an electron donor or acceptor, and FAD or FMN transfers electrons from/to NAD(P)H. Electron transfer functions might be added to these common characteristics by the addition of functional domains through the evolution of group 3 proteins. Based on the phylogenetic analyses in this study and previous studies, we inferred the phylogeny of the energy metabolism systems as follows: photosynthesis (and possibly aerobic respiration) and the sulfur/nitrogen assimilation system first diverged, then the sulfur/nitrogen dissimilation system was produced from the latter system.

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

PubMed

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

2015-06-18

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

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.

Non-Transition-Metal Catalytic System for N 2 Reduction to NH 3: A Density Functional Theory Study of Al-Doped Graphene

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

Tian, Yong-Hui; Hu, Shuangli; Sheng, Xiaolan

The prevalent catalysts for natural and artificial N 2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N 2 to NH 3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N 2 and its various downstream N xH y intermediates. The initial hydrogenation of N 2 canmore » readily take place via an internal H-transfer process with the assistance of a Li + ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N 2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N 2 fixation.« less

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings

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

Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas

2013-02-07

Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlapmore » matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Angstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.« less

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings.

PubMed

Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas; Neugebauer, Johannes

2013-02-07

Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Ångstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.

MD studies of electron transfer at ambient and elevated pressures

NASA Astrophysics Data System (ADS)

Giles, Alex; Spooner, Jacob; Weinberg, Noham

2013-06-01

The effect of pressure on the rate constants of outer-sphere electron transfer reactions has often been described using the Marcus-Hush theory. This theory agrees well with experiment when internal reorganization of the ionic system is negligible, however it does not offer a recipe for calculation of the effects that result from significant solute restructuring. We have recently developed a molecular dynamics technique that accurately describes structural dependence of molecular volumes in non-polar and weakly polar systems. We are now extending this approach to the case of highly polar ionic systems where both solvent and solute restructuring components are important. For this purpose we construct pressure-dependent two-dimensional surfaces for electron transfer reactions in coordinate system composed of interionic distance and Marcus-type solvent polarization coordinate, and use these surfaces to describe pressure effects on reaction kinetics. R.A. Marcus. J. Chem. Phys. 24, 966 (1956); 24, 979 (1956); 26, 867 (1957). Discuss. Faraday Soc. 29, 21 (1960). Faraday Discuss. Chem. Soc. 74, 7 (1982); N.S. Hush. Trans. Faraday Soc. 57, 557 (1961).

Non-Transition-Metal Catalytic System for N 2 Reduction to NH 3: A Density Functional Theory Study of Al-Doped Graphene

DOE PAGES

Tian, Yong-Hui; Hu, Shuangli; Sheng, Xiaolan; ...

2018-01-16

The prevalent catalysts for natural and artificial N 2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N 2 to NH 3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N 2 and its various downstream N xH y intermediates. The initial hydrogenation of N 2 canmore » readily take place via an internal H-transfer process with the assistance of a Li + ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N 2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N 2 fixation.« less

Charge-Transfer-Induced Fluorescence Quenching of Anthracene Derivatives and Selective Detection of Picric Acid.

PubMed

Santra, Dines Chandra; Bera, Manas Kumar; Sukul, Pradip Kumar; Malik, Sudip

2016-02-01

2,6-Divinylpyridine-appended anthracene derivatives flanked by two alkyl chains at the 9,10-position of the core have been designed, synthesized, and characterized by NMR, MALDI-TOF, FTIR, and single-crystal XRD. These anthracene derivatives are able to recognize picric acid (2,4,6-trinitrophenol, PA) selectively down to parts per billion (ppb) level in aqueous as well as nonaqueous medium. Fluorescence emission of these derivatives in solution is significantly quenched by adding trace amounts of PA, even in the presence of other competing analogues, such as 2,4-dinitrophenol (2,4-DNP), 4-nitrophenol (NP), nitrobenzene (NB), benzoic acid (BA), and phenol (PH). The high sensitivity of these derivatives toward PA is considered as a combined effect of the proton-induced intramolecular charge transfer (ICT) as well as electron transfer from the electron-rich anthracene to the electron-deficient PA. Moreover, visual detection of PA has been successfully demonstrated in the solid state by using different substrates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

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...

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...

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...

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...

40 CFR Table I-2 to Subpart I - Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry

Code of Federal Regulations, 2012 CFR

2012-07-01

... Fluorinated Heat Transfer Fluids Used by the Electronics Industry I Table I-2 to Subpart I Protection of... REPORTING Electronics Manufacturing Pt. 98, Subpt. I, Table I-2 Table I-2 to Subpart I—Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry Product type...

On judgement of electron transfer between two regions divided by the separatrix of confronting divergent magnetic fields applied to an inductively coupled plasma

NASA Astrophysics Data System (ADS)

Sugawara, Hirotake; Yamamoto, Tappei

2016-09-01

In order to quantitatively evaluate the electron confinement effect of the confronting divergent magnetic fields (CDMFs) applied to an inductively coupled plasma, we analyzed the electron transfer between two regions divided by the separatrix of the CDMFs in Ar at 0.67 Pa at 300 K using a Monte Carlo method. A conventional transfer judgement was simply based on the electron passage across the separatrix from the upstream source region to the downstream diffusion region. An issue was an overestimation of the transfer due to temporary stay of electrons in the downstream region. Electrons may pass the downstream region during their gyration even in case they are effectively bound to the upstream region, where their guiding magnetic flux lines run. More than half of the transfers were temporary ones and such seeming transfers were relevantly excluded from the statistics by introducing a newly chosen criterion based on the passage of electron gyrocenters across the separatrix and collisional events in the downstream region. Simulation results showed a tendency that the ratio of the temporary transfers excluded was higher under stronger magnetic fields because of higher cyclotron frequency. Work supported by JSPS Kakenhi Grant Number 16K05626.

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

New insights into the nonadiabatic state population dynamics of model proton-coupled electron transfer reactions from the mixed quantum-classical Liouville approach

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

Shakib, Farnaz A.; Hanna, Gabriel, E-mail: gabriel.hanna@ualberta.ca

In a previous study [F. A. Shakib and G. Hanna, J. Chem. Phys. 141, 044122 (2014)], we investigated a model proton-coupled electron transfer (PCET) reaction via the mixed quantum-classical Liouville (MQCL) approach and found that the trajectories spend the majority of their time on the mean of two coherently coupled adiabatic potential energy surfaces. This suggested a need for mean surface evolution to accurately simulate observables related to ultrafast PCET processes. In this study, we simulate the time-dependent populations of the three lowest adiabatic states in the ET-PT (i.e., electron transfer preceding proton transfer) version of the same PCET modelmore » via the MQCL approach and compare them to the exact quantum results and those obtained via the fewest switches surface hopping (FSSH) approach. We find that the MQCL population profiles are in good agreement with the exact quantum results and show a significant improvement over the FSSH results. All of the mean surfaces are shown to play a direct role in the dynamics of the state populations. Interestingly, our results indicate that the population transfer to the second-excited state can be mediated by dynamics on the mean of the ground and second-excited state surfaces, as part of a sequence of nonadiabatic transitions that bypasses the first-excited state surface altogether. This is made possible through nonadiabatic transitions between different mean surfaces, which is the manifestation of coherence transfer in MQCL dynamics. We also investigate the effect of the strength of the coupling between the proton/electron and the solvent coordinate on the state population dynamics. Drastic changes in the population dynamics are observed, which can be understood in terms of the changes in the potential energy surfaces and the nonadiabatic couplings. Finally, we investigate the state population dynamics in the PT-ET (i.e., proton transfer preceding electron transfer) and concerted versions of the model. The PT-ET results confirm the participation of all of the mean surfaces, albeit in different proportions compared to the ET-PT case, while the concerted results indicate that the mean of the ground- and first-excited state surfaces only plays a role, due to the large energy gaps between the ground- and second-excited state surfaces.« less

Prediction of FAD binding sites in electron transport proteins according to efficient radial basis function networks and significant amino acid pairs.

PubMed

Le, Nguyen-Quoc-Khanh; Ou, Yu-Yen

2016-07-30

Cellular respiration is a catabolic pathway for producing adenosine triphosphate (ATP) and is the most efficient process through which cells harvest energy from consumed food. When cells undergo cellular respiration, they require a pathway to keep and transfer electrons (i.e., the electron transport chain). Due to oxidation-reduction reactions, the electron transport chain produces a transmembrane proton electrochemical gradient. In case protons flow back through this membrane, this mechanical energy is converted into chemical energy by ATP synthase. The convert process is involved in producing ATP which provides energy in a lot of cellular processes. In the electron transport chain process, flavin adenine dinucleotide (FAD) is one of the most vital molecules for carrying and transferring electrons. Therefore, predicting FAD binding sites in the electron transport chain is vital for helping biologists understand the electron transport chain process and energy production in cells. We used an independent data set to evaluate the performance of the proposed method, which had an accuracy of 69.84 %. We compared the performance of the proposed method in analyzing two newly discovered electron transport protein sequences with that of the general FAD binding predictor presented by Mishra and Raghava and determined that the accuracy of the proposed method improved by 9-45 % and its Matthew's correlation coefficient was 0.14-0.5. Furthermore, the proposed method enabled reducing the number of false positives significantly and can provide useful information for biologists. We developed a method that is based on PSSM profiles and SAAPs for identifying FAD binding sites in newly discovered electron transport protein sequences. This approach achieved a significant improvement after we added SAAPs to PSSM features to analyze FAD binding proteins in the electron transport chain. The proposed method can serve as an effective tool for predicting FAD binding sites in electron transport proteins and can help biologists understand the functions of the electron transport chain, particularly those of FAD binding sites. We also developed a web server which identifies FAD binding sites in electron transporters available for academics.

Interaction of inorganic nanoparticles with graphene.

PubMed

Das, Barun; Choudhury, Biswajit; Gomathi, A; Manna, Arun K; Pati, S K; Rao, C N R

2011-04-04

The changes in the electronic and magnetic properties of graphene induced by interaction with semiconducting oxide nanoparticles such as ZnO and TiO(2) and with magnetic nanoparticles such as Fe(3)O(4), CoFe(2)O(4), and Ni are investigated by using Raman spectroscopy, magnetic measurements, and first-principles calculations. Significant electronic and magnetic interactions between the nanoparticles and graphene are found. The findings suggest that changes in magnetization as well as the Raman shifts are directly linked to charge transfer between the deposited nanoparticles and graphene. The study thus demonstrates significant effects in tailoring the electronic structure of graphene for applications in futuristic electronic devices. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Macek, Joseph H; Sternberg, James; Ovchinnikov, Serguei Yurevich

Deep minima in He(e,2e)He{sup +} triply differential cross sections are traced to vortices in atomic wave functions. Such vortices have been predicted earlier, but the present calculations show that they have also been observed experimentally, although not recognized as vortices. Their observation in (e,2e) measurements shows that vortices play an important role in electron correlations related to the transfer of angular momentum between incident and ejected electrons. The vortices significantly extend the list of known features that summarize the general picture of electron correlations in impact ionization.

Electrical control of spin dynamics in finite one-dimensional systems

NASA Astrophysics Data System (ADS)

Pertsova, A.; Stamenova, M.; Sanvito, S.

2011-10-01

We investigate the possibility of the electrical control of spin transfer in monoatomic chains incorporating spin impurities. Our theoretical framework is the mixed quantum-classical (Ehrenfest) description of the spin dynamics, in the spirit of the s-d model, where the itinerant electrons are described by a tight-binding model while localized spins are treated classically. Our main focus is on the dynamical exchange interaction between two well-separated spins. This can be quantified by the transfer of excitations in the form of transverse spin oscillations. We systematically study the effect of an electrostatic gate bias Vg on the interconnecting channel and we map out the long-range dynamical spin transfer as a function of Vg. We identify regions of Vg giving rise to significant amplification of the spin transmission at low frequencies and relate this to the electronic structure of the channel.

Graphene and Carbon-Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties.

PubMed

Wang, Aijian; Ye, Jun; Humphrey, Mark G; Zhang, Chi

2018-04-01

In recent years, there has been a rapid growth in studies of the optoelectronic properties of graphene, carbon nanotubes (CNTs), and their derivatives. The chemical functionalization of graphene and CNTs is a key requirement for the development of this field, but it remains a significant challenge. The focus here is on recent advances in constructing nanohybrids of graphene or CNTs covalently linked to porphyrins or phthalocyanines, as well as their application in nonlinear optics. Following a summary of the syntheses of nanohybrids constructed from graphene or CNTs and porphyrins or phthalocyanines, explicit intraconjugate electronic interactions between photoexcited porphyrins/phthalocyanines and graphene/CNTs are introduced classified by energy transfer, electron transfer, and charge transfer, and their optoelectronic applications are also highlighted. The major current challenges for the development of covalently linked nanohybrids of porphyrins or phthalocyanines and carbon nanostructures are also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combined high and low-thrust geostationary orbit insertion with radiation constraint

NASA Astrophysics Data System (ADS)

Macdonald, Malcolm; Owens, Steven Robert

2018-01-01

The sequential use of an electric propulsion system is considered in combination with a high-thrust propulsion system for application to the propellant-optimal Geostationary Orbit insertion problem, whilst considering both temporal and radiation flux constraints. Such usage is found to offer a combined propellant mass saving when compared with an equivalent high-thrust only transfer. This propellant mass saving is seen to increase as the allowable transfer duration is increased, and as the thrust from the low-thrust system is increased, assuming constant specific impulse. It was found that the required plane change maneuver is most propellant-efficiently performed by the high-thrust system. The propellant optimal trajectory incurs a significantly increased electron flux when compared to an equivalent high-thrust only transfer. However, the electron flux can be reduced to a similar order of magnitude by increasing the high-thrust propellant consumption, whilst still delivering an improved mass fraction.

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.

Effect of π-bridge units on properties of A-π-D-π-A-type nonfullerene acceptors for organic solar cells.

PubMed

Wang, Yan-Ling; Li, Quan-Song; Li, Ze-Sheng

2018-05-15

Acceptor-π-donor-π-acceptor (A-π-D-π-A)-types of small molecules are very promising nonfullerene acceptors to overcome the drawbacks of fullerene derivatives such as the weak absorption ability and electronic adjustability. However, only few attempts have been made to develop π-bridge units to construct highly efficient acceptors in OSCs. Herein, taking the reported acceptor P1 as a reference, five small-structured acceptors (P2, P3, P4, P5, and P6) have been designed via the replacement of the π-bridge unit. A combination of quantum chemistry and Marcus theory approaches is employed to investigate the effect of different π-bridge units on the optical, electronic, and charge transport properties of P1-P6. The calculation results show that the designed molecules P2 and P5 can become potential acceptor replacements of P1 due to their red-shifted absorption bands, appropriate energy levels, low exciton binding energy, and high electron affinity and electron mobility. Additionally, compared with P3HT/P1, P3HT/P2 and P3HT/P5 exhibit stronger and wider absorption peaks, larger electron transfer distances (DCT), greater transferred charge amounts (Δq), and smaller overlaps (Λ), which shows that P2 and P5 have more significant electron transfer characteristics and favorable exciton dissociation capabilities for enhancing the short-circuit current density (JSC) and thus, they are potential acceptors in OSCs.

Direct observation of ultrafast-electron-transfer reactions unravels high effectiveness of reductive DNA damage

PubMed Central

Nguyen, Jenny; Ma, Yuhan; Luo, Ting; Bristow, Robert G.; Jaffray, David A.; Lu, Qing-Bin

2011-01-01

Both water and electron-transfer reactions play important roles in chemistry, physics, biology, and the environment. Oxidative DNA damage is a well-known mechanism, whereas the relative role of reductive DNA damage is unknown. The prehydrated electron (), a novel species of electrons in water, is a fascinating species due to its fundamental importance in chemistry, biology, and the environment. is an ideal agent to observe reductive DNA damage. Here, we report both the first in situ femtosecond time-resolved laser spectroscopy measurements of ultrafast-electron-transfer (UET) reactions of with various scavengers (KNO3, isopropanol, and dimethyl sulfoxide) and the first gel electrophoresis measurements of DNA strand breaks induced by and OH• radicals co-produced by two-UV-photon photolysis of water. We strikingly found that the yield of reductive DNA strand breaks induced by each is twice the yield of oxidative DNA strand breaks induced by each OH• radical. Our results not only unravel the long-standing mystery about the relative role of radicals in inducing DNA damage under ionizing radiation, but also challenge the conventional notion that oxidative damage is the main pathway for DNA damage. The results also show the potential of femtomedicine as a new transdisciplinary frontier and the broad significance of UET reactions of in many processes in chemistry, physics, biology, and the environment. PMID:21730183

Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) Study.

PubMed

Kang, Guo-Jun; Song, Chao; Ren, Xue-Feng

2016-11-25

The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH₃-YD2 and TPhe-YD) were systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO₂ cluster were fully investigated. From the analyses of natural bond orbital (NBO), extended charge decomposition analysis (ECDA), and electron density variations (Δρ) between the excited state and ground state, it was found that the introduction of N(CH₃)₂ and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT) character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH₃)₂ and 1,1,2-triphenylethene groups. NCH₃-YD2 with N(CH₃)₂ groups in the donor part is an effective way to improve the interactions between the dyes and TiO₂ surface, light having efficiency (LHE), and free energy change (ΔG inject ), which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs).

Accelerating anodic biofilms formation and electron transfer in microbial fuel cells: Role of anionic biosurfactants and mechanism.

PubMed

Zhang, Yunshu; Jiang, Junqiu; Zhao, Qingliang; Gao, YunZhi; Wang, Kun; Ding, Jing; Yu, Hang; Yao, Yue

2017-10-01

Anodic electron transfer is the predominant electricity generation process of MFCs. To accelerate anodic biofilms formation and electron transfer, 40mg/L, 80mg/L, and 120mg/L of rhamnolipid biosurfactants were added to the anolyte, resulting in an increased abiotic capacitance from 15.12F/m 2 (control) to 16.54F/m 2 , 18.00F/m 2 , and 19.39F/m 2 , respectively. Anodic biofilm formation was facilitated after dosing 40mg/L of rhamnolipids on the 7th day after inoculation, resulting in an increased anodic biofilm coverage from 0.43% to 42.51%, and an increased maximum power density from 6.92±1.18W/m 3 to 9.93±0.88W/m 3 . Furthermore, the adsorption of rhamnolipids on the anode caused the Frumkin effect, leading to a decrease of equilibrium potential from -0.43V to -0.56V, and an increase of exchange current density from 5.09×10 -3 A/m 2 to 8.72×10 -3 A/m 2 . However, electron transfer was blocked when the rhamnolipid concentration was further increased to 80mg/L, and 120mg/L. Analysis of the anodic bacterial communities revealed that rhamnolipids facilitated the enrichment of exoelectrogen, increasing the total proportion from 65% to 81%. Additionally, biosurfactants were found to have significant impacts on the composition of exoelectrogens. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron shuttles in biotechnology.

PubMed

Watanabe, Kazuya; Manefield, Mike; Lee, Matthew; Kouzuma, Atsushi

2009-12-01

Electron-shuttling compounds (electron shuttles [ESs], or redox mediators) are essential components in intracellular electron transfer, while microbes also utilize self-produced and naturally present ESs for extracellular electron transfer. These compounds assist in microbial energy metabolism by facilitating electron transfer between microbes, from electron-donating substances to microbes, and/or from microbes to electron-accepting substances. Artificially supplemented ESs can create new routes of electron flow in the microbial energy metabolism, thereby opening up new possibilities for the application of microbes to biotechnology processes. Typical examples of such processes include halogenated-organics bioremediation, azo-dye decolorization, and microbial fuel cells. Herein we suggest that ESs can be applied widely to create new microbial biotechnology processes.

