WorldWideScience

Sample records for b-branch electron transfer

  1. Quinone (QB) reduction by B-branch electron transfer in mutant bacterial reaction centers from Rhodobacter sphaeroides: quantum efficiency and X-ray structure.

    Science.gov (United States)

    Paddock, M L; Chang, C; Xu, Q; Abresch, E C; Axelrod, H L; Feher, G; Okamura, M Y

    2005-05-10

    The photosynthetic reaction center (RC) from purple bacteria converts light into chemical energy. Although the RC shows two nearly structurally symmetric branches, A and B, light-induced electron transfer in the native RC occurs almost exclusively along the A-branch to a primary quinone electron acceptor Q(A). Subsequent electron and proton transfer to a mobile quinone molecule Q(B) converts it to a quinol, Q(B)H(2). We report the construction and characterization of a series of mutants in Rhodobacter sphaeroides designed to reduce Q(B) via the B-branch. The quantum efficiency to Q(B) via the B-branch Phi(B) ranged from 0.4% in an RC containing the single mutation Ala-M260 --> Trp to 5% in a quintuple mutant which includes in addition three mutations to inhibit transfer along the A-branch (Gly-M203 --> Asp, Tyr-M210 --> Phe, Leu-M214 --> His) and one to promote transfer along the B-branch (Phe-L181 --> Tyr). Comparing the value of 0.4% for Phi(B) obtained in the AW(M260) mutant, which lacks Q(A), to the 100% quantum efficiency for Phi(A) along the A-branch in the native RC, we obtain a ratio for A-branch to B-branch electron transfer of 250:1. We determined the structure of the most effective (quintuple) mutant RC at 2.25 A (R-factor = 19.6%). The Q(A) site did not contain a quinone but was occupied by the side chain of Trp-M260 and a Cl(-). In this structure a nonfunctional quinone was found to occupy a new site near M258 and M268. The implications of this work to trap intermediate states are discussed.

  2. Light induced EPR spectra of reaction centers from Rhodobacter sphaeroides at 80K: Evidence for reduction of QB by B-branch electron transfer in native reaction centers.

    Science.gov (United States)

    Paddock, M. L; Isaacson, R. A.; Abresch, E. C.; Okamura, M. Y.

    2006-01-01

    Photosynthetic reaction centers (RCs) from Rhodobacter sphaeroides capture solar energy by electron transfer from primary donor, D, to quinone acceptor, QB, through the active A-branch of electron acceptors, but not the inactive B-branch. The light induced EPR spectrum from native RCs that had Fe2+ replaced by Zn2+ was investigated at cryogenic temperature (80K, 35 GHz). In addition to the light induced signal due to formation of D+•QA−• observed previously, a small fraction (~5%) of the signal displayed very different characteristics: (1) The signal was absent in RCs in which the QB was displaced by the inhibitor stigmatellin. (2) Its decay time (τ=6 s) was the same as observed for D+•QB−• in mutant RCs lacking QA, which is significantly slower than for D+•QA−• (τ=30 ms). (3) Its EPR spectrum was identical to that of D+•QB−•. (4) The quantum efficiency for forming the major component of the signal was the same as that found for mutant RCs lacking QA (Φ =0.2%) and was temperature independent. These results are explained by direct photochemical reduction of QB via B-branch electron transfer in a small fraction of native RCs. PMID:18163156

  3. Trapped Conformational States of Semiquinone (D+•QB−•) Formed by B-Branch Electron Transfer at Low Temperature in Rhodobacter sphaeroides Reaction Centers‡

    Science.gov (United States)

    Paddock, M. L.; Flores, M.; Isaacson, R.; Chang, C.; Abresch, E. C.; Selvaduray, P.; Okamura, M.Y.

    2006-01-01

    The reaction center (RC) from Rhodobacter sphaeroides captures light energy by electron transfer between quinones QA and QB, involving a conformational gating step. In this work, conformational states of D+•QB−• were trapped (80K) and studied using EPR spectroscopy in mutant RCs that lack QA in which QB was reduced by the bacteriopheophytin along the B-branch. In mutant RCs frozen in the dark, a light induced EPR signal due to D+•QB−• formed in 30% of the sample with low quantum yield (0.2%–20%) and decayed in 6 s. A small signal with similar characteristics was also observed in native RCs. In contrast, the EPR signal due to D+QB− in mutant RCs illuminated while freezing formed in ~ 95% of the sample that did not decay (τ >107s) at 80K. In all samples, the observed g-values were the same (g=2.0026) indicating that all active QB−• was located in a proximal conformation coupled with the non-heme Fe2+. We propose that before electron transfer at 80K, the majority (~70%) of QB, structurally located in the distal site, cannot be stably reduced, while the minor (~30%) active configurations are in the proximal site. The large difference in the lifetimes of the un-relaxed and relaxed D+•QB−• states is attributed to relaxation of protein residues and internal water molecules that stabilize D+•QB−•. These results demonstrate energetically significant conformational changes involved in stabilizing the D+•QB−• state. The unrelaxed and relaxed states can be considered to be the initial and final states along the reaction coordinate for conformationally-gated electron transfer. PMID:17115698

  4. Trapped conformational states of semiquinone (D+*QB-*) formed by B-branch electron transfer at low temperature in Rhodobacter sphaeroides reaction centers.

    Science.gov (United States)

    Paddock, M L; Flores, M; Isaacson, R; Chang, C; Abresch, E C; Selvaduray, P; Okamura, M Y

    2006-11-28

    The reaction center (RC) from Rhodobacter sphaeroides captures light energy by electron transfer between quinones QA and QB, involving a conformational gating step. In this work, conformational states of D+*QB-* were trapped (80 K) and studied using EPR spectroscopy in native and mutant RCs that lack QA in which QB was reduced by the bacteriopheophytin along the B-branch. In mutant RCs frozen in the dark, a light induced EPR signal due to D+*QB-* formed in 30% of the sample with low quantum yield (0.2%-20%) and decayed in 6 s. A small signal with similar characteristics was also observed in native RCs. In contrast, the EPR signal due to D+*QB-* in mutant RCs illuminated while freezing formed in approximately 95% of the sample did not decay (tau >107 s) at 80 K (also observed in the native RC). In all samples, the observed g-values were the same (g = 2.0026), indicating that all active QB-*'s were located in a proximal conformation coupled with the nonheme Fe2+. We propose that before electron transfer at 80 K, the majority (approximately 70%) of QB, structurally located in the distal site, was not stably reducible, whereas the minority (approximately 30%) of active configurations was in the proximal site. The large difference in the lifetimes of the unrelaxed and relaxed D+*QB-* states is attributed to the relaxation of protein residues and internal water molecules that stabilize D+*QB-*. These results demonstrate energetically significant conformational changes involved in stabilizing the D+*QB-* state. The unrelaxed and relaxed states can be considered to be the initial and final states along the reaction coordinate for conformationally gated electron transfer.

  5. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

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

  6. Electron transfer in peptides.

    Science.gov (United States)

    Shah, Afzal; Adhikari, Bimalendu; Martic, Sanela; Munir, Azeema; Shahzad, Suniya; Ahmad, Khurshid; Kraatz, Heinz-Bernhard

    2015-02-21

    In this review, we discuss the factors that influence electron transfer in peptides. We summarize experimental results from solution and surface studies and highlight the ongoing debate on the mechanistic aspects of this fundamental reaction. Here, we provide a balanced approach that remains unbiased and does not favor one mechanistic view over another. Support for a putative hopping mechanism in which an electron transfers in a stepwise manner is contrasted with experimental results that support electron tunneling or even some form of ballistic transfer or a pathway transfer for an electron between donor and acceptor sites. In some cases, experimental evidence suggests that a change in the electron transfer mechanism occurs as a result of donor-acceptor separation. However, this common understanding of the switch between tunneling and hopping as a function of chain length is not sufficient for explaining electron transfer in peptides. Apart from chain length, several other factors such as the extent of the secondary structure, backbone conformation, dipole orientation, the presence of special amino acids, hydrogen bonding, and the dynamic properties of a peptide also influence the rate and mode of electron transfer in peptides. Electron transfer plays a key role in physical, chemical and biological systems, so its control is a fundamental task in bioelectrochemical systems, the design of peptide based sensors and molecular junctions. Therefore, this topic is at the heart of a number of biological and technological processes and thus remains of vital interest.

  7. Electron Transfer Chain Catalysis

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Electron-transfer chain (ETC) catalysis belongs to the family of chain reactions where the electron is the catalyst. The ETC mechanism could be initiated by chemical activation, electrochemistry, or photolysis. If this pathway is applied to the preparation of organometallic complexes, it utilizes the greatly enhanced reactivity of organometallic 17e and 19e radicals. The chemical propagation is followed by the cross electron-transfer while the electron-transfer step is also followed by the chemical propagation, creating a loop in which reactants are facilely transformed into products. Interestingly the overall reaction is without any net redox change.

  8. Electron Transfer Chain Catalysis

    Institute of Scientific and Technical Information of China (English)

    LIU; LingKang

    2001-01-01

    Electron-transfer chain (ETC) catalysis belongs to the family of chain reactions where the electron is the catalyst. The ETC mechanism could be initiated by chemical activation, electrochemistry, or photolysis. If this pathway is applied to the preparation of organometallic complexes, it utilizes the greatly enhanced reactivity of organometallic 17e and 19e radicals. The chemical propagation is followed by the cross electron-transfer while the electron-transfer step is also followed by the chemical propagation, creating a loop in which reactants are facilely transformed into products. Interestingly the overall reaction is without any net redox change.  ……

  9. Electron transfer in proteins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1991-01-01

    Electron migration between and within proteins is one of the most prevalent forms of biological energy conversion processes. Electron transfer reactions take place between active centers such as transition metal ions or organic cofactors over considerable distances at fast rates and with remarkable...... specificity. The electron transfer is attained through weak electronic interaction between the active sites, so that considerable research efforts are centered on resolving the factors that control the rates of long-distance electron transfer reactions in proteins. These factors include (in addition......-containing proteins. These proteins serve almost exclusively in electron transfer reactions, and as it turns out, their metal coordination sites are endowed with properties uniquely optimized for their function....

  10. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

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

  11. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1995-01-01

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

  12. Heterostructure Intervalley Transferred Electron Effects

    Institute of Scientific and Technical Information of China (English)

    XUE Fang-Shi

    2001-01-01

    A Gunn active layer is used as an X electron probe to detect the X tunnelling current in the GaAs-AlAs heterostructure, from which a new heterostructure intervalley transferred electron (HITE) device is obtained. In the 8 mm band, the highest pulse output power of these diodes is 2.65 W and the highest conversion efficiency is 18%. The dc and rf performance of the HITE devices was simulated by the band mixing resonant tunnelling theory and Monte Carlo transport simulation. The HITE effect has transformed the transit-time dipole-layer mode in the Gunn diode into a relaxation oscillation mode in the HITE device. From the comparison of simulated results to the measured data, the HITE effect is demonstrated straightforwardly

  13. Exocellular electron transfer in anaerobic microbial communities

    NARCIS (Netherlands)

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

    2006-01-01

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

  14. Hierarchical control of electron-transfer

    DEFF Research Database (Denmark)

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

    1997-01-01

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

  15. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    OpenAIRE

    2007-01-01

    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...

  16. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

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

    2012-01-01

    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. PMID:23226907

  17. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

    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.

  18. Heat Transfer Augmentation for Electronic Cooling

    Directory of Open Access Journals (Sweden)

    Suabsakul Gururatana

    2012-01-01

    Full Text Available Problem statement: The performance of electronic devices has been improving along with the rapid technology development. Cooling of electronic systems is consequently essential in controlling the component temperature and avoiding any hot spot. The study aims to review the present electronic cooling methods which are widely used in electronic devices. Approach: There are several methods to cool down the electronics components such as the pin-fin heat sink, confined jet impingement, heat pipe, micro heat sink and so on. Results: The cooling techniques can obviously increase heat transfer rate. Nonetheless, for active and passive cooling methods the pressure drop could extremely rise, when the heat transfer rate is increased. Conclusion: When the cooling techniques are used, it is clearly seen that the heat transfer increases with pressure drop. To avoid excessive expense due to high pressure drop, optimization method is required to obtain optimum cost and cooling rate.

  19. Photoselected electron transfer pathways in DNA photolyase.

    Science.gov (United States)

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

    2007-01-16

    Cyclobutane dimer photolyases are proteins that bind to UV-damaged DNA containing cyclobutane pyrimidine dimer lesions. They repair these lesions by photo-induced electron transfer. The electron donor cofactor of a photolyase is a two-electron-reduced flavin adenine dinucleotide (FADH(-)). When FADH(-) is photo-excited, it transfers an electron from an excited pi --> pi* singlet state to the pyrimidine dimer lesion of DNA. We compute the lowest excited singlet states of FADH(-) using ab initio (time-dependent density functional theory and time-dependent Hartree-Fock), and semiempirical (INDO/S configuration interaction) methods. The calculations show that the two lowest pi --> pi* singlet states of FADH(-) are localized on the side of the flavin ring that is proximal to the dimer lesion of DNA. For the lowest-energy donor excited state of FADH(-), we compute the conformationally averaged electronic coupling to acceptor states of the thymine dimer. The coupling calculations are performed at the INDO/S level, on donor-acceptor cofactor conformations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. These calculations demonstrate that the localization of the (1)FADH(-)* donor state on the flavin ring enhances the electronic coupling between the flavin and the dimer by permitting shorter electron-transfer pathways to the dimer that have single through-space jumps. Therefore, in photolyase, the photo-excitation itself enhances the electron transfer rate by moving the electron towards the dimer.

  20. Electron transfer across a thermal gradient.

    Science.gov (United States)

    Craven, Galen T; Nitzan, Abraham

    2016-08-23

    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.

  1. Ultrafast Photoinduced Electron Transfer from Peroxide Dianion.

    Science.gov (United States)

    Anderson, Bryce L; Maher, Andrew G; Nava, Matthew; Lopez, Nazario; Cummins, Christopher C; Nocera, Daniel G

    2015-06-18

    The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)3(2+) and the peroxide dianion occurs with a rate constant of 2.0 × 10(10) M(-1) s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 × 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)3(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

  2. Unusual distance dependences of electron transfer rates.

    Science.gov (United States)

    Kuss-Petermann, Martin; Wenger, Oliver S

    2016-07-28

    Usually the rates for electron transfer (kET) decrease with increasing donor-acceptor distance, but Marcus theory predicts a regime in which kET is expected to increase when the transfer distance gets longer. Until recently, experimental evidence for such counter-intuitive behavior had been very limited, and consequently this effect is much less well-known than the Gaussian free energy dependence of electron transfer rates leading to the so-called inverted driving-force effect. This article presents the theoretical concepts that lead to the prediction of electron transfer rate maxima at large donor-acceptor distances, and it discusses conditions that are expected to favor experimental observations of such behavior. It continues with a consideration of specific recent examples in which electron transfer rates were observed to increase with increasing donor-acceptor distance, and it closes with a discussion of the importance of this effect in the context of light-to-chemical energy conversion.

  3. Quantifying electron transfer reactions in biological systems

    DEFF Research Database (Denmark)

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

    2015-01-01

    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...

  4. Facile Interfacial Electron Transfer of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Chunhai Fan

    2005-12-01

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

  5. 75 FR 16579 - Electronic Fund Transfers

    Science.gov (United States)

    2010-04-01

    ... From the Federal Register Online via the Government Publishing Office ] Part II Federal Reserve System 12 CFR Part 205 Electronic Fund Transfers; Final Rule #0;#0;Federal Register / Vol. 75 , No. 62... Consumers from Hidden Gift Card Fees Secretly Draining Shoppers' Pockets'', Press Release, Mar. 27,...

  6. Electronic Energy Transfer in Polarizable Heterogeneous Environments

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Kongsted, Jacob

    2015-01-01

    Theoretical prediction of transport and optical properties of protein-pigment complexes is of significant importance when aiming at understanding the structure versus function relationship in such systems. Electronic energy transfer (EET) couplings represent a key property in this respect since...

  7. Biotechnological Aspects of Microbial Extracellular Electron Transfer

    Science.gov (United States)

    Kato, Souichiro

    2015-01-01

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

  8. Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

    Science.gov (United States)

    Antoniou, P; Ma, Z; Zhang, P; Beratan, D N; Skourtis, S S

    2015-12-14

    Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer system or irreversibly change its molecular structure. For bridge-mediated electron-transfer reactions, infrared (vibrational) excitation of the bridge linking the electron donor to the electron acceptor was suggested as being capable of influencing the electron-transfer rate by modulating the bridge-mediated donor-to-acceptor electronic coupling. This kind of electron-transfer experiment has been realized, demonstrating that bridge-mediated electron-transfer rates can be changed by exciting vibrational modes of the bridge. Here, we use simple models and ab initio computations to explore the physical constraints on one's ability to vibrationally perturb electron-transfer rates using infrared excitation. These constraints stem from the nature of molecular vibrational spectra, the strengths of the electron-vibrational coupling, and the interaction between molecular vibrations and infrared radiation. With these constraints in mind, we suggest parameter regimes and molecular architectures that may enhance the vibrational control of electron transfer for fast coherent electron-transfer reactions.

  9. Education and solar conversion. Demonstrating electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Smestad, Greg P. [Institute of Physical Chemistry, ICP-2, Swiss Federal Institute of Technology, EPFL, CH-1015 Lausanne (Switzerland)

    1998-07-23

    A simplified solar cell fabrication procedure is presented that uses natural anthocyanin or chlorophyll dyes extracted from plants. This procedure illustrates how interdisciplinary science can be taught at lower division university and upper division high school levels for an understanding of renewable energy as well as basic science concepts. Electron transfer occurs on the Earth in the mitochondrial membranes found in living cells, and in the thylakoid membranes found in the photosynthetic cells of green plants. Since we depend on the results of this electron and energy transfer, e.g. in our use of petroleum and agricultural products, it is desirable to understand and communicate how the electron transfer works. The simplified solar cell fabrication procedure, based on nanocrystalline dye-sensitized solar cells, has therefore been developed so that it can be inexpensively reproduced and utilized in the teaching of basic principles in biology, chemistry, physics, and environmental science. A water-based solution of commercial nanocrystalline titanium dioxide (TiO{sub 2}) powder is used to deposit a highly porous semiconductor electron acceptor. This acceptor couples the light-driven processes occurring at an organic dye to the macroscopic world and an external electrical circuit. Materials science and semiconductor physics are emphasized during the deposition of the sintered TiO{sub 2} nanocrystalline ceramic film. Chelation, complexation and molecular self-assembly are demonstrated during the attachment of the dye molecule to the surface of the TiO{sub 2} semiconductor particles. Environmental chemistry and energy conversion can be linked to these concepts via the regenerative oxidation and reduction cycle found in the cell. The resulting device, made in under 3 h, can be used as a light detector or power generator that produces 0.4-0.5 V at open circuit, and 1-2 mA per square cm under solar illumination

  10. Heat transfer in high density electronics packaging

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In order to get an insight into the thermal characteristic and to evaluate the thermal reliability of the "System in Packaging"(SIP), a new solution of electronics packaging, a heat transfer model of SIP was developed to predict the heat dissipation capacity and to investigate the effect of different factors on the temperature distribution in the electronics. The affecting parameters under consideration include the thermophysical properties of the substrates, the coefficient of convection heat transfer, the thickness of the chip, and the density of power dissipation. ALGOR, a kind of finite element analysis software,was used to do the model simulation. Based on the sinulation and analysis of the heat conduction and convection resistance, criteria for the thermal design were established and possible measurement for enhancing power dissipation was provided, The results show that the heat transfer model provides a new and effective way to the thermal design and thermal analysis of SIP and to the mechanical analysis for the further investigation of SIP.

  11. 14 CFR 1260.69 - Electronic funds transfer payment methods.

    Science.gov (United States)

    2010-01-01

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

  12. Electron transfer pathways in microbial oxygen biocathodes

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-01-01

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

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

    NARCIS (Netherlands)

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

    2010-01-01

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

  14. Electron transfer at sensitized semiconductor electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Spitler, M.T.