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory.

PubMed

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G

2011-08-28

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi-Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi-Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. © 2011 American Institute of Physics

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory

PubMed Central

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G.

2011-01-01

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi–Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi–Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. PMID:21895159

Investigation of the redox-dependent modulation of structure and dynamics in human cytochrome c.

PubMed

Imai, Mizue; Saio, Tomohide; Kumeta, Hiroyuki; Uchida, Takeshi; Inagaki, Fuyuhiko; Ishimori, Koichiro

2016-01-22

Redox-dependent changes in the structure and dynamics of human cytochrome c (Cyt c) were investigated by solution NMR. We found significant structural changes in several regions, including residues 23-28 (loop 3), which were further corroborated by chemical shift differences between the reduced and oxidized states of Cyt c. These differences are essential for discriminating redox states in Cyt c by cytochrome c oxidase (CcO) during electron transfer reactions. Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments identified that the region around His33 undergoes conformational exchanges on the μs-ms timescale, indicating significant redox-dependent structural changes. Because His33 is not part of the interaction site for CcO, our data suggest that the dynamic properties of the region, which is far from the interaction site for CcO, contribute to conformational changes during electron transfer to CcO. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

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

40 CFR Table I-2 to Subpart I of... - Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry

Code of Federal Regulations, 2013 CFR

2013-07-01

... Fluorinated Heat Transfer Fluids Used by the Electronics Industry I Table I-2 to Subpart I of Part 98... GREENHOUSE GAS REPORTING Electronics Manufacturing Pt. 98, Subpt. I, Table I-2 Table I-2 to Subpart I of Part 98—Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry...

48 CFR 252.232-7011 - Payments in Support of Emergencies and Contingency Operations.

Code of Federal Regulations, 2011 CFR

2011-10-01

.... Internal Revenue Code. (ix) Electronic funds transfer banking information. (A) The Contractor shall include electronic funds transfer banking information on the invoice only if required elsewhere in this contract. (B) If electronic funds transfer banking information is not required to be on the invoice, in order for...

76 FR 52862 - Time for Payment of Certain Excise Taxes, and Quarterly Excise Tax Payments for Small Alcohol...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-24

... 40 Cigars and cigarettes, Claims, Electronic fund transfers, Excise taxes, Labeling, Packaging and... that are not required to pay taxes through electronic funds transfer (EFT), this first payment period..., Electronic funds transfers, Excise taxes, Exports, Food additives, Fruit juices, Labeling, Liquors, Packaging...

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.

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.

Long-Range Superexchange in Electron Transport Proteins

NASA Astrophysics Data System (ADS)

Gruschus, James Michael

A new Hamiltonian model for the calculation of long-range electronic couplings in complex molecular systems is presented. These couplings make possible the electron transfers occurring at several critical steps in photosynthesis and respiration. The couplings studied are demonstrated to arise from a mechanism known as superexchange, where the electrons of the insulating medium are intimately involved in the delocalization of the donor wavefunction tail, allowing significant interaction with the acceptor at much greater separations than could be achieved were the medium absent. Superexchange phenomena in molecules of moderate complexity are first compared to couplings calculated with the model Hamiltonian, with very encouraging results. The method is then applied to several cytochrome c proteins where electron transfer has been measured between a zinc-substituted porphyrin and a ruthenium complex ligated to several sites at the protein surface. The calculated couplings are in unprecedented agreement with experiment. Novel, analytical derivatives of the superexchange coupling with respect to the orbital energies and interactions are then carried out on these proteins yielding the general, chemically relevant result that the entire three-dimensional zone between redox sites is important in mediating the superexchange coupling, in contrast to the prevailing assumption that the coupling can be characterized by a one-dimensional pathway consisting primarily of chains of bonded atoms. In addition, the derivatives provide the most comprehensive ever, atom-by -atom visualization of the superexchange process. Using AMBER molecular dynamics trajectories of the cytochrome c proteins, the effect of structural fluctuations on superexchange is examined. The calculated couplings show a substantial variability, a result contrary to the constant coupling implicit in most present-day transfer rate theory. Couplings are also calculated on surfaces enveloping several variants of cytochrome c, as well as plastocyanin, cytochrome b _5, and cytochrome c peroxidase. The surfaces reveal important clues as to which conformations of the electron transport protein complexes actually give rise to electron transfer, a subject of broad biological interest.

Conformational control of cofactors in nature: The effect of methoxy group orientation on the electronic structure of ubisemiquinone

NASA Astrophysics Data System (ADS)

De Almeida, Wagner B.; O'Malley, Patrick J.

2018-03-01

Ubiquinone is the key electron and proton transfer agent in biology. Its mechanism involves the formation of its intermediate one-electron reduced form, the ubisemiquinone radical. This is formed in a protein-bound form which permits the semiquinone to vary its electronic and redox properties. This can be achieved by hydrogen bonding acceptance by one or both oxygen atoms or as we now propose by restricted orientations for the methoxy groups of the headgroup. We show how the orientation of the two methoxy groups of the quinone headgroup affects the electronic structure of the semiquinone form and demonstrate a large dependence of the ubisemiquinone spin density distribution on the orientation each methoxy group takes with respect to the headgroup ring plane. This is shown to significantly modify associated hyperfine couplings which in turn needs to be accounted for in interpreting experimental values in vivo. The study uncovers the key potential role the methoxy group orientation can play in controlling the electronic structure and spin density of ubisemiquinone and provides an electronic-level insight into the variation in electron affinity and redox potential of ubiquinone as a function of the methoxy orientation. Taken together with the already known influence of cofactor conformation on heme and chlorophyll electronic structure, it reveals a more widespread role for cofactor conformational control of electronic structure and associated electron transfer in biology.

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.

A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

PubMed

Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

2018-03-15

The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

Photoinduced Oxidative DNA Damage Revealed by an Agarose Gel Nicking Assay: A Biophysical Chemistry Laboratory Experiment

NASA Astrophysics Data System (ADS)

Shafirovich, Vladimir; Singh, Carolyn; Geacintov, Nicholas E.

2003-11-01

Oxidative damage of DNA molecules associated with electron-transfer reactions is an important phenomenon in living cells, which can lead to mutations and contribute to carcinogenesis and the aging processes. This article describes the design of several simple experiments to explore DNA damage initiated by photoinduced electron-transfer reactions sensitized by the acridine derivative, proflavine (PF). A supercoiled DNA agarose gel nicking assay is employed as a sensitive probe of DNA strand cleavage. A low-cost experimental and computer-interfaced imaging apparatus is described allowing for the digital recording and analysis of the gel electrophoresis results. The first experiment describes the formation of direct strand breaks in double-stranded DNA induced by photoexcitation of the intercalated PF molecules. The second experiment demonstrates that the addition of the well-known electron acceptor, methylviologen, gives rise to a significant enhancement of the photochemical DNA strand cleavage effect. This occurs by an electron transfer step to methylviologen that renders the inital photoinduced charge separation between photoexcited PF and DNA irreversible. The third experiment demonstrates that the action spectrum of the DNA photocleavage matches the absorption spectrum of DNA-bound, intercalated PF molecules, which differs from that of free PF molecules. This result demonstrates that the photoinduced DNA strand cleavage is initiated by intercalated rather than free PF molecules.

Multiple electron injection dynamics in linearly-linked two dye co-sensitized nanocrystalline metal oxide electrodes for dye-sensitized solar cells.

PubMed

Shen, Qing; Ogomi, Yuhei; Park, Byung-wook; Inoue, Takafumi; Pandey, Shyam S; Miyamoto, Akari; Fujita, Shinsuke; Katayama, Kenji; Toyoda, Taro; Hayase, Shuzi

2012-04-07

Understanding the electron transfer dynamics at the interface between dye sensitizer and semiconductor nanoparticle is very important for both a fundamental study and development of dye-sensitized solar cells (DSCs), which are a potential candidate for next generation solar cells. In this study, we have characterized the ultrafast photoexcited electron dynamics in a newly produced linearly-linked two dye co-sensitized solar cell using both a transient absorption (TA) and an improved transient grating (TG) technique, in which tin(IV) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (NcSn) and cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium) (N719) are molecularly and linearly linked and are bonded to the surface of a nanocrystalline tin dioxide (SnO(2)) electrode by a metal-O-metal linkage (i.e. SnO(2)-NcSn-N719). By comparing the TA and TG kinetics of NcSn, N719, and hybrid NcSn-N719 molecules adsorbed onto both of the SnO(2) and zirconium dioxide (ZrO(2)) nanocrystalline films, the forward and backward electron transfer dynamics in SnO(2)-NcSn-N719 were clarified. We found that there are two pathways for electron injection from the linearly-linked two dye molecules (NcSn-N719) to SnO(2). The first is a stepwise electron injection, in which photoexcited electrons first transfer from N719 to NcSn with a transfer time of 0.95 ps and then transfer from NcSn to the conduction band (CB) of SnO(2) with two timescales of 1.6 ps and 4.2 ps. The second is direct photoexcited electron transfer from N719 to the CB of SnO(2) with a timescale of 20-30 ps. On the other hand, back electron transfer from SnO(2) to NcSn is on a timescale of about 2 ns, which is about three orders of magnitude slower compared to the forward electron transfer from NcSn to SnO(2). The back electron transfer from NcSn to N719 is on a timescale of about 40 ps, which is about one order slower compared to the forward electron transfer from N719 to NcSn. These results demonstrate that photoexcited electrons can be effectively injected into SnO(2) from both of the N719 and NcSn dyes.

Transferable and flexible thin film devices for engineering applications

NASA Astrophysics Data System (ADS)

Mutyala, Madhu Santosh K.; Zhou, Jingzhou; Li, Xiaochun

2014-05-01

Thin film devices can be of significance for manufacturing, energy conversion systems, solid state electronics, wireless applications, etc. However, these thin film sensors/devices are normally fabricated on rigid silicon substrates, thus neither flexible nor transferrable for engineering applications. This paper reports an innovative approach to transfer polyimide (PI) embedded thin film devices, which were fabricated on glass, to thin metal foils. Thin film thermocouples (TFTCs) were fabricated on a thin PI film, which was spin coated and cured on a glass substrate. Another layer of PI film was then spin coated again on TFTC/PI and cured to obtain the embedded TFTCs. Assisted by oxygen plasma surface coarsening of the PI film on the glass substrate, the PI embedded TFTC was successfully transferred from the glass substrate to a flexible copper foil. To demonstrate the functionality of the flexible embedded thin film sensors, they were transferred to the sonotrode tip of an ultrasonic metal welding machine for in situ process monitoring. The dynamic temperatures near the sonotrode tip were effectively measured under various ultrasonic vibration amplitudes. This technique of transferring polymer embedded electronic devices onto metal foils yield great potentials for numerous engineering applications.

Charge Transfer Processes in Collisions of Si4+ Ions with He Atoms at Intermediate Energies

NASA Astrophysics Data System (ADS)

Suzuki, R.; Watanabe, A.; Sato, H.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Kimura, M.; Stancil, P. C.

Charge transfer in collisions of Si4+ ions with He atoms below 100 keV/u is studied by using a molecular orbital representation within both the semiclassical and quantal representations. Single transfer reaction Si4++He →Si3++He+ has been studied by a number of theoretical investigations. In addition to the reaction (1), the first semiclassical MOCC calculations are performed for the double transfer channel Si4++HE→Si2++He2+ Nine molecular states that connect both with single and double electron transfer processes are considered in the present model. Electronic states and corresponding couplings are determined by the multireference single- and double- excitation configuration interaction method. The present cross sections tie well with the earlier calculations of Stancil et al., Phys. Rev. A 55, 1064 (1997) at lower energies, but show a rather different magnitude from those of Bacchus-Montabonel and Ceyzeriat, Phys. Rev. A 58, 1162 (1998). The present rate constant is found to be significantly different from the experimental finding of Fang and Kwong, Phys. Rev. A 59, 342 (1996) at 4,600 K, and hence does not support the experiment.

12 CFR 205.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2011 CFR

2011-01-01

... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.9 Receipts at electronic terminals; periodic..., a financial institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following...

12 CFR 205.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2013 CFR

2013-01-01

... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.9 Receipts at electronic terminals; periodic..., a financial institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following...

12 CFR 205.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2014 CFR

2014-01-01

... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.9 Receipts at electronic terminals; periodic..., a financial institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following...

12 CFR 205.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2010 CFR

2010-01-01

... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.9 Receipts at electronic terminals; periodic..., a financial institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following...

12 CFR 205.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2012 CFR

2012-01-01

... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.9 Receipts at electronic terminals; periodic..., a financial institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following...

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

PubMed

Horke, Daniel A; Li, Quansong; Blancafort, Lluís; Verlet, Jan R R

2013-08-01

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

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. 2009 Elsevier B.V. All rights reserved.

Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

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

Jensen, Stephen C.; Bettis Homan, Stephanie; Weiss, Emily A.

2016-01-28

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecondmore » time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.« less

Unraveling the charge transfer/electron transport in mesoporous semiconductive TiO2 films by voltabsorptometry.

PubMed

Renault, Christophe; Nicole, Lionel; Sanchez, Clément; Costentin, Cyrille; Balland, Véronique; Limoges, Benoît

2015-04-28

In this work, we demonstrate that chronoabsorptometry and more specifically cyclic voltabsorptometry are particularly well suited techniques for acquiring a comprehensive understanding of the dynamics of electron transfer/charge transport within a transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye. This is illustrated with the quantitative analysis of the spectroelectrochemical responses of two distinct heme-based redox probes adsorbed in highly-ordered mesoporous TiO2 thin films (prepared from evaporation-induced self-assembly, EISA). On the basis of a finite linear diffusion-reaction model as well as the establishment of the analytical expressions governing the limiting cases, it was possible to quantitatively analyse, predict and interpret the unusual voltabsorptometric responses of the adsorbed redox species as a function of the potential applied to the semiconductive film (i.e., as a function of the transition from an insulating to a conductive state or vice versa). In particular, we were able to accurately determine the interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor. Another important and unexpected finding, inferred from the voltabsorptograms, is an interfacial electron transfer process predominantly governed by the extended conduction band states of the EISA TiO2 film and not by the localized traps in the bandgap. This is a significant result that contrasts those previously observed for dye-sensitized solar cells formed of randomly sintered TiO2 nanoparticles, a behaviour that was ascribed to a particularly low density of localized surface states in EISA TiO2. The present methodology also provides a unique and straightforward access to an activation-driving force relationship according to the Marcus theory, thus opening new opportunities not only to investigate the driving-force effects on electron recombination dynamics in dye-sensitized solar cells but also to study the electron transfer/transport mechanisms in heterogeneous photoelectrocatalytic systems combining nanostructured semiconductor electrodes and heterogeneous redox-active catalysts.

Quantum state transfer in double-quantum-well devices

NASA Technical Reports Server (NTRS)

Jakumeit, Jurgen; Tutt, Marcel; Pavlidis, Dimitris

1994-01-01

A Monte Carlo simulation of double-quantum-well (DQW) devices is presented in view of analyzing the quantum state transfer (QST) effect. Different structures, based on the AlGaAs/GaAs system, were simulated at 77 and 300 K and optimized in terms of electron transfer and device speed. The analysis revealed the dominant role of the impurity scattering for the QST. Different approaches were used for the optimization of QST devices and basic physical limitations were found in the electron transfer between the QWs. The maximum transfer of electrons from a high to a low mobility well was at best 20%. Negative differential resistance is hampered by the almost linear rather than threshold dependent relation of electron transfer on electric field. By optimizing the doping profile the operation frequency limit could be extended to 260 GHz.

Photo-Initiated Electron Transfer Within the P. denitrificans Cytochrome bc1 Complex: The mobility of the Iron Sulfur Protein is modulated by the occupant of the Qo site†

PubMed Central

Havens, Jeffrey; Castellani, Michela; Kleinschroth, Thomas; Ludwig, Bernd; Durham, Bill; Millett, Francis

2011-01-01

Domain rotation of the Rieske iron-sulfur protein (ISP) between the cytochrome (cyt) b and cyt c1 redox centers plays a key role in the mechanism of the cyt bc1 complex. Electron transfer within the cyt bc1 complex of P. denitrificans was studied using a ruthenium dimer to rapidly photo-oxidize cyt c1 within 1 μs and initiate the reaction. In the absence of any added quinol or inhibitor of the bc1 complex at pH 8.0, electron transfer from reduced ISP to cyt c1 was biphasic with rate constants of k1f = 6300 ± 3000 s−1 and k1s = 640 ± 300 s−1 and amplitudes of 10 ± 3% and 16 ± 4 % of the total amount of cyt c1 photooxidized. Upon addition of any of the Pm type inhibitors MOA-stilbene, myxothiazol, or azoxystrobin to cyt bc1 in the absence of quinol, the total amplitude increased 2-fold, consistent with a decrease in redox potential of the ISP. In addition, the relative amplitude of the fast phase increased significantly, consistent with a change in the dynamics of the ISP domain rotation. In contrast, addition of the Pf type inhibitors JG-144 and famoxadone decreased the rate constant k1f by 5 to 10-fold, and increased the amplitude over 2-fold. Addition of quinol substrate in the absence of inhibitors led to a two-fold increase in the amplitude of the k1f phase. The effect of QH2 on the kinetics of electron transfer from reduced ISP to cyt c1 was thus similar to that of the Pm inhibitors and very different from that of the Pf inhibitors. The current results indicate that the species occupying the Qo site has a significant conformational influence on the dynamics of the ISP domain rotation. PMID:22026826

EGaIn-Assisted Room-Temperature Sintering of Silver Nanoparticles for Stretchable, Inkjet-Printed, Thin-Film Electronics.

PubMed

Tavakoli, Mahmoud; Malakooti, Mohammad H; Paisana, Hugo; Ohm, Yunsik; Marques, Daniel Green; Alhais Lopes, Pedro; Piedade, Ana P; de Almeida, Anibal T; Majidi, Carmel

2018-05-29

Coating inkjet-printed traces of silver nanoparticle (AgNP) ink with a thin layer of eutectic gallium indium (EGaIn) increases the electrical conductivity by six-orders of magnitude and significantly improves tolerance to tensile strain. This enhancement is achieved through a room-temperature "sintering" process in which the liquid-phase EGaIn alloy binds the AgNP particles (≈100 nm diameter) to form a continuous conductive trace. Ultrathin and hydrographically transferrable electronics are produced by printing traces with a composition of AgNP-Ga-In on a 5 µm-thick temporary tattoo paper. The printed circuit is flexible enough to remain functional when deformed and can support strains above 80% with modest electromechanical coupling (gauge factor ≈1). These mechanically robust thin-film circuits are well suited for transfer to highly curved and nondevelopable 3D surfaces as well as skin and other soft deformable substrates. In contrast to other stretchable tattoo-like electronics, the low-cost processing steps introduced here eliminate the need for cleanroom fabrication and instead requires only a commercial desktop printer. Most significantly, it enables functionalities like "electronic tattoos" and 3D hydrographic transfer that have not been previously reported with EGaIn or EGaIn-based biphasic electronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dioxygen in Polyoxometalate Mediated Reactions.

PubMed

Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny

2018-03-14

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.

Picture of the Week: Hacking the bio-nano interface for better biofuels

Science.gov Websites

) influence electron transfer between the enzyme and the electrode to determine the best placement of enzymes compounds) influence electron transfer between the enzyme and the electrode to determine the best placement studied how three quinones (a class of organic compounds) influence electron transfer between the enzyme

Effects of p-(Trifluoromethoxy)benzyl and p-(Trifluoromethoxy)phenyl Molecular Architecture on the Performance of Naphthalene Tetracarboxylic Diimide-Based Air-Stable n-Type Semiconductors.

PubMed

Zhang, Dongwei; Zhao, Liang; Zhu, Yanan; Li, Aiyuan; He, Chao; Yu, Hongtao; He, Yaowu; Yan, Chaoyi; Goto, Osamu; Meng, Hong

2016-07-20

N,N'-Bis(4-trifluoromethoxyphenyl) naphthalene-1,4,5,8-tetracarboxylic acid diimide (NDI-POCF3) and N,N'-bis(4-trifluoromethoxybenzyl) naphthalene-1,4,5,8-tetracarboxylic acid diimide (NDI-BOCF3) have similar optical and electrochemical properties with a deep LUMO level of approximately 4.2 eV, but exhibit significant differences in electron mobility and molecular packing. NDI-POCF3 exhibits nondetectable charge mobility. Interestingly, NDI-BOCF3 shows air-stable electron transfer performance with enhanced mobility by increasing the deposition temperature onto the octadecyltrichlorosilane (OTS)-modified SiO2/Si substrates and achieves electron mobility as high as 0.7 cm(2) V(-1) s(-1) in air. The different mobilities of those two materials can be explained by several factors including thin-film morphology and crystallinity. In contrast to the poor thin-film morphology and crystallinity of NDI-POCF3, NDI-BOCF3 exhibits larger grain sizes and improved crystallinities due to the higher deposition temperature. In addition, the theoretical calculated transfer integrals of the intermolecular lowest unoccupied molecular orbital (LUMO) of the two materials further show that a large intermolecular orbital overlap of NDI-BOCF3 can transfer electron more efficiently than NDI-POCF3 in thin-film transistors. On the basis of fact that the theoretical calculations are consistent with the experimental results, it can be concluded that the p-(trifluoromethoxy) benzyl (BOCF3) molecular architecture on the former position of the naphthalene tetracarboxylic diimides (NDI) core provides a more effective way to enhance the intermolecular electron transfer property than the p-(trifluoromethoxy) phenyl (POCF3) group for the future design of NDI-related air-stable n-channel semiconductor.

Electronic structure evolution and energy level alignment at C60/4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine]/MoOx/indium tin oxide interfaces

NASA Astrophysics Data System (ADS)

Liu, Xiaoliang; Yi, Shijuan; Wang, Chenggong; Wang, Congcong; Gao, Yongli

2014-04-01

The electronic structure evolution and energy level alignment have been investigated at interfaces comprising fullerene (C60)/4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine] (TAPC)/ molybdenum oxide (MoOx)/ indium tin oxide with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. With deposition of TAPC upon MoOx, a dipole of 1.58 eV was formed at the TAPC/MoOx interface due to electron transfer from TAPC to MoOx. The highest occupied molecular orbital (HOMO) onset of TAPC was pinned closed to the Fermi level, leading to a p-doped region and thus increasing the carrier concentration at the very interface. The downward band bending and the resulting built-in field in TAPC were favorable for the hole transfer toward the TAPC/MoOx interface. The rigid downward shift of energy levels of TAPC indicated no significant interface chemistry at the interface. With subsequent deposition of C60 on TAPC, a dipole of 0.27 eV was observed at the C60/TAPC heterojunction due to the electron transfer from TAPC to C60. This led to a drop of the HOMO of TAPC near the C60/TAPC interface, and hence further enhanced the band bending in TAPC. The band bending behavior was also observed in C60, similarly creating a built-in field in C60 film and improving the electron transfer away from the C60/TAPC interface. It can be deduced from the interface analysis that a promising maximum open circuit voltage of 1.5 eV is achievable in C60/TAPC-based organic photovoltaic cells.

Hybrid super electron donors - preparation and reactivity.

PubMed

Garnier, Jean; Thomson, Douglas W; Zhou, Shengze; Jolly, Phillip I; Berlouis, Leonard E A; Murphy, John A

2012-01-01

Neutral organic electron donors, featuring pyridinylidene-imidazolylidene, pyridinylidene-benzimidazolylidene and imidazolylidene-benzimidazolylidene linkages are reported. The pyridinylidene-benzimidazolylidene and imidazolylidene-benzimidazolylidene hybrid systems were designed to be the first super electron donors to convert iodoarenes to aryl radicals at room temperature, and indeed both show evidence for significant aryl radical formation at room temperature. The stronger pyridinylidene-imidazolylidene donor converts iodoarenes to aryl anions efficiently under appropriate conditions (3 equiv of donor). The presence of excess sodium hydride base has a very important and selective effect on some of these electron-transfer reactions, and a rationale for this is proposed.

Atomic bonding effects in annular dark field scanning transmission electron microscopy. I. Computational predictions

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

Odlyzko, Michael L.; Mkhoyan, K. Andre, E-mail: mkhoyan@umn.edu; Himmetoglu, Burak

2016-07-15

Annular dark field scanning transmission electron microscopy (ADF-STEM) image simulations were performed for zone-axis-oriented light-element single crystals, using a multislice method adapted to include charge redistribution due to chemical bonding. Examination of these image simulations alongside calculations of the propagation of the focused electron probe reveal that the evolution of the probe intensity with thickness exhibits significant sensitivity to interatomic charge transfer, accounting for observed thickness-dependent bonding sensitivity of contrast in all ADF-STEM imaging conditions. Because changes in image contrast relative to conventional neutral atom simulations scale directly with the net interatomic charge transfer, the strongest effects are seen inmore » crystals with highly polar bonding, while no effects are seen for nonpolar bonding. Although the bonding dependence of ADF-STEM image contrast varies with detector geometry, imaging parameters, and material temperature, these simulations predict the bonding effects to be experimentally measureable.« less

Ultrafast electron transfer at organic semiconductor interfaces: Importance of molecular orientation

DOE PAGES

Ayzner, Alexander L.; Nordlund, Dennis; Kim, Do -Hwan; ...

2014-12-04

Much is known about the rate of photoexcited charge generation in at organic donor/acceptor (D/A) heterojunctions overaged over all relative arrangements. However, there has been very little experimental work investigating how the photoexcited electron transfer (ET) rate depends on the precise relative molecular orientation between D and A in thin solid films. This is the question that we address in this work. We find that the ET rate depends strongly on the relative molecular arrangement: The interface where the model donor compound copper phthalocyanine is oriented face-on with respect to the fullerene C 60 acceptor yields a rate that ismore » approximately 4 times faster than that of the edge-on oriented interface. Our results suggest that the D/A electronic coupling is significantly enhanced in the face-on case, which agrees well with theoretical predictions, underscoring the importance of controlling the relative interfacial molecular orientation.« less

Photosynthesis.

PubMed

Johnson, Matthew P

2016-10-31

Photosynthesis sustains virtually all life on planet Earth providing the oxygen we breathe and the food we eat; it forms the basis of global food chains and meets the majority of humankind's current energy needs through fossilized photosynthetic fuels. The process of photosynthesis in plants is based on two reactions that are carried out by separate parts of the chloroplast. The light reactions occur in the chloroplast thylakoid membrane and involve the splitting of water into oxygen, protons and electrons. The protons and electrons are then transferred through the thylakoid membrane to create the energy storage molecules adenosine triphosphate (ATP) and nicotinomide-adenine dinucleotide phosphate (NADPH). The ATP and NADPH are then utilized by the enzymes of the Calvin-Benson cycle (the dark reactions), which converts CO 2 into carbohydrate in the chloroplast stroma. The basic principles of solar energy capture, energy, electron and proton transfer and the biochemical basis of carbon fixation are explained and their significance is discussed. © 2016 The Author(s).

Reflective Coating on Fibrous Insulation for Reduced Heat Transfer

NASA Technical Reports Server (NTRS)

Hass, Derek D.; Prasad, B. Durga; Glass, David E.; Wiedemann, Karl E.

1997-01-01

Radiative heat transfer through fibrous insulation used in thermal protection systems (TPS) is significant at high temperatures (1200 C). Decreasing the radiative heat transfer through the fibrous insulation can thus have a major impact on the insulating ability of the TPS. Reflective coatings applied directly to the individual fibers in fibrous insulation should decrease the radiative heat transfer leading to an insulation with decreased effective thermal conductivity. Coatings with high infrared reflectance have been developed using sol-gel techniques. Using this technique, uniform coatings can be applied to fibrous insulation without an appreciable increase in insulation weight or density. Scanning electron microscopy, Fourier Transform infrared spectroscopy, and ellipsometry have been performed to evaluate coating performance.

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.

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.

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

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.

Role of direct electron-phonon coupling across metal-semiconductor interfaces in thermal transport via molecular dynamics.

PubMed

Lin, Keng-Hua; Strachan, Alejandro

2015-07-21

Motivated by significant interest in metal-semiconductor and metal-insulator interfaces and superlattices for energy conversion applications, we developed a molecular dynamics-based model that captures the thermal transport role of conduction electrons in metals and heat transport across these types of interface. Key features of our model, denoted eleDID (electronic version of dynamics with implicit degrees of freedom), are the natural description of interfaces and free surfaces and the ability to control the spatial extent of electron-phonon (e-ph) coupling. Non-local e-ph coupling enables the energy of conduction electrons to be transferred directly to the semiconductor/insulator phonons (as opposed to having to first couple to the phonons in the metal). We characterize the effect of the spatial e-ph coupling range on interface resistance by simulating heat transport through a metal-semiconductor interface to mimic the conditions of ultrafast laser heating experiments. Direct energy transfer from the conduction electrons to the semiconductor phonons not only decreases interfacial resistance but also increases the ballistic transport behavior in the semiconductor layer. These results provide new insight for experiments designed to characterize e-ph coupling and thermal transport at the metal-semiconductor/insulator interfaces.

Electrochemically enhanced microbial CO conversion to volatile fatty acids using neutral red as an electron mediator.

PubMed

Im, Chae Ho; Kim, Changman; Song, Young Eun; Oh, Sang-Eun; Jeon, Byong-Hun; Kim, Jung Rae

2018-01-01

Conversion of C1 gas feedstock, including carbon monoxide (CO), into useful platform chemicals has attracted considerable interest in industrial biotechnology. Nevertheless, the low conversion yield and/or growth rate of CO-utilizing microbes make it difficult to develop a C1 gas biorefinery process. The Wood-Ljungdahl pathway which utilize CO is a pathway suffered from insufficient electron supply, in which the conversion can be increased further when an additional electron source like carbohydrate or hydrogen is provided. In this study, electrode-based electron transference using a bioelectrochemical system (BES) was examined to compensate for the insufficient reducing equivalent and increase the production of volatile fatty acids. The BES including neutral red (BES-NR), which facilitated electron transfer between bacteria and electrode, was compared with BES without neutral red and open circuit control. The coulombic efficiency based on the current input to the system and the electrons recovered into VFAs, was significantly higher in BES-NR than the control. These results suggest that the carbon electrode provides a platform to regulate the redox balance for improving the bioconversion of CO, and amending the conventional C1 gas fermentation. Copyright © 2017 Elsevier Ltd. All rights reserved.

CRADA Payment Options | NCI Technology Transfer Center | TTC

Cancer.gov

NCI TTC CRADA PAYMENT OPTIONS: Electronic Payments by Wire Transfer via Fedwire, Mail a check to the Institute or Center, or Automated Clearing House (ACH)/Electronic Funds Transfer (ETF) payments via Pay.gov (NCI ONLY).

Transfer coefficients in ultracold strongly coupled plasma

NASA Astrophysics Data System (ADS)

Bobrov, A. A.; Vorob'ev, V. S.; Zelener, B. V.

2018-03-01

We use both analytical and molecular dynamic methods for electron transfer coefficients in an ultracold plasma when its temperature is small and the coupling parameter characterizing the interaction of electrons and ions exceeds unity. For these conditions, we use the approach of nearest neighbor to determine the average electron (ion) diffusion coefficient and to calculate other electron transfer coefficients (viscosity and electrical and thermal conductivities). Molecular dynamics simulations produce electronic and ionic diffusion coefficients, confirming the reliability of these results. The results compare favorably with experimental and numerical data from earlier studies.

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 single connectivity, the rate constant for electron transfer from a valence-localized (class-II) donor can readily be tuned over several orders of magnitude by introducing differences in the electronic potentials at the two metal sites of the donor. These results indicate that theories of cluster-based electron transfer, in order to be realistic, need to consider both intrinsic electronic structure and extrinsic interactions of the cluster with the protein environment.

Proton transfer in microbial electrolysis cells

DOE PAGES

Borole, Abhijeet P.; Lewis, Alex J.

2017-02-15

Proton transfer and electron transfer are of prime importance in the development of microbial electrochemical cells. While electron transfer is primarily controlled by biology, proton transfer is controlled by process engineering and cell design. To develop commercially feasible technologies around the concept of a bioelectrochemical cell, real feedstocks have to be explored and associated limitations have to be identified. Here in this study, the proton transfer rate was quantified for a microbial electrolysis cell (MEC) and its dependence on process parameters was investigated using a proton balance model. The reaction system consisted of a biomass-derived pyrolytic aqueous stream as amore » substrate producing hydrogen in a flow-through MEC. The proton transfer rate increased with anode flow rate and organic loading rate up to a maximum of 0.36 ± 0.01 moles per m 2 per h, equivalent to a hydrogen production rate of 9.08 L per L per day. Higher rates of hydrogen production, reaching 11.7 ± 0.2 L per L per day were achieved, when additional protons were provided via the cathode buffer. Electrochemical impedance spectroscopy shows that proton transfer was the dominant resistance in the production of hydrogen. The quantification of proton transfer rates for MECs with potential for biorefinery application and the demonstration of high hydrogen production rates approaching those required for commercial consideration indicate the strong potential of this technology for renewable hydrogen production. Understanding the transport phenomenon in bioelectrochemical cells is of great significance since these systems have potential for wide-ranging applications including energy production, bioremediation, chemical and nanomaterial synthesis, electro-fermentation, energy storage, desalination, and produced water treatment. Electron transfer in anode biofilms has been investigated extensively, but proton transfer studies are also important, since many cathodic half reactions require protons as the reactant. Determination of transport rates via proton balance was investigated in microbial electrolysis cells, which can be applied to other forms of microbial electrochemical systems. Lastly, these systems have a unique niche in the development of future biorefineries as a means of recovering energy from waste streams with potential for water recycle, making them an integral part of the water–energy nexus focus area.« less

Proton transfer in microbial electrolysis cells

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

Borole, Abhijeet P.; Lewis, Alex J.

Proton transfer and electron transfer are of prime importance in the development of microbial electrochemical cells. While electron transfer is primarily controlled by biology, proton transfer is controlled by process engineering and cell design. To develop commercially feasible technologies around the concept of a bioelectrochemical cell, real feedstocks have to be explored and associated limitations have to be identified. Here in this study, the proton transfer rate was quantified for a microbial electrolysis cell (MEC) and its dependence on process parameters was investigated using a proton balance model. The reaction system consisted of a biomass-derived pyrolytic aqueous stream as amore » substrate producing hydrogen in a flow-through MEC. The proton transfer rate increased with anode flow rate and organic loading rate up to a maximum of 0.36 ± 0.01 moles per m 2 per h, equivalent to a hydrogen production rate of 9.08 L per L per day. Higher rates of hydrogen production, reaching 11.7 ± 0.2 L per L per day were achieved, when additional protons were provided via the cathode buffer. Electrochemical impedance spectroscopy shows that proton transfer was the dominant resistance in the production of hydrogen. The quantification of proton transfer rates for MECs with potential for biorefinery application and the demonstration of high hydrogen production rates approaching those required for commercial consideration indicate the strong potential of this technology for renewable hydrogen production. Understanding the transport phenomenon in bioelectrochemical cells is of great significance since these systems have potential for wide-ranging applications including energy production, bioremediation, chemical and nanomaterial synthesis, electro-fermentation, energy storage, desalination, and produced water treatment. Electron transfer in anode biofilms has been investigated extensively, but proton transfer studies are also important, since many cathodic half reactions require protons as the reactant. Determination of transport rates via proton balance was investigated in microbial electrolysis cells, which can be applied to other forms of microbial electrochemical systems. Lastly, these systems have a unique niche in the development of future biorefineries as a means of recovering energy from waste streams with potential for water recycle, making them an integral part of the water–energy nexus focus area.« less

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

Sulfate-reducing bacteria: Microbiology and physiology

NASA Technical Reports Server (NTRS)

Peck, H. D.

1985-01-01

The sulfate reducing bacteria, the first nonphotosynthetic anaerobic bacteria demonstrated to contain c type cytochromes, perform electron transfer coupled to phosphorylation. A new bioenergetic scheme for the formation of a proton gradient for growth of Desulfovibrio on organic substrates and sulfate involving vectors electron transfer and consistent with the cellular localization of enzymes and electron transfer components was proposed. Hydrogen is produced in the cytoplasm from organic substrates and, as a permease molecule diffuses rapidly across the cytoplasmic membrane, it is oxidized to protons and electrons by the periplasmic hydrogenase. The electrons only are transferred across the cytoplasmic membrane to the cytoplasm where they are used to reduce sulfate to sulfide. The protons are used for transport or to drive a reversible ATPOSE. The net effect is the transfer of protons across the cytoplasmic membrane with the intervention of a proton pump. This type of H2 cycling is relevant to the bioenergetics of other types of anaerobic microorganisms.

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

Electron energy distribution function, effective electron temperature, and dust charge in the temporal afterglow of a plasma

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

Denysenko, I. B.; Azarenkov, N. A.; Kersten, H.

2016-05-15

Analytical expressions describing the variation of electron energy distribution function (EEDF) in an afterglow of a plasma are obtained. Especially, the case when the electron energy loss is mainly due to momentum-transfer electron-neutral collisions is considered. The study is carried out for different EEDFs in the steady state, including Maxwellian and Druyvesteyn distributions. The analytical results are not only obtained for the case when the rate for momentum-transfer electron-neutral collisions is independent on electron energy but also for the case when the collisions are a power function of electron energy. Using analytical expressions for the EEDF, the effective electron temperaturemore » and charge of the dust particles, which are assumed to be present in plasma, are calculated for different afterglow durations. An analytical expression for the rate describing collection of electrons by dust particles for the case when the rate for momentum-transfer electron-neutral collisions is independent on electron energy is also derived. The EEDF profile and, as a result, the effective electron temperature and dust charge are sufficiently different in the cases when the rate for momentum-transfer electron-neutral collisions is independent on electron energy and when the rate is a power function of electron energy.« less

Molecular dynamics simulations give insight into the conformational change, complex formation, and electron transfer pathway for cytochrome P450 reductase

PubMed Central

Sündermann, Axel; Oostenbrink, Chris

2013-01-01

Cytochrome P450 reductase (CYPOR) undergoes a large conformational change to allow for an electron transfer to a redox partner to take place. After an internal electron transfer over its cofactors, it opens up to facilitate the interaction and electron transfer with a cytochrome P450. The open conformation appears difficult to crystallize. Therefore, a model of a human CYPOR in the open conformation was constructed to be able to investigate the stability and conformational change of this protein by means of molecular dynamics simulations. Since the role of the protein is to provide electrons to a redox partner, the interactions with cytochrome P450 2D6 (2D6) were investigated and a possible complex structure is suggested. Additionally, electron pathway calculations with a newly written program were performed to investigate which amino acids relay the electrons from the FMN cofactor of CYPOR to the HEME of 2D6. Several possible interacting amino acids in the complex, as well as a possible electron transfer pathway were identified and open the way for further investigation by site directed mutagenesis studies. PMID:23832577

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

Ultrafast Electron Transfer across a Nanocapsular Wall: Coumarins as Donors, Viologen as Acceptor, and Octa Acid Capsule as the Mediator.