    1977-03-01

    Electron transfer from the excited state of sensitizing dyes to the conduction band of semiconductors has been studied through photoelectrochemical techniques. Two systems were analyzed in detail: rhodamine B on ZnO and rose bengal on TiO/sub 2/. Prior to electrochemical experimentation, the adsorption characteristics of these dyes were investigated using ZnO, ZnS, and TiO/sub 2/ single crystals as substrates. Absorbance measurements of the adsorbed dye were taken as a function of the solution concentration of the dye. Adsorption isotherms heats of adsorption were also established; they were similar to literature data reported for adsorption of these dyes on powdered substrates. Using the absorbance data, the quantum efficiency for photoinjection of electrons from rhodamine B into a ZnO electrode was determined to be 2.7 x 10/sup -2/. This value was independent of the dye surface concentration down to 50% coverage of the electrode. With the assumption that not all of the rhodamine B adsorbed on the electrode has the same rate of electron injection, a kinetic model for the time decay of the photocurrent was developed; data were analyzed according to this theory. A rate constant for photoreduction of the adsorbed dye was determined for the reducing agents. 86 references.

  15. Transfer line TT70 (electrons from PS to SPS)

    CERN Multimedia

    CERN PhotoLab

    1981-01-01

    As injectors for LEP, PS and SPS had to be converted to the acceleration of electrons and positrons. So far, only positively charged particles had been transferred from the PS to the SPS, for the negatively charged electrons a new transfer line, TT70, had to be built. Due to the difference in level of the two machines, the transfer line slopes and tilts.

  16. GPU-accelerated computation of electron transfer.

    Science.gov (United States)

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

    2012-11-05

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

  17. Soliton-like Solutions and Electron Transfer in DNA.

    Science.gov (United States)

    Lakhno, V D

    2000-06-01

    We consider various mechanisms of long-range electron transfer in DNAwhich enable us to explain recent controversial experiments. We show thatcontinuous super-exchange theory can explain the values of electron rateconstants in short fragments of DNA. The soliton-type electron transfer inlong segments of DNA is also dealt with.

  18. Soliton-like Solutions and Electron Transfer in DNA

    OpenAIRE

    Lakhno, V.D.

    2000-01-01

    We consider various mechanisms of long-range electron transfer in DNAwhich enable us to explain recent controversial experiments. We show thatcontinuous super-exchange theory can explain the values of electron rateconstants in short fragments of DNA. The soliton-type electron transfer inlong segments of DNA is also dealt with.

  19. Electronic and Nuclear Factors in Charge and Excitation Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Piotr Piotrowiak

    2004-09-28

    We report the and/or state of several subprojects of our DOE sponsored research on Electronic and Nuclear Factors in Electron and Excitation Transfer: (1) Construction of an ultrafast Ti:sapphire amplifier. (2) Mediation of electronic interactions in host-guest molecules. (3) Theoretical models of electrolytes in weakly polar media. (4) Symmetry effects in intramolecular excitation transfer.

  20. Respiratory electron transfer in Escherichia coli : components, energetics and regulation

    NARCIS (Netherlands)

    Bekker, M.

    2009-01-01

    The respiratory chain that is housed in the bacterial cytoplasmic membrane, generally transfers electrons from NADH to oxygen; in the absence of oxygen it can use several alternative electron acceptors, such as nitrate and fumarate. Transfer of electrons through this chain is usually coupled to the

  1. Theory of interrelated electron and proton transfer processes

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2003-01-01

    A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic and nonadiaba......A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic...

  2. [Electron transfer between globular proteins. Evaluation of a matrix element].

    Science.gov (United States)

    Lakhno, V D; Chuev, G N; Ustinin, M N

    1998-01-01

    The dependence of the matrix element of the probability of interprotein electron transfer on the mutual orientation of the donor and acceptor centers and the distance between them was calculated. The calculations were made under the assumption that electron transfer proceeds mainly by a collective excitation of polaron nature, like a solvated electron state. The results obtained are consistent with experimental data and indicate the nonexponential behavior of this dependence in the case when the distance transfer is less than 20 A.

  3. Electron transfer and interfacial behavior of redox proteins

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    This paper reviews the recent progress in the electron transfer and interfacial behavior of redox proteins. Significant achievements in the relevant fields are summarized including the direct electron transfer between proteins and electrodes, the thermodynamic and kinetic properties, catalytic activities and activity regulation of the redox proteins. It has been demonstrated that the electrochemical technique is an effective tool for protein studies, especially for probing into the electron transfer and interfacial behavior of redox proteins.

  4. Cation-modulated electron-transfer channel: H-atom transfer vs proton-coupled electron transfer with a variable electron-transfer channel in acylamide units.

    Science.gov (United States)

    Chen, Xiaohua; Bu, Yuxiang

    2007-08-08

    The mechanism of proton transfer (PT)/electron transfer (ET) in acylamide units was explored theoretically using density functional theory in a representative model (a cyclic coupling mode between formamide and the N-dehydrogenated formamidic radical, FF). In FF, PT/ET normally occurs via a seven-center cyclic proton-coupled electron transfer (PCET) mechanism with a N-->N PT and an O-->O ET. However, when different hydrated metal ions are bound to the two oxygen sites of FF, the PT/ET mechanism may significantly change. In addition to their inhibition of PT/ET rate, the hydrated metal ions can effectively regulate the FF PT/ET cooperative mechanism to produce a single pathway hydrogen atom transfer (HAT) or a flexible proton coupled electron transfer (PCET) mechanism by changing the ET channel. The regulation essentially originates from the change in the O...O bond strength in the transition state, subject to the binding ability of the hydrated metal ions. In general, the high valent metal ions and those with large binding energies can promote HAT, and the low valent metal ions and those with small binding energies favor PCET. Hydration may reduce the Lewis acidity of cations, and thus favor PCET. Good correlations among the binding energies, barrier heights, spin density distributions, O...O contacts, and hydrated metal ion properties have been found, which can be used to interpret the transition in the PT/ET mechanism. These findings regarding the modulation of the PT/ET pathway via hydrated metal ions may provide useful information for a greater understanding of PT/ET cooperative mechanisms, and a possible method for switching conductance in nanoelectronic devices.

  5. Vibrationally Resolved Electron Transfer Rates in Solution

    Science.gov (United States)

    Spears, Kenneth G.

    2002-03-01

    We have re-examined our earlier report of electron transfer in the [Co(Cp)_2|V(CO)_6] radical-pair using ultrafast infrared transient absorption spectroscopy in room temperature solutions. The radical-pair is created from the [Co(Cp)_2^+|V(CO)_6^-] ion-pair by ultrafast visible charge-transfer excitation. Transient absorption experiments with ps time constants. A small ET component with a 75 ps time constant is due to some separation and reformation of the radical-pairs. Transient absorption experiments monitoring the recovery of the ion-pair state shows that both fast components are due to ET rather than some other vibrational relaxation (VR) process in the radical state. We analyze the visible charge-transfer band and assign the two fast ET decay times to two ion-pair contact geometries with absorption origins different by about 1250 ± 350 cm-1. For excitation at 800 and 700 nm the 700 fs ET lifetime depends on the vibrational quantum state of the nontotally symmetric CO stretch in the V(CO)6 radical, where the lifetime decreases by 10% for the first vibrational quantum and 45% for the second quantum. There is no quantum effect for the second ion-pair geometry with a 5 ps ET lifetime. Standard ET rate models cannot explain the rate dependence upon vibrational quantum state for a nontotally symmetric vibration, and it may arise from a breakdown of the Condon approximation. We also report rates for IVR of CO stretching modes and for VR of low frequency vibrations. At excitation wavelengths of 620 and 555 nm there is sufficient internal vibrational energy in low-frequency vibrations to cause geometric inter-conversion between energetically similar Jahn-Teller geometries in the V(CO)6 radical. This process creates a 200 fs rise time for the V(CO)6 radical species to assume a stable geometry, which requires VR of low frequency vibrations to the solvent. These results demonstrate that earlier ET measurements from our group on the same molecule had insufficient time

  6. Electronic transfer of sensitive patient data.

    Science.gov (United States)

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

    2015-01-01

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

  7. Kinetics of electron transfer from photoexcited superlattice electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Nozik, A.J.; Turner, J.A.; Peterson, M.W.

    1988-05-05

    A kinetic model has been developed that quantitatively describes electron transfer from photoexcited superlattice electrodes into liquid solutions. The model permits electron transfer from all quantum levels as well as from surface states; it also takes into account recombination in the bulk, space charge layer, and surfaces states, and band-edge movement. The model calculations define the values of the rate constants for heterogeneous electron transfer and hot electron thermalization among the various energy levels in the supperlattice quantum wells that are necessary to achieve hot electron transfer from excited quantum states. The question of whether hot electron transfer is manifested by a dependence of the photocurrent action spectra on acceptor redox potential is examined in detail.

  8. Photoinitiated electron transfer in multichromophoric species: Synthetic tetrads and pentads

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1993-03-01

    This project involves the design, synthesis and study of molecules which mimic some of the important aspects of photosynthetic electron and energy transfer. This research project is leading to a better understanding of the energy conserving steps of photosynthesis via the study of synthetic model systems which abstract features of the natural photosynthetic apparatus. The knowledge gained from these studies will aid in the design of artificial photosynthetic reaction centers which employ the basic chemistry and physics of photosynthesis to help meet mankind`s energy needs. The approach to artificial photosynthesis employed in this project is to use synthetic pigments, electron donors, and electron acceptors similar to those found in biological reaction centers, but to replace the protein component with covalent bonds. These chemical linkages determine the electronic coupling between the various moieties by controlling separation, relative orientation, and overlap of electronic orbitals. The model systems are designed to mimic the following aspects of natural photosynthetic electron transfer: electron donation from a tetrapyrrole excited single state, electron transfer between tetrapyrroles, electron transfer from tetrapyrroles to quinones, and electron transfer between quinones with different redox properties. In addition, they mimic carotenoid antenna function in photosynthesis (singlet-singlet energy transfer from carotenoid polyenes to chlorophyll) and carotenoid photoprotection from singlet oxygen damage (triplet-triplet energy transfer from chlorophyll to carotenoids).

  9. 77 FR 6310 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ... PROTECTION 12 CFR Part 1005 RIN 3170-AA15 Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer... Financial Protection (Bureau) is proposing to amend Regulation E, which implements the Electronic Fund... phrase ``normal course of business'' in the definition of ``remittance transfer provider.''...

  10. Time-resolved EPR identifies unexpected electron transfer in cryptochrome**

    Science.gov (United States)

    Biskup, Till; Hitomi, Kenichi; Getzoff, Elizabeth D.; Krapf, Sebastian; Koslowski, Thorsten; Schleicher, Erik

    2012-01-01

    Tuning photoinduced electron transfer: Subtle differences in local sequence and conformation can produce diversity and specificity in electron transfer (ET) in proteins, despite high structural conservation of redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of ET partners, and therefore, stabilization of charge-separated states contribute substantially. PMID:22086606

  11. 78 FR 66251 - Electronic Fund Transfers(Regulation E)

    Science.gov (United States)

    2013-11-05

    ... PROTECTION 12 CFR Part 1005 RIN 3170-AA33 Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer... countries that qualify for an exception in subpart B of Regulation E, which implements the Electronic Fund....consumerfinance.gov/remittances-transfer-rule-amendment-to-regulation-e/ . SUPPLEMENTARY INFORMATION: The...

  12. THE ELECTRONIC COURSE OF HEAT AND MASS TRANSFER

    Directory of Open Access Journals (Sweden)

    Alexander P. Solodov

    2013-01-01

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

  13. Electron and hole transfer from indium phosphide quantum dots.

    Science.gov (United States)

    Blackburn, J L; Selmarten, D C; Ellingson, R J; Jones, M; Micic, O; Nozik, A J

    2005-02-24

    Electron- and hole-transfer reactions are studied in colloidal InP quantum dots (QDs). Photoluminescence quenching and time-resolved transient absorption (TA) measurements are utilized to examine hole transfer from photoexcited InP QDs to the hole acceptor N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) and electron transfer to nanocrystalline titanium dioxide (TiO2) films. Core-confined holes are effectively quenched by TMPD, resulting in a new approximately 4-ps component in the TA decay. It is found that electron transfer to TiO2 is primarily mediated through surface-localized states on the InP QDs.

  14. Heme electron transfer in peroxidases: the propionate e-pathway.

    Science.gov (United States)

    Guallar, Victor

    2008-10-23

    Computational modeling offers a new insight about the electron transfer pathway in heme peroxidases. Available crystal structures have revealed an intriguing arrangement of the heme propionate side chains in heme-heme and heme-substrate complexes. By means of mixed quantum mechanical/molecular mechanics calculations, we study the involvement of these propionate groups into the substrate oxidation in ascorbate peroxidase and into the heme to heme electron transfer in bacterial cytochrome c peroxidase. By selectively turning on/off different quantum regions, we obtain the electron transfer pathway which directly involves the porphyrin ring and the heme propionates. Furthermore, in ascorbate peroxidase the presence of the substrate appears to be crucial for the activation of the electron transfer channel. The results might represent a general motif for electron transfer from/to the heme group and change our view for the propionate side chains as simple electrostatic binding anchors. We name the new mechanism "the propionate e-pathway".

  15. Density matrix theory for reductive electron transfer in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Kleinekathoefer, Ulrich [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany)]. E-mail: kleinekathoefer@physik.tu-chemnitz.de; Li Guangqi [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany); Schreiber, Michael [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany)

    2006-07-15

    Reductive electron transfer in DNA is investigated using the reduced density matrix formalism. For reductive electron transfer in DNA an electron donor is attached to the DNA. The photo-excitation of this donor by ultrashort laser pulses is described explicitly in the current investigation, as well as the transfer of the electron from the donor to the acceptor. In addition, the effect of an additional bridge molecule is studied. All these studies are performed using three different quantum master equations: a Markovian one and two non-Markovian ones derived from either a time-local or a time-nonlocal formalism. The deviations caused by these three different approaches are discussed.

  16. Variable Electron Transfer Pathways in an Amphibian Cryptochrome

    Science.gov (United States)

    Biskup, Till; Paulus, Bernd; Okafuji, Asako; Hitomi, Kenichi; Getzoff, Elizabeth D.; Weber, Stefan; Schleicher, Erik

    2013-01-01

    Electron transfer reactions play vital roles in many biological processes. Very often the transfer of charge(s) proceeds stepwise over large distances involving several amino acid residues. By using time-resolved electron paramagnetic resonance and optical spectroscopy, we have studied the mechanism of light-induced reduction of the FAD cofactor of cryptochrome/photolyase family proteins. In this study, we demonstrate that electron abstraction from a nearby amino acid by the excited FAD triggers further electron transfer steps even if the conserved chain of three tryptophans, known to be an effective electron transfer pathway in these proteins, is blocked. Furthermore, we were able to characterize this secondary electron transfer pathway and identify the amino acid partner of the resulting flavin-amino acid radical pair as a tyrosine located at the protein surface. This alternative electron transfer pathway could explain why interrupting the conserved tryptophan triad does not necessarily alter photoreactions of cryptochromes in vivo. Taken together, our results demonstrate that light-induced electron transfer is a robust property of cryptochromes and more intricate than commonly anticipated. PMID:23430261

  17. Intermolecular and intramolecular electron transfer from eosin ester to viologen

    Institute of Scientific and Technical Information of China (English)

    张丰雷; 张曼华; 沈涛

    1996-01-01

    The covalently -(CH2)10- linked eosin-butylviologen compound has been synthesized. The photoinduced electron transfer of eosin ester and butylviologen as well as the influence of addition of cyclodextrin or amylose into the solution of linked compound on the system have been studied by the absorption spectra, fluorescence spectra and fluorescence lifetime. The results indicated that the intramolecular electron transfer is much more efficient than the intermolecular one. Due to the formation of inclusion complex, the process of intramolecular electron transfer was changed after adding cydodextrin or amylose.

  18. REFLECTIONS ON THE TWO-STATE ELECTRON TRANSFER MODEL.

    Energy Technology Data Exchange (ETDEWEB)

    Brunschwig, B.S.

    2000-01-12

    There is general agreement that the two most important factors determining electron transfer rates in solution are the degree of electronic interaction between the donor and acceptor sites, and the changes in the nuclear configurations of the donor, acceptor, and surrounding medium that occur upon the gain or loss of an electron Ll-51. The electronic interaction of the sites will be very weak, and the electron transfer slow, when the sites are far apart or their interaction is symmetry or spin forbidden. Since electron motion is much faster than nuclear motion, energy conservation requires that, prior to the actual electron transfer, the nuclear configurations of the reactants and the surrounding medium adjust from their equilibrium values to a configuration (generally) intermediate between that of the reactants and products. In the case of electron transfer between , two metal complexes in a polar solvent, the nuclear configuration changes involve adjustments in the metal-ligand and intraligand bond lengths and angles, and changes in the orientations of the surrounding solvent molecules. In common with ordinary chemical reactions, an electron transfer reaction can then be described in terms of the motion of the system on an energy surface from the reactant equilibrium configuration (initial state) to the product equilibrium configuration (final state) via the activated complex (transition state) configuration.

  19. [Electron transfer between globular proteins. Dependence of the rate of transfer on distance].

    Science.gov (United States)

    Lakhno, V D; Chuev, G N; Ustinin, M N; Komarov, V M

    1998-01-01

    Based on the assumption that electron transfer between globular proteins occurs by a collective excitation of polaron type, the dependence of the rate of this process on the distance between the donor and acceptor centers with regard to their detailed electron structure was calculated. The electron structure of the heme was calculated by the quantum-chemical MNDO-PM3 method. The results were compared with experimental data on interprotein and intraglobular electron transfer. It is shown that, in the framework of this model, the electron transfer is not exponential and does not require a particular transfer pathway since the whole protein macromolecule is involved in the formation of the electron excited state.

  20. Extracellular electron transfer mechanisms between microorganisms and minerals

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-30

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

  1. 76 FR 29901 - Electronic Fund Transfers

    Science.gov (United States)

    2011-05-23

    ... trust in the provider, security, reliability (i.e., having funds available at the specified time), and... group participants identified cost, convenience, and security among the most important factors when... provider to advertise, solicit, or market remittance transfer services at a particular office, with...

  2. Promoting Knowledge Transfer with Electronic Note Taking

    Science.gov (United States)

    Katayama, Andrew D.; Shambaugh, R. Neal; Doctor, Tasneem

    2005-01-01

    We investigated the differences between (a) copying and pasting text versus typed note-taking methods of constructing study notes simultaneously with (b) vertically scaffolded versus horizontally scaffold notes on knowledge transfer. Forty-seven undergraduate educational psychology students participated. Materials included 2 electronic…

  3. Supramolecular networks with electron transfer in two dimensions

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Analysis of transmission efficiency of SSRF electron beam transfer lines

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In this article, the main factors which influence transmission efficiency of the SSRF electron beam transfer lines are described, including physical requirements for magnet system, vacuum system, beam diagnostic system,trajectory correction system, etc. The dynamic simulation calculation and transmission efficiency analysis of the SSRF electron beam transfer lines are presented, and the studies show that the design purpose of efficient beam transmission and injection will be achieved.

  5. 78 FR 30661 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2013-05-22

    ... Transfers (Regulation E); Final Rule #0;#0;Federal Register / Vol. 78 , No. 99 / Wednesday, May 22, 2013... Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer Financial Protection. ACTION: Final rule.../regulations/final-remittance-rule-amendment-regulation-e/ . SUPPLEMENTARY INFORMATION: I. Summary of the...

  6. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive ...... vibrational frequency changes, local mode anharmonicity, and rotational reorganization, in both diabatic and adiabatic limits. Systems for which this formalism is appropriate are discussed....

  7. Real-time electron dynamics simulation of two-electron transfer reactions induced by nuclear motion

    Science.gov (United States)

    Suzuki, Yasumitsu; Yamashita, Koichi

    2012-04-01

    Real-time electron dynamics of two-electron transfer reactions induced by nuclear motion is calculated by three methods: the numerically exact propagation method, the time-dependent Hartree (TDH) method and the Ehrenfest method. We find that, as long as the nuclei move as localized wave packets, the TDH and Ehrenfest methods can reproduce the exact electron dynamics of a simple charge transfer reaction model containing two electrons qualitatively well, even when nonadiabatic transitions between adiabatic states occur. In particular, both methods can reproduce the cases where a complete two-electron transfer reaction occurs and those where it does not occur.

  8. Electron Donor-Acceptor Quenching and Photoinduced Electron Transfer for Coumarin Dyes.

    Science.gov (United States)

    1983-10-31

    Mechanism of cousarin photodegradation . Ithe behavior of eoiuma dyes is water ad In aqueous detergent media,. and the effsects of medism aud, additives on...D-i36 345 ELECTRON DONOR-ACCEPTOR UENCHING AND PHOTOINDUCED i/i Ai ELECTRON TRANSFER FOR COUMARIN DYES (U) BOSTON UNIY MR DEPT OF CHEMISTRY G JONES...TYPE OF REPORT & PEIOD COVERED Electron Donor-acceptor Quenching and Photo- Technical, 1/1/82-10/31/82 induced Electron Transfer for Coumarin Dyes S

  9. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    inside the enclosures to be able to protect the electronic systems.In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce theCPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which...

  11. Transcriptomic and genetic analysis of direct interspecies electron transfer

    DEFF Research Database (Denmark)

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

    2013-01-01

    The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens was the elect......The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens...... was the electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7-fold lower in cocultures with G. metallireducens than in cocultures with P. carbinolicus...

  12. Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.

    Science.gov (United States)

    Sukegawa, Junpei; Schubert, Christina; Zhu, Xiaozhang; Tsuji, Hayato; Guldi, Dirk M; Nakamura, Eiichi

    2014-10-01

    Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor-bridge-acceptor molecules, in which π-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron-vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.

  13. Bacterial Electron Transfer Chains Primed by Proteomics

    NARCIS (Netherlands)

    Wessels, H.; Almeida, N.M. de; Kartal, B.; Keltjens, J.T.

    2016-01-01

    Electron transport phosphorylation is the central mechanism for most prokaryotic species to harvest energy released in the respiration of their substrates as ATP. Microorganisms have evolved incredible variations on this principle, most of these we perhaps do not know, considering that only a fracti

  14. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

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

    2014-01-01

    to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were...

  15. Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; Lee, Yong-Min; Nam, Wonwoo

    2015-12-01

    Redox-inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal-oxygen intermediates, such as metal-oxo and metal-peroxo complexes. The mechanisms of the oxidative CH bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)-oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate-determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3 ) by iron(III)-oxo complexes. All logarithms of the observed second-order rate constants of Lewis acid-promoted oxidative CH bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)-oxo complexes exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal-oxo moiety has been confirmed for Mn(IV) -oxo complexes. The enhancement of the electron-transfer reactivity of metal-oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox-inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)-peroxo complexes, resulting in acceleration of the electron-transfer reduction but deceleration of the electron-transfer oxidation. Such a control on the reactivity of metal-oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca(2+) in the oxidation of water to dioxygen by the oxygen-evolving complex in photosystem II.

  16. Imaging population transfer in atoms with ultrafast electron pulses

    Science.gov (United States)

    Shao, Hua-Chieh; Starace, Anthony F.

    2016-05-01

    Ultrafast electron diffraction and microscopy have made significant progress recently in investigating atomic-scale structural dynamics in gas-phase and condensed materials. With these advances, direct imaging of electronic motions in atoms and molecules by ultrafast electron diffraction is anticipated. We propose imaging a laser-driven coherent population transfer in lithium atoms by femtosecond ultrafast electron pulses. Valuable information and insight can be obtained from studying such a system in order to refine ultrafast electron techniques and to interpret experimental results. Adiabatic passage by level crossing is used to transfer the electron population from the 2 s to the 2 p state. Our simulations demonstrate the ability of ultrafast electron diffraction to image this population transfer, as the time-dependent diffraction images reflect the electronic motion in the scattering intensity and angular distribution. Furthermore, asymmetric diffraction patterns indicate that even the relative phases of the electronic wave function can be resolved, provided there is sufficient temporal resolution. This work has been supported in part by DOE Award No. DE-SC0012193 [H.-C.S.] and by NSF Grant No. PHYS-1505492 [A.F.S.].

  17. [Electron transfer, ionization, and excitation in atomic collisions]. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1992-12-31

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

  18. Plugging in or Going Wireless: Strategies for Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Pravin Malla Shrestha

    2014-05-01

    Full Text Available Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET in which two species establish electrical contacts is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. It seems likely that there are additional alternative strategies for interspecies electrical connections that have yet to be discovered. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions.

  19. Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri.

    Science.gov (United States)

    Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Liu, Fanghua; Markovaite, Beatrice; Chen, Shanshan; Nevin, Kelly P; Lovley, Derek R

    2014-08-01

    Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri to participate in DIET was evaluated in coculture with Geobacter metallireducens. Cocultures formed aggregates that shared electrons via DIET during the stoichiometric conversion of ethanol to methane. Cocultures could not be initiated with a pilin-deficient G. metallireducens strain, suggesting that long-range electron transfer along pili was important for DIET. Amendments of granular activated carbon permitted the pilin-deficient G. metallireducens isolates to share electrons with M. barkeri, demonstrating that this conductive material could substitute for pili in promoting DIET. When M. barkeri was grown in coculture with the H2-producing Pelobacter carbinolicus, incapable of DIET, M. barkeri utilized H2 as an electron donor but metabolized little of the acetate that P.carbinolicus produced. This suggested that H2, but not electrons derived from DIET, inhibited acetate metabolism. P. carbinolicus-M. barkeri cocultures did not aggregate, demonstrating that, unlike DIET, close physical contact was not necessary for interspecies H2 transfer. M. barkeri is the second methanogen found to accept electrons via DIET and the first methanogen known to be capable of using either H2 or electrons derived from DIET for CO2 reduction. Furthermore, M. barkeri is genetically tractable,making it a model organism for elucidating mechanisms by which methanogens make biological electrical connections with other cells.

  20. Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer

    Science.gov (United States)

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

    2015-12-01

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

  1. Electron transfer statistics and thermal fluctuations in molecular junctions.

    Science.gov (United States)

    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 to 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.

  2. Marcus Electron Transfer Reactions with Bulk Metallic Catalysis

    CERN Document Server

    Widom, A; Srivastava, Y N

    2015-01-01

    Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such electron transfer chemical reaction events occur in the neighborhood of metallic plates, then electrodynamic interface fields must also be considered in addition to mechanical oscillations. Such electrodynamic interfacial electric fields in principle strongly effect the chemical reaction rates. The thermodynamic states of the metal are unchanged by the reaction which implies that metallic plates are purely catalytic chemical agents.

  3. PHOTOINDUCED CHARGE TRANSFER POLYMERIZATION OF STYRENE INITIATED BY ELECTRON ACCEPTOR

    Institute of Scientific and Technical Information of China (English)

    CAO Weixiao; ZHANG Peng; FENG Xinde

    1995-01-01

    Photoinduced charge transfer polymerization of styrene(St) with electron acceptor as initiator was investigated. In case of fumaronitrile (FN) or maleic anhydride (MA) as initiator the polymerization takes place regularly, whereas the tetrachloro-1, 4-benzenequinone (TCQ), 2, 3-dichloro-5, 6-dicyano-1, 4-benzenequinone (DDQ) . or tetracyano ethylene (TCNE) as initiator the polymerization proceeds reluctantly only after the photoaddition reaction. A mechanism was proposed that free radicals would be formed following the charge and proton transfer in the exciplex formed between St and electron acceptors.

  4. Photoinduced electron transfer in singly labeled thiouredopyrenetrisulfonate azurin derivatives

    DEFF Research Database (Denmark)

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

    1999-01-01

    efficiency. TUPS derivatives of azurin, singly labeled at specific lysine residues, were prepared and purified to homogeneity by ion exchange HPLC. Transient absorption spectroscopy was used to directly monitor the rates of the electron transfer reaction from the photoexcited triplet state of TUPS to Cu...... of the crystal structure of Pseudomonas aeruginosa azurin and molecular structure calculation of the TUPS modified proteins, electron transfer pathways were calculated. Analysis of the results revealed a good correlation between separation distance from donor to Cu ligating atom (His-N or Cys-S) and the observed...

  5. Investigation of transferred-electron oscillations in diamond

    Science.gov (United States)

    Suntornwipat, N.; Majdi, S.; Gabrysch, M.; Isberg, J.

    2016-05-01

    The recent discovery of Negative Differential Mobility (NDM) in intrinsic single-crystalline diamond enables the development of devices for high frequency applications. The Transferred-Electron Oscillator (TEO) is one example of such devices that uses the benefit of NDM to generate continuous oscillations. This paper presents theoretical investigations of a diamond TEO in the temperature range of 110 to 140 K where NDM has been observed. Our simulations map out the parameter space in which transferred-electron oscillations are expected to occur for a specific device geometry. The results are promising and indicate that it is possible to fabricate diamond based TEO devices.

  6. High-pressure effects on intramolecular electron transfer compounds

    CERN Document Server

    He Li Ming; Li Hong; Zhang Bao Wen; Li Yi; Yang Guo Qiang

    2002-01-01

    We explore the effect of pressure on the fluorescence spectra of the intramolecular electron transfer compound N-(1-pyrenylmethyl), N-methyl-4-methoxyaniline (Py-Am) and its model version, with poly(methyl methacrylate) blended in, at high pressure up to 7 GPa. The emission properties of Py-Am and pyrene show distinct difference with the increase of pressure. This difference indicates the strength of the charge transfer interaction resulting from the adjusting of the conformation of Py-Am with increase of pressure. The relationship between the electronic state of the molecule and pressure is discussed.

  7. Reactant-Product Quantum Coherence in Electron Transfer Reactions

    CERN Document Server

    Kominis, I K

    2012-01-01

    We investigate the physical meaning of quantum superposition states between reactants and products in electron transfer reactions. We show that such superpositions are strongly suppressed and to leading orders of perturbation theory do not pertain in electron transfer reactions. This is because of the intermediate manifold of states separating the reactants from the products. We provide an intuitive description of these considerations with Feynman diagrams. We also discuss the relation of such quantum coherences to understanding the fundamental quantum dynamics of spin-selective radical-ion-pair reactions.

  8. 12 CFR 205.15 - Electronic fund transfer of government benefits.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 2 2010-01-01 2010-01-01 false Electronic fund transfer of government benefits... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.15 Electronic fund transfer of government... consumer for use in initiating an electronic fund transfer of government benefits from an account,...

  9. Conduction mechanism studies on electron transfer of disordered system

    Institute of Scientific and Technical Information of China (English)

    徐慧; 宋祎璞; 李新梅

    2002-01-01

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

  10. Charge transfer to ground-state ions produces free electrons

    Science.gov (United States)

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

    2017-01-01

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

  11. Photoinduced Reductive Electron Transfer in LNA:DNA Hybrids

    DEFF Research Database (Denmark)

    Wenge, Ulrike; Wengel, Jesper; Wagenknecht, Hans-Achim

    2012-01-01

    Lock it, but not too much: LNA units (locked or bridging nucleic acids) in LNA:DNA hybrids lead to a negative effect on electron transfer (ET), but they also force the nucleic acid structure in the A-type double helix, which allows a better base stacking than the normal B-type and thus positively...... influences the ET. This result is significant for the design of nucleic acids of molecular electronics....

  12. Quantum Mechanical Hysteresis and the Electron Transfer Problem

    CERN Document Server

    Etchegoin, P G

    2004-01-01

    We study a simple quantum mechanical symmetric donor-acceptor model for electron transfer (ET) with coupling to internal deformations. The model contains several basic properties found in biological ET in enzymes and photosynthetic centers; it produces tunnelling with hysteresis thus providing a simple explanation for the slowness of the reversed rate and the near 100% efficiency of ET in many biological systems. The model also provides a conceptual framework for the development of molecular electronics memory elements based on electrostatic architectures.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lian, Tianquan

    2014-04-22

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

  14. Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri

    DEFF Research Database (Denmark)

    Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Liu, Fanghua;

    2014-01-01

    Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri, to participate in DIET was evaluated in co-culture with Geobacter...

  15. Electron transfer in syntrophic communities of anaerobic bacteria and archaea

    NARCIS (Netherlands)

    Stams, A.J.M.; Plugge, C.M.

    2009-01-01

    Interspecies electron transfer is a key process in methanogenic and sulphate-reducing environments. Bacteria and archaea that live in syntrophic communities take advantage of the metabolic abilities of their syntrophic partner to overcome energy barriers and break down compounds that they cannot dig

  16. Dimers of Azurin as model systems for electron transfer

    NARCIS (Netherlands)

    Jongh, Thyra Estrid de

    2006-01-01

    This thesis describes the investigation of crosslinked complexes of the blue copper protein azurin by means of spectroscopic techniques such as Uv-Vis and NMR as well as by X-ray crystallography. These non-physiological dimers serve as model systems for interprotein electron transfer (ET) and allow

  17. Electron transfer flavoprotein deficiency: Functional and molecular aspects

    DEFF Research Database (Denmark)

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

    2006-01-01

    Multiple acyl-CoA dehydrogenase deficiency (MADD) is a recessively inherited metabolic disorder that can be due to a deficiency of electron transfer flavoprotein (ETF) or its dehydrogenase (ETF-ubiquinone oxidoreductase). ETF is a mitochondrial matrix protein consisting of alpha- (30kDa) and beta...

  18. Polymer glass transitions switch electron transfer in individual molecules

    NARCIS (Netherlands)

    Siekierzycka, J.R.; Hippius, C.; Würthner, F.; Williams, R.M.; Brouwer, A.M.

    2010-01-01

    Essentially complete photoinduced electron transfer quenching of the fluorescence of a perylene−calixarene compound occurs in poly(methyl acrylate) and poly(vinyl acetate) above their glass transition temperatures (T-g), but the fluorescence is completely recovered upon cooling the polymer matrix to

  19. Correlating electronic and vibrational motions in charge transfer systems

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Munira [Univ. of Washington, Seattle, WA (United States)

    2014-06-27

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

  20. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  1. A molecularly based theory for electron transfer reorganization energy

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Bilin; Wang, Zhen-Gang, E-mail: zgw@cheme.caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

    2015-12-14

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

  2. Electron transfer in pH-sensitive nitroxide radicals

    Science.gov (United States)

    Barbon, Antonio; Bortolus, Marco; Isse, Abdirisak A.; Reznikov, Vladimir A.; Weiner, Lev

    2016-11-01

    Two pH-sensitive stable nitroxide radicals are characterized by EPR spectroscopy and cyclic voltammetry in aqueous solution at different pH values. The rates of the photochemically-induced electron transfer reactions from the protonated and deprotonated forms of the radicals to a ruthenium complex are determined.

  3. The intramolecular electron transfer between copper sites of nitrite reductase

    DEFF Research Database (Denmark)

    Farver, O; Eady, R R; Abraham, Z H

    1998-01-01

    The intramolecular electron transfer (ET) between the type 1 Cu(I) and the type 2 Cu(II) sites of Alcaligenes xylosoxidans dissimilatory nitrite reductase (AxNiR) has been studied in order to compare it with the analogous process taking place in ascorbate oxidase (AO). This internal process...

  4. Fundamental Research on Convective Heat Transfer in Electronic Cooling Technology

    Institute of Scientific and Technical Information of China (English)

    C.F.Ma; Y.P.Gan; 等

    1992-01-01

    During the past six years comprehensive research programs have been conducted at the Beijing Polytechnic University to provide a better understanding of heat transfer characteristics of existing and condidate cooling techniques for electronic and microelestanding of heat transfer characteristics of existing and condidate cooling techniques for electronic and microleectronic devices.This paper provides a review and summary of the programs with emphasis on direct liquid cooling.Included in this review are the heat transfer investigations related to the following cooling modes:liquid free,mixed and forced convection.liquid jet impingement,flowing liquid film cooling,pool boiling,spray cooling,foreign gas jet impingement in liquid pool,and forced convection air-cooling.

  5. Photoinduced electron transfer of chlorophyll in lipid bilayer system

    Indian Academy of Sciences (India)

    D K Lee; K W Seo; Y S Kang

    2002-12-01

    Photoinduced electron transfer from chlorophyll- through the interface of dipalmitoylphosphatidylcholine (DPPC) headgroup of the lipid bilayers was studied with electron magnetic resonance (EMR). The photoproduced radicals were identified with electron spin resonance (ESR) and radical yields of chlorophyll- were determined by double integration ESR spectra. The formation of vesicles was identified by changes in measured max values from diethyl ether solutions to vesicles solutions indirectly, and observed directly with SEM and TEM images. The efficiency of photosynthesis in model system was determined by measuring the amount of chlorophyll-a radical yields which were obtained from integration of ESR spectra.

  6. Ultrafast proton coupled electron transfer (PCET dynamics in 9-anthranol-aliphatic amine system

    Directory of Open Access Journals (Sweden)

    Nibbering Erik T. J.

    2013-03-01

    Full Text Available Femtosecond infrared absorption studies strongly suggest that photoexcited 9-anthranol takes part in an ultrafast electron transfer (ET reaction in electron-donating triethylamine solvent, but that ultrafast proton coupled electron transfer (PCET occurs in diethylamine solvent.

  7. Protein dynamics modulated electron transfer kinetics in early stage photosynthesis.

    Science.gov (United States)

    Kundu, Prasanta; Dua, Arti

    2013-01-28

    A recent experiment has probed the electron transfer kinetics in the early stage of photosynthesis in Rhodobacter sphaeroides for the reaction center of wild type and different mutants [Science 316, 747 (2007)]. By monitoring the changes in the transient absorption of the donor-acceptor pair at 280 and 930 nm, both of which show non-exponential temporal decay, the experiment has provided a strong evidence that the initial electron transfer kinetics is modulated by the dynamics of protein backbone. In this work, we present a model where the electron transfer kinetics of the donor-acceptor pair is described along the reaction coordinate associated with the distance fluctuations in a protein backbone. The stochastic evolution of the reaction coordinate is described in terms of a non-Markovian generalized Langevin equation with a memory kernel and Gaussian colored noise, both of which are completely described in terms of the microscopics of the protein normal modes. This model provides excellent fits to the transient absorption signals at 280 and 930 nm associated with protein distance fluctuations and protein dynamics modulated electron transfer reaction, respectively. In contrast to previous models, the present work explains the microscopic origins of the non-exponential decay of the transient absorption curve at 280 nm in terms of multiple time scales of relaxation of the protein normal modes. Dynamic disorder in the reaction pathway due to protein conformational fluctuations which occur on time scales slower than or comparable to the electron transfer kinetics explains the microscopic origin of the non-exponential nature of the transient absorption decay at 930 nm. The theoretical estimates for the relative driving force for five different mutants are in close agreement with the experimental estimates obtained using electrochemical measurements.

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

    Science.gov (United States)

    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.

  9. Electromicrobiology: Electron Transfer via Biowires in Nature and Practical Applications

    Directory of Open Access Journals (Sweden)

    Lovley Derek

    2016-01-01

    Full Text Available One of the most exciting developments in the field of electromicrobiology has been the discovery of electrically conductive pili (e-pili in Geobacter species that transport electrons with a metallic-like mechanism. The e-pili are essential for extracellular electron transport to Fe(III oxides and longrange electron transport through the conductive biofilms that form on the anodes of microbial fuel cells. The e-pili also facilitate direct interspecies electron transfer between Geobacter and Methanosaeta or Methanosarcina species. Metatranscriptomic studies have demonstrated that Geobacter/Methanosaeta DIET is an important process in anaerobic digesters converting brewery wastes to methane. Increasing e-pili expression through genetic modification of regulatory systems or adaptive evolution yields strains with enhanced rates of extracellular electron transfer. Measurement of the conductivity of individual e-pili has demonstrated that they have conductivities higher than those of a number of synthetic conducting organic polymers. Multiple lines of evidence have demonstrated that aromatic amino acids play an important role in the electron transport along e-pili, suggesting opportunities to tune e-pili conductivity via genetic manipulation of the amino acid composition of e-pili. It is expected that e-pili will be harnessed to improve microbe-electrode processes such as microbial electrosynthesis and for the development of novel biosensors. Also, e-pili show promise as a sustainable ‘green’ replacement for electronic materials that contain toxic components and/or are produced with harsh chemicals.

  10. Syntrophic Growth via Quinone-Mediated Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Jessica A Smith

    2015-02-01

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

  11. Alternating electron and proton transfer steps in photosynthetic water oxidation.

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-02

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

  12. A polaron model for electron transfer in globular proteins.

    Science.gov (United States)

    Chuev, G N; Lakhno, V D

    1993-07-07

    Polaron models have been considered for the electron states in protein globules existing in a solvent. These models account for two fundamental effects, viz, polarization interaction of an electron with the conformational vibrations and the heterogeneity of the medium. Equations have been derived to determine the electron state in a protein globule. The parameters of this state show that it is an extended state with an energy of 2 eV. The electron transfer rate for cyt C self-exchange reaction has been calculated in the polaron model. Reorganization energy, tunneling matrix element and the rate constant have also been estimated. The results are compared with experimental data. The influence of model parameters on the significance of the data obtained has been studied. The potentialities of the model are discussed.