PubMed

Chuang, Chi-Hung; Porel, Mintu; Choudhury, Rajib; Burda, Clemens; Ramamurthy, V

2018-01-11

Results of our study on ultrafast electron transfer (eT) dynamics from coumarins (coumarin-1, coumarin-480, and coumarin-153) incarcerated within octa acid (OA) capsules as electron donors to methyl viologen dissolved in water as acceptor are presented. Upon photoexcitation, coumarin inside the OA capsule transfers an electron to the acceptor electrostatically attached to the capsule leading to a long-lived radical-ion pair separated by the OA capsular wall. This charge-separated state returns to the neutral ground state via back electron transfer on the nanosecond time scale. This system allows for ultrafast electron transfer processes through a molecular wall from the apolar capsular interior to the highly polar (aqueous) environment on the femtosecond time scale. Employing femtosecond transient absorption spectroscopy, distinct rates of both forward (1-25 ps) and backward eT (700-1200 ps) processes were measured. Further understanding of the energetics is provided using Rehm-Weller analysis for the investigated photoinduced eT reactions. The results provide the rates of the eT across a molecular wall, akin to an isotropic solution, depending on the standard free energy of the reaction. The insights from this work could be utilized in the future design of efficient electron transfer processes across interfaces separating apolar and polar environments.

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.

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)

Ru–protein–Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function† †Electronic supplementary information (ESI) available: Time traces of photocatalysis, additional EPR spectra and parameters, UV-visible spectroscopy data, and kinetic fits of TA traces. See DOI: 10.1039/c6sc03121h Click here for additional data file.

PubMed Central

Soltau, Sarah R.; Dahlberg, Peter D.; Niklas, Jens; Poluektov, Oleg G.; Mulfort, Karen L.

2016-01-01

A series of Ru–protein–Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru–Fd–Co biohybrid produces up to 650 turnovers of H2 utilizing an oxidative quenching mechanism for Ru(ii)* and a sequential electron transfer pathway via the native [2Fe–2S] cluster to generate a Ru(iii)–Fd–Co(i) charge separated state that lasts for ∼6 ms. In contrast, a direct electron transfer pathway occurs for the Ru–ApoFld–Co biohybrid, which lacks an internal electron relay, generating Ru(i)–ApoFld–Co(i) charge separated state that persists for ∼800 μs and produces 85 turnovers of H2 by a reductive quenching mechanism for Ru(ii)*. This work demonstrates the utility of protein architectures for linking donor and catalytic function via direct or sequential electron transfer pathways to enable stabilized charge separation which facilitates photocatalysis for solar fuel production. PMID:28451142

Photogeneration of Charge Carriers in Bilayer Assemblies of Conjugated Rigid-Rod Polymers

DTIC Science & Technology

1994-07-08

photoinduced electron transfer and exciplex formation at the bilayer interface. Thus photocarrier generation on photoexcitation of the conjugated rigid...rod polymers in the bilayer occurs by photoinduced electron transfer, forming intermolecular exciplexes which dissociate efficiently in electric field...photogeneration, conjugated rigid-rod polymers, is. MACI COD bilayer assemblies, electron transfer, exciplexes . 11. SEOJUTY CLASUICA 10. 51(11MIE CLASSIMIAVION

Telematics and satellites. Part 1: Information systems

NASA Astrophysics Data System (ADS)

Burke, W. R.

1980-06-01

Telematic systems are identified and described. The applications are examined emphasizing the role played by satellite links. The discussion includes file transfer, examples of distributed processor systems, terminal communication, information retrieval systems, office information systems, electronic preparation and publishing of information, electronic systems for transfer of funds, electronic mail systems, record file transfer characteristics, intra-enterprise networks, and inter-enterprise networks.

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

PubMed Central

Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM

2008-01-01

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in size associated with a decrease in density with further annealing. PMID:18534025

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics.

PubMed

Ramana, C V; Becker, U; Shutthanandan, V; Julien, C M

2008-06-05

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA).Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400 degrees C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in size associated with a decrease in density with further annealing.

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.

Microbial Biofilm Voltammetry: Direct Electrochemical Characterization of Catalytic Electrode-Attached Biofilms▿ †

PubMed Central

Marsili, Enrico; Rollefson, Janet B.; Baron, Daniel B.; Hozalski, Raymond M.; Bond, Daniel R.

2008-01-01

While electrochemical characterization of enzymes immobilized on electrodes has become common, there is still a need for reliable quantitative methods for study of electron transfer between living cells and conductive surfaces. This work describes growth of thin (<20 μm) Geobacter sulfurreducens biofilms on polished glassy carbon electrodes, using stirred three-electrode anaerobic bioreactors controlled by potentiostats and nondestructive voltammetry techniques for characterization of viable biofilms. Routine in vivo analysis of electron transfer between bacterial cells and electrodes was performed, providing insight into the main redox-active species participating in electron transfer to electrodes. At low scan rates, cyclic voltammetry revealed catalytic electron transfer between cells and the electrode, similar to what has been observed for pure enzymes attached to electrodes under continuous turnover conditions. Differential pulse voltammetry and electrochemical impedance spectroscopy also revealed features that were consistent with electron transfer being mediated by an adsorbed catalyst. Multiple redox-active species were detected, revealing complexity at the outer surfaces of this bacterium. These techniques provide the basis for cataloging quantifiable, defined electron transfer phenotypes as a function of potential, electrode material, growth phase, and culture conditions and provide a framework for comparisons with other species or communities. PMID:18849456

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

NASA Space Engineering Research Center for VLSI System Design

NASA Technical Reports Server (NTRS)

1993-01-01

This annual report outlines the activities of the past year at the NASA SERC on VLSI Design. Highlights for this year include the following: a significant breakthrough was achieved in utilizing commercial IC foundries for producing flight electronics; the first two flight qualified chips were designed, fabricated, and tested and are now being delivered into NASA flight systems; and a new technology transfer mechanism has been established to transfer VLSI advances into NASA and commercial systems.

Scalable High-Performance Ultraminiature Graphene Micro-Supercapacitors by a Hybrid Technique Combining Direct Writing and Controllable Microdroplet Transfer.

PubMed

Shen, Daozhi; Zou, Guisheng; Liu, Lei; Zhao, Wenzheng; Wu, Aiping; Duley, Walter W; Zhou, Y Norman

2018-02-14

Miniaturization of energy storage devices can significantly decrease the overall size of electronic systems. However, this miniaturization is limited by the reduction of electrode dimensions and the reproducible transfer of small electrolyte drops. This paper reports first a simple scalable direct writing method for the production of ultraminiature microsupercapacitor (MSC) electrodes, based on femtosecond laser reduced graphene oxide (fsrGO) interlaced pads. These pads, separated by 2 μm spacing, are 100 μm long and 8 μm wide. A second stage involves the accurate transfer of an electrolyte microdroplet on top of each individual electrode, which can avoid any interference of the electrolyte with other electronic components. Abundant in-plane mesopores in fsrGO induced by a fs laser together with ultrashort interelectrode spacing enables MSCs to exhibit a high specific capacitance (6.3 mF cm -2 and 105 F cm -3 ) and ∼100% retention after 1000 cycles. An all graphene resistor-capacitor (RC) filter is also constructed by combining the MSC and a fsrGO resistor, which is confirmed to exhibit highly enhanced performance characteristics. This new hybrid technique combining fs laser direct writing and precise microdroplet transfer easily enables scalable production of ultraminiature MSCs, which is believed to be significant for practical application of micro-supercapacitor microelectronic systems.

Dexter energy transfer pathways

PubMed Central

Skourtis, Spiros S.; Liu, Chaoren; Antoniou, Panayiotis; Virshup, Aaron M.; Beratan, David N.

2016-01-01

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor–acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways. PMID:27382185

Dexter energy transfer pathways.

PubMed

Skourtis, Spiros S; Liu, Chaoren; Antoniou, Panayiotis; Virshup, Aaron M; Beratan, David N

2016-07-19

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor-acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways.

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.

Ultrafast electron and hole transfer dynamics of a solar cell dye containing hole acceptors on mesoporous TiO2 and Al2O3.

PubMed

Scholz, Mirko; Flender, Oliver; Boschloo, Gerrit; Oum, Kawon; Lenzer, Thomas

2017-03-08

The stability of dye cations against recombination with conduction band electrons in mesoporous TiO 2 electrodes is a key property for improving light harvesting in dye-sensitised solar cells. Using ultrafast transient broadband absorption spectroscopy, we monitor efficient intramolecular hole transfer in the solar cell dye E6 having two peripheral triarylamine acceptors. After photoexcitation, two hole transfer mechanisms are identified: a concerted mechanism for electron injection and hole transfer (2.4 ps) and a sequential mechanism with time constants of 3.9 ps and 30 ps. This way the dye retards unwanted recombination with a TiO 2 conduction band electron by quickly moving the hole further away from the surface. Contact of the E6/TiO 2 surface with the solvent acetonitrile has almost no influence on the electron injection and hole transfer kinetics. Fast hole transfer (2.8 ps) is also observed on a "non-injecting" Al 2 O 3 surface generating a radical cation-radical anion species with a lifetime of 530 ps. The findings confirm the good intramolecular hole transfer properties of this dye on both thin films. In contrast, intramolecular hole transfer does not occur in the mid-polar organic solvent methyl acetate. This is confirmed by TDDFT calculations suggesting a polarity-induced reduction of the driving force for hole transfer. In methyl acetate, only the relaxation of the initially photoexcited core chromophore is observed including solvent relaxation processes of the electronically excited state S 1 /ICT.

Electronic Data Interchange: Using Technology to Exchange Transcripts.

ERIC Educational Resources Information Center

Stewart, John T.

1994-01-01

Describes the Florida Automated System for Transferring Educational Records (FASTER) project, which permits the electronic exchange of student transcripts; uses of similar electronic data interchange (EDI) programs in other states; and the national SPEEDE/ExPRESS project, which uses a standard format for transferring electronic transcripts.…

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.

Electronic structural dependence of the photophysical properties of fluorescent heteroditopic ligands - implications in designing molecular fluorescent indicators.

PubMed

Younes, Ali H; Zhang, Lu; Clark, Ronald J; Davidson, Michael W; Zhu, Lei

2010-12-07

Two fluorescent heteroditopic ligands (2a and 2b) for zinc ion were synthesized and studied. The efficiencies of two photophysical processes, intramolecular charge transfer (ICT) and photoinduced electron transfer (PET), determine the magnitudes of emission bathochromic shift and enhancement, respectively, when a heteroditopic ligand forms mono- or dizinc complexes. The electron-rich 2b is characterized by a high degree of ICT in the excited state with little propensity for PET, which is manifested in a large bathochromic shift of emission upon Zn(2+) coordination without enhancement in fluorescence quantum yield. The electron-poor 2a displays the opposite photophysical consequence where Zn(2+) binding results in greatly enhanced emission without significant spectral shift. The electronic structural effects on the relative efficiencies of ICT and PET in 2a and 2b as well as the impact of Zn(2+)-coordination are probed using experimental and computational approaches. This study reveals that the delicate balance between various photophysical pathways (e.g. ICT and PET) engineered in a heteroditopic ligand is sensitively dependent on the electronic structure of the ligand, i.e. whether the fluorophore is electron-rich or poor, whether it possesses a donor-acceptor type of structure, and where the metal binding occurs.

Relaxation Process of Photoexcited meso-Naphthylporphyrins while Interacting with DNA and Singlet Oxygen Generation.

PubMed

Hirakawa, Kazutaka; Taguchi, Makoto; Okazaki, Shigetoshi

2015-10-15

Electron donor-connecting cationic porphyrins meso-(1-naphthyl)-tris(N-methyl-p-pyridinio)porphyrin (1-NapTMPyP) and meso-(2-naphthyl)-tris(N-methyl-p-pyridinio)porphyrin (2-NapTMPyP) were designed and synthesized. DFT calculations speculate that the photoexcited states of 1- and 2-NapTMPyPs can be deactivated via intramolecular electron transfer from the naphthyl moiety to the porphyrin moiety. However, the quenching effect through the intramolecular electron transfer is insufficient, possibly due to the orthogonal position of the electron donor and the porphyrin ring and the relatively small driving force: Gibbs energies are 0.11 and 0.07 eV for 1- and 2-NapTMPyPs, respectively. It was speculated that more than 0.3 eV of the driving force is required to realize effective electron transfer in similar electron-donor connecting porphyrin systems. These porphyrins aggregated around the DNA strand, accelerating the deactivation of their excited singlet state and decreasing their photosensitized singlet oxygen-generating activities. In the presence of a sufficiently large concentration of DNA, these porphyrins can bind to a DNA strand stably, leading to an increased fluorescence quantum yield and lifetime. Singlet oxygen generation was also suppressed by the aggregation of porphyrins around DNA. Although the quantum yield of singlet oxygen generation was recovered in the presence of sufficient DNA, the singlet oxygen generated by DNA-binding porphyrins was significantly smaller than that without DNA. These results suggest that DNA-binding drugs limit the generation of photosensitized singlet oxygen by quenching the DNA strand.

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.

Large discrepancies observed in theoretical studies of ion-impact ionization of the atomic targets at large momentum transfer

NASA Astrophysics Data System (ADS)

Ghorbani, Omid; Ghanbari-Adivi, Ebrahim

2017-12-01

A full quantum mechanical version of the three-body distorted wave-eikonal initial state (3DW-EIS) theory is developed to study of the single ionization of the atomic targets by ion impact at different momentum transfers. The calculations are performed both with and without including the internuclear interaction in the transition amplitude. For 16 \\text{Mev} \\text{O}7+ \\text{-He}~(1s2 ) and 24 \\text{Mev} \\text{O}8+\\text{-Li}~(2s ) collisions, the emission of the active electron into the scattering plane is considered and the fully differential cross-sections (FDCSs) are calculated for a fixed value of the ejected electron energy and a variety of momentum transfers. For both the specified collision systems, the obtained results are compared with the experimental data and with the cross-sections obtained using the semi-classical continuum distorted wave-eikonal initial state (CDW-EIS) approach. For 16 \\text{Mev} \\text{O}7+ \\text{-He}~(1s^2) , we also compared the results with those of a four-body three-Coulomb-wave (3CW) model. In general, we find some large discrepancies between the results obtained by different theories. These discrepancies are much more significant at larger momentum transfers. Also, for some ranges of the electron emission angles the results are much more sensitive to the internuclear interaction to be either turned on or off.

Electron transfer statistics and thermal fluctuations in molecular junctions

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

Goswami, Himangshu Prabal; Harbola, Upendra

2015-02-28

We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend tomore » suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects.« less

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

PubMed

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

Investigation of North Pond crustal fluids by poised potential methods

NASA Astrophysics Data System (ADS)

Jones, R. M.; Orcutt, B.

2017-12-01

Microbes are present in the deep subsurface but their rates of activity, potential metabolisms and roles in the environment are still largely unknown. The marine deep crustal subsurface accounts for approximately 2.3x1018 m2 of the earth's volume, making this environment potentially significant to earth processes despite low productivity inherent in resource limited conditions. This has implications for geochemical cycling and exploring limits of life, linking to the `follow the energy' approach for defining habitability on earth and further afield. Most resources for life in the marine deep crust originate from rock. One subset of lithotrophic interactions involves direct transfer between electron acceptors and donors embedded in minerals and microbes. In this investigation, poised potential methods such as chronoamperometry were used to investigate mineral-microbe electron transfer interactions in the context of North Pond, a Mid-Atlantic ridge site representative of cool, sediment-covered basalts that make up the majority of the deep marine subsurface. Electrodes were poised at potentials corresponding approximately to particular lithotrophic oxidation reactions to enrich for sub-sections of North Pond deep subsurface fluid communities that were associated with direct electron transfer at these potentials.

Solving Kinetic Equations for the Laser Flash Photolysis Experiment on Nitric Oxide Synthases: Effect of Conformational Dynamics on the Interdomain Electron Transfer.

PubMed

Astashkin, Andrei V; Feng, Changjian

2015-11-12

The production of nitric oxide by the nitric oxide synthase (NOS) enzyme depends on the interdomain electron transfer (IET) between the flavin mononucleotide (FMN) and heme domains. Although the rate of this IET has been measured by laser flash photolysis (LFP) for various NOS proteins, no rigorous analysis of the relevant kinetic equations was performed so far. In this work, we provide an analytical solution of the kinetic equations underlying the LFP approach. The derived expressions reveal that the bulk IET rate is significantly affected by the conformational dynamics that determines the formation and dissociation rates of the docking complex between the FMN and heme domains. We show that in order to informatively study the electron transfer across the NOS enzyme, LFP should be used in combination with other spectroscopic methods that could directly probe the docking equilibrium and the conformational change rate constants. The implications of the obtained analytical expressions for the interpretation of the LFP results from various native and modified NOS proteins are discussed. The mathematical formulas derived in this work should also be applicable for interpreting the IET kinetics in other modular redox enzymes.

Structural principles for computational and de novo design of 4Fe-4S metalloproteins

PubMed Central

Nanda, Vikas; Senn, Stefan; Pike, Douglas H.; Rodriguez-Granillo, Agustina; Hansen, Will; Khare, Sagar D.; Noy, Dror

2017-01-01

Iron-sulfur centers in metalloproteins can access multiple oxidation states over a broad range of potentials, allowing them to participate in a variety of electron transfer reactions and serving as catalysts for high-energy redox processes. The nitrogenase FeMoCO cluster converts di-nitrogen to ammonia in an eight-electron transfer step. The 2(Fe4S4) containing bacterial ferredoxin is an evolutionarily ancient metalloprotein fold and is thought to be a primordial progenitor of extant oxidoreductases. Controlling chemical transformations mediated by iron-sulfur centers such as nitrogen fixation, hydrogen production as well as electron transfer reactions involved in photosynthesis are of tremendous importance for sustainable chemistry and energy production initiatives. As such, there is significant interest in the design of iron-sulfur proteins as minimal models to gain fundamental understanding of complex natural systems and as lead-molecules for industrial and energy applications. Herein, we discuss salient structural characteristics of natural iron-sulfur proteins and how they guide principles for design. Model structures of past designs are analyzed in the context of these principles and potential directions for enhanced designs are presented, and new areas of iron-sulfur protein design are proposed. PMID:26449207

Potential for direct interspecies electron transfer in an electric-anaerobic system to increase methane production from sludge digestion.

PubMed

Zhao, Zhiqiang; Zhang, Yaobin; Wang, Liying; Quan, Xie

2015-06-09

Direct interspecies electron transfer (DIET) between Geobacter species and Methanosaeta species is an alternative to interspecies hydrogen transfer (IHT) in anaerobic digester, which however has not been established in anaerobic sludge digestion as well as in bioelectrochemical systems yet. In this study, it was found that over 50% of methane production of an electric-anaerobic sludge digester was resulted from unknown pathway. Pyrosequencing analysis revealed that Geobacter species were significantly enriched with electrodes. Fluorescence in situ hybridization (FISH) further confirmed that the dominant Geobacter species enriched belonged to Geobacter metallireducens. Together with Methanosaeta species prevailing in the microbial communities, the direct electron exchange between Geobacter species and Methanosaeta species might be an important reason for the "unknown" increase of methane production. Conductivity of the sludge in this electric-anaerobic digester was about 30% higher than that of the sludge in a control digester without electrodes. This study not only revealed for the first time that DIET might be the important mechanism on the methanogenesis of bioelectrochemical system, but also provided a new method to enhance DIET by means of bioelectric enrichment of Geobacter species.