  13. Electron-Nuclear Spin Transfer in Triple Quantum Dot Networks

    Science.gov (United States)

    Prada, Marta; Toonen, Ryan; Harrison, Paul

    2005-03-01

    We investigate the conductance spectra of coupled quantum dots to study systematically the nuclear spin relaxation of delta- and y-junction networks and observe spin blockade dependence on the electronic configurations. We derive the conductance using the Beenakker approach generalised to an array of quantum dots where we consider the nuclear spin transfer to electrons by hyperfine coupling. This allows us to predict the relevant memory effects on the different electronic states by studying the evolution of the single electron resonances in presence of nuclear spin relaxation. We find that the gradual depolarisation of the nuclear system is imprinted in the conductance spectra of the multidot system. Our calculations of the temporal evolution of the conductance resonance reveal that spin blockade can be lifted by hyperfine coupling.

  14. Electron nuclear spin transfer in quantum-dot networks

    Science.gov (United States)

    Prada, M.; Toonen, R. C.; Blick, R. H.; Harrison, P.

    2005-05-01

    We investigate the conductance spectra of coupled quantum dots to study systematically the nuclear spin relaxation of different geometries of a two-dimensional network of quantum dots and observe spin blockade dependence on the electronic configurations. We derive the conductance using the Beenakker approach generalized to an array of quantum dots where we consider the nuclear spin transfer to electrons by hyperfine coupling. This allows us to predict the relevant memory effects on the different electronic states by studying the evolution of the single electron resonances in the presence of nuclear spin relaxation. We find that the gradual depolarization of the nuclear system is imprinted in the conductance spectra of the multidot system. Our calculations of the temporal evolution of the conductance resonance reveal that spin blockade can be lifted by hyperfine coupling.

  15. The Electron Transfer Reaction between p-Nitrobenzoates and β-N, N-Dimethylaminonaphthalene

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A few of p-nitrobenzoates were synthesized, and the electron transfer of them with β-N, N-dimethylaminonaphthalene (DMAN) in methanol solution was studied. Steady-state fluore-scence results showed the cyclodextrin moiety in p-nitrobenzoyl-β-cyclodextrin would block the electron transfer pathway from DMAN compared with other electron acceptors, thus, reduced the electron transfer efficiency.

  16. Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor

    Science.gov (United States)

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

    2017-02-01

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

  17. Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Miller, David C; Choi, Gilbert J; Orbe, Hudson S; Knowles, Robert R

    2015-10-28

    Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

  18. Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor

    Science.gov (United States)

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

    2017-01-01

    Direct Electron Transfer biosensors, facilitating direct communication between the biomolecule of interest and electrode surface, are preferable compared to enzymatic and mediator based sensors. Although hemoglobin (Hb) contains four redox active iron centres, direct detection is not possible due to inaccessibility of iron centres and formation of dimers, blocking electron transfer. Through the coordination of iron with aza-heterocyclic receptors - pyridine and imidazole - we report a cost effective, highly sensitive and simple electrochemical Hb sensor using cyclic voltammetry and chronoamperometry. The receptor can be either in the form of liquid micro-droplet mixed with blood or dry chemistry embedded in paper membrane on top of screen printed carbon electrodes. We demonstrate excellent linearity and robustness against interference using clinical samples. A truly point of care technology is demonstrated by integrating disposable test strips with handheld reader, enabling finger prick to result in less than a minute. PMID:28169325

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

    Energy Technology Data Exchange (ETDEWEB)

    Levi, B.G.

    1993-01-01

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

  20. Nanoscale and single-molecule interfacial electron transfer

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Wackerbarth, Hainer; Nielsen, Jens Ulrik;

    2003-01-01

    Electrochemical science and technology in the 21st century have reached high levels of sophistication. A fundamental quantum mechanical theoretical frame for interfacial electrochemical electron transfer (ET) was introduced by Revaz Dogonadze. This frame has remained for four decades as a basis f...... differential resistance patterns, and by ET dynamics of organized assemblies of biological macromolecules, such as redox metalloproteins and oligonucleotides on single-crystal Au(III)-electrode surfaces....

  1. Hetero-cycloreversions Mediated by Photoinduced Electron Transfer

    OpenAIRE

    Pérez Ruiz, Raul; Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

    2014-01-01

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) versi...

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

    KAUST Repository

    Alsulami, Qana A.

    2016-11-30

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

  3. The Electron Transfer System of Syntrophically Grown Desulfovibrio vulgaris

    Energy Technology Data Exchange (ETDEWEB)

    PBD; ENIGMA; GTL; VIMSS; Walker, Christopher B.; He, Zhili; Yang, Zamin K.; Ringbauer Jr., Joseph A.; He, Qiang; Zhou, Jizhong; Voordouw, Gerrit; Wall, Judy D.; Arkin, Adam P.; Hazen, Terry C.; Stolyar, Sergey; Stahl, David A.

    2009-06-22

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

  4. The electron transfer system of syntrophically grown Desulfovibrio vulgaris

    Energy Technology Data Exchange (ETDEWEB)

    Walker, C.B.; He, Z.; Yang, Z.K.; Ringbauer, Jr., J.A.; He, Q.; Zhou, J.; Voordouw, G.; Wall, J.D.; Arkin, A.P.; Hazen, T.C.; Stolyar, S.; Stahl, D.A.

    2009-05-01

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

  5. First-Principles Calculations of Electron Transfer in Organic Molecules

    Science.gov (United States)

    Pati, Ranjit; Karna, Shashi P.

    2000-03-01

    Suitably tailored organic structures are considered potential candidates as components in molecular electronic devices. A common molecular architecture for electronics consists of an electron donor (D) and an electron acceptor (A) moiety bonded together by a chemically inert bridging moiety, called spacer (S). The D-S-A combination constitutes the basic component equivalent of a solid state capacitor. A useful physical property that determines the applicability of molecular structures in moletronics is the electron transfer (ET) rate, which is related, in a two-state approximation, to the coupling matrix between the two electronic states representing the localization of electrons. In an effort to model potential organic structures, we have calculated the ET coupling matrix elements in a number of D-, S-, and A-type organic molecules with the use of ab initio Hartree-Fock method and two different basis sets, namely an STO-3G and a double zeta plus polarization (DZP). A number of important findings have emerged from this study: (i) The ET coupling matrix strongly depends upon the geometrical arrangement of the molecular fragment(s) in the architecture. (ii) In an oligomeric chain, the ET matrix decreases exponentially with molecular length (number of monomer units). (iii) In cyclic alkanes, the magnitude of the ET coupling matrix decreases with increasing size of fused rings.

  6. Theoretical study on electron transfer in biological systems (Ⅲ)——Intramolecular electron transfer in metal-containing spiro π-electron system

    Institute of Scientific and Technical Information of China (English)

    翟宇峰; 蒋华良; 朱维良; 顾健德; 陈建忠; 陈凯先; 嵇汝运

    1999-01-01

    Intramolecular electron transfer of metal-containing spiro π-electron system was studied by AM1 method in the MOPAC-ET program developed by the present group. The results indicated that with the increasing of the outer electric field F, the activation energy of the reaction decreased. When F reaches a certain threshold value, the activation energy barrier becomes zero and the rate of reaction achieves the largest value. The results also indicated that electron transfer matrix elements VAB and reorganization energy λ were not obviously affected by outer electric field while the exothermicity ΔE was directly proportional to it.

  7. Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-09

    Microbial phototrophs are key primary producers on Earth. Currently known electron donors for microbial photosynthesis include H2O, H2, H2S and other reduced inorganic compounds. We describe a new form of metabolism linking anoxygenic photosynthesis to anaerobic respiration, or “syntrophic anoxygenic photosynthesis.” We show that photoautotrophy in green sulfur bacterium Prosthecochloris aestaurii can be driven not only by electrons from a graphite electrode, but also by acetate oxidation via interspecies electron transfer from heterotrophic partner bacterium Geobacter sulfurreducens. P. aestuarii photosynthetic growth using reductant provided by either an electrode or syntrophy was robust and light-dependent. By contrast, P. aestuarii did not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer,. This syntrophic interaction suggests revisitation of global carbon cycling in anoxic environments and lays a foundation for further engineering of phototrophic microbial communities for biotechnological applications, such as waste treatment and bioenergy production.

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born–Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate...... the electron transfer. We observe how Jahn–Teller distortion effects play out in solution, when the molecule has energetically close-lying states, and how this distortion is averaged out in the thermal sampling. Finally, we demonstrate how the solvent helps stabilize and localize the separated charge...

  9. Noise-assisted quantum electron transfer in photosynthetic complexes

    CERN Document Server

    Nesterov, Alexander I; Martínez, José Manuel Sánchez; Sayre, Richard T

    2013-01-01

    Electron transfer (ET) between primary electron donors and acceptors is modeled in the photosystem II reaction center (RC). Our model includes (i) two discrete energy levels associated with donor and acceptor, interacting through a dipole-type matrix element and (ii) two continuum manifolds of electron energy levels ("sinks"), which interact directly with the donor and acceptor. Namely, two discrete energy levels of the donor and acceptor are embedded in their independent sinks through the corresponding interaction matrix elements. We also introduce classical (external) noise which acts simultaneously on the donor and acceptor (collective interaction). We derive a closed system of integro-differential equations which describes the non-Markovian quantum dynamics of the ET. A region of parameters is found in which the ET dynamics can be simplified, and described by coupled ordinary differential equations. Using these simplified equations, both sharp and flat redox potentials are analyzed. We analytically and nu...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-01-01

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

  11. Reduced density matrix hybrid approach: application to electronic energy transfer.

    Science.gov (United States)

    Berkelbach, Timothy C; Markland, Thomas E; Reichman, David R

    2012-02-28

    Electronic energy transfer in the condensed phase, such as that occurring in photosynthetic complexes, frequently occurs in regimes where the energy scales of the system and environment are similar. This situation provides a challenge to theoretical investigation since most approaches are accurate only when a certain energetic parameter is small compared to others in the problem. Here we show that in these difficult regimes, the Ehrenfest approach provides a good starting point for a dynamical description of the energy transfer process due to its ability to accurately treat coupling to slow environmental modes. To further improve on the accuracy of the Ehrenfest approach, we use our reduced density matrix hybrid framework to treat the faster environmental modes quantum mechanically, at the level of a perturbative master equation. This combined approach is shown to provide an efficient and quantitative description of electronic energy transfer in a model dimer and the Fenna-Matthews-Olson complex and is used to investigate the effect of environmental preparation on the resulting dynamics.

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

    DEFF Research Database (Denmark)

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

    2000-01-01

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

  13. Polyoxometalate-mediated electron transfer-oxygen transfer oxidation of cellulose and hemicellulose to synthesis gas.

    Science.gov (United States)

    Sarma, Bidyut Bikash; Neumann, Ronny

    2014-08-01

    Terrestrial plants contain ~70% hemicellulose and cellulose that are a significant renewable bioresource with potential as an alternative to petroleum feedstock for carbon-based fuels. The efficient and selective deconstruction of carbohydrates to their basic components, carbon monoxide and hydrogen, so called synthesis gas, is an important key step towards the realization of this potential, because the formation of liquid hydrocarbon fuels from synthesis gas are known technologies. Here we show that by using a polyoxometalate as an electron transfer-oxygen transfer catalyst, carbon monoxide is formed by cleavage of all the carbon-carbon bonds through dehydration of initially formed formic acid. In this oxidation-reduction reaction, the hydrogen atoms are stored on the polyoxometalate as protons and electrons, and can be electrochemically released from the polyoxometalate as hydrogen. Together, synthesis gas is formed. In a hydrogen economy scenario, this method can also be used to convert carbon monoxide to hydrogen.

  14. Hetero-cycloreversions mediated by photoinduced electron transfer.

    Science.gov (United States)

    Pérez-Ruiz, Raúl; Jiménez, M Consuelo; Miranda, Miguel A

    2014-04-15

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the

  15. Local operator partitioning of electronic energy for electronic energy transfer: An efficient algorithm

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul

    2013-01-01

    An efficient computational algorithm to implement a local operator approach to partitioning electronic energy in general molecular systems is presented. This approach, which rigorously defines the electronic energy on any subsystem within a molecule, gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. We apply the technique to the $9-$(($1-$naphthyl)$-$methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH$_2-$naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety of different behaviors amongst these excited electronic states.

  16. MATHEMATICAL MODELING OF EXTRACELLULAR ELECTRON TRANSFER IN BIOFILMS

    Energy Technology Data Exchange (ETDEWEB)

    Renslow, Ryan S.; Babauta, Jerome T.; Kuprat, Andrew P.; Schenk, Jim; Ivory, Cornelius; Fredrickson, Jim K.; Beyenal, Haluk

    2015-09-12

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

  17. Microbial extracellular electron transfer and its relevance to iron corrosion.

    Science.gov (United States)

    Kato, Souichiro

    2016-03-01

    Extracellular electron transfer (EET) is a microbial metabolism that enables efficient electron transfer between microbial cells and extracellular solid materials. Microorganisms harbouring EET abilities have received considerable attention for their various biotechnological applications, including bioleaching and bioelectrochemical systems. On the other hand, recent research revealed that microbial EET potentially induces corrosion of iron structures. It has been well known that corrosion of iron occurring under anoxic conditions is mostly caused by microbial activities, which is termed as microbiologically influenced corrosion (MIC). Among diverse MIC mechanisms, microbial EET activity that enhances corrosion via direct uptake of electrons from metallic iron, specifically termed as electrical MIC (EMIC), has been regarded as one of the major causative factors. The EMIC-inducing microorganisms initially identified were certain sulfate-reducing bacteria and methanogenic archaea isolated from marine environments. Subsequently, abilities to induce EMIC were also demonstrated in diverse anaerobic microorganisms in freshwater environments and oil fields, including acetogenic bacteria and nitrate-reducing bacteria. Abilities of EET and EMIC are now regarded as microbial traits more widespread among diverse microbial clades than was thought previously. In this review, basic understandings of microbial EET and recent progresses in the EMIC research are introduced.

  18. Mechanisms of bridge-mediated electron transfer: a TDDFT electronic dynamics study.

    Science.gov (United States)

    Ding, Feizhi; Chapman, Craig T; Liang, Wenkel; Li, Xiaosong

    2012-12-14

    We present a time-dependent density functional theory approach for probing the dynamics of electron transfer on a donor-bridge-acceptor polyene dye scaffold. Two kinds of mechanisms, namely, the superexchange mechanism and the sequential mechanism, may be involved in the electron transfer process. In this work, we have focused on the crossover between these two charge transfer mechanisms on a series of donor-bridge-acceptor polyene dye systems with varying lengths of conjugated bridges. A number of methods and quantities are used to assist in the analysis, including the phase relationship of charge evolution and frequency domain spectra of the time-dependent dipole. Our simulations show that the superexchange mechanism plays a dominant role in the electron transfer from donor to acceptor when the bridge length is small, and the sequential mechanism becomes more important as the polyene bridge is lengthened. Full Ehrenfest dynamics with nuclear motion show that molecular vibrations play a very small role in such ultrafast charge transfer processes.

  19. Gunn effect and transferred electron devices. Citations from the NTIS data base

    Science.gov (United States)

    Reed, W. E.

    1980-06-01

    A bibliography containing 99 abstracts addressing the Gunn effect and transferred electron devices is presented. The application of Gunn effect and transferred electron devices to microwave generation, amplification, and control is included. The Gunn effect in semiconductors is dicussed along with the design, fabrication, and properties of Gunn diodes and transferred electron devices.

  20. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thanulov

    2003-01-01

    We have studied the adsorption and electron-transfer dynamics of Saccharomyces cerevisiae (yeast) iso-l-cytochrome c adsorbed on Au(lll) electrodes in aqueous phosphate buffer media. This cytochrome possesses a thiol group dos e to the protein surface (Cysl02) suitable for linking the protein...... negative ofthe equilibrium potential of YCC, where the protein is electrochemically functional. The MCS data show tensile differential stress signals when YCC is adsorbed on a gold-coate d MCS, with distinguishable adsorption phases in the time range from

  1. Electron transfer pathway analysis in bacterial photosynthetic reaction center

    CERN Document Server

    Kitoh-Nishioka, Hirotaka

    2016-01-01

    A new computational scheme to analyze electron transfer (ET) pathways in large biomolecules is presented with applications to ETs in bacterial photosynthetic reaction center. It consists of a linear combination of fragment molecular orbitals and an electron tunneling current analysis, which enables an efficient first-principles analysis of ET pathways in large biomolecules. The scheme has been applied to the ET from menaquinone to ubiquinone via nonheme iron complex in bacterial photosynthetic reaction center. It has revealed that not only the central Fe$^{2+}$ ion but also particular histidine ligands are involved in the ET pathways in such a way to mitigate perturbations that can be caused by metal ion substitution and depletion, which elucidates the experimentally observed insensitivity of the ET rate to these perturbations.

  2. The electronic transfer of information and aerospace knowledge diffusion

    Science.gov (United States)

    Pinelli, Thomas E.; Bishop, Ann P.; Barclay, Rebecca O.; Kennedy, John M.

    1992-01-01

    Increasing reliance on and investment in information technology and electronic networking systems presupposes that computing and information technology will play a motor role in the diffusion of aerospace knowledge. Little is known, however, about actual information technology needs, uses, and problems within the aerospace knowledge diffusion process. The authors state that the potential contributions of information technology to increased productivity and competitiveness will be diminished unless empirically derived knowledge regarding the information-seeking behavior of the members of the social system - those who are producing, transferring, and using scientific and technical information - is incorporated into a new technology policy framework. Research into the use of information technology and electronic networks by U.S. aerospace engineers and scientists, collected as part of a research project designed to study aerospace knowledge diffusion, is presented in support of this assertion.

  3. Molecular Models for Conductance in Junctions and Electrochemical Electron Transfer

    Science.gov (United States)

    Mazinani, Shobeir Khezr Seddigh

    This thesis develops molecular models for electron transport in molecular junctions and intra-molecular electron transfer. The goal is to identify molecular descriptors that afford a substantial simplification of these electronic processes. First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon's tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer. Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed. Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of

  4. Electromagnetic field generation by ATP-induced reverse electron transfer.

    Science.gov (United States)

    Steele, Richard H

    2003-03-01

    This paper describes a mechanism to explain low-level light emission in biology. A biological analog of the electrical circuitry, modeled on the parallel plate capacitor, traversed by a helical structure, required to generate electromagnetic radiation in the optical spectral range, is described. The charge carrier required for the emissions is determined to be an accelerating electron driven by an ATP-induced reverse electron transfer. The radial velocity component, the emission trajectory, of the moving charges traversing helical protein structures in a cyclotron-type mechanism is proposed to be imposed by the ferromagnetic field components of the iron in the iron-sulfur proteins. The redox systems NADH, riboflavin, and chlorophyll were examined with their long-wavelength absorption maxima determining the energetic parameters for the calculations. Potentials calculated from the axial velocity components for the riboflavin and NADH systems were found to equal the standard redox potentials of these systems as measured electrochemically and enzymatically. The mechanics for the three systems determined the magnetic moments, the angular momenta, and the orbital magnetic fluxes to be adiabatic invariant parameters. The De Broglie dual wave-particle equation, the fundamental equation of wave mechanics, and the key idea of quantum mechanics, establishes the wavelengths for accelerating electrons which, divided into a given radial velocity, gives its respective emission frequency. Electrons propelled through helical structures, traversed by biologically available electric and magnetic fields, make accessible to the internal environment the optical spectral frequency range that the solar spectrum provides to the external environment.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...... new light on how oxidative enzymes present in plant degraders may act in concert....

  7. Determination of the electronics transfer function for current transient measurements

    CERN Document Server

    Scharf, Christian

    2014-01-01

    We describe a straight-forward method for determining the transfer function of the readout of a sensor for the situation in which the current transient of the sensor can be precisely simulated. The method relies on the convolution theorem of Fourier transforms. The specific example is a planar silicon pad diode connected with a 50 $\\Omega $ cable to an amplifier followed by a 5 GS/s sampling oscilloscope. The charge carriers in the sensor were produced by picosecond lasers with light of wavelengths of 675 and 1060 nm. The transfer function is determined from the 1060 nm data with the pad diode biased at 1000 V. It is shown that the simulated sensor response convoluted with this transfer function provides an excellent description of the measured transients for the laser light of both wavelengths, at voltages 50 V above the depletion voltage of about 90 V up to the maximum applied voltage of 1000 V. The method has been developed for the precise measurement of the dependence of the drift velocity of electrons an...

  8. MD studies of electron transfer at ambient and elevated pressures

    Science.gov (United States)

    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).

  9. Linear energy relationships in ground state proton transfer and excited state proton-coupled electron transfer.

    Science.gov (United States)

    Gamiz-Hernandez, Ana P; Magomedov, Artiom; Hummer, Gerhard; Kaila, Ville R I

    2015-02-12

    Proton-coupled electron transfer (PCET) processes are elementary chemical reactions involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects, and reaction barriers of both ground state proton transfer (pT) and photoinduced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photoexcitation leads to a PCET reaction, for which we find that the excited state reaction barrier depends on the thermodynamic driving force with a Brønsted slope of 1/2. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and the acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes.

  10. Vibrational dynamics in photoinduced electron transfer. Progress report, December 1, 1992--November 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Spears, K.G.

    1993-09-08

    Objective is to perform a new type of measurement for optically excited electron transfer processes that can provide unique experimental insight into the molecular mechanism of electron transfer. Measurements of optically excited electron transfer are done with picosecond infrared (IR) absorption spectroscopy to monitor the vibrational motions of the molecules immediately after electron transfer. Theory and experiment suggest that molecular vibrations and distortions are important controlling elements for electron transfer, and direct information has yet to be obtained on these elements of electron transfer mechanisms. The second period of funding has been dedicated to finishing technique development and performing studies of electron transfer in ion pair systems to identify if vibrational dependent electron transfer rates are present in this system. We have succeeded in measuring, for the first time, electron transfer rates as a function of vibrational state in an ion pair complex in solution. In a different area of electron transfer research we have proposed a new mechanism of solvent gated electron transfer.

  11. Mitochondrial nitric oxide production supported by reverse electron transfer.

    Science.gov (United States)

    Bombicino, Silvina S; Iglesias, Darío E; Zaobornyj, Tamara; Boveris, Alberto; Valdez, Laura B

    2016-10-01

    Heart phosphorylating electron transfer particles (ETPH) produced NO at 1.2 ± 0.1 nmol NO. min(-1) mg protein(-1) by the mtNOS catalyzed reaction. These particles showed a NAD(+) reductase activity of 64 ± 3 nmol min(-1) mg protein(-1) sustained by reverse electron transfer (RET) at expenses of ATP and succinate. The same particles, without NADPH and in conditions of RET produced 0.97 ± 0.07 nmol NO. min(-1) mg protein(-1). Rotenone inhibited NO production supported by RET measured in ETPH and in coupled mitochondria, but did not reduce the activity of recombinant nNOS, indicating that the inhibitory effect of rotenone on NO production is due to an electron flow inhibition and not to a direct action on mtNOS structure. NO production sustained by RET corresponds to 20% of the total amount of NO released from heart coupled mitochondria. A mitochondrial fraction enriched in complex I produced 1.7 ± 0.2 nmol NO. min(-1) mg protein(-1) and reacted with anti-75 kDa complex I subunit and anti-nNOS antibodies, suggesting that complex I and mtNOS are located contiguously. These data show that mitochondrial NO production can be supported by RET, and suggest that mtNOS is next to complex I, reaffirming the idea of a functional association between these proteins.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Mingyu, E-mail: mingyujo@eis.hokudai.ac.jp; Uchida, Takafumi; Tsurumaki-Fukuchi, Atsushi; Arita, Masashi; Takahashi, Yasuo [Graduate School of Information Science and Technology, Hokkaido University, Sapporo 060-0814 (Japan); Fujiwara, Akira; Nishiguchi, Katsuhiko [NTT Basic Research Laboratories, NTT Corporation, 3-1 Morinosato Wakamiya, Atsugi 243-0198 (Japan); Ono, Yukinori [Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Inokawa, Hiroshi [Research Institute of Electronics, Shizuoka University, 3-5-1, Johoku, Hamamatsu 432-8011 (Japan)

    2015-12-07

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

  13. Mechanically Controlled Electron Transfer in a Single-Polypeptide Transistor

    Science.gov (United States)

    Sheu, Sheh-Yi; Yang, Dah-Yen

    2017-01-01

    Proteins are of interest in nano-bio electronic devices due to their versatile structures, exquisite functionality and specificity. However, quantum transport measurements produce conflicting results due to technical limitations whereby it is difficult to precisely determine molecular orientation, the nature of the moieties, the presence of the surroundings and the temperature; in such circumstances a better understanding of the protein electron transfer (ET) pathway and the mechanism remains a considerable challenge. Here, we report an approach to mechanically drive polypeptide flip-flop motion to achieve a logic gate with ON and OFF states during protein ET. We have calculated the transmission spectra of the peptide-based molecular junctions and observed the hallmarks of electrical current and conductance. The results indicate that peptide ET follows an NC asymmetric process and depends on the amino acid chirality and α-helical handedness. Electron transmission decreases as the number of water molecules increases, and the ET efficiency and its pathway depend on the type of water-bridged H-bonds. Our results provide a rational mechanism for peptide ET and new perspectives on polypeptides as potential candidates in logic nano devices.

  14. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    Science.gov (United States)

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  15. Carboxylate shifts steer interquinone electron transfer in photosynthesis.

    Science.gov (United States)

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2011-02-18

    Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolution x-ray absorption spectroscopy after laser-flash excitation of PSII. After formation of the reduced primary quinone, Q(A)(-), the x-ray spectral changes revealed a transition (t½ ≈ 150 μs) from a bidentate to a monodentate coordination of the bicarbonate at the Fe(II) (carboxylate shift), which reverted concomitantly with the slower ET to the secondary quinone Q(B). A redox change of the iron during the ET was excluded. Density-functional theory calculations corroborated the carboxylate shift both in PSII and bacterial RCs and disclosed underlying changes in electronic configuration. We propose that the iron-carboxyl complex facilitates the first interquinone ET by optimizing charge distribution and hydrogen bonding within the Q(A)FeQ(B) triad for high yield Q(B) reduction. Formation of a specific priming intermediate by nuclear rearrangements, setting the stage for subsequent ET, may be a common motif in reactions of biological redox cofactors.

  16. Studies on photooxidation (VIII)——Electron transfer photooxygenation mechanism of acenaphthenone as electron donor

    Institute of Scientific and Technical Information of China (English)

    吴树屏; 刘继峰; 江致勤

    1996-01-01

    The photooxidation and its electron transfer (ET) mechanism of acenaphthenone (ANO) sensitized by 9,10-dicyanoanthracence (DCA) are investigated. It has been found that the reaction with a stepwise manner led to the formation of 1,8- (3’-hydroxy)-β-naphthalene lactone and 1,8-naphthalenedicarboxylic anhydride. By cyclic voltammetry, fluorescence quenching, exciplex emission, co-sensitbation of biphenyl/DCA as well as CIDNP studies, it is verified that ANO can behave as an electron donor to undergo ET reaction with singlet DCA which is a thermodynamically-favored process.

  17. Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Soumya; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2016-06-14

    Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play an essential role in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We present a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This approach incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectric continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  18. Electron Transfer Reactions: Generalized Spin-Boson Approach

    CERN Document Server

    Merkli, Marco

    2012-01-01

    We introduce a mathematically rigorous analysis of a generalized spin-boson system for the treatment of a donor-acceptor (reactant-product) quantum system coupled to a thermal quantum noise. The donor/acceptor probability dynamics describes transport reactions in chemical processes in presence of a noisy environment -- such as the electron transfer in a photosynthetic reaction center. Besides being rigorous, our analysis has the advantages over previous ones that (1) we include a general, non energy-conserving system-environment interaction, and that (2) we allow for the donor or acceptor to consist of multiple energy levels lying closely together. We establish explicit expressions for the rates and the efficiency (final donor-acceptor population difference) of the reaction. In particular, we show that the rate increases for a multi-level acceptor, but the efficiency does not.

  19. Transfer of optical orbital angular momentum to a bound electron

    Science.gov (United States)

    Schmiegelow, Christian T.; Schulz, Jonas; Kaufmann, Henning; Ruster, Thomas; Poschinger, Ulrich G.; Schmidt-Kaler, Ferdinand

    2016-10-01

    Photons can carry angular momentum, not only due to their spin, but also due to their spatial structure. This extra twist has been used, for example, to drive circular motion of microscopic particles in optical tweezers as well as to create vortices in quantum gases. Here we excite an atomic transition with a vortex laser beam and demonstrate the transfer of optical orbital angular momentum to the valence electron of a single trapped ion. We observe strongly modified selection rules showing that an atom can absorb two quanta of angular momentum from a single photon: one from the spin and another from the spatial structure of the beam. Furthermore, we show that parasitic ac-Stark shifts from off-resonant transitions are suppressed in the dark centre of vortex beams. These results show how light's spatial structure can determine the characteristics of light-matter interaction and pave the way for its application and observation in other systems.

  20. Redox induced electron transfer in doublet azo-anion diradical rhenium(II) complexes. Characterization of complete electron transfer series.

    Science.gov (United States)

    Paul, Nandadulal; Samanta, Subhas; Goswami, Sreebrata

    2010-03-15

    Reactions of dirhenium decacarbonyl with the two azoaromatic ligands, L(a) = (2-phenylazo)pyridine and L(b) = (4-chloro-2-phenylazo)pyridine (general abbreviation of the ligands is L) afford paramagnetic rhenium(II) complexes, [Re(II)(L(*-))(2)(CO)(2)] (1) (S = 1/2 ground state) with two one-electron reduced azo-anion radical ligands in an octahedral geometrical arrangement. At room temperature (300 K) the complexes 1a-b, showed magnetic moments (mu(eff)) close to 1.94 mu(B), which is suggestive of the existence of strong antiferromagnetic interactions in the complexes. The results of magnetic measurements on one of the complexes, 1b, in the temperature range 2-300 K are reported. The above complexes showed two cathodic and two anodic responses in cyclic voltammetry where one-electron oxidation leads to an unusual redox event involving simultaneous reduction of the rhenium(II) and oxidation of the second ligand via intramolecular electron transfer. The oxidized complexes 1a(+) and 1b(+) are air stable and were isolated as crystalline solids as their tri-iodide (I(3)(-)) salts. The structures of the two representative complexes, 1b and [1b]I(3), as determined by X-ray crystallography, are compared. The anionic complexes, [1](-) and [1](2-) were characterized in solution by their spectral properties.

  1. ELECTRON TRANSFER COLLISION OF NEON IONS WITH Ne IN A RF ION TRAP

    Institute of Scientific and Technical Information of China (English)

    满宝元; 王象泰; 等

    1995-01-01

    The pulsed electron beam rf ion stroage system is used to study neon ions electron transfer,The rate coefficients for electron transfer of the neon ions with the neon gas are measured.the results are better than those in other ion storage system.

  2. Enhanced electron transfer dissociation through fixed charge derivatization of cysteines.

    Science.gov (United States)

    Vasicek, Lisa; Brodbelt, Jennifer S

    2009-10-01

    Electron transfer dissociation (ETD) has proven to be a promising new ion activation method for proteomics applications due to its ability to generate c- and z-type fragment ions in comparison to the y- and b-type ions produced upon the more conventional collisional activation of peptides. However, low precursor charge states hinder the success of electron-based activation methods due to competition from nondissociative charge reduction and incomplete sequence coverage. In the present report, the reduction and alkylation of disulfide bonds prior to ETD analysis is evaluated by comparison of three derivatization reagents: iodoacetamide (IAM), N,N-dimethyl-2-chloro-ethylamine (DML), and (3-acrylamidopropyl)-trimethyl ammonium chloride (APTA). While both the DML and APTA modifications lead to an increase in the charge states of peptides, the APTA-peptides provided the most significant improvement in percent fragmentation and sequence coverage for all peptides upon ETD, including formation of diagnostic ions that allow characterization of both the C- and N-termini. In addition, the formation of product ions in multiple charge states upon ETD is minimized for the APTA-modified peptides.

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  4. Modular electron transfer circuits for synthetic biology: Insulation of an engineered biohydrogen pathway

    OpenAIRE

    Agapakis, Christina M; Silver, Pamela A

    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 assay...

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Direct interspecies electron transfer (DIET) through biological electrical connections is an alternative to interspecies H2 transfer as a mechanism for electron exchange in syntrophic cultures. However, it has not previously been determined whether electrons received via DIET yield energy...... dehydrogenase, the pilus-associated c-type cytochrome OmcS and pili consistent with electron transfer via DIET. These results suggest that electrons transferred via DIET can serve as the sole energy source to support anaerobic respiration....... to support cell growth. In order to investigate this, co-cultures of Geobacter metallireducens, which can transfer electrons to wild-type G. sulfurreducens via DIET, were established with a citrate synthase-deficient G. sulfurreducens strain that can receive electrons for respiration through DIET only...

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

    KAUST Repository

    Hyun, Byung-Ryool

    2011-05-11

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

  7. Thermodynamic, kinetic and electronic structure aspects of a charge-transfer active bichromophoric organofullerene

    Indian Academy of Sciences (India)

    K Senthil Kumar; Archita Patnaik

    2013-03-01

    Our recent work on charge transfer in the electronically push-pull dimethylaminoazobenzene-fullerene C60 donor-bridge-acceptor dyad through orbital picture revealed charge displacement from the n(N=N) (non-bonding) and (N=N) type orbitals centred on the donor part to the purely fullerene centred LUMOs and (LUMO+n) orbitals, delocalized over the entire molecule. Consequently, this investigation centres around the kinetic and thermodynamic parameters involved in the solvent polarity dependent intramolecular photo-induced electron transfer processes in the dyad, indispensable for artificial photosynthetic systems. A quasi-reversible electron transfer pathway was elucidated with electrode-specific heterogeneous electron transfer rate constants.

  8. Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

    Science.gov (United States)

    Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also

  9. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

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

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

    Science.gov (United States)

    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.

  11. [Theory of long-distance electron transfer in nanoscale biological structures].

    Science.gov (United States)

    Krasil'nikov, P M

    2011-01-01

    Macromolecular biological systems accomplishing the directed electron transfer are nano-sized structures. The distance between carrier molecules (cofactors), which represent practically isolated electron localization centers, reaches tens of angstroms. The electron transfer theory based on the concept of delocalized electron states, which is conventionally used in biophysics, is unable to adequately interpret the results of concrete observations in many cases. On the basis of the theory of electronic transitions in the case of localized states, developed in the physics of disorder matter, a mechanism of long distance electron transfer in biological systems is suggested. The molecular relaxation of the microenvironment of electron localization centers that accompanies the electron transfer process is also considered.

  12. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    Science.gov (United States)

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  13. [Mechanisms of electron transfer to insoluble terminal acceptors in chemoorganotrophic bacteria].

    Science.gov (United States)

    Samarukha, I A

    2014-01-01

    The mechanisms of electron transfer of association of chemoorganotrophic bacteria to the anode in microbial fuel cells are summarized in the survey. These mechanisms are not mutually exclusive and are divided into the mechanisms of mediator electron transfer, mechanisms of electron transfer with intermediate products of bacterial metabolism and mechanism of direct transfer of electrons from the cell surface. Thus, electron transfer mediators are artificial or synthesized by bacteria riboflavins and phenazine derivatives, which also determine the ability of bacteria to antagonism. The microorganisms with hydrolytic and exoelectrogenic activity are involved in electron transfer mechanisms that are mediated by intermediate metabolic products, which are low molecular carboxylic acids, alcohols, hydrogen etc. The direct transfer of electrons to insoluble anode is possible due to membrane structures (cytochromes, pili, etc.). Association of microorganisms, and thus the biochemical mechanisms of electron transfer depend on the origin of the inoculum, substrate composition, mass transfer, conditions of aeration, potentials and location of electrodes and others, that are defined by technological and design parameters.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-11-30

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

  15. Effects of quantum coherence in metalloprotein electron transfer

    Science.gov (United States)

    Dorner, Ross; Goold, John; Heaney, Libby; Farrow, Tristan; Vedral, Vlatko

    2012-09-01

    Many intramolecular electron transfer (ET) reactions in biology are mediated by metal centers in proteins. This process is commonly described by a model of diffusive hopping according to the semiclassical theories of Marcus and Hopfield. However, recent studies have raised the possibility that nontrivial quantum mechanical effects play a functioning role in certain biomolecular processes. Here, we investigate the potential effects of quantum coherence in biological ET by extending the semiclassical model to allow for the possibility of quantum coherent phenomena using a quantum master equation based on the Holstein Hamiltonian. We test the model on the structurally defined chain of seven iron-sulfur clusters in nicotinamide adenine dinucleotide plus hydrogen:ubiquinone oxidoreductase (complex I), a crucial respiratory enzyme and one of the longest chains of metal centers in biology. Using experimental parameters where possible, we find that, in limited circumstances, a small quantum mechanical contribution can provide a marked increase in the ET rate above the semiclassical diffusive-hopping rate. Under typical biological conditions, our model reduces to well-known diffusive behavior.

  16. Proton-Coupled Electron Transfer: Moving Together and Charging Forward

    Energy Technology Data Exchange (ETDEWEB)

    Hammes-Schiffer, Sharon

    2015-07-22

    Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa’s for molecular electrocatalysts, as well as methods for simulating the nonadiabatic dynamics of photoinduced processes, are also described. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future. The work described herein was supported by National Science Foundation Grant CHE-13-61293 (theory development), National Institutes of Health Grant GM056207 (soybean lipoxygenase), Center for Chemical Innovation of the National Science Foundation Solar Fuels Grant CHE-1305124 (cobalt catalysts), Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (nickel catalysts), and Air Force Office of Scientific Research Award No. FA9550-14-1-0295 (photoinduced PCET).

  17. Revisiting direct electron transfer in nanostructured carbon laccase oxygen cathodes.

    Science.gov (United States)

    Adam, Catherine; Scodeller, Pablo; Grattieri, Matteo; Villalba, Matías; Calvo, Ernesto J

    2016-06-01

    The biocatalytic electroreduction of oxygen has been studied on large surface area graphite and Vulcan® carbon electrodes with adsorbed Trametes trogii laccase. The electrokinetics of the O2 reduction reaction (ORR) was studied at different electrode potentials, O2 partial pressures and concentrations of hydrogen peroxide. Even though the overpotential at 0.25 mA·cm(-2) for the ORR at T1Cu of the adsorbed laccase on carbon is 0.8 V lower than for Pt of similar geometric area, the rate of the reaction and thus the operative current density is limited by the enzyme reaction rate at the T2/T3 cluster site for the adsorbed enzyme. The transition potential for the rate determining step from the direct electron transfer (DET) to the enzyme reaction shifts to higher potentials at higher oxygen partial pressure. Hydrogen peroxide produced by the ORR on bare carbon support participates in an inhibition mechanism, with uncompetitive predominance at high H2O2 concentration, non-competitive contribution can be detected at low inhibitor concentration.

  18. Synthetic Applications of Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Gentry, Emily C; Knowles, Robert R

    2016-08-16

    Redox events in which an electron and proton are exchanged in a concerted elementary step are commonly referred to as proton-coupled electron transfers (PCETs). PCETs are known to operate in numerous important biological redox processes, as well as recent inorganic technologies for small molecule activation. These studies suggest that PCET catalysis might also function as a general mode of substrate activation in organic synthesis. Over the past three years, our group has worked to advance this hypothesis and to demonstrate the synthetic utility of PCET through the development of novel catalytic radical chemistries. The central aim of these efforts has been to demonstrate the ability of PCET to homolytically activate a wide variety of common organic functional groups that are energetically inaccessible using known molecular H atom transfer catalysts. To do so, we made use of a simple formalism first introduced by Mayer and co-workers that allowed us to predict the thermodynamic capacity of any oxidant/base or reductant/acid pair to formally add or remove H· from a given substrate. With this insight, we were able to rationally select catalyst combinations thermodynamically competent to homolyze the extraordinarily strong E-H σ-bonds found in many common protic functional groups (BDFEs > 100 kcal/mol) or to form unusually weak bonds to hydrogen via the reductive action of common organic π-systems (BDFEs < 35 kcal/mol). These ideas were reduced to practice through the development of new catalyst systems for reductive PCET activations of ketones and oxidative PCET activation of amide N-H bonds to directly furnish reactive ketyl and amidyl radicals, respectively. In both systems, the reaction outcomes were found to be successfully predicted using the effective bond strength formalism, suggesting that these simple thermochemical considerations can provide useful and actionable insights into PCET reaction design. The ability of PCET catalysis to control

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

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S

    2016-07-21

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

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

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

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

  1. 77 FR 77187 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-12-31

    ... disclosure. Sensitive personal information, such as account numbers or social security numbers, should not be... companies are not remittance transfer providers subject to the February Final Rule because they do not... remittance transfer providers, whether transfers are sent through closed network or open network systems,...