Potential for direct interspecies electron transfer in an electric-anaerobic system to increase methane production from sludge digestion

PubMed Central

Zhao, Zhiqiang; Zhang, Yaobin; Wang, Liying; Quan, Xie

2015-01-01

Direct interspecies electron transfer (DIET) between Geobacter species and Methanosaeta species is an alternative to interspecies hydrogen transfer (IHT) in anaerobic digester, which however has not been established in anaerobic sludge digestion as well as in bioelectrochemical systems yet. In this study, it was found that over 50% of methane production of an electric-anaerobic sludge digester was resulted from unknown pathway. Pyrosequencing analysis revealed that Geobacter species were significantly enriched with electrodes. Fluorescence in situ hybridization (FISH) further confirmed that the dominant Geobacter species enriched belonged to Geobacter metallireducens. Together with Methanosaeta species prevailing in the microbial communities, the direct electron exchange between Geobacter species and Methanosaeta species might be an important reason for the “unknown” increase of methane production. Conductivity of the sludge in this electric-anaerobic digester was about 30% higher than that of the sludge in a control digester without electrodes. This study not only revealed for the first time that DIET might be the important mechanism on the methanogenesis of bioelectrochemical system, but also provided a new method to enhance DIET by means of bioelectric enrichment of Geobacter species. PMID:26057581

Ternary Pt/SnO(x)/TiO2 photocatalysts for hydrogen production: consequence of Pt sites for synergy of dual co-catalysts.

PubMed

Gu, Quan; Long, Jinlin; Zhuang, Huaqiang; Zhang, Chaoqiang; Zhou, Yangen; Wang, Xuxu

2014-06-28

A variety of ternary nanoheterostructures composed of Pt nanoparticles (NPs), SnOx species, and anatase TiO2 are designed elaborately to explore the effect of interfacial electron transfer on photocatalytic H2 evolution from a biofuel-water solution. Among numerous factors controlling the H2 evolution, the significance of Pt sites for the H2 evolution is highlighted by tuning the loading procedure of Pt NPs and SnOx species over TiO2. A synergistic enhancement of H2 evolution can be achieved over the Pt/SnOx/TiO2 heterostructures formed by anchoring Pt NPs at atomically-isolated Sn-oxo sites, whereas the Pt/TiO2/SnOx counterparts prepared by grafting single-site Sn-oxo species on Pt/TiO2 show a marked decrease in the rate of H2 evolution. The characterization results clearly reveal that the synergy of Pt NPs and SnOx species originates from the vectorial electron transfer of TiO2 → SnOx → Pt occurring on the former, while the latter results from the competitive electron transfer from TiO2 to SnOx and to Pt NPs.

Effect of introduction of a new electronic anesthesia record (Epic) system on the safety and efficiency of patient care in a gastrointestinal endoscopy suite-comparison with historical cohort.

PubMed

Goudra, B; Singh, P M; Borle, A; Gouda, G

2016-01-01

Use of electronic medical record systems has increased in the recent years. Epic is one such system gaining popularity in the USA. Epic is a private company, which invented the electronic documentation system adopted in our hospital. In spite of many presumed advantages, its use is not critically analyzed. Some of the perceived advantages are increased efficiency and protection against litigation as a result of accurate documentation. In this study, retrospective data of 305 patients who underwent endoscopic retrograde cholangiopancreatography (wherein electronic charting was used - "Epic group") were compared with 288 patients who underwent the same procedure with documentation saved on a paper chart ("paper group"). Time of various events involved in the procedure such as anesthesia start, endoscope insertion, endoscope removal, and transfer to the postanesthesia care unit were routinely documented. From this data, the various time durations were calculated. Both "anesthesia start to scope insertion" times and "scope removal to transfer" times were significantly less in the Epic group compared to the paper group. Use of Epic system led to a saving of 4 min of procedure time per patient. However, the mean oxygen saturation was significantly less in the Epic group. In spite of perceived advantages of Epic documentation system, significant hurdles remain with its use. Although the system allows seamless flow of patients, failure to remove all artifacts can lead to errors and become a source of potential litigation hazard.

Energetics of bacterial photosynthesis.

PubMed

Lebard, David N; Matyushov, Dmitry V

2009-09-10

We report the results of extensive numerical simulations and theoretical calculations of electronic transitions in the reaction center of Rhodobacter sphaeroides photosynthetic bacterium. The energetics and kinetics of five electronic transitions related to the kinetic scheme of primary charge separation have been analyzed and compared to experimental observations. Nonergodic formulation of the reaction kinetics is required for the calculation of the rates due to a severe breakdown of the system ergodicity on the time scale of primary charge separation, with the consequent inapplicability of the standard canonical prescription to calculate the activation barrier. Common to all reactions studied is a significant excess of the charge-transfer reorganization energy from the width of the energy gap fluctuations over that from the Stokes shift of the transition. This property of the hydrated proteins, breaking the linear response of the thermal bath, allows the reaction center to significantly reduce the reaction free energy of near-activationless electron hops and thus raise the overall energetic efficiency of the biological charge-transfer chain. The increase of the rate of primary charge separation with cooling is explained in terms of the temperature variation of induction solvation, which dominates the average donor-acceptor energy gap for all electronic transitions in the reaction center. It is also suggested that the experimentally observed break in the Arrhenius slope of the primary recombination rate, occurring near the temperature of the dynamical transition in proteins, can be traced back to a significant drop of the solvent reorganization energy close to that temperature.

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.

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

Bose, A; Gardel, EJ; Vidoudez, C

Oxidation-reduction reactions underlie energy generation in nearly all life forms. Although most organisms use soluble oxidants and reductants, some microbes can access solid-phase materials as electron-acceptors or -donors via extracellular electron transfer. Many studies have focused on the reduction of solid-phase oxidants. Far less is known about electron uptake via microbial extracellular electron transfer, and almost nothing is known about the associated mechanisms. Here we show that the iron-oxidizing photoautotroph Rhodopseudomonas palustris TIE-1 accepts electrons from a poised electrode, with carbon dioxide as the sole carbon source/electron acceptor. Both electron uptake and ruBisCo form I expression are stimulated by light.more » Electron uptake also occurs in the dark, uncoupled from photosynthesis. Notably, the pioABC operon, which encodes a protein system essential for photoautotrophic growth by ferrous iron oxidation, influences electron uptake. These data reveal a previously unknown metabolic versatility of photoferrotrophs to use extracellular electron transfer for electron uptake.« less

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...

12 CFR 1005.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2014 CFR

2014-01-01

... TRANSFERS (REGULATION E) General § 1005.9 Receipts at electronic terminals; periodic statements. (a... institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following information, as applicable...

12 CFR 1005.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2013 CFR

2013-01-01

... TRANSFERS (REGULATION E) General § 1005.9 Receipts at electronic terminals; periodic statements. (a... institution shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following information, as applicable...

12 CFR 1005.9 - Receipts at electronic terminals; periodic statements.

Code of Federal Regulations, 2012 CFR

2012-01-01

... TRANSFERS (REGULATION E) § 1005.9 Receipts at electronic terminals; periodic statements. (a) Receipts at... shall make a receipt available to a consumer at the time the consumer initiates an electronic fund transfer at an electronic terminal. The receipt shall set forth the following information, as applicable...

78 FR 48913 - Agency Information Collection Activities: Submission to OMB for Reinstatement, Without Change, of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-12

... electronic funds transfer information to maintain its vendor (credit union) records to make electronic... maintain current electronic funds transfer data for its vendor (credit union) electronic routing and... the information on the respondents such as through the use of automated collection techniques or other...

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

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

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.

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

NASA Technical Reports Server (NTRS)

Fischer, U.

1985-01-01

Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

Frenkel versus charge-transfer exciton dispersion in molecular crystals

NASA Astrophysics Data System (ADS)

Cudazzo, Pierluigi; Gatti, Matteo; Rubio, Angel; Sottile, Francesco

2013-11-01

By solving the many-body Bethe-Salpeter equation at finite momentum transfer, we characterize the exciton dispersion in two prototypical molecular crystals, picene and pentacene, in which localized Frenkel excitons compete with delocalized charge-transfer excitons. We explain the exciton dispersion on the basis of the interplay between electron and hole hopping and electron-hole exchange interaction, unraveling a simple microscopic description to distinguish Frenkel and charge-transfer excitons. This analysis is general and can be applied to other systems in which the electron wave functions are strongly localized, as in strongly correlated insulators.

Extracellular Electron Uptake: Among Autotrophs and Mediated by Surfaces.

PubMed

Tremblay, Pier-Luc; Angenent, Largus T; Zhang, Tian

2017-04-01

Autotrophic microbes can acquire electrons from solid donors such as steel, other microbial cells, or electrodes. Based on this feature, bioprocesses are being developed for the microbial electrosynthesis (MES) of useful products from the greenhouse gas CO 2 . Extracellular electron-transfer mechanisms involved in the acquisition of electrons from metals by electrical microbially influenced corrosion (EMIC), from other living cells by interspecies electron transfer (IET), or from an electrode during MES rely on: (i) mediators such as H 2 ; (ii) physical contact through electron-transfer proteins; or (iii) mediator-generating enzymes detached from cells. This review explores the interactions of autotrophs with solid electron donors and their importance in nature and for biosustainable technologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2007-11-01

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

A molecular Debye-Hückel approach to the reorganization energy of electron transfer reactions in an electric cell

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

Xiao, Tiejun; Department of Chemistry, Iowa State University, Ames, Iowa 50011; Song, Xueyu

2014-10-07

Electron transfer near an electrode immersed in ionic fluids is studied using the linear response approximation, namely, mean value of the vertical energy gap can be used to evaluate the reorganization energy, and hence any linear response model that can treat Coulomb interactions successfully can be used for the reorganization energy calculation. Specifically, a molecular Debye-Hückel theory is used to calculate the reorganization energy of electron transfer reactions in an electric cell. Applications to electron transfer near an electrode in molten salts show that the reorganization energies from our molecular Debye-Hückel theory agree well with the results from MD simulations.

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.

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

Curvilinear electronics formed using silicon membrane circuits and elastomeric transfer elements.

PubMed

Ko, Heung Cho; Shin, Gunchul; Wang, Shuodao; Stoykovich, Mark P; Lee, Jeong Won; Kim, Dong-Hun; Ha, Jeong Sook; Huang, Yonggang; Hwang, Keh-Chih; Rogers, John A

2009-12-01

Materials and methods to achieve electronics intimately integrated on the surfaces of substrates with complex, curvilinear shapes are described. The approach exploits silicon membranes in circuit mesh structures that can be deformed in controlled ways using thin, elastomeric films. Experimental and theoretical studies of the micromechanics of such curvilinear electronics demonstrate the underlying concepts. Electrical measurements illustrate the high yields that can be obtained. The results represent significant experimental and theoretical advances over recently reported concepts for creating hemispherical photodetectors in electronic eye cameras and for using printable silicon nanoribbons/membranes in flexible electronics. The results might provide practical routes to the integration of high performance electronics with biological tissues and other systems of interest for new applications.

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.

Relationship between the structures of flavonoids and oxygen radical absorbance capacity values: a quantum chemical analysis.

PubMed

Zhang, Di; Liu, Yixiang; Chu, Le; Wei, Ying; Wang, Dan; Cai, Shengbao; Zhou, Feng; Ji, Baoping

2013-02-28

Various radical-scavenging activities (RSA) assessment assays are based on discrete mechanisms and on using different radical sources. Few studies have analyzed the structural significance of flavonoids in their peroxyl radical activities in the oxygen radical absorbance capacity (ORAC) assay. In this study, the RSA of 13 flavonoids in two ORAC assays with different probes (fluorescein and pyrogallol red) were investigated. Neither O-H bond dissociation enthalpy nor ionization potential values of flavonoids correlated with ORAC values. The proton affinity (PA) and electron transfer enthalpy (ETE) values, which were obtained via the sequential proton-loss electron-transfer mechanism, were significantly associated with the ORAC(pyrogallol Red) and ORAC(fluorescein) assays, respectively. Thus, PA represented the kinetic aspect of RSA, whereas ETE reflected the RSA extent. The PA values and the most acidic sites of flavonoids were affected by intramolecular electronic interactions, H-bonding, 3-hydroxyl group in the C ring, and conjugation systems. The stability of the deprotonated flavonoid determined the ETE value. Apart from the PA and ETE values in the first oxidation step of flavonoids, the PA and ETE values in the second oxidation step also affected the ORAC values of flavonoids.

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.

2-Oxoglutarate dehydrogenase is a more significant source of O2(·-)/H2O2 than pyruvate dehydrogenase in cardiac and liver tissue.

PubMed

Mailloux, Ryan J; Gardiner, Danielle; O'Brien, Marisa

2016-08-01

Pyruvate dehydrogenase (Pdh) and 2-oxoglutarate dehydrogenase (Ogdh) are vital for Krebs cycle metabolism and sources of reactive oxygen species (ROS). O2(·-)/H2O2 formation by Pdh and Ogdh from porcine heart were compared when operating under forward or reverse electron transfer conditions. Comparisons were also conducted with liver and cardiac mitochondria. During reverse electron transfer (RET) from NADH, purified Ogdh generated ~3-3.5× more O2(·-)/H2O2 in comparison to Pdh when metabolizing 0.5-10µM NADH. Under forward electron transfer (FET) conditions Ogdh generated ~2-4× more O2(·-)/H2O2 than Pdh. In both liver and cardiac mitochondria, Ogdh displayed significantly higher rates of ROS formation when compared to Pdh. Ogdh was also a significant source of ROS in liver mitochondria metabolizing 50µM and 500µM pyruvate or succinate. Finally, we also observed that DTT directly stimulated O2(·-)/H2O2 formation by purified Pdh and Ogdh and in cardiac or liver mitochondria in the absence of substrates and cofactors. Taken together, Ogdh is a more potent source of ROS than Pdh in liver and cardiac tissue. Ogdh is also an important ROS generator regardless of whether pyruvate or succinate serve as the sole source of carbon. Our observations provide insight into the ROS generating capacity of either complex in cardiac and liver tissue. The evidence presented herein also indicates DTT, a reductant that is routinely added to biological samples, should be avoided when assessing mitochondrial O2(·-)/H2O2 production. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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

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.

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

DOE PAGES

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; ...

2014-10-08

Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We concludemore » that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.« less

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

PubMed Central

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

2014-01-01

The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

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.

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.

Identifying involvement of Lys251/Asp252 pair in electron transfer and associated proton transfer at the quinone reduction site of Rhodobacter capsulatus cytochrome bc1.

PubMed

Kuleta, Patryk; Sarewicz, Marcin; Postila, Pekka; Róg, Tomasz; Osyczka, Artur

2016-10-01

Describing dynamics of proton transfers in proteins is challenging, but crucial for understanding processes which use them for biological functions. In cytochrome bc1, one of the key enzymes of respiration or photosynthesis, proton transfers engage in oxidation of quinol (QH2) and reduction of quinone (Q) taking place at two distinct catalytic sites. Here we evaluated by site-directed mutagenesis the contribution of Lys251/Asp252 pair (bacterial numbering) in electron transfers and associated with it proton uptake to the quinone reduction site (Qi site). We showed that the absence of protonable group at position 251 or 252 significantly changes the equilibrium levels of electronic reactions including the Qi-site mediated oxidation of heme bH, reverse reduction of heme bH by quinol and heme bH/Qi semiquinone equilibrium. This implicates the role of H-bonding network in binding of quinone/semiquinone and defining thermodynamic properties of Q/SQ/QH2 triad. The Lys251/Asp252 proton path is disabled only when both protonable groups are removed. With just one protonable residue from this pair, the entrance of protons to the catalytic site is sustained, albeit at lower rates, indicating that protons can travel through parallel routes, possibly involving water molecules. This shows that proton paths display engineering tolerance for change as long as all the elements available for functional cooperation secure efficient proton delivery to the catalytic site. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Reduced energy offset via substitutional doping for efficient organic/inorganic hybrid solar cells.

PubMed

Jin, Xiao; Sun, Weifu; Zhang, Qin; Ruan, Kelian; Cheng, Yuanyuan; Xu, Haijiao; Xu, Zhongyuan; Li, Qinghua

2015-06-01

Charge carrier transport in bulk heterojunction that is central to the device performance of solar cells is sensitively dependent on the energy level alignment of acceptor and donor. However, the effect of energy level regulation induced by nickel ions on the primary photoexcited electron transfer and the performance of P3HT/TiO₂ hybrid solar cells remains being poorly understood and rarely studied. Here we demonstrate that the introduction of the versatile nickel ions into TiO₂ nanocrystals can significantly elevate the conduction and valence band energy levels of the acceptor, thus resulting in a remarkable reduction of energy level offset between the conduction band of acceptor and lowest unoccupied molecular orbital of donor. By applying transient photoluminescence and femtosecond transient absorption spectroscopies, we demonstrate that the electron transfer becomes more competitive after incorporating nickel ions. In particular, the electron transfer life time is shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO₂ acceptor, thus leading to a notable increase of power conversion efficiency in organic/inorganic hybrid solar cells. This work underscores the promising virtue of engineering the reduction of 'excess' energy offset to accelerate electron transport and demonstrates the potential of nickel ions in applications of solar energy conversion and photon detectors.

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

Stimulated Electron Desorption Studies from Microwave Vacuum Electronics / High Power Microwave Materials

DTIC Science & Technology

2010-02-11

purchase a new gun. Mr. Mike Ackeret ( Transfer Engineering Inc.) Transfer Engineering’s expertise in specialty UHV work and machining propelled...modifications they helped design for the test stand. With UNLV guidance, Transfer Engineering designed and built the original UNLV SEE Test Stand...Staib electron gun, an isolated beam drift tube, a hexanode delay line with a chevron microchannel plate (MCP) stack, an isolated grid, an isolated

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.

Modeling the free energy surfaces of electron transfer in condensed phases

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.; Voth, Gregory A.

2000-10-01

We develop a three-parameter model of electron transfer (ET) in condensed phases based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states (a classical limit of the quantum Kubo-Toyozawa model). The exact analytical solution for the ET free energy surfaces demonstrates the following features: (i) the range of ET reaction coordinates is limited by a one-sided fluctuation band, (ii) the ET free energies are infinite outside the band, and (iii) the free energy surfaces are parabolic close to their minima and linear far from the minima positions. The model provides an analytical framework to map physical phenomena conflicting with the Marcus-Hush two-parameter model of ET. Nonlinear solvation, ET in polarizable charge-transfer complexes, and configurational flexibility of donor-acceptor complexes are successfully mapped onto the model. The present theory leads to a significant modification of the energy gap law for ET reactions.

MS-CASPT2 study of hole transfer in guanine-indole complexes using the generalized Mulliken-Hush method: effective two-state treatment.

PubMed

Butchosa, C; Simon, S; Blancafort, L; Voityuk, A

2012-07-12

Because hole transfer from nucleobases to amino acid residues in DNA-protein complexes can prevent oxidative damage of DNA in living cells, computational modeling of the process is of high interest. We performed MS-CASPT2 calculations of several model structures of π-stacked guanine and indole and derived electron-transfer (ET) parameters for these systems using the generalized Mulliken-Hush (GMH) method. We show that the two-state model commonly applied to treat thermal ET between adjacent donor and acceptor is of limited use for the considered systems because of the small gap between the ground and first excited states in the indole radical cation. The ET parameters obtained within the two-state GMH scheme can deviate significantly from the corresponding matrix elements of the two-state effective Hamiltonian based on the GMH treatment of three adiabatic states. The computed values of diabatic energies and electronic couplings provide benchmarks to assess the performance of less sophisticated computational methods.

Dependence of intramolecular electron-transfer rates on driving force, pH, and temperature in ammineruthenium-modified ferrocytochromes c

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

Wishart, J.F.; Sun, J.; Su, C.

1997-01-23

Several ruthenium ammine complexes were used to modify horse-heart cytochrome c at histidine-33, creating a series of (NH{sub 3}){sub 4}(L)Ru-Cyt c derivatives (L = H{sub 2}O/OH{sup -}, ammonia, 4-ethylpyridine, 3,5-lutidine, pyridine, isonicotinamide, N-methylpyrazinium) with a wide range of driving forces for Fe-to-Ru electron transfer (-{Delta}G{degree} = -0.125 to +0.46 eV). Electron-transfer rates and activation parameters were measured by pulse radiolysis using azide or carbonate radicals. The driving-force dependence of electron-transfer rates between redox centers of the same charge types obeys Marcus-Hush theory. The activationless rate limit for all of the ruthenium derivatives except the N-methylpyrazinium complex is 3.9x10{sup 5} s{supmore » -1}. Thermodynamic parameters obtained from nonisothermal differential pulse voltammetry show that the electron-transfer reactions are entropy-driven. The thermodynamic and kinetic effects of phosphate ion binding to the ruthenium center are examined. The rate of intramolecular electron transfer in (NH{sub 3}){sub 4}(isn)Ru{sup III}-Cyt c{sup II} decreases at high pH, with a midpoint at pH 9.1. 28 refs., 4 figs., 3 tabs.« less

Excitation energy transfer in the photosystem I

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

Webber, Andrew N

2012-09-25

Photosystem I is a multimeric pigment protein complex in plants, green alage and cyanobacteria that functions in series with Photosystem II to use light energy to oxidize water and reduce carbon dioxide. The Photosystem I core complex contains 96 chlorophyll a molecules and 22 carotenoids that are involved in light harvesting and electron transfer. In eucaryotes, PSI also has a peripheral light harvesting complex I (LHCI). The role of specific chlorophylls in excitation and electron transfer are still unresolved. In particular, the role of so-called bridging chlorophylls, located between the bulk antenna and the core electron transfer chain, in themore » transfer of excitation energy to the reaction center are unknown. During the past funding period, site directed mutagenesis has been used to create mutants that effect the physical properties of these key chlorophylls, and to explore how this alters the function of the photosystem. Studying these mutants using ultrafast absorption spectroscopy has led to a better understanding of the process by which excitation energy is transferred from the antenna chlorophylls to the electron transfer chain chlorophylls, and what the role of connecting chlorophylls and A_0 chlorophylls is in this process. We have also used these mutants to investigate whch of the central group of six chlorophylls are involved in the primary steps of charge separation and electron transfer.« less

Dynamics of charge-transfer excitons in type-II semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Stein, M.; Lammers, C.; Richter, P.-H.; Fuchs, C.; Stolz, W.; Koch, M.; Vänskä, O.; Weseloh, M. J.; Kira, M.; Koch, S. W.

2018-03-01

The formation, decay, and coherence properties of charge-transfer excitons in semiconductor heterostructures are investigated by applying four-wave-mixing and terahertz spectroscopy in combination with a predictive microscopic theory. A charge-transfer process is identified where the optically induced coherences decay directly into a charge-transfer electron-hole plasma and exciton states. It is shown that charge-transfer excitons are more sensitive to the fermionic electron-hole substructure than regular excitons.

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...

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

NASA Astrophysics Data System (ADS)

Perlík, Václav; Seibt, Joachim; Cranston, Laura J.; Cogdell, Richard J.; Lincoln, Craig N.; Savolainen, Janne; Šanda, František; Mančal, Tomáš; Hauer, Jürgen

2015-06-01

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system's Hamiltonian, reproduces all measured quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.

Model-based confirmation of alternative substrates of mitochondrial electron transport chain.

PubMed

Kleessen, Sabrina; Araújo, Wagner L; Fernie, Alisdair R; Nikoloski, Zoran

2012-03-30

Discrimination of metabolic models based on high throughput metabolomics data, reflecting various internal and external perturbations, is essential for identifying the components that contribute to the emerging behavior of metabolic processes. Here, we investigate 12 different models of the mitochondrial electron transport chain (ETC) in Arabidopsis thaliana during dark-induced senescence in order to elucidate the alternative substrates to this metabolic pathway. Our findings demonstrate that the coupling of the proposed computational approach, based on dynamic flux balance analysis, with time-resolved metabolomics data results in model-based confirmations of the hypotheses that, during dark-induced senescence in Arabidopsis, (i) under conditions where the main substrate for the ETC are not fully available, isovaleryl-CoA dehydrogenase and 2-hydroxyglutarate dehydrogenase are able to donate electrons to the ETC, (ii) phytanoyl-CoA does not act even as an indirect substrate of the electron transfer flavoprotein/electron-transfer flavoprotein:ubiquinone oxidoreductase complex, and (iii) the mitochondrial γ-aminobutyric acid transporter has functional significance in maintaining mitochondrial metabolism. Our study provides a basic framework for future in silico studies of alternative pathways in mitochondrial metabolism under extended darkness whereby the role of its components can be computationally discriminated based on available molecular profile data.

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

Heterogeneous catalysis with lasers

NASA Astrophysics Data System (ADS)

George, T. F.

1986-06-01

Theoretical techniques have been developed to describe a variety of laser-induced molecular rate processes occurring at solid surfaces which are involved in heterogeneous catalysis. Such processes include adsorption, migration, chemical reactions and desorption. The role of surface phonons in laser-selective processes and laser heating has been analyzed. The importance of electronic degrees of freedom has been considered for semiconductor and metal substrates, with special emphasis on the laser excitation of surface states. Surface-modified photochemistry has also been investigated, where the effect of a metal surface on the resonance fluorescence spectrum of a laser-driven atom/molecule has been assessed by means of surface-dressed optical Bloch equations. It is seen that the spectrum can be significantly different from the gas-phase case. Two related gas-surface collision processes have also been studied. First, the feasibility of the formation of the electron-hole pairs in a semiconductor by vibrationally excited molecules has been explored. Second, charge transfer in ion-surface collisions has been examined for both one-electron and two-electron transfer processes. Work has been initiated on microstructures and rough structures, including clusters and surface gratings.

Stimulated Raman adiabatic passage preparation of a coherent superposition of ThO H3Δ1 states for an improved electron electric-dipole-moment measurement

NASA Astrophysics Data System (ADS)

Panda, C. D.; O'Leary, B. R.; West, A. D.; Baron, J.; Hess, P. W.; Hoffman, C.; Kirilov, E.; Overstreet, C. B.; West, E. P.; DeMille, D.; Doyle, J. M.; Gabrielse, G.

2016-05-01

Experimental searches for the electron electric-dipole moment (EDM) probe new physics beyond the standard model. The current best EDM limit was set by the ACME Collaboration [Science 343, 269 (2014), 10.1126/science.1248213], constraining time-reversal symmetry (T ) violating physics at the TeV energy scale. ACME used optical pumping to prepare a coherent superposition of ThO H3Δ1 states that have aligned electron spins. Spin precession due to the molecule's internal electric field was measured to extract the EDM. We report here on an improved method for preparing this spin-aligned state of the electron by using stimulated Raman adiabatic passage (STIRAP). We demonstrate a transfer efficiency of 75 %±5 % , representing a significant gain in signal for a next-generation EDM experiment. We discuss the particularities of implementing STIRAP in systems such as ours, where molecular ensembles with large phase-space distributions are transferred via weak molecular transitions with limited laser power and limited optical access.

Enhanced photocatalytic activity of graphitic carbon nitride/carbon nanotube/Bi2WO6 ternary Z-scheme heterojunction with carbon nanotube as efficient electron mediator.

PubMed

Jiang, Deli; Ma, Wanxia; Xiao, Peng; Shao, Leqiang; Li, Di; Chen, Min

2018-02-15

All-solid-state Z-scheme heterojunction has attracted much attention in photocatalytic field because of its strong ability in charge separation and transfer. In the present study, all-solid-state ternary Z-scheme heterojunction constructed by graphitic carbon nitride (CN) nanosheet, carbon nanotube (CNT), and Bi 2 WO 6 (BWO) nanosheet, in which CNT was employed as the electron mediator. The CN/CNT/BWO ternary Z-scheme heterojunction shows the enhanced photocatalytic activity towards the degradation of tetracycline hydrochloride (TC) as compared to the pristine g-C 3 N 4 , Bi 2 WO 6 , CNT/BWO, CNT/CN, and CN/BWO. The significantly improved photocatalytic activity can be mainly ascribed to the formed CNT-mediated Z-scheme heterojunction, which facilitates the separation and transfer of photogenerated electron-hole pairs. Our work provides a rational design of all-solid-state Z-scheme heterojunction with CNT as the electron mediator for highly efficient photocatalysis. Copyright © 2017 Elsevier Inc. All rights reserved.

Graphene-ferromagnet interfaces: hybridization, magnetization and charge transfer.

PubMed

Abtew, Tesfaye; Shih, Bi-Ching; Banerjee, Sarbajit; Zhang, Peihong

2013-03-07

Electronic and magnetic properties of graphene-ferromagnet interfaces are investigated using first-principles electronic structure methods in which a single layer graphene is adsorbed on Ni(111) and Co(111) surfaces. Due to the symmetry matching and orbital overlap, the hybridization between graphene pπ and Ni (or Co) d(z(2)) states is very strong. This pd hybridization, which is both spin and k dependent, greatly affects the electronic and magnetic properties of the interface, resulting in a significantly reduced (by about 20% for Ni and 10% for Co) local magnetic moment of the top ferromagnetic layer at the interface and an induced spin polarization on the graphene layer. The calculated induced magnetic moment on the graphene layer agrees well with a recent experiment. In addition, a substantial charge transfer across the graphene-ferromagnet interfaces is observed. We also investigate the effects of thickness of the ferromagnet slab on the calculated electronic and magnetic properties of the interface. The strength of the pd hybridization and the thickness-dependent interfacial properties may be exploited to design structures with desirable magnetic and transport properties for spintronic applications.

12 CFR 205.7 - Initial disclosures.

Code of Federal Regulations, 2014 CFR

2014-01-01

... TRANSFERS (REGULATION E) § 205.7 Initial disclosures. (a) Timing of disclosures. A financial institution shall make the disclosures required by this section at the time a consumer contracts for an electronic fund transfer service or before the first electronic fund transfer is made involving the consumer's...

12 CFR 205.7 - Initial disclosures.

Code of Federal Regulations, 2010 CFR

2010-01-01

... TRANSFERS (REGULATION E) § 205.7 Initial disclosures. (a) Timing of disclosures. A financial institution shall make the disclosures required by this section at the time a consumer contracts for an electronic fund transfer service or before the first electronic fund transfer is made involving the consumer's...

Glutaric aciduria type II presenting as myopathy and rhabdomyolysis in a teenager.

PubMed

Prasad, Manish; Hussain, Shanawaz

2015-01-01

Late-onset glutaric aciduria type II has been described recently as a rare but treatable cause of proximal myopathy in teenagers and adults. It is an autosomal recessive disease affecting fatty acid, amino acid, and choline metabolism. This is usually a result of 2 defective flavoproteins: either electron transfer flavoprotein (ETF) or electron transfer flavoprotein-ubiquinone oxidoreductase (ETF:QO). We present a 14-year-old boy with a background of autistic spectrum disorder who presented with severe muscle weakness and significant rhabdomyolysis. Before the onset of muscle weakness, he was very active but was completely bedridden at presentation. Diagnosis was established quickly by urine organic acid and plasma acylcarnitine analysis. He has shown significant improvement after starting oral riboflavin supplementation and is now fully mobile. This case highlights that late-onset glutaric aciduria type II is an important differential diagnosis to consider in teenagers presenting with proximal myopathy and rhabdomyolysis and it may not be associated with hypoglycemia. © The Author(s) 2014.

Electroactive microorganisms in bulk solution contribute significantly to methane production in bioelectrochemical anaerobic reactor.

PubMed

Feng, Qing; Song, Young-Chae; Ahn, Yongtae

2018-07-01

The role of anaerobic microorganisms suspended in the bulk solution on methane production was investigated in a bioelectrochemical anaerobic reactor with the electrode polarized at 0.5 V. The electron transfer from substrate to methane and hydrogen were 25% and 7.5%, respectively, in the absence of the anaerobic microorganisms in the bulk solution. As the anaerobic microorganisms increased to 4400 mg/L, the electrons transferred to methane increased to 83.3% but decreased to 0.3% in hydrogen. The electroactive microorganisms (EAM), including exoelectrogens and electrotrophs, enriched in the bulk solution that confirmed by the redox peaks in the cyclic voltammogram was proportional to the anaerobic microorganism. The methane yield based on COD removal was dependent on the anaerobic microorganisms in the bulk solution rather than on the bioelectrode surface. The EAM suspended in the bulk solution are enriched by the polarized electrode, and significantly improve methane production in bioelectrochemical anaerobic reactor. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

PubMed

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

2015-04-10

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

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

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

Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang, E-mail: howesiang@ntu.edu.sg

2015-06-07

The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysismore » of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.« less

12 CFR 205.11 - Procedures for resolving errors.

Code of Federal Regulations, 2010 CFR

2010-01-01

... institution's findings and shall note the consumer's right to request the documents that the institution... transfer; (ii) An incorrect electronic fund transfer to or from the consumer's account; (iii) The omission... made by the financial institution relating to an electronic fund transfer; (v) The consumer's receipt...

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.

Influences of Quantum Mechanically Mixed Electronic and Vibrational Pigment States in 2D Electronic Spectra of Photosynthetic Systems: Strong Electronic Coupling Cases

DOE PAGES

Fujihashi, Yuta; Fleming, Graham R.; Ishizaki, Akihito

2015-09-07

In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and several theoretical studies have suggested that the beats are produced by quantum mechanically mixed electronic and vibrational states. Concerning the electronic-vibrational quantum mixtures, the impact of protein-induced fluctuations was examined by calculating the 2D electronic spectra of a weakly coupled dimer with the Franck-Condon active vibrational modes in the resonant condition. This analysis demonstrated that quantum mixtures of the vibronic resonance are rather robust under the influence of the fluctuations at cryogenic temperatures, whereas the mixtures are eradicated by the fluctuations at physiological temperatures.more » However, this conclusion cannot be generalized because the magnitude of the coupling inducing the quantum mixtures is proportional to the inter-pigment electronic coupling. In this paper, we explore the impact of the fluctuations on electronic-vibrational quantum mixtures in a strongly coupled dimer with an off-resonant vibrational mode. Toward this end, we calculate energy transfer dynamics and 2D electronic spectra of a model dimer that corresponds to the most strongly coupled bacteriochlorophyll molecules in the Fenna-Matthews-Olson complex in a numerically accurate manner. The quantum mixtures are found to be robust under the exposure of protein-induced fluctuations at cryogenic temperatures, irrespective of the resonance. At 300 K, however, the quantum mixing is disturbed more strongly by the fluctuations, and therefore, the beats in the 2D spectra become obscure even in a strongly coupled dimer with a resonant vibrational mode. Further, the overall behaviors of the energy transfer dynamics are demonstrated to be dominated by the environment and coupling between the 0 0 vibronic transitions as long as the Huang-Rhys factor of the vibrational mode is small. Finally, the electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics despite contributing to the enhancement of long-lived quantum beating in the 2D spectra.« less

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

Down-regulated PAR-2 is associated in part with interrupted melanosome transfer in pigmented basal cell epithelioma.

PubMed

Sakuraba, Kazuko; Hayashi, Nobukazu; Kawashima, Makoto; Imokawa, Genji

2004-08-01

In pigmented basal cell epithelioma (BCE), there seems to be an abnormal transfer of melanized melanosomes from proliferating melanocytes to basaloid tumor cells. In this study, the interruption of that melanosome transfer was studied with special respect to the altered function of a phagocytic receptor, protease-activated receptor (PAR)-2 in the basaloid tumor cells. We used electron microscopy to clarify the disrupted transfer at the ultrastructural level and then performed immunohistochemistry and reverse transcription-polymerase chain reaction (RT-PCR) to examine the regulation of a phagocytic receptor, PAR-2, expressed on basaloid tumor cells. Electron microscopic analysis revealed that basaloid tumor cells of pigmented BCE have a significantly lower population of melanosomes ( approximately 16.4%) than do normal keratinocytes located in the perilesional normal epidermis ( approximately 91.0%). In contrast, in pigmented seborrheic keratosis (SK), a similarly pigmented epidermal tumor, the distribution of melanin granules does not differ between the lesional ( approximately 93.9%) and the perilesional normal epidermis ( approximately 92.2 %), indicating that interrupted melanosome transfer occurs in BCE but not in all pigmented epithelial tumors. RT-PCR analysis demonstrated that the expression of PAR-2 mRNA transcripts in basaloid cells is significantly decreased in pigmented BCE compared with the perilesional normal epidermis. In contrast, in pigmented SK, where melanosome transfer to basaloid tumor cells is not interrupted, the expression of PAR-2 mRNA transcripts is comparable between the basaloid tumor cells and the perilesional normal epidermis. Immunohistochemistry demonstrated that basaloid cells in pigmented BCE have less immunostaining for PAR-2 than do keratinocytes in the perilesional normal epidermis whereas in pigmented SK, there is no difference in immunostaining for PAR-2 between the basaloid tumor and the perilesional normal epidermis. These findings suggest that the decreased expression of PAR-2 in the basaloid cells is associated in part with the observed interruption of melanosome transfer in pigmented BCE.

Tracking Electron Uptake from a Cathode into Shewanella Cells: Implications for Energy Acquisition from Solid-Substrate Electron Donors

PubMed Central

Rajeev, Pournami; Jain, Abhiney; Pirbadian, Sahand; Okamoto, Akihiro; Gralnick, Jeffrey A.; El-Naggar, Mohamed Y.; Nealson, Kenneth H.