  2. Electron-transfer acceleration investigated by time resolved infrared spectroscopy.

    Science.gov (United States)

    Vlček, Antonín; Kvapilová, Hana; Towrie, Michael; Záliš, Stanislav

    2015-03-17

    Ultrafast electron transfer (ET) processes are important primary steps in natural and artificial photosynthesis, as well as in molecular electronic/photonic devices. In biological systems, ET often occurs surprisingly fast over long distances of several tens of angströms. Laser-pulse irradiation is conveniently used to generate strongly oxidizing (or reducing) excited states whose reactions are then studied by time-resolved spectroscopic techniques. While photoluminescence decay and UV-vis absorption supply precise kinetics data, time-resolved infrared absorption (TRIR) and Raman-based spectroscopies have the advantage of providing additional structural information and monitoring vibrational energy flows and dissipation, as well as medium relaxation, that accompany ultrafast ET. We will discuss three cases of photoinduced ET involving the Re(I)(CO)3(N,N) moiety (N,N = polypyridine) that occur much faster than would be expected from ET theories. [Re(4-N-methylpyridinium-pyridine)(CO)3(N,N)](2+) represents a case of excited-state picosecond ET between two different ligands that remains ultrafast even in slow-relaxing solvents, beating the adiabatic limit. This is caused by vibrational/solvational excitation of the precursor state and participation of high-frequency quantum modes in barrier crossing. The case of Re-tryptophan assemblies demonstrates that excited-state Trp → *Re(II) ET is accelerated from nanoseconds to picoseconds when the Re(I)(CO)3(N,N) chromophore is appended to a protein, close to a tryptophan residue. TRIR in combination with DFT calculations and structural studies reveals an interaction between the N,N ligand and the tryptophan indole. It results in partial electronic delocalization in the precursor excited state and likely contributes to the ultrafast ET rate. Long-lived vibrational/solvational excitation of the protein Re(I)(CO)3(N,N)···Trp moiety, documented by dynamic IR band shifts, could be another accelerating factor. The last

  3. 27 CFR 40.357 - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 40.357 Section 40.357 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Manufacture of Cigarette Papers and Tubes Taxes § 40.357 Payment of tax by electronic fund transfer. (a) General. (1) Each taxpayer who was liable, during...

  4. 27 CFR 41.115a - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 41.115a Section 41.115a Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Puerto Rican Tobacco Products and Cigarette Papers and....115a Payment of tax by electronic fund transfer. (a) General. (1) Each taxpayer who was liable,...

  5. 27 CFR 41.63 - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 41.63 Section 41.63 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Taxes Customs' Collection of Taxes § 41.63 Payment of tax by electronic fund transfer. (a) Each importer who was liable, during a calendar year, for a...

  6. 27 CFR 40.165a - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... making payment by electronic fund transfer (EFT) of taxes on tobacco products, cigarette papers, and... electronic fund transfer. 40.165a Section 40.165a Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Operations by Manufacturers of Tobacco...

  7. 41 CFR 102-118.70 - Must my agency make all payments via electronic funds transfer?

    Science.gov (United States)

    2010-07-01

    ... payments via electronic funds transfer? 102-118.70 Section 102-118.70 Public Contracts and Property... Services § 102-118.70 Must my agency make all payments via electronic funds transfer? Yes, under 31 U.S.C. 3332, et seq., your agency must make all payments for goods and services via EFT (this includes...

  8. Superexchange coupling and electron transfer in globular proteins via polaron excitations.

    Science.gov (United States)

    Chuev, G N; Lakhno, V D; Ustitnin, M N

    2000-06-01

    The polaron approach is used to treat long-range electron transfersbetween globular proteins. A rate expression for the polaron transfer model is given along with a description of appropriate conditions forits use. Assuming that electrons transfer via a superexchange couplingdue to a polaron excitation, we have estimated the distance dependenceof the rate constant for the self-exchange reactions between globularproteins in solutions. The distance dependence of the polaron coupling andsolvent reorganization energy are provided as a basis forunderstanding and interpreting a long-range electron transfer experiment.The difficulties and problems of the polaron treatment of long-rangeelectron transfers are discussed, and suggestions for new experimentsare made.

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

    KAUST Repository

    Khan, Jafar Iqbal

    2014-11-01

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

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

    Science.gov (United States)

    Matyushov, Dmitry V.

    2015-12-01

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

  11. Bio-batteries and bio-fuel cells: leveraging on electronic charge transfer proteins.

    Science.gov (United States)

    Kannan, A M; Renugopalakrishnan, V; Filipek, S; Li, P; Audette, G F; Munukutla, L

    2009-03-01

    Bio-fuel cells are alternative energy devises based on bio-electrocatalysis of natural substrates by enzymes or microorganisms. Here we review bio-fuel cells and bio-batteries based on the recent literature. In general, the bio-fuel cells are classified based on the type of electron transfer; mediated electron transfer and direct electron transfer or electronic charge transfer (ECT). The ECT of the bio-fuel cells is critically reviewed and a variety of possible applications are considered. The technical challenges of the bio-fuel cells, like bioelectrocatalysis, immobilization of bioelectrocatalysts, protein denaturation etc. are highlighted and future research directions are discussed leveraging on the use of electron charge transfer proteins. In addition, the packaging aspects of the bio-fuel cells are also analyzed and the found that relatively little work has been done in the engineering development of bio-fuel cells.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    –310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using...... a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer...... photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported...

  13. A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Wishart J. F.; Lee, H.Y.; Issa, J.B.; Isied, S.S.; Castner, Jr., E.W.; Pan, Y.; Hussey, C.L.; Lee, K.S.

    2012-03-01

    The effect of ionic liquids on photoinduced electron-transfer reactions in a donor-bridge-acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor-bridge-acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (-{Delta}G > {lambda}) in all four solvents, with driving forces of -1.6 to -1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor-acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.

  14. Redox potential of the terminal quinone electron acceptor QB in photosystem II reveals the mechanism of electron transfer regulation.

    Science.gov (United States)

    Kato, Yuki; Nagao, Ryo; Noguchi, Takumi

    2016-01-19

    Photosystem II (PSII) extracts electrons from water at a Mn4CaO5 cluster using light energy and then transfers them to two plastoquinones, the primary quinone electron acceptor QA and the secondary quinone electron acceptor QB. This forward electron transfer is an essential process in light energy conversion. Meanwhile, backward electron transfer is also significant in photoprotection of PSII proteins. Modulation of the redox potential (Em) gap of QA and QB mainly regulates the forward and backward electron transfers in PSII. However, the full scheme of electron transfer regulation remains unresolved due to the unknown Em value of QB. Here, for the first time (to our knowledge), the Em value of QB reduction was measured directly using spectroelectrochemistry in combination with light-induced Fourier transform infrared difference spectroscopy. The Em(QB (-)/QB) was determined to be approximately +90 mV and was virtually unaffected by depletion of the Mn4CaO5 cluster. This insensitivity of Em(QB (-)/QB), in combination with the known large upshift of Em(QA (-)/QA), explains the mechanism of PSII photoprotection with an impaired Mn4CaO5 cluster, in which a large decrease in the Em gap between QA and QB promotes rapid charge recombination via QA (-).

  15. Redox potential of the terminal quinone electron acceptor QB in photosystem II reveals the mechanism of electron transfer regulation

    Science.gov (United States)

    Kato, Yuki; Nagao, Ryo; Noguchi, Takumi

    2016-01-01

    Photosystem II (PSII) extracts electrons from water at a Mn4CaO5 cluster using light energy and then transfers them to two plastoquinones, the primary quinone electron acceptor QA and the secondary quinone electron acceptor QB. This forward electron transfer is an essential process in light energy conversion. Meanwhile, backward electron transfer is also significant in photoprotection of PSII proteins. Modulation of the redox potential (Em) gap of QA and QB mainly regulates the forward and backward electron transfers in PSII. However, the full scheme of electron transfer regulation remains unresolved due to the unknown Em value of QB. Here, for the first time (to our knowledge), the Em value of QB reduction was measured directly using spectroelectrochemistry in combination with light-induced Fourier transform infrared difference spectroscopy. The Em(QB−/QB) was determined to be approximately +90 mV and was virtually unaffected by depletion of the Mn4CaO5 cluster. This insensitivity of Em(QB−/QB), in combination with the known large upshift of Em(QA−/QA), explains the mechanism of PSII photoprotection with an impaired Mn4CaO5 cluster, in which a large decrease in the Em gap between QA and QB promotes rapid charge recombination via QA−. PMID:26715751

  16. Where Does the Electron Go? Stable and Metastable Peptide Cation Radicals Formed by Electron Transfer

    Science.gov (United States)

    Pepin, Robert; Layton, Erik D.; Liu, Yang; Afonso, Carlos; Tureček, František

    2017-01-01

    Electron transfer to doubly and triply charged heptapeptide ions containing polar residues Arg, Lys, and Asp in combination with nonpolar Gly, Ala, and Pro or Leu generates stable and metastable charge-reduced ions, (M + 2H)+●, in addition to standard electron-transfer dissociation (ETD) fragment ions. The metastable (M + 2H)+● ions spontaneously dissociate upon resonant ejection from the linear ion trap, giving irregularly shaped peaks with offset m/ z values. The fractions of stable and metastable (M + 2H)+● ions and their mass shifts depend on the presence of Pro-4 and Leu-4 residues in the peptides, with the Pro-4 sequences giving larger fractions of the stable ions while showing smaller mass shifts for the metastables. Conversion of the Asp and C-terminal carboxyl groups to methyl esters further lowers the charge-reduced ion stability. Collisional activation and photodissociation at 355 nm of mass-selected (M + 2H)+● results in different dissociations that give sequence specific MS3 spectra. With a single exception of charge-reduced (LKGLADR + 2H)+●, the MS3 spectra do not produce ETD sequence fragments of the c and z type. Hence, these (M + 2H)+● ions are covalent radicals, not ion-molecule complexes, undergoing dramatically different dissociations in the ground and excited electronic states. The increased stability of the Pro-4 containing (M + 2H)+● ions is attributed to radicals formed by opening of the Pro ring and undergoing further stabilization by hydrogen atom migrations. UV-VIS photodissociation action spectroscopy and time-dependent density functional theory calculations are used in a case in point study of the stable (LKGPADR + 2H)+● ion produced by ETD. In contrast to singly-reduced peptide ions, doubly reduced (M + 3H)+ ions are stable only when formed from the Pro-4 precursors and show all characteristics of even electron ions regarding no photon absorption at 355 nm or ion-molecule reactions, and exhibiting proton driven

  17. Studies on electron transfer reactions of Keggin-type mixed addenda heteropolytungstovanadophosphates with NADH

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Kasi Rajasekaran

    2009-03-01

    The coenzyme nicotinamide adenine dinucleotide (NADH) undergoes facile electron transfer reaction with vanadium (V) substituted Keggin-type heteropolyanions (HPA) [PVVW11O40]4- (PV1) and [PV$^{V}_{2}$W10O40]5- (PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1 : 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one electron reduced heteropoly blues (HPB), viz. [PVIVW11O40]5- and [PVIVVVW10O40]6-. Oxygraph measurements show that there is no uptake of molecular oxygen during the course of reaction. The reaction proceeds through multi-step electron-proton-electron transfer mechanism, with rate limiting initial one electron transfer from NADH to HPA by outer sphere electron transfer process. Bimolecular rate constant for electron transfer reaction between NADH and PV2 in phosphate buffer of pH = 6 has been determined spectrophotometrically.

  18. Concerted proton-coupled electron transfer from a metal-hydride complex.

    Science.gov (United States)

    Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif

    2014-02-01

    Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H2. In these reactions, electrons and protons are transferred to or from separate acceptors or donors in bidirectional protoncoupled electron transfer (PCET) steps. The mechanistic interpretation of PCET reactions of metal hydrides has focused on the stepwise transfer of electrons and protons. A concerted transfer may, however, occur with a lower reaction barrier and therefore proceed at higher catalytic rates. Here we investigate the feasibility of such a reaction by studying the oxidation–deprotonation reactions of a tungsten hydride complex. The rate dependence on the driving force for both electron transfer and proton transfer—employing different combinations of oxidants and bases—was used to establish experimentally the concerted, bidirectional PCET of a metal-hydride species. Consideration of the findings presented here in future catalyst designs may lead to more-efficient catalysts.

  19. High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis

    Science.gov (United States)

    Chandra, Sourov; Pradhan, Saheli; Mitra, Shouvik; Patra, Prasun; Bhattacharya, Ankita; Pramanik, Panchanan; Goswami, Arunava

    2014-03-01

    A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH). Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06079a

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

    Directory of Open Access Journals (Sweden)

    Chih-Hung Hsu

    2014-01-01

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

  1. Sequential energy and electron transfer in a three-component system aligned on a clay nanosheet.

    Science.gov (United States)

    Fujimura, Takuya; Ramasamy, Elamparuthi; Ishida, Yohei; Shimada, Tetsuya; Takagi, Shinsuke; Ramamurthy, Vaidhyanathan

    2016-02-21

    To achieve the goal of energy transfer and subsequent electron transfer across three molecules, a phenomenon often utilized in artificial light harvesting systems, we have assembled a light absorber (that also serves as an energy donor), an energy acceptor (that also serves as an electron donor) and an electron acceptor on the surface of an anionic clay nanosheet. Since neutral organic molecules have no tendency to adsorb onto the anionic surface of clay, a positively charged water-soluble organic capsule was used to hold neutral light absorbers on the above surface. A three-component assembly was prepared by the co-adsorption of a cationic bipyridinium derivative, cationic zinc porphyrin and cationic octaamine encapsulated 2-acetylanthracene on an exfoliated anionic clay surface in water. Energy and electron transfer phenomena were monitored by steady state fluorescence and picosecond time resolved fluorescence decay. The excitation of 2-acetylanthracene in the three-component system resulted in energy transfer from 2-acetylanthracene to zinc porphyrin with 71% efficiency. Very little loss due to electron transfer from 2-acetylanthracene in the cavitand to the bipyridinium derivative was noticed. Energy transfer was followed by electron transfer from the zinc porphyrin to the cationic bipyridinium derivative with 81% efficiency. Analyses of fluorescence decay profiles confirmed the occurrence of energy transfer and subsequent electron transfer. Merging the concepts of supramolecular chemistry and surface chemistry we realized sequential energy and electron transfer between three hydrophobic molecules in water. Exfoliated transparent saponite clay served as a matrix to align the three photoactive molecules at a close distance in aqueous solutions.

  2. 48 CFR 52.232-33 - Payment by Electronic Funds Transfer-Central Contractor Registration.

    Science.gov (United States)

    2010-10-01

    ... Government under this contract shall be made by electronic funds transfer (EFT), except as provided in... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Payment by Electronic... CONTRACT CLAUSES Text of Provisions and Clauses 52.232-33 Payment by Electronic Funds...

  3. Photoinduced electron transfer processes in oligothiophene/C60 composite films

    NARCIS (Netherlands)

    Janssen, R.A.J.; Christiaans, M.P.T.; Pakbaz, K.; Moses, D.; Hummelen, Jan C.; Sariciftci, N.S.

    1995-01-01

    We present near steady-state photoinduced absorption (PIA) spectroscopy and steady-state light-induced electron spin resonance (LESR) studies on photoinduced electron transfer reactions in composite films of well defined α-oligothiophenes (Tn, n=6, 7, 9, and 11) as electron donor with buckminsterful

  4. High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis.

    Science.gov (United States)

    Chandra, Sourov; Pradhan, Saheli; Mitra, Shouvik; Patra, Prasun; Bhattacharya, Ankita; Pramanik, Panchanan; Goswami, Arunava

    2014-04-07

    A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).

  5. Theoretical Study of Electron Transfer in Bimolecular System of NH3 and H2O

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G(d,p) for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that electron transfers from NH3 to H2O. MK and CHelpG population analyses indicate more electron transfer than Mulliken and NPA ones. The atomic charges resulted from MK and CHelpG schemes infer that electron transfers from N in NH3 to H in H2O, which confirms that this bimolecular complex possesses linear structure as H3N…HOH.

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

    Science.gov (United States)

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

    2016-03-01

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

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

    Science.gov (United States)

    Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.; Abramavicius, D.

    2016-09-01

    Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

  8. The Role of Protein Fluctuation Correlations in Electron Transfer in Photosynthetic Complexes

    CERN Document Server

    Nesterov, Alexander I

    2014-01-01

    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 obtain analytic expressions for the electron transfer rates. We compare 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.

  9. Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Neta, P.

    1995-02-01

    The pulse radiolysis technique is applied to the study of electron transfer processes in a variety of chemical systems. Reactive intermediates are produced in solution by electron pulse irradiation and the kinetics of their reactions are followed by time resolved absorption spectrophotometry. Complementary experiments are carried out with excimer laser flash photolysis. These studies are concerned with mechanisms, kinetics, and thermodynamics of reactions of organic and inorganic radicals and unstable oxidation states of metal ions. Reactions are studied in both aqueous and non-aqueous solutions. The studies focus on the unique ability of pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, species that are key intermediates in many chemical processes. A special concern of this work is the study of electron transfer reactions of metalloporphyrins, which permits evaluation of these molecules as intermediates in solar energy conversion. Metalloporphyrins react with free radicals via electron transfer, involving the ligand or the metal center, or via bonding to the metal, leading to a variety of chemical species whose behavior is also investigated. The highlights of the results during the past three years are summarized below under the following sections: (a) electron transfer reactions of peroxyl radicals, concentrating on the characterization of new peroxyl radicals derived from vinyl, phenyl, other aryl, and pyridyl; (b) solvent effects on electron transfer reactions of inorganic and organic peroxyl radicals, including reactions with porphyrins, and (c) electron transfer and alkylation reactions of metalloporphyrins and other complexes.

  10. Electron Transfer in Flavodoxin-based Redox Maquettes

    NARCIS (Netherlands)

    Alagaratnam, S.

    2005-01-01

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

  11. [Long-range electron transfer in globular proteins by polaron excitation].

    Science.gov (United States)

    Lakhno, V L; Chuev, G N

    1997-01-01

    Considering polaron model, we have calculated an electron state localized in the protein heme. Using these calculations: the electron density and electron energy, we estimated the self-exchange rate constant for cyt c (horse heart), its reorganization energy, matrix element, and dependence of this rate on the distance between hemes. The results are compared with the experimental data and other theoretical estimations. We discuss the role of polaron excitations in the long-range electron transfer in globular proteins.

  12. An electron-transfer photochromic crystalline MOF accompanying photoswitchable luminescence in a host-guest system.

    Science.gov (United States)

    Liu, Yu-Shuang; Luo, Yu-Hui; Li, Li; Zhang, Hong

    2017-03-23

    A new electron transfer type photoactive host-guest supramolecule was constructed by introducing (CH3)2NH2(+) cations to the MOF framework. The resulting compound 1 exhibits reversible photochromic property without using photochromic components, resulting from photoinduced electron-transfer between the electron-rich anionic framework and the electron-deficient guest ions. In addition, a photoluminescence "on/off switch" occurs during the coloration-decoloration process. The raw materials are non-poisonous and harmless, hence compound 1 may be more cost-effective, clean, and harmless to the heath than existing photochromic materials.

  13. 77 FR 71035 - Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT...

    Science.gov (United States)

    2012-11-28

    ... Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT) Market Research Study AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION: Notice and Request for comments. SUMMARY: The Financial Management Service, as part of its...

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    Science.gov (United States)

    2012-06-08

    ... Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Transfer Account (ETA) Financial Agency Agreement AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION: Notice and Request for comments. SUMMARY: The Financial Management Service, as part of...

  15. ElectronTransfer Induced Ring Opening of α-Epoxyketones: Spirodioxolane Formation

    Directory of Open Access Journals (Sweden)

    Farzad Nikpour

    2002-01-01

    Full Text Available Stereospecific formation of spirodioxolanes has been observed on electron transfer induced ring opening of α-epoxyketones by 2,4,6-triphenylpyrylium tetrafluoroborate in the presence of cyclohexanone

  16. 77 FR 10373 - Greenhouse Gas Reporting Program: Electronics Manufacturing: Revisions to Heat Transfer Fluid...

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    2012-02-22

    ... AGENCY 40 CFR Part 98 RIN 2060-AR09 Greenhouse Gas Reporting Program: Electronics Manufacturing... category of the Greenhouse Gas Reporting Rule related to fluorinated heat transfer fluids. More... INFORMATION CONTACT: Carole Cook, Climate Change Division, Office of Atmospheric Programs...

  17. 77 FR 6193 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ... Report, Hearing Before House Subcomm. on Domestic and Int'l Monetary Policy, Trade, and Technology, House...-to-consumer transfers of low monetary value, often made via non-depository companies known as ``money... Chishti, Migration Policy Institute, The Rise in Remittances to India: A Closer Look (February...

  18. Transferred metal electrode films for large-area electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jin-Guo [Department of Physics, National University of Singapore, Lower Kent Ridge Road, Singapore S117543 (Singapore); NUS Graduate School for Integrative Sciences and Engineering (NGS), National University of Singapore, Medical Drive, Singapore S117456 (Singapore); Kam, Fong-Yu [Department of Chemistry, National University of Singapore, Lower Kent Ridge Road, Singapore S117543 (Singapore); Chua, Lay-Lay [Department of Chemistry, National University of Singapore, Lower Kent Ridge Road, Singapore S117543 (Singapore); Department of Physics, National University of Singapore, Lower Kent Ridge Road, Singapore S117543 (Singapore)

    2014-11-10

    The evaporation of metal-film gate electrodes for top-gate organic field-effect transistors (OFETs) limits the minimum thickness of the polymer gate dielectric to typically more than 300 nm due to deep hot metal atom penetration and damage of the dielectric. We show here that the self-release layer transfer method recently developed for high-quality graphene transfer is also capable of giving high-quality metal thin-film transfers to produce high-performance capacitors and OFETs with superior dielectric breakdown strength even for ultrathin polymer dielectric films. Dielectric breakdown strengths up to 5–6 MV cm{sup −1} have been obtained for 50-nm thin films of polystyrene and a cyclic olefin copolymer TOPAS{sup ®} (Zeon). High-quality OFETs with sub-10 V operational voltages have been obtained this way using conventional polymer dielectrics and a high-mobility polymer semiconductor poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene-2,5-diyl]. The transferred metal films can make reliable contacts without damaging ultrathin polymer films, self-assembled monolayers and graphene, which is not otherwise possible from evaporated or sputtered metal films.

  19. Enhanced ionization of embedded clusters by Electron Transfer Mediated Decay in helium nanodroplets

    CERN Document Server

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

    2015-01-01

    Here, we report the observation of electron transfer mediated decay For Mg clusters embedded in He nanodroplets. The process is mediated by the initial ionization of helium followed by an autoionization process by electron transfer in the Mg clusters. The photoelectron spectrum (PES) reveal a low energy ETMD peak. For Mg clusters larger than 7 atoms, we observe the formation of stable doubly ionized clusters. The process is shown to be the primamry ionization mechanism for embedded clusters.

  20. Characterization and modelling of interspecies electron transfer mechanisms and microbial community dynamics of a syntrophic association

    DEFF Research Database (Denmark)

    Nagarajan, Harish; Embree, Mallory; Rotaru, Amelia-Elena

    2013-01-01

    Syntrophic associations are central to microbial communities and thus have a fundamental role in the global carbon cycle. Despite biochemical approaches describing the physiological activity of these communities, there has been a lack of a mechanistic understanding of the relationship between...... metallireducens and Geobacter sulfurreducens. Genome-scale modelling of direct interspecies electron transfer reveals insights into the energetics of electron transfer mechanisms. While G. sulfurreducens adapts to rapid syntrophic growth by changes at the genomic and transcriptomic level, G. metallireducens...

  1. Single-sphere model for solvent reorganization energy and its application to electron transfer

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In this work, the authors give detailed deductions and develop the single-sphere model of solvent reorganization energy in electron transfer with point dipole approximation. At the level of DFT/6- 31++G**, the electron transfer between 7,7,8,8-tetracyanoquinodimethane and its anion has been investigated. Using the novel single-sphere model, the authors evaluate the solvent reorganization energy of this system, and the computational result proves rational in comparison with the experimental estimations.

  2. Pathways of electron transfer in Escherichia coli DNA photolyase: Trp306 to FADH.

    OpenAIRE

    1999-01-01

    We describe the results of a series of theoretical calculations of electron transfer pathways between Trp306 and *FADH. in the Escherichia coli DNA photolyase molecule, using the method of interatomic tunneling currents. It is found that there are two conformationally orthogonal tryptophans, Trp359 and Trp382, between donor and acceptor that play a crucial role in the pathways of the electron transfer process. The pathways depend vitally on the aromaticity of tryptophans and the flavin molecu...

  3. 76 FR 35219 - Federal Acquisition Regulation; Information Collection; Payment by Electronic Fund Transfer

    Science.gov (United States)

    2011-06-16

    ... Regulation; Information Collection; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD... transfer. Public comments are particularly invited on: Whether this collection of information is necessary... those who are to respond, through the use of appropriate technological collection techniques or...

  4. 9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions.

    Science.gov (United States)

    Boutaghou, M Nazim; Cole, Richard B

    2012-08-01

    The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume.

  5. Electrostatic effect on electron transfer between cytochrome b5 and cytochrome c

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The binding and electron transfer between wild type, E44A, E56A, E44/56A, E44/48/56A/D60Aand F35Y variants of cytochrome b5 and cytochrome c were studied. When mixed with cytochrome c, the cytochrome b5E44/48/56A/D60A did not show the typical UV-vis difference spectrum of absorption, indicating that the alteration ofthe surface electrostatic potential obviously influenced the spectrum. The electron transfer rates of wild type cytochromeb5, its variants and cytochrome e at different temperature and ionic strength exhibited an order of F35Y > wild type >E56A > E44A > E44/48/56A/D60A. The enthalpy and entropy of the reaction did not change obviously, suggestingthat the mutation did not significantly disturb the electron transfer conformation. The investigation of electron transfer rateconstants at different ionic strength demonstrated that electrostatic interaction obviously affected the electron transfer pro-cess. The significant difference of Cyt b5 F35Y and E44/48/56A/D60A from the wild type protein further confirmed thegreat importance of the electrostatic interaction in the protein electron transfer.

  6. Solvent-mediated electron hopping: long-range charge transfer in IBr-(CO2) photodissociation.

    Science.gov (United States)

    Sheps, Leonid; Miller, Elisa M; Horvath, Samantha; Thompson, Matthew A; Parson, Robert; McCoy, Anne B; Lineberger, W Carl

    2010-04-09

    Chemical bond breaking involves coupled electronic and nuclear dynamics that can take place on multiple electronic surfaces. Here we report a time-resolved experimental and theoretical investigation of nonadiabatic dynamics during photodissociation of a complex of iodine monobromide anion with carbon dioxide [IBr-(CO2)] on the second excited (A') electronic state. Previous experimental work showed that the dissociation of bare IBr- yields only I- + Br products. However, in IBr-(CO2), time-resolved photoelectron spectroscopy reveals that a subset of the dissociating molecules undergoes an electron transfer from iodine to bromine 350 femtoseconds after the initial excitation. Ab initio calculations and molecular dynamics simulations elucidate the mechanism for this charge hop and highlight the crucial role of the carbon dioxide molecule. The charge transfer between two recoiling atoms, assisted by a single solvent-like molecule, provides a notable limiting case of solvent-driven electron transfer over a distance of 7 angstroms.

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

    Science.gov (United States)

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

    1980-01-01

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

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

    Science.gov (United States)

    Hannemann, Frank; Guyot, Arnaud; Zöllner, Andy; Müller, Jürgen J; Heinemann, Udo; Bernhardt, Rita

    2009-07-01

    Dipole moments of proteins arise from helical dipoles, hydrogen bond networks and charged groups at the protein surface. High protein dipole moments were suggested to contribute to the electrostatic steering between redox partners in electron transport chains of respiration, photosynthesis and steroid biosynthesis, although so far experimental evidence for this hypothesis was missing. In order to probe this assumption, we changed the dipole moment of the electron transfer protein adrenodoxin and investigated the influence of this on protein-protein interactions and electron transfer. In bovine adrenodoxin, the [2Fe-2S] ferredoxin of the adrenal glands, a dipole moment of 803 Debye was calculated for a full-length adrenodoxin model based on the Adx(4-108) and the wild type adrenodoxin crystal structures. Large distances and asymmetric distribution of the charged residues in the molecule mainly determine the observed high value. In order to analyse the influence of the resulting inhomogeneous electric field on the biological function of this electron carrier the molecular dipole moment was systematically changed. Five recombinant adrenodoxin mutants with successively reduced dipole moment (from 600 to 200 Debye) were analysed for their redox properties, their binding affinities to the redox partner proteins and for their function during electron transfer-dependent steroid hydroxylation. None of the mutants, not even the quadruple mutant K6E/K22Q/K24Q/K98E with a dipole moment reduced by about 70% showed significant changes in the protein function as compared with the unmodified adrenodoxin demonstrating that neither the formation of the transient complex nor the biological activity of the electron transfer chain of the endocrine glands was affected. This is the first experimental evidence that the high dipole moment observed in electron transfer proteins is not involved in electrostatic steering among the proteins in the redox chain.

  9. Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers.

    Science.gov (United States)

    Neville, Simon P; Kirkby, Oliver M; Kaltsoyannis, Nikolas; Worth, Graham A; Fielding, Helen H

    2016-04-21

    Photoinduced electron transfer is central to many biological processes and technological applications, such as the harvesting of solar energy and molecular electronics. The electron donor and acceptor units involved in electron transfer are often held in place by covalent bonds, π-π interactions or hydrogen bonds. Here, using time-resolved photoelectron spectroscopy and ab initio calculations, we reveal the existence of a new, low-energy, photoinduced electron-transfer mechanism in molecules held together by an NH⋯π bond. Specifically, we capture the electron-transfer process in a pyrrole dimer, from the excited π-system of the donor pyrrole to a Rydberg orbital localized on the N-atom of the acceptor pyrrole, mediated by an N-H stretch on the acceptor molecule. The resulting charge-transfer state is surprisingly long lived and leads to efficient electronic relaxation. We propose that this relaxation pathway plays an important role in biological and technological systems containing the pyrrole building block.

  10. Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers

    Science.gov (United States)

    Neville, Simon P.; Kirkby, Oliver M.; Kaltsoyannis, Nikolas; Worth, Graham A.; Fielding, Helen H.

    2016-04-01

    Photoinduced electron transfer is central to many biological processes and technological applications, such as the harvesting of solar energy and molecular electronics. The electron donor and acceptor units involved in electron transfer are often held in place by covalent bonds, π-π interactions or hydrogen bonds. Here, using time-resolved photoelectron spectroscopy and ab initio calculations, we reveal the existence of a new, low-energy, photoinduced electron-transfer mechanism in molecules held together by an NH⋯π bond. Specifically, we capture the electron-transfer process in a pyrrole dimer, from the excited π-system of the donor pyrrole to a Rydberg orbital localized on the N-atom of the acceptor pyrrole, mediated by an N-H stretch on the acceptor molecule. The resulting charge-transfer state is surprisingly long lived and leads to efficient electronic relaxation. We propose that this relaxation pathway plays an important role in biological and technological systems containing the pyrrole building block.

  11. Transfer printing of thermoreversible ion gels for flexible electronics.

    Science.gov (United States)

    Lee, Keun Hyung; Zhang, Sipei; Gu, Yuanyan; Lodge, Timothy P; Frisbie, C Daniel

    2013-10-09

    Thermally assisted transfer printing was employed to pattern thin films of high capacitance ion gels on polyimide, poly(ethylene terephthalate), and SiO2 substrates. The ion gels consisted of 20 wt % block copolymer poly(styrene-b-ethylene oxide-b-styrene and 80 wt % ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)amide. Patterning resolution was on the order of 10 μm. Importantly, ion gels containing the block polymer with short PS end blocks (3.4 kg/mol) could be transfer-printed because of thermoreversible gelation that enabled intimate gel-substrate contact at 100 °C, while gels with long PS blocks (11 kg/mol) were not printable at the same temperature due to poor wetting contact between the gel and substrates. By using printed ion gels as high-capacitance gate insulators, electrolyte-gated thin-film transistors were fabricated that operated at low voltages (<1 V) with high on/off current ratios (∼10(5)). Statistical analysis of carrier mobility, turn-on voltage, and on/off ratio for an array of printed transistors demonstrated the excellent reproducibility of the printing technique. The results show that transfer printing is an attractive route to pattern high-capacitance ion gels for flexible thin-film devices.

  12. Long-distance electron transfer by cable bacteria in aquifer sediments

    DEFF Research Database (Denmark)

    Müller, Hubert; Bosch, Julian; Griebler, Christian

    2016-01-01

    The biodegradation of organic pollutants in aquifers is often restricted to the fringes of contaminant plumes where steep countergradients of electron donors and acceptors are separated by limited dispersive mixing. However, long-distance electron transfer (LDET) by filamentous ‘cable bacteria’ h...

  13. A semiclassical theory of electron transfer reactions in Condon approximation and beyond

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Sokolov, V. V.; Ulstrup, Jens

    2001-01-01

    The effect of the modulation of the electronic wave functions by configurational fluctuations of the molecular environment on the kinetic parameters of electron transfer reactions is discussed. A self-consistent algorithm for the calculation of the potential profile along the reaction coordinate ...

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

    Science.gov (United States)

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

    2011-03-17

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

  15. Nanoparticle Facilitated Extracellular Electron Transfer in Microbial Fuel Cells

    Science.gov (United States)

    2014-10-13

    modeling of the response of G. sulfurreducens biofilms cultured on a rotating disk electrode indicated that electron transport limits the respiration...tances.19 Nanoscale materials and devices, such as metal /semi- conductor nanoparticles, nanowires, and carbon nanotubes, have been widely exploited...redox centers. In addition, dissimilatory intermembrane and intramembrane reduction of metals into nanoparticles has been well-documented29,30

  16. Multistep photoinduced electron transfer in a photoacceptor terminated molecular triode

    NARCIS (Netherlands)

    Bakker, N.A.C.; Wiering, P.G.; Brouwer, A.M.; Warman, J.M.; Verhoeven, J.W.

    1990-01-01

    A mol.ecular triode (I) containing a nonconjugatively interconnected array (D2-D1-Pa) of 2 potential 1-electron donor (D) moieties and a powerful photoacceptor (Pa), is described. In a related diode (II) consisting of the array D1-Pa excitation of the photoacceptor, Pa, induces charge-separation as

  17. Kinetic pathway for interfacial electron transfer from a semiconductor to a molecule

    Science.gov (United States)

    Hu, Ke; Blair, Amber D.; Piechota, Eric J.; Schauer, Phil A.; Sampaio, Renato N.; Parlane, Fraser G. L.; Meyer, Gerald J.; Berlinguette, Curtis P.

    2016-09-01

    Molecular approaches to solar-energy conversion require a kinetic optimization of light-induced electron-transfer reactions. At molecular-semiconductor interfaces, this optimization has previously been accomplished through control of the distance between the semiconductor donor and the molecular acceptor and/or the free energy that accompanies electron transfer. Here we show that a kinetic pathway for electron transfer from a semiconductor to a molecular acceptor also exists and provides an alternative method for the control of interfacial kinetics. The pathway was identified by the rational design of molecules in which the distance and the driving force were held near parity and only the geometric torsion about a xylyl- or phenylthiophene bridge was varied. Electronic coupling through the phenyl bridge was a factor of ten greater than that through the xylyl bridge. Comparative studies revealed a significant bridge dependence for electron transfer that could not be rationalized by a change in distance or driving force. Instead, the data indicate an interfacial electron-transfer pathway that utilizes the aromatic bridge orbitals.

  18. Photoinduced Electron Transfer within Supramolecular Donor-Acceptor Peptide Nanostructures under Aqueous Conditions.

    Science.gov (United States)

    Sanders, Allix M; Magnanelli, Timothy J; Bragg, Arthur E; Tovar, John D

    2016-03-16

    We report the synthesis, self-assembly, and electron transfer capabilities of peptide-based electron donor-acceptor molecules and supramolecular nanostructures. These modified peptides contain π-conjugated oligothiophene electron donor cores that are peripherally substituted with naphthalene diimide electron acceptors installed via imidation of site-specific lysine residues. These molecules self-assemble into one-dimensional nanostructures in aqueous media, as shown through steady-state absorption, photoluminescence, and circular dichroism spectra, as well as transmission electron microscopy. Excitation of the oligothiophene donor moieties results in electron transfer to the acceptor units, ultimately creating polar, charge-separated states that persist for over a nanosecond as observed with transient absorption spectroscopy. This study demonstrates how transient electric fields can be engineered into aqueous nanomaterials of biomedical relevance through external, temporally controlled photonic inputs.

  19. Riboflavin-shuttled extracellular electron transfer from Enterococcus faecalis to electrodes in microbial fuel cells.

    Science.gov (United States)

    Zhang, Enren; Cai, Yamin; Luo, Yue; Piao, Zhe

    2014-11-01

    Great attention has been focused on Gram-negative bacteria in the application of microbial fuel cells. In this study, the Gram-positive bacterium Enterococcus faecalis was employed in microbial fuel cells. Bacterial biofilms formed by E. faecalis ZER6 were investigated with respect to electricity production through the riboflavin-shuttled extracellular electron transfer. Trace riboflavin was shown to be essential for transferring electrons derived from the oxidation of glucose outside the peptidoglycan layer in the cell wall of E. faecalis biofilms formed on the surface of electrodes, in the absence of other potential electron mediators (e.g., yeast extract).

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

    Science.gov (United States)

    Cave, Robert J.; Newton, Marshall D.

    1996-01-01

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

  1. Direct observation of electron-to-hole energy transfer in CdSe quantum dots.

    Science.gov (United States)

    Hendry, E; Koeberg, M; Wang, F; Zhang, H; de Mello Donegá, C; Vanmaekelbergh, D; Bonn, M

    2006-02-10

    We independently determine the subpicosecond cooling rates for holes and electrons in CdSe quantum dots. Time-resolved luminescence and terahertz spectroscopy reveal that the rate of hole cooling, following photoexcitation of the quantum dots, depends critically on the electron excess energy. This constitutes the first direct, quantitative measurement of electron-to-hole energy transfer, the hypothesis behind the Auger cooling mechanism proposed in quantum dots, which is found to occur on a 1 +/- 0.15 ps time scale.

  2. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    KAUST Repository

    Li, Jingrui

    2015-07-29

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  3. Expanding the Diet for DIET: Electron Donors Supporting Direct Interspecies Electron Transfer (DIET in Defined Co-Cultures

    Directory of Open Access Journals (Sweden)

    Li-YIng eWang

    2016-03-01

    Full Text Available Direct interspecies electron transfer (DIET has been recognized as an alternative to interspecies H2 transfer as a mechanism for syntrophic growth, but previous studies on DIET with defined co-cultures have only documented DIET with ethanol as the electron donor in the absence of conductive materials. Co-cultures of Geobacter metallireducens and Geobacter sulfurreducens metabolized propanol, butanol, propionate, and butyrate with the reduction of fumarate to succinate. G. metallireducens utilized each of these substrates whereas only electrons available from DIET supported G. sulfurreducens respiration. A co-culture of G. metallireducens and a strain of G. sulfurreducens that could not metabolize acetate oxidized acetate with fumarate as the electron acceptor, demonstrating that acetate can also be syntrophically metabolized via DIET. A co-culture of G. metallireducens and Methanosaeta harundinacea previously shown to syntrophically convert ethanol to methane via DIET metabolized propanol or butanol as the sole electron donor, but not propionate or butyrate. The stoichiometric accumulation of propionate or butyrate in the propanol- or butanol-fed cultures demonstrated that M. harundinaceae could conserve energy to support growth solely from electrons derived from DIET. Co-cultures of G. metallireducens and Methanosarcina barkeri could also incompletely metabolize propanol and butanol and did not metabolize propionate or butyrate as sole electron donors. These results expand the range of substrates that are known to be syntrophically metabolized through DIET, but suggest that claims of propionate and butyrate metabolism via DIET in mixed microbial communities warrant further validation.