2018-01-01

ABSTRACT While typically investigated as a microorganism capable of extracellular electron transfer to minerals or anodes, Shewanella oneidensis MR-1 can also facilitate electron flow from a cathode to terminal electron acceptors, such as fumarate or oxygen, thereby providing a model system for a process that has significant environmental and technological implications. This work demonstrates that cathodic electrons enter the electron transport chain of S. oneidensis when oxygen is used as the terminal electron acceptor. The effect of electron transport chain inhibitors suggested that a proton gradient is generated during cathode oxidation, consistent with the higher cellular ATP levels measured in cathode-respiring cells than in controls. Cathode oxidation also correlated with an increase in the cellular redox (NADH/FMNH2) pool determined with a bioluminescence assay, a proton uncoupler, and a mutant of proton-pumping NADH oxidase complex I. This work suggested that the generation of NADH/FMNH2 under cathodic conditions was linked to reverse electron flow mediated by complex I. A decrease in cathodic electron uptake was observed in various mutant strains, including those lacking the extracellular electron transfer components necessary for anodic-current generation. While no cell growth was observed under these conditions, here we show that cathode oxidation is linked to cellular energy acquisition, resulting in a quantifiable reduction in the cellular decay rate. This work highlights a potential mechanism for cell survival and/or persistence on cathodes, which might extend to environments where growth and division are severely limited. PMID:29487241

Investigating molecule-semiconductor interfaces with nonlinear spectroscopies

NASA Astrophysics Data System (ADS)

Giokas, Paul George

Knowledge of electronic structures and transport mechanisms at molecule-semiconductor interfaces is motivated by their ubiquity in photoelectrochemical cells. In this dissertation, optical spectroscopies are used uncover the influence of electronic coupling, coherent vibrational motion, and molecular geometry, and other factors on dynamics initiated by light absorption at such interfaces. These are explored for a family of ruthenium bipyridyl chromophores bound to titanium dioxide. Transient absorption measurements show molecular singlet state electron injection in 100 fs or less. Resonance Raman intensity analysis suggests the electronic excitations possess very little charge transfer character. The connections drawn in this work between molecular structure and photophysical behavior contribute to the general understanding of photoelectrochemical cells. Knowledge of binding geometry in nanocrystalline films is challenged by heterogeneity of semiconductor surfaces. Polarized resonance Raman spectroscopy is used to characterize the ruthenium chromophore family on single crystal titanium dioxide . Chromophores display a broad distribution of molecular geometries at the interface, with increased variation in binding angle due to the presence of a methylene bridge, as well as additional phosphonate anchors. This result implies multiple binding configurations for chromophores which incorporate multiple phosphonate ligands, and indicates the need for careful consideration when developing surface-assembled chromophore-catalyst cells. Electron transfer transitions occurring on the 100 fs time scale challenge conventional second-order approximations made when modeling these reactions. A fourth-order perturbative model which includes the relationship between coincident electron transfer and nuclear relaxation processes is presented. Insights provided by the model are illustrated for a two-level donor molecule. The presented fourth-order rate formula constitutes a rigorous and intuitive framework for understanding sub-picosecond photoinduced electron transfer dynamics. Charge transfer systems fit by this model include catechol-sensitized titanium dioxide nanoparticles and a closely-related molecular complex. These systems exhibit vibrational coherence coincident with back-electron transfer in the first picosecond after excitation, which suggests that intramolecular nuclear motion strongly influences the electronic transfer process and plays an important role in the dynamics of interfacial systems following light absorption.

A Versatile High-Vacuum Cryo-transfer System for Cryo-microscopy and Analytics

PubMed Central

Tacke, Sebastian; Krzyzanek, Vladislav; Nüsse, Harald; Wepf, Roger Albert; Klingauf, Jürgen; Reichelt, Rudolf

2016-01-01

Cryogenic microscopy methods have gained increasing popularity, as they offer an unaltered view on the architecture of biological specimens. As a prerequisite, samples must be handled under cryogenic conditions below their recrystallization temperature, and contamination during sample transfer and handling must be prevented. We present a high-vacuum cryo-transfer system that streamlines the entire handling of frozen-hydrated samples from the vitrification process to low temperature imaging for scanning transmission electron microscopy and transmission electron microscopy. A template for cryo-electron microscopy and multimodal cryo-imaging approaches with numerous sample transfer steps is presented. PMID:26910419

Layered-metal-hydroxide nanosheet arrays with controlled nanostructures to assist direct electronic communication at biointerfaces.

PubMed

An, Zhe; Lu, Shan; Zhao, Liwei; He, Jing

2011-10-18

In this work, ordered vertical arrays of layered double hydroxide (LDH) nanosheets have been developed to achieve electron transfer (eT) at biointerfaces in electrochemical devices. It is found that tailoring the gap size of LDH nanosheet arrays could significantly promote the eT rate. This research has successfully extended nanomaterials for efficient modifications of electrode surfaces from nanoparticles, nanowires, nanorods, and nanotubes to nanosheets. © 2011 American Chemical Society

Coherent pump pulses in Double Electron Electron Resonance Spectroscopy

PubMed Central

Tait, Claudia E.; Stoll, Stefan

2016-01-01

The recent introduction of shaped pulses to Double Electron Electron Resonance (DEER) spectroscopy has led to significant enhancements in sensitivity through increased excitation bandwidths and improved control over spin dynamics. The application of DEER has so far relied on the presence of an incoherent pump channel to average out most undesired coherent effects of the pump pulse(s) on the observer spins. However, in fully coherent EPR spectrometers that are increasingly used to generate shaped pulses, the presence of coherent pump pulses means that these effects need to be explicitly considered. In this paper, we examine the effects of coherent rectangular and sech/tanh pump pulses in DEER experiments with up to three pump pulses. We show that, even in the absence of significant overlap of the observer and pump pulse excitation bandwidths, coherence transfer pathways involving both types of pulses generate spin echoes of considerable intensity. These echoes introduce artefacts, which, if not identified and removed, can easily lead to misinterpretation. We demonstrate that the observed echoes can be quantitatively modelled using a simple spin quantum dynamics approach that includes instrumental transfer functions. Based on an analysis of the echo crossing artefacts, we propose efficient phase cycling schemes for their suppression. This enables the use of advanced DEER experiments, characterized by high sensitivity and increased accuracy for long-distance measurements, on novel fully coherent EPR spectrometers. PMID:27339858

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

DOE PAGES

Wilker, Molly B.; Utterback, James K.; Greene, Sophie; ...

2017-12-08

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

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

Wilker, Molly B.; Utterback, James K.; Greene, Sophie

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

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.

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.

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.

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

Development of flange and reticulate wall ingrowths in maize (Zea mays L.) endosperm transfer cells.

PubMed

Monjardino, Paulo; Rocha, Sara; Tavares, Ana C; Fernandes, Rui; Sampaio, Paula; Salema, Roberto; da Câmara Machado, Artur

2013-04-01

Maize (Zea mays L.) endosperm transfer cells are essential for kernel growth and development so they have a significant impact on grain yield. Although structural and ultrastructural studies have been published, little is known about the development of these cells, and prior to this study, there was a general consensus that they contain only flange ingrowths. We characterized the development of maize endosperm transfer cells by bright field microscopy, transmission electron microscopy, and confocal laser scanning microscopy. The most basal endosperm transfer cells (MBETC) have flange and reticulate ingrowths, whereas inner transfer cells only have flange ingrowths. Reticulate and flange ingrowths are mostly formed in different locations of the MBETC as early as 5 days after pollination, and they are distinguishable from each other at all stages of development. Ingrowth structure and ultrastructure and cellulose microfibril compaction and orientation patterns are discussed during transfer cell development. This study provides important insights into how both types of ingrowths are formed in maize endosperm transfer cells.

Theoretical investigation of the electron transfer dynamics and photodegradation pathways in a hydrogen-evolving ruthenium-palladium photocatalyst.

PubMed

Staniszewska, Magdalena; Kupfer, Stephan; Guthmuller, Julien

2018-05-16

Time-dependent density functional theory calculations combined with the Marcus theory of electron transfer (ET) were applied on the molecular photocatalyst [(tbbpy)2Ru(tpphz)PdCl2]2+ in order to elucidate the light-induced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational results show that after the initial excitation, metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are energetically accessible, but that an ET toward the catalytic center (PdCl2) from these states is a slow process, with estimated time constants above 1 ns. Instead, the calculations predict that low-lying Pd-centered states are efficiently populated - associated to an energy transfer toward the catalytic center. Thus, it is postulated that these states lead to the dissociation of a Cl- and are consequently responsible for the experimentally observed degradation of the catalytic center. Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated states are significantly increased (i.e. 10^5-10^6 times larger). This demonstrates that alteration of the catalytic center generates efficient charge separation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photocurrent production by bio-dyes of photosynthetic macromolecules on designed TiO2 film

PubMed Central

Yu, Daoyong; Wang, Mengfei; Zhu, Guoliang; Ge, Baosheng; Liu, Shuang; Huang, Fang

2015-01-01

The macromolecular pigment-protein complex has the merit of high efficiency for light-energy capture and transfer after long-term photosynthetic evolution. Here bio-dyes of A. platensis photosystem I (PSI) and spinach light-harvesting complex II (LHCII) are spontaneously sensitized on three types of designed TiO2 films, to assess the effects of pigment-protein complex on the performance of bio-dye sensitized solar cells (SSC). Adsorption models of bio-dyes are proposed based on the 3D structures of PSI and LHCII, and the size of particles and inner pores in the TiO2 film. PSI shows its merit of high efficiency for captured energy transfer, charge separation and transfer in the electron transfer chain (ETC), and electron injection from FB to the TiO2 conducting band. After optimization, the best short current (JSC) and photoelectric conversion efficiency (η) of PSI-SSC and LHCII-SSC are 1.31 mA cm-2 and 0.47%, and 1.51 mA cm-2 and 0.52%, respectively. The potential for further improvement of this PSI based SSC is significant and could lead to better utilization of solar energy. PMID:25790735

Excitation and charge transfer in low-energy hydrogen atom collisions with neutral iron

NASA Astrophysics Data System (ADS)

Barklem, P. S.

2018-05-01

Data for inelastic processes due to hydrogen atom collisions with iron are needed for accurate modelling of the iron spectrum in late-type stars. Excitation and charge transfer in low-energy Fe+H collisions is studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multi-channel Landau-Zener model. An extensive calculation including 166 covalent states and 25 ionic states is presented and rate coefficients are calculated for temperatures in the range 1000-20 000 K. The largest rates are found for charge transfer processes to and from two clusters of states around 6.3 and 6.6 eV excitation, corresponding in both cases to active 4d and 5p electrons undergoing transfer. Excitation and de-excitation processes among these two sets of states are also significant. Full Tables and rate coefficient data are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A90

Electronically type-sorted carbon nanotube-based electrochemical biosensors with glucose oxidase and dehydrogenase.

PubMed

Muguruma, Hitoshi; Hoshino, Tatsuya; Nowaki, Kohei

2015-01-14

An electrochemical enzyme biosensor with electronically type-sorted (metallic and semiconducting) single-walled carbon nanotubes (SWNTs) for use in aqueous media is presented. This research investigates how the electronic types of SWNTs influence the amperometric response of enzyme biosensors. To conduct a clear evaluation, a simple layer-by-layer process based on a plasma-polymerized nano thin film (PPF) was adopted because a PPF is an inactive matrix that can form a well-defined nanostructure composed of SWNTs and enzyme. For a biosensor with the glucose oxidase (GOx) enzyme in the presence of oxygen, the response of a metallic SWNT-GOx electrode was 2 times larger than that of a semiconducting SWNT-GOx electrode. In contrast, in the absence of oxygen, the response of the semiconducting SWNT-GOx electrode was retained, whereas that of the metallic SWNT-GOx electrode was significantly reduced. This indicates that direct electron transfer occurred with the semiconducting SWNT-GOx electrode, whereas the metallic SWNT-GOx electrode was dominated by a hydrogen peroxide pathway caused by an enzymatic reaction. For a biosensor with the glucose dehydrogenase (GDH; oxygen-independent catalysis) enzyme, the response of the semiconducting SWNT-GDH electrode was 4 times larger than that of the metallic SWNT-GDH electrode. Electrochemical impedance spectroscopy was used to show that the semiconducting SWNT network has less resistance for electron transfer than the metallic SWNT network. Therefore, it was concluded that semiconducting SWNTs are more suitable than metallic SWNTs for electrochemical enzyme biosensors in terms of direct electron transfer as a detection mechanism. This study makes a valuable contribution toward the development of electrochemical biosensors that employ sorted SWNTs and various enzymes.

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.

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... Property NATIONAL ARCHIVES AND RECORDS ADMINISTRATION RECORDS MANAGEMENT TRANSFER OF RECORDS 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...

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...

Monte-Carlo modelling of nano-material photocatalysis: bridging photocatalytic activity and microscopic charge kinetics.

PubMed

Liu, Baoshun

2016-04-28

In photocatalysis, it is known that light intensity, organic concentration, and temperature affect the photocatalytic activity by changing the microscopic kinetics of holes and electrons. However, how the microscopic kinetics of holes and electrons relates to the photocatalytic activity was not well known. In the present research, we developed a Monte-Carlo random walking model that involved all of the charge kinetics, including the photo-generation, the recombination, the transport, and the interfacial transfer of holes and electrons, to simulate the overall photocatalytic reaction, which we called a "computer experiment" of photocatalysis. By using this model, we simulated the effect of light intensity, temperature, and organic surface coverage on the photocatalytic activity and the density of the free electrons that accumulate in the simulated system. It was seen that the increase of light intensity increases the electron density and its mobility, which increases the probability for a hole/electron to find an electron/hole for recombination, and consequently led to an apparent kinetics that the quantum yield (QY) decreases with the increase of light intensity. It was also seen that the increase of organic surface coverage could increase the rate of hole interfacial transfer and result in the decrease of the probability for an electron to recombine with a hole. Moreover, the increase of organic coverage on the nano-material surface can also increase the accumulation of electrons, which enhances the mobility for electrons to undergo interfacial transfer, and finally leads to the increase of photocatalytic activity. The simulation showed that the temperature had a more complicated effect, as it can simultaneously change the activation of electrons, the interfacial transfer of holes, and the interfacial transfer of electrons. It was shown that the interfacial transfer of holes might play a main role at low temperature, with the temperature-dependence of QY conforming to the Arrhenius model. The activation of electrons from the traps to the conduction band might become important at high temperature, which accelerates the electron movement for recombination and leads to a temperature dependence of QY that deviates from the Arrhenius model.

12 CFR 205.3 - Coverage.

Code of Federal Regulations, 2014 CFR

2014-01-01

... to initiate a one-time electronic fund transfer from a consumer's account. The consumer must...-time electronic fund transfer (in providing a check to a merchant or other payee for the MICR encoding... information for the transfer shall also provide a notice to the consumer at the same time it provides the...

12 CFR 205.3 - Coverage.

Code of Federal Regulations, 2011 CFR

2011-01-01

... to initiate a one-time electronic fund transfer from a consumer's account. The consumer must...-time electronic fund transfer (in providing a check to a merchant or other payee for the MICR encoding... information for the transfer shall also provide a notice to the consumer at the same time it provides the...

12 CFR 205.3 - Coverage.

Code of Federal Regulations, 2013 CFR

2013-01-01

... to initiate a one-time electronic fund transfer from a consumer's account. The consumer must...-time electronic fund transfer (in providing a check to a merchant or other payee for the MICR encoding... information for the transfer shall also provide a notice to the consumer at the same time it provides the...

Charge-transfer complexes and their role in exciplex emission and near-infrared photovoltaics.

PubMed

Ng, Tsz-Wai; Lo, Ming-Fai; Fung, Man-Keung; Zhang, Wen-Jun; Lee, Chun-Sing

2014-08-20

Charge transfer and interactions at organic heterojunctions (OHJs) are known to have critical influences on various properties of organic electronic devices. In this Research News article, a short review is given from the electronic viewpoint on how the local molecular interactions and interfacial energetics at P/N OHJs contribute to the recombination/dissociation of electron-hole pairs. Very often, the P-type materials donate electrons to the N-type materials, giving rise to charge-transfer complexes (CTCs) with a P(δ+) -N(δ-) configuration. A recently observed opposite charge-transfer direction in OHJs is also discussed (i.e., N-type material donates electrons to P-type material to form P(δ-) -N(δ+) ). Recent studies on the electronic structures of CTC-forming material pairs are also summarized. The formation of P(δ-) -N(δ+) -type CTCs and their correlations with exciplex emission are examined. Furthermore, the potential applications of CTCs in NIR photovoltaic devices are reviewed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT.

PubMed

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-14

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT

NASA Astrophysics Data System (ADS)

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-01

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

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.

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 energy conversion, and broadly applicable to problems in interface chemistry and surface physics.« less

Electrostatic orientation of the electron-transfer complex between plastocyanin and cytochrome c.

PubMed

Roberts, V A; Freeman, H C; Olson, A J; Tainer, J A; Getzoff, E D

1991-07-15

To understand the specificity and efficiency of protein-protein interactions promoting electron transfer, we evaluated the role of electrostatic forces in precollision orientation by the development of two new methods, computer graphics alignment of protein electrostatic fields and a systematic orientational search of intermolecular electrostatic energies for two proteins at present separation distances. We applied these methods to the plastocyanin/cytochrome c interaction, which is faster than random collision, but too slow for study by molecular dynamics techniques. Significant electrostatic potentials were concentrated on one-fourth (969 A2) of the plastocyanin surface, with the greatest negative potential centered on the Tyr-83 hydroxyl within the acidic patch, and on one-eighth (632 A2) of the cytochrome c surface, with the greatest positive potential centered near the exposed heme edge. Coherent electrostatic fields occurred only over these regions, suggesting that local, rather than global, charge complementarity controls productive recognition. The three energetically favored families of pre-collision orientations all directed the positive region surrounding the heme edge of cytochrome c toward the acidic patch of plastocyanin but differed in heme plane orientation. Analysis of electrostatic fields, electrostatic energies of precollision orientations with 12 and 6 A separation distances, and surface topographies suggested that the favored orientations should converge to productive complexes promoting a single electron-transfer pathway from the cytochrome c heme edge to Tyr-83 of plastocyanin. Direct interactions of the exposed Cu ligand in plastocyanin with the cytochrome c heme edge are not unfavorable sterically or electrostatically but should occur no faster than randomly, indicating that this is not the primary pathway for electron transfer.

Conformational Changes of NADPH-Cytochrome P450 Oxidoreductase Are Essential for Catalysis and Cofactor Binding*

PubMed Central

Xia, Chuanwu; Hamdane, Djemel; Shen, Anna L.; Choi, Vivian; Kasper, Charles B.; Pearl, Naw May; Zhang, Haoming; Im, Sang-Choul; Waskell, Lucy; Kim, Jung-Ja P.

2011-01-01

The crystal structure of NADPH-cytochrome P450 reductase (CYPOR) implies that a large domain movement is essential for electron transfer from NADPH via FAD and FMN to its redox partners. To test this hypothesis, a disulfide bond was engineered between residues Asp147 and Arg514 in the FMN and FAD domains, respectively. The cross-linked form of this mutant protein, designated 147CC514, exhibited a significant decrease in the rate of interflavin electron transfer and large (≥90%) decreases in rates of electron transfer to its redox partners, cytochrome c and cytochrome P450 2B4. Reduction of the disulfide bond restored the ability of the mutant to reduce its redox partners, demonstrating that a conformational change is essential for CYPOR function. The crystal structures of the mutant without and with NADP+ revealed that the two flavin domains are joined by a disulfide linkage and that the relative orientations of the two flavin rings are twisted ∼20° compared with the wild type, decreasing the surface contact area between the two flavin rings. Comparison of the structures without and with NADP+ shows movement of the Gly631–Asn635 loop. In the NADP+-free structure, the loop adopts a conformation that sterically hinders NADP(H) binding. The structure with NADP+ shows movement of the Gly631–Asn635 loop to a position that permits NADP(H) binding. Furthermore, comparison of these mutant and wild type structures strongly suggests that the Gly631–Asn635 loop movement controls NADPH binding and NADP+ release; this loop movement in turn facilitates the flavin domain movement, allowing electron transfer from FMN to the CYPOR redox partners. PMID:21345800

Molecular dynamics simulations of the orientation properties of cytochrome c on the surface of single-walled carbon nanotubes.

PubMed

Zhang, Bing; Xu, Jia; Mo, Shu-Fan; Yao, Jian-Xi; Dai, Song-Yuan

2016-12-01

Electron transfer between cytochrome c (Cytc) and electrodes can be influenced greatly by the orientation of protein on the surface of the electrodes. In the present study, different initial orientations of Cytc on the surface of five types of single-walled carbon nanotubes (SWNTs), with different diameters and chirality, were constructed. Properties of the orientations of proteins on the surface of these tubes were first investigated through molecular dynamics simulations. It was shown that variations in SWNT diameter do not significantly affect the orientation; however, the chirality of the SWNTs is crucial to the orientation of the heme embedded in Cytc, and the orientation of the protein can consequently be influenced by the heme orientation. A new electron pathway between Cytc and SWNT, which hopefully benefits electron transfer efficiency, has also been proposed. This study promises to provide theoretical guidance for the rational design of bio-sensors or bio-fuel cells by using Cytc-decorated carbon nanotube electrodes.

Complexes of carboxyl-containing polymer and monosubstituted bipyridinium salts

NASA Astrophysics Data System (ADS)

Merekalova, N. D.; Bondarenko, G. N.; Krylsky, D. W.; Zakirov, M. I.; Talroze, R. V.

2013-09-01

Semi-empirical PM3 method for the quantum calculations of molecular electronic structure based on NDDO integral approximation is used to investigate the complex formation of monosubstituted 4,4‧-bipyridinium salts BpyR (Hal) containing a halide anion interacting with the quaternary nitrogen atom and carboxylic group of the two-units construct. Significant effect of the BpyR (Hal) electronic structure is unveiled that contributes in two different structures of these salts, namely, partial charge transfer complex and ion pair structure, both having stable energy minima. We demonstrate that (i) the structure of the N-substituent modulates the energy and electronic characteristics of monosubstituted salts BpyR with chlorine and bromine anions and (ii) the coulomb interactions between quaternary N-atom, halogen anion, and the proton of carboxylic group stimulate the transformation of the charge transfer complex into the ion pair structure. Results of calculations are compared with the experimental FTIR spectra of blends of BpyR(Hal) with Eudragit copolymer.

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

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.

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.

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

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.

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

NASA Astrophysics Data System (ADS)

Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H.

2014-08-01

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where "quantum" coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the "inverted regime" in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

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

Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H., E-mail: millerwh@berkeley.edu

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where “quantum” coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation functionmore » framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the “inverted regime” in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.« less

Role of cation size in the energy of electron transfer to 1:1 polyoxometalate ion pairs {(M+)(Xn+VW11O40)}(8–n)–(M=Li, Na, K)

Treesearch

Vladimir A. Grigoriev; Craig L. Hill; Ira A. Weinstock

2000-01-01

The use of soluble salts of polyoxometalates (d0-early-transition metal oxygen-anion clusters or POMs) as selective oxidation or electron-transfer catalysts, as probes in physical-organic and biological chemistry, and in the study of electron-and energy-transfer phenomena constitutes a substantial and rapidly growing literature. While rarely addressed, however, POM...

Special Inspector General for Iraq Reconstruction. Quarterly Report and Semiannual Report to the United States Congress

DTIC Science & Technology

2008-01-30

Energy Fusion Cell, and allocations include $110 million for oil pipeline exclusion zones—which aim to prevent illegal tapping and sabotage of...sectors in Iraq. This quarter SIGIR highlights two of these programs: the electronic funds transfer ( EFT ) system and U.S. advisory support provided to...the Iraq Stock Exchange. eleCTroniC funds Transfer SIGIR noted last quarter that Iraq finally acti- vated an electronic funds transfer ( EFT ) system

Special Inspector General for Iraq Reconstruction: Quarterly Report and Semiannual Report to the United States Congress

DTIC Science & Technology

2008-01-30

Cell, and allocations include $110 million for oil pipeline exclusion zones—which aim to prevent illegal tapping and sabotage of pipelines—$51...This quarter SIGIR highlights two of these programs: the electronic funds transfer ( EFT ) system and U.S. advisory support provided to the Iraq Stock...Exchange. eleCTroniC funds Transfer SIGIR noted last quarter that Iraq finally acti- vated an electronic funds transfer ( EFT ) system. The United

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.

Molecular implementation of molecular shift register memories

NASA Technical Reports Server (NTRS)

Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

1991-01-01

An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

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.

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

PubMed Central

Yoon, Jongwon; Jeong, Yunkyung; Kim, Heeje; Yoo, Seonggwang; Jung, Hoon Sun; Kim, Yonghun; Hwang, Youngkyu; Hyun, Yujun; Hong, Woong-Ki; Lee, Byoung Hun; Choa, Sung-Hoon; Ko, Heung Cho

2016-01-01

Electronic textile (e-textile) allows for high-end wearable electronic devices that provide easy access for carrying, handling and using. However, the related technology does not seem to be mature because the woven fabric hampers not only the device fabrication process directly on the complex surface but also the transfer printing of ultrathin planar electronic devices. Here we report an indirect method that enables conformal wrapping of surface with arbitrary yet complex shapes. Artificial cilia are introduced in the periphery of electronic devices as adhesive elements. The cilia also play an important role in confining a small amount of glue and damping mechanical stress to maintain robust electronic performance under mechanical deformation. The example of electronic applications depicts the feasibility of cilia for ‘stick-&-play' systems, which provide electronic functions by transfer printing on unconventional complex surfaces. PMID:27248982

Nonadiabatic one-electron transfer mechanism for the O-O bond formation in the oxygen-evolving complex of photosystem II

NASA Astrophysics Data System (ADS)

Shoji, Mitsuo; Isobe, Hiroshi; Shigeta, Yasuteru; Nakajima, Takahito; Yamaguchi, Kizashi

2018-04-01

The reaction mechanism of the O2 formation in the S4 state of the oxygen-evolving complex of photosystem II was clarified at the quantum mechanics/molecular mechanics (QM/MM) level. After the Yz (Y161) oxidation and the following proton transfer in the S3 state, five reaction steps are required to produce the molecular dioxygen. The highest barrier step is the first proton transfer reaction (0 → 1). The following reactions involving electron transfers were precisely analyzed in terms of their energies, structures and spin densities. We found that the one-electron transfer from the Mn4Ca cluster to Y161 triggers the O-O sigma bond formation.

12 CFR 205.10 - Preauthorized transfers.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 12 Banks and Banking 2 2011-01-01 2011-01-01 false Preauthorized transfers. 205.10 Section 205.10 Banks and Banking FEDERAL RESERVE SYSTEM BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC...'s account—(1) Notice by financial institution. When a person initiates preauthorized electronic fund...

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.

Elucidating nitric oxide synthase domain interactions by molecular dynamics.

PubMed

Hollingsworth, Scott A; Holden, Jeffrey K; Li, Huiying; Poulos, Thomas L

2016-02-01

Nitric oxide synthase (NOS) is a multidomain enzyme that catalyzes the production of nitric oxide (NO) by oxidizing L-Arg to NO and L-citrulline. NO production requires multiple interdomain electron transfer steps between the flavin mononucleotide (FMN) and heme domain. Specifically, NADPH-derived electrons are transferred to the heme-containing oxygenase domain via the flavin adenine dinucleotide (FAD) and FMN containing reductase domains. While crystal structures are available for both the reductase and oxygenase domains of NOS, to date there is no atomic level structural information on domain interactions required for the final FMN-to-heme electron transfer step. Here, we evaluate a model of this final electron transfer step for the heme-FMN-calmodulin NOS complex based on the recent biophysical studies using a 105-ns molecular dynamics trajectory. The resulting equilibrated complex structure is very stable and provides a detailed prediction of interdomain contacts required for stabilizing the NOS output state. The resulting equilibrated complex model agrees well with previous experimental work and provides a detailed working model of the final NOS electron transfer step required for NO biosynthesis. © 2015 The Protein Society.

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

Ultrafast electronic dynamics driven by nuclear motion

NASA Astrophysics Data System (ADS)

Vendrell, Oriol

2016-05-01

The transfer of electrical charge on a microscopic scale plays a fundamental role in chemistry, in biology, and in technological applications. In this contribution, we will discuss situations in which nuclear motion plays a central role in driving the electronic dynamics of photo-excited or photo-ionized molecular systems. In particular, we will explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we will illustrate how the double hole can be transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. We thank the Hamburg Centre for Ultrafast Imaging and the Volkswagen Foundation for financial support.

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 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. Electronic supplementary information (ESI) available: Experimental methods, DNA and protein sequences, additional STM statistical analysis and images, electrochemical data and It-z data analysis. See DOI: 10.1039/c2nr32131a

Synthesis and room temperature photo-induced electron transfer in biologically active bis(terpyridine)ruthenium(II)-cytochrome c bioconjugates and the effect of solvents on the bioconjugation of cytochrome c.

PubMed

Peterson, Joshua R; Smith, Trevor A; Thordarson, Pall

2010-01-07

Photo-active bis(terpyridine)ruthenium(ii) chromophores were synthesised and attached to the redox enzyme iso-1 cytochrome c in a mixed solvent system to form photo-induced bioconjugates in greater than 40% yield after purification. The effects of up to 20% (v/v) of acetonitrile, tetrahydrofuran, dimethylformamide, or dimethyl sulfoxide at 4, 25 and 35 degrees C on the stability and biological activity of cytochrome c and its reactivity towards the model compound 4,4'-dithiodipyridine (DTDP) was measured. The second-order rate constant for the DTDP reaction was found to range between k = 2.5-4.3 M(-1) s(-1) for reactions with 5% organic solvent added compared to k = 5.6 M(-1) s(-1) in pure water at 25 degrees C. Use of 20% solvent generally results in significant protein oxidation, and 20% acetonitrile and tetrahydrofuran in particular result in significant protein dimerization, which competes with the bioconjugation reaction. Cyclic voltammetry studies indicated that the rate of electron transfer to the heme in solution was reduced in the bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates compared to unmodified cytochrome c. Steady-state fluorescence studies on these bioconjugates showed that energy or electron transfer is taking place between the bis(terpyridine)ruthenium(ii) chromophores and cytochrome c. The bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates demonstrate room temperature photo-activated electron transfer from the bis(terpyridine)ruthenium(ii) donor to the protein acceptor. Two sacrificial donors were used; in 50% glycerol, the bioconjugates were reduced in about 15 min while in 20 mM EDTA the bioconjugates were fully reduced in less than 5 min upon irradiation with a xenon lamp source. Under these conditions, the reduction of the non-covalent mixture of cytochrome c and bis(terpyridine)ruthenium(ii) mixtures took over 30 min. Control experiments showed that the photo-induced reduction of cytochrome c only occurs in the absence of oxygen and presence of a sacrificial donor. These results are encouraging for future incorporation of these bioconjugates in light-responsive bioelectronic circuits, including photo-activated biosensors and biofuel cells.

2012 Gordon Research Conference, Electron donor-acceptor interactions, August 5-10 2012

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

McCusker, James

The upcoming incarnation of the Gordon Research Conference on Electron Donor Acceptor Interactions will feature sessions on classic topics including proton-coupled electron transfer, dye-sensitized solar cells, and biological electron transfer, as well as emerging areas such as quantum coherence effects in donor-acceptor interactions, spintronics, and the application of donor-acceptor interactions in chemical synthesis.

Factors affecting nursing staff use of a communication tool to reduce potentially preventable acute care transfers in long-term care.

PubMed

Ballard, Stephanie A; Peretti, Matteo; Lungu, Ovidiu; Voyer, Philippe; Tabamo, Fruan; Alfonso, Linda; Cetin-Sahin, Deniz; Johnson, Sarasa M A; Wilchesky, Machelle

Although specialized communication tools can effectively reduce acute care transfers, few studies have assessed the factors that may influence the use of such tools by nursing staff at the individual level. We evaluated the associations between years of experience, tool-related training, nursing attitudes, and intensity of use of a communication tool developed to reduce transfers in a long-term care facility. We employed a mixed methods design using data from medical charts, electronic records, and semi-structured interviews. Experienced nurses used the tool significantly less than inexperienced nurses, and training had a significant positive impact on tool use. Nurses found the purpose of the tool to be confusing. No significant differences in attitude were observed based on years of experience or intensity of use. Project findings indicate that focused efforts to enrich training may increase intervention adherence. Experienced nurses in particular should be made aware of the benefits of utilizing communication tools. Copyright © 2017 Elsevier Inc. All rights reserved.

Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters

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

Perlík, Václav; Seibt, Joachim; Šanda, František

The initial energy transfer steps in photosynthesis occur on ultrafast timescales. We analyze the carotenoid to bacteriochlorophyll energy transfer in LH2 Marichromatium purpuratum as well as in an artificial light-harvesting dyad system by using transient grating and two-dimensional electronic spectroscopy with 10 fs time resolution. We find that Förster-type models reproduce the experimentally observed 60 fs transfer times, but overestimate coupling constants, which lead to a disagreement with both linear absorption and electronic 2D-spectra. We show that a vibronic model, which treats carotenoid vibrations on both electronic ground and excited states as part of the system’s Hamiltonian, reproduces all measuredmore » quantities. Importantly, the vibronic model presented here can explain the fast energy transfer rates with only moderate coupling constants, which are in agreement with structure based calculations. Counterintuitively, the vibrational levels on the carotenoid electronic ground state play the central role in the excited state population transfer to bacteriochlorophyll; resonance between the donor-acceptor energy gap and the vibrational ground state energies is the physical basis of the ultrafast energy transfer rates in these systems.« less

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.

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

Peters, K.S.; Freilich, S.C.; Schaeffer, C.G.

Studies were initiated utilizing picosecond (ps) absorption spectroscopy, to directly monitor the dynamics of electron transfer from 1,4-diazabicyclo(2.2.2)octane (Dabco) to the excited states of benzophenone and fluorenone. These two systems were chosen because of their contrasting photochemistry. The quantum yield for photoreduction of benzophenone in polar solvents is generally greater than 0.1, while that of fluorenone is zero. In polar solvents, the proposed mechanism dictates that an electron is transferred to the excited singlet state fluorenone, which then back-transfers the electron, regenerating ground-state fluorenone and amine. Photolysis of benzophenone in the presence of an amine transfers an electron to anmore » excited triplet state, forming an ion pair that is stable relative to diffusional separation. The results of this study verify this proposal.« less

Flavins in Coastal Marine Sediments: New Perspectives on Diagenetic Electron Transfer

NASA Astrophysics Data System (ADS)

Monteverde, D.; Berelson, W.; Baronas, J. J.; Sanudo-Wilhelmy, S. A.

2016-02-01

Coastal marine sediments play a critical role in the global cycling of metals and nutrients, many of which undergo diagenetic alteration. Central to these transformations are redox reactions where electron-rich organic matter is oxidized via transfer to terminal electron acceptors (NO3-, MnOx, FeOx, SO42-). The flavins (flavin adenine dinucleotide [FAD], flavin mononucleotide [FMN], and riboflavin [B2]) are microbially synthesized organic coenzymes that perform both single and double electron transfer and are known to mediate reduction of insoluble metal oxides. Culture experiments have found high rates of flavin excretion in metal-reducing Shewanella and Geobacter species, however environmental measurements of these highly labile molecules have not been previously reported. Here we present porewater measurements of FAD, FMN, and B2 from San Pedro Basin. This California Borderland basin is silled, suboxic, 900 m deep, and experiences high sedimentation. Flavin concentrations ranged from pico- (FAD: 0- 60 pM; B2: 40 - 90 pM) to nanomolar (FMN: 0.4 - 1.2 nM). The concentration cascade of FMN>B2>FAD fits well within culture experiments. Interestingly, profiles of all three flavins show a near linear increase with depth from 0-30 cm and a relatively steady concentration from 30-45 cm, supporting likely in situ production. Additionally, the flavins showed a negative correlation with dissolved Fe (R2 = 0.7 for FMN, 0.8 for FAD, and 0.9 for B2), which decreased linearly with depth from 160µM to 65µM. We discuss hypothesized mechanisms controlling flavin concentrations based on a suite of sediment geochemical parameters (dissolved Fe, Mn, TCO2, δ13C, NH3, DOM, and SO42-) as well as implications for microbial redox syntrophy. These data provide a critical link between the extensive culture-based mechanistic understanding of flavin function and the sedimentary environment. Furthermore, these results demonstrate that flavins likely serve as a significant electron transfer intermediaries in the marine sediment carbon cycle.

The surface plasmon-induced hot carrier effect on the catalytic activity of CO oxidation on a Cu2O/hexoctahedral Au inverse catalyst.

PubMed

Lee, Si Woo; Hong, Jong Wook; Lee, Hyunhwa; Wi, Dae Han; Kim, Sun Mi; Han, Sang Woo; Park, Jeong Young

2018-06-14

The intrinsic correlation between an enhancement of catalytic activity and the flow of hot electrons generated at metal-oxide interfaces suggests an intriguing way to control catalytic reactions and is a significant subject in heterogeneous catalysis. Here, we show surface plasmon-induced catalytic enhancement by the peculiar nanocatalyst design of hexoctahedral (HOH) Au nanocrystals (NCs) with Cu2O clusters. We found that this inverse catalyst comprising a reactive oxide for the catalytic portion and a metal as the source of electrons by localized surface plasmon resonance (localized SPR) exhibits a change in catalytic activity by direct hot electron transfer or plasmon-induced resonance energy transfer (PIRET) when exposed to light. We prepared two types of inverse catalysts, Cu2O at the vertex sites of HOH Au NCs (Cu2O/Au vertex site) and a HOH Au NC-Cu2O core-shell structure (HOH Au@Cu2O), to test the structural effect on surface plasmons. Under broadband light illumination, the Cu2O/Au vertex site catalyst showed 30-90% higher catalytic activity and the HOH Au@Cu2O catalyst showed 10-30% higher catalytic activity than when in the dark. Embedding thin SiO2 layers between the HOH Au NCs and the Cu2O verified that the dominant mechanism for the catalytic enhancement is direct hot electron transfer from the HOH Au to the Cu2O. Finite-difference time domain calculations show that a much stronger electric field was formed on the vertex sites after growing the Cu2O on the HOH Au NCs. These results imply that the catalytic activity is enhanced when hot electrons, created from photon absorption on the HOH Au metal and amplified by the presence of surface plasmons, are transferred to the reactive Cu2O.

Engineered Proteins: Redox Properties and Their Applications

PubMed Central

Prabhulkar, Shradha; Tian, Hui; Wang, Xiaotang; Zhu, Jun-Jie

2012-01-01

Abstract Oxidoreductases and metalloproteins, representing more than one third of all known proteins, serve as significant catalysts for numerous biological processes that involve electron transfers such as photosynthesis, respiration, metabolism, and molecular signaling. The functional properties of the oxidoreductases/metalloproteins are determined by the nature of their redox centers. Protein engineering is a powerful approach that is used to incorporate biological and abiological redox cofactors as well as novel enzymes and redox proteins with predictable structures and desirable functions for important biological and chemical applications. The methods of protein engineering, mainly rational design, directed evolution, protein surface modifications, and domain shuffling, have allowed the creation and study of a number of redox proteins. This review presents a selection of engineered redox proteins achieved through these methods, resulting in a manipulation in redox potentials, an increase in electron-transfer efficiency, and an expansion of native proteins by de novo design. Such engineered/modified redox proteins with desired properties have led to a broad spectrum of practical applications, ranging from biosensors, biofuel cells, to pharmaceuticals and hybrid catalysis. Glucose biosensors are one of the most successful products in enzyme electrochemistry, with reconstituted glucose oxidase achieving effective electrical communication with the sensor electrode; direct electron-transfer-type biofuel cells are developed to avoid thermodynamic loss and mediator leakage; and fusion proteins of P450s and redox partners make the biocatalytic generation of drug metabolites possible. In summary, this review includes the properties and applications of the engineered redox proteins as well as their significance and great potential in the exploration of bioelectrochemical sensing devices. Antioxid. Redox Signal. 17, 1796–1822. PMID:22435347