  4. Ultrafast electron and hole transfer in bulk heterojunctions of low-bandgap polymers

    Science.gov (United States)

    Kozlov, Oleg V.; Pavelyev, Vlad G.; de Gier, Hilde D.; Havenith, Remco W. A.; van Loosdrecht, Paul H. M.; Hummelen, Jan C.; Pshenichnikov, Maxim S.

    2016-12-01

    In modern bulk heterojunction (BHJ) organic solar cells, blends of low-bandgap polymer and [70]PCBM acceptor are used in the active layer. In this combination, the polymer absorbs photons from the red and near-IR parts of the solar spectrum, while the blue and near-UV photons are harvested by [70]PCBM. As a result, both electron transfer from polymer to [70]PCBM and hole transfer from [70]PCBM to polymer are of utmost importance in free charge generation and have to be optimized simultaneously. Here we study electron and hole transfer processes in BHJ blends of two low-bandgap polymers, BTT-DPP and PCPDTBT, by ultrafast photoinduced spectroscopy (PIA). By tracking the PIA dynamics, we observed substantially different charge separation pathways in BHJs of the two polymers with [70]PCBM. From the photoinduced anisotropy dynamics, we demonstrated that in the PCPDTBT:[70]PCBM system both electron and hole transfer processes are highly efficient, while in the BTTBPP:[ 70]PCBM electron transfer is blocked due to the unfortunate energy level alignment leaving hole transfer the only pathway to free charge generation. Calculations at the density functional theory level are used to gain more insight into our findings. The presented results highlight the importance of the energy level alignment on the charge separation process.

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

    Science.gov (United States)

    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.

  6. [Electron transfer, ionization, and excitation in atomic collisions]. [Pennsylvania State Univ

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

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

  7. Electron transfer NO2++NO→NO2+NO+ in aromatic nitration

    Institute of Scientific and Technical Information of China (English)

    李象远; 何福城

    1997-01-01

    A simple model for computing the electron transfer rate constant of a cross-reaction has been proposed in the framework of semiclassical theory and employed to investigate the electron transfer system NO2+/NO.The encounter complex of electron transfer NO2++NO→NO2+NO+has been optimized at the level of UHF/6-31G.In the construction of diabatic potential energy surfaces the linear coordinate was used and the kinetic quantities,such as the activation energies and the electron transfer matrix elements,have been obtained.For comparison,the related self-exchange reation systems NO2+/NO2 and NO+/NO were kinetically investigated.The calculated activation energies for the electron transfer reactions of systems NO2+/NO,NO2+/NO2,and NO+/NO are 81 4,128.8,and 39.8kJ mol-1,respectively With the solvent effect taken into account,the contribution of solvent reorganization to the activation energy has been estimated according to the geometric parameters of the transition states.The obtained rate constants show that the

  8. Transient W-band EPR study of sequential electron transfer in photosynthetic bacterial reaction centers

    Energy Technology Data Exchange (ETDEWEB)

    Tang, J.; Utschig, L.M.; Poluektov, O.; Thurnauer, M.C. [Argonne National Lab., IL (United States). Chemistry Div.

    1999-06-17

    The key reaction of photosynthetic solar energy conversion involves the photoexcitation of a primary donor (P) followed by rapid, sequential electron transfer to a series of acceptors resulting in charge separation. Electron-spin polarized (ESP) EPR spectra at W-band (95 GHz) were obtained for deuterated Fe-removed/Zn-substituted photosynthetic bacterial reaction centers (RCs) to investigate the influence of the rate of charge separation on the observed P{sup +}Q{sub A}{sup {minus}} charge separated state. Temperature dependent ESP EPR spectra for kinetically characterized Zn-substituted RCs from Rb. sphaeroides R-26 having different rates (k{sub Q}) of the electron transfer from the bacteriopheophytin to the quinone acceptor were obtained. The Zn-RCs exhibited either the native fast (200 ps){sup {minus}1} k{sub Q} or a slow (3--6 ns){sup {minus}1} k{sub Q} at 298 K as determined from transient optical measurements. Sequential electron-transfer polarization modeling of the polarized W-band EPR spectra obtained with these samples was used to address the reason for the differences in the electron-transfer rates. Here, the authors report the k{sub Q} rate constant, the temperature dependence of k{sub Q}, and the reorganization energy for the P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}} electron-transfer step determined from SETP modeling of the experimental spectra. The reorganization energy for the electron-transfer process between P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}}, and not structural changes in the donor or acceptor, was found to be the dominant factor that is altered during Fe-removal procedures.

  9. Effectiveness of perturbation theory approaches for computing non-condon electron transfer dynamics in condensed phases.

    Science.gov (United States)

    Cook, William R; Coalson, Rob D; Evans, Deborah G

    2009-08-20

    A description of electron transfer in condensed-phase media requires models that adequately describe the coupling of the electronic degrees of freedom to the surrounding nuclear coordinates. The spin-boson model has been the canonical model used to understand quantum dynamic processes in condensed-phase media over the last 25 years. Inherent in the standard model of a two-state quantum system coupled to a bosonic bath is the assumption that the Condon approximation is valid. In this context, the Condon approximation assumes that the bath configurations (coordinates) have no effect on the nonadiabatic coupling matrix element. While this is a useful model for electron transfer in small molecular systems, the validity of this approximation is less likely when large-scale motions of solvent molecules are strongly coupled to the electron transfer event, e.g., in molecular clamps and long-range electron transfer in biopolymers. In the present paper a general model for two-state electron transfer which allows for system-bath coupling in both the diagonal and off-diagonal (nonadiabatic) terms is studied. Time-dependent perturbation theory for this Hamiltonian is developed using a small polaron transformation. As noted in several recent studies, in a certain regime of parameter space, the relevant Hamiltonian admits an exact solution, termed the exactly solvable non-Condon Hamiltonian (or NCE). This limit, for which exact solutions are available, is used to benchmark the short- and long-time accuracy of various perturbative approaches. The validated perturbation equations are subsequently used to explore the role of non-Condon effects on electron transfer by systematically increasing the strength of the non-Condon coupling term from zero (i.e., the canonical spin-boson model) to the value that pertains to the exactly solvable non-Condon model (where non-Condon effects are significant).

  10. Photoinduced 2-way electron transfer in composites of metal nanoclusters and semiconductor quantum dots

    Science.gov (United States)

    Mondal, Navendu; Paul, Sneha; Samanta, Anunay

    2016-07-01

    In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation between the QDs and NCs in a giant BSA-capped system, a higher electron transfer rate in this composite suggests that unlike other smaller capping agents, which act more like insulators, BSA allows much better electron conduction, as indicated previously.In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation

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

    Science.gov (United States)

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

    2006-07-01

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

  12. Recent Advances in Photoinduced Electron Transfer Processes of Fullerene-Based Molecular Assemblies and Nanocomposites

    Directory of Open Access Journals (Sweden)

    Osamu Ito

    2012-05-01

    Full Text Available Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide variety of electron donors; in addition, fullerenes in the ground state also act as good electron acceptors in the presence of light-absorbing electron donors such as porphyrins. With single-wall carbon nanotubes (SWCNTs, the photoexcited fullerenes act as electron acceptor. In the case of triple fullerene/porphyrin/SWCNT architectures, the photoexcited porphyrins act as electron donors toward the fullerene and SWCNT. These mechanisms are rationalized with the molecular orbital considerations performed for these huge supramolecules. For the confirmation of the electron transfer processes, transient absorption methods have been used, in addition to time-resolved fluorescence spectral measurements. The kinetic data obtained in solution are found to be quite useful to predict the efficiencies of photovoltaic cells.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-30

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

  14. A new extension of classical molecular dynamics: An electron transfer algorithm.

    Science.gov (United States)

    Raskovalov, Anton

    2017-05-05

    The molecular dynamics is one of the most widely used methods for the simulation of the properties corresponding to ionic motion. Unfortunately, classical molecular dynamics cannot be applied for electron transfer simulation. Suggested modification of the molecular dynamics allows performing the electron transfer from one particle to another during simulation runtime. All additional data structure and the corresponding algorithms are presented in this article. The method can be applied to the systems with pair Van der Waals and Coulomb interactions. Moreover, it may be extended for many-bodied interatomic interactions. In addition, an algorithm of transference numbers calculation has been designed. This extension is not an independent method but it can be useful for simulating the systems with high concentration of electron donors and acceptors. © 2017 Wiley Periodicals, Inc.

  15. Femtosecond spectroscopic studies of photoinduced electron transfer in MDMO-PPV:ZnO hybrid bulk heterojunctions

    Energy Technology Data Exchange (ETDEWEB)

    Cecchetto, E.; De Cola, L. [Institute of Physics, University of Muenster, Mendelstrasse 7, 48149 Muenster (Germany); Slooff, H. [ECN Solar Energy, P.O. Box 1, 1755 ZG Petten (Netherlands); Zhang, H. [Van ' t Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam (Netherlands)

    2007-01-15

    The photophysics of charge carriers (polaron) in MDMO-PPV:ZnO hybrid bulk heterojunction is studied at 80 K by femtosecond transient absorption spectroscopy. A short-lived positive polaron is observed in the blend phase in MDMO-PPV:ZnO blend films with a weight ratio of 1:1 and 1:2. Further increase of ZnO weight ratio results in a significant quenching of the polaron absorption. The results are discussed in the concept that both pristine polymer and MDMO-PPV:ZnO blend phases coexist in the blend films. It is concluded that a polaron is photogenerated within the excitation laser pulse (<100 fs) and electron transfer efficiency is highest in blend films 1:1 and 1:2. Lack of the interfacial area and faster back electron transfer process are discussed to be responsible for the quenching of the electron transfer efficiency in blend film 1:3.

  16. Mechanism of electron transfer reaction for xanthene dye-sensitized formation of methyl viologen radical

    Energy Technology Data Exchange (ETDEWEB)

    Usui, Y.; Misawa, H.; Sakuragi, H.; Tokumaru, K.

    1987-05-01

    Sensitized reduction of methyl viologen, MV/sup 2 +/, occurs efficiently through electron transfer from triplet xanthene dyes to MV/sup 2 +/ followed by electron transfer to the resulting semioxidized dyes from a reductant like triethanolamine. Unreactive ion pair complexes between these dyes and MV/sup 2 +/ are formed (formation constant: 1.2 x 10/sup 3/ M/sup -1/ for Eosine Y and MV/sup 2 +/ in 50% aqueous ethanol solution). The quantum yield for the reduced methyl viologen radical depends on the concentrations of MV/sup 2 +/ and the amine and on the ionic strength of solution. The efficiency of the electron transfer from triplet dyes to MV/sup 2 +/ is increased by addition of alcohol, and solvent effects on the reaction mechanism are discussed. 38 references, 5 figures, 2 tables.

  17. Enhanced rate of intramolecular electron transfer in an engineered purple CuA azurin

    DEFF Research Database (Denmark)

    Farver, O; Lu, Y; Ang, M C

    1999-01-01

    V for blue copper azurin). The reorganization energy of the CuA center is calculated to be 0.4 eV, which is only 50% of that found for the wild-type azurin. These results represent a direct comparison of electron transfer properties of the blue and purple CuA sites in the same protein framework and provide...... and CuA centers are placed in the same location in the protein while all other structural elements remain the same. Long-range electron transfer is induced between the disulfide radical anion, produced pulse radiolytically, and the oxidized binuclear CuA center in the purple azurin mutant. The rate...... support for the notion that the binuclear purple CuA center is a more efficient electron transfer agent than the blue single copper center because reactivity of the former involves a lower reorganization energy....

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

    Energy Technology Data Exchange (ETDEWEB)

    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 producing a charge separation. Decreasing the temperature effects the yield of charge transfer, but not the kinetics.

  19. Theory and experiment on the cuprous-cupric electron transfer rate at a copper electrode.

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J. W.; Smith, B. B.; Walbran, S.; Curtiss, L. A.; Rigney, R. O.; Sutjianto, A.; Hung, N. C.; Yonco, R. M.; Nagy, Z.; Univ. of Minnesota; NREL

    1999-04-01

    We describe results of experiment and theory of the cuprous-cupric electron transfer rate in an aqueous solution at a copper electrode. The methods are similar to those we reported earlier for the ferrous-ferric rate. The comparison strongly suggests that, in marked distinction to the ferrous-ferric case, the electron transfer reaction is adiabatic. The model shows that the activation barrier is dominated by the energy required for the ion to approach the electrode, rather than by the energy required for rearrangement of the solvation shell, also in sharp distinction to the case of the ferric-ferrous electron transfer at a gold electrode. Calculated activation barriers based on this image agree with the experimental results reported here.

  20. Theory and experiment on the cuprous{endash}cupric electron transfer rate at a copper electrode

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J.W. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Smith, B.B. [National Renewable Energy Laboratory, Golden, Colorado (United States); Walbran, S. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Curtiss, L.A.; Rigney, R.O.; Sutjianto, A.; Hung, N.C.; Yonco, R.M.; Nagy, Z. [Argonne National Laboratory, Divisions of Materials Science, Chemistry and Chemical Technology, Argonne, Illinois 60439-4837 (United States)

    1999-04-01

    We describe results of experiment and theory of the cuprous{endash}cupric electron transfer rate in an aqueous solution at a copper electrode. The methods are similar to those we reported earlier for the ferrous{endash}ferric rate. The comparison strongly suggests that, in marked distinction to the ferrous{endash}ferric case, the electron transfer reaction is adiabatic. The model shows that the activation barrier is dominated by the energy required for the ion to approach the electrode, rather than by the energy required for rearrangement of the solvation shell, also in sharp distinction to the case of the ferric{endash}ferrous electron transfer at a gold electrode. Calculated activation barriers based on this image agree with the experimental results reported here. {copyright} {ital 1999 American Institute of Physics.}

  1. Electron transfer mechanism in Shewanella loihica PV-4 biofilms formed at graphite electrode.

    Science.gov (United States)

    Jain, Anand; Zhang, Xiaoming; Pastorella, Gabriele; Connolly, Jack O; Barry, Niamh; Woolley, Robert; Krishnamurthy, Satheesh; Marsili, Enrico

    2012-10-01

    Electron transfer mechanisms in Shewanella loihica PV-4 viable biofilms formed at graphite electrodes were investigated in potentiostat-controlled electrochemical cells poised at oxidative potentials (0.2V vs. Ag/AgCl). Chronoamperometry (CA) showed a repeatable biofilm growth of S. loihica PV-4 on graphite electrode. CA, cyclic voltammetry (CV) and its first derivative shows that both direct electron transfer (DET) mediated electron transfer (MET) mechanism contributes to the overall anodic (oxidation) current. The maximum anodic current density recorded on graphite was 90 μA cm(-2). Fluorescence emission spectra shows increased concentration of quinone derivatives and riboflavin in the cell-free supernatant as the biofilm grows. Differential pulse voltammetry (DPV) show accumulation of riboflavin at the graphite interface, with the increase in incubation period. This is the first study to observe a gradual shift from DET to MET mechanism in viable S. loihica PV-4 biofilms.

  2. Photoinduced Electron Transfer Reaction between Poly-guanylic Acid (5`) with Anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The electron transfer reaction between triplet anthraquinone-2-sulfonate with poly-guanylic acid (5) (poly[G]) in acetonitrile-H2O has been investigated by 248 nm laser flash photolysis. The transient absorption spectra of radical cation of poly[G] and radical anion of anthraqunione-2-sulfonate(AQS) arising from electron transfer reaction has been observed simultaneously for the first time. The formation processes of radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate as well as the decay processes of triplet anthraquinone-2-sulfonate have also been observed, the apparent rate constants for the formation and decay of transient species have been determined. The free energy changes in the process of the electron transfer was also calculated.

  3. Time-resolved fluorescence study of electron transfer in a model peptide system

    Science.gov (United States)

    Donald, Fiona; Hungerford, Graham; Moore, Barry D.; Birch, David J. S.

    1994-08-01

    At present there is a great deal of interest in the study of the transference of energy in biological systems. For example, electron transfer is of major importance in many synthetic and biological processes and in nature is mediated by proteins. Information regarding this process is therefore useful in leading to a greater understanding of phenomena such as photosynthesis and respiration. Previous work on protein systems has shown the electron transfer process to be complex to analyze because of the presence of competing pathways. This has led to the use of model systems to simplify the kinetics. We have synthesized novel model systems using peptides containing both a fluorescent methoxy- naphthalene donor and a dicyanoethylene group as a potential electron acceptor and observed fluorescence quenching for both dipeptide and oligopeptide systems. Biexponential fluorescence decay behavior was observed for all donor acceptor systems, with an increase in the amount of the shorter fluorescence decay component on increasing temperature.

  4. Technology transfer present and futures in the electronic arts

    Directory of Open Access Journals (Sweden)

    Brian Degger

    2008-01-01

    Full Text Available We are entering an era where creating the fantastical is possible in the arts. In the areas of mixed reality and biological arts, responsive works are created based on advances in basic science and technology. This is enabling scientists and artists to pose new questions. As the time between discovery and application is so short, artists need imaginative ways of accessing new technology in order to critique and use it.These are the new paints that the majority of artists cannot afford or access, technology to enable cloning of DNA, to print channels on a chip, to access proprietary 3G networks. Currently, partnerships or residencies are used to facilitate artist’s access to these technologies. What would they do if technology was available that enabled them to make any art work they so desire? Are the limitations in current technology an advantage rather than a disadvantage in some of their works? Does interaction with technologists make their work more robust? Are there disadvantages? How do they get access to the technology they require? Open source or proprietary? Or have they encountered the situation where their vision is greater than technology allows. When their work breaks because of this fact, is their art broken? Blast Theory (Brighton,UK, FoAM(Brussels, Belgium and Amsterdam, Netherlands, SymbioticA (Perth, Australia are organisations pushing technological boundaries in the service of art. This paper addresses some questions of technology transfer in relation to recent artworks, particularly I like Frank in Adelaide (Blast Theory, transient reality generators (trg (FoAM and Multi electrode array artist (MeART (SymbioticA.

  5. Quenching of the excited state of hydrated Europium(III) ions by electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, K.

    1993-08-01

    This thesis explores the oxidation-reduction chemistry of the excited state of Eu(III) ions, *Eu{sub aq}{sup 3+}, in aqueous solutions. Evidence is presented for the quenching of *Eu{sup 3+} by reductive electron transfer. It is concluded that *Eu{sup 3+} is not a strong energy transfer reagent. The reactivity of *Eu{sub aq}{sup 3+} is compared with that of *UO{sub 2}{sup 2+}.

  6. Catalytic electron-transfer oxygenation of substrates with water as an oxygen source using manganese porphyrins.

    Science.gov (United States)

    Fukuzumi, Shunichi; Mizuno, Takuya; Ojiri, Tetsuya

    2012-12-03

    Manganese(V)-oxo-porphyrins are produced by the electron-transfer oxidation of manganese-porphyrins with tris(2,2'-bipyridine)ruthenium(III) ([Ru(bpy)(3)](3+); 2 equiv) in acetonitrile (CH(3)CN) containing water. The rate constants of the electron-transfer oxidation of manganese-porphyrins have been determined and evaluated in light of the Marcus theory of electron transfer. Addition of [Ru(bpy)(3)](3+) to a solution of olefins (styrene and cyclohexene) in CH(3)CN containing water in the presence of a catalytic amount of manganese-porphyrins afforded epoxides, diols, and aldehydes efficiently. Epoxides were converted to the corresponding diols by hydrolysis, and were further oxidized to the corresponding aldehydes. The turnover numbers vary significantly depending on the type of manganese-porphyrin used owing to the difference in their oxidation potentials and the steric bulkiness of the ligand. Ethylbenzene was also oxidized to 1-phenylethanol using manganese-porphyrins as electron-transfer catalysts. The oxygen source in the substrate oxygenation was confirmed to be water by using (18)O-labeled water. The rate constant of the reaction of the manganese(V)-oxo species with cyclohexene was determined directly under single-turnover conditions by monitoring the increase in absorbance attributable to the manganese(III) species produced in the reaction with cyclohexene. It has been shown that the rate-determining step in the catalytic electron-transfer oxygenation of cyclohexene is electron transfer from [Ru(bpy)(3)](3+) to the manganese-porphyrins.

  7. A systematic study of electron or hole transfer along DNA dimers, trimers and polymers

    CERN Document Server

    Simserides, Constantinos

    2014-01-01

    A systematic study of electron or hole transfer along DNA dimers, trimers and polymers is presented with a tight-binding approach at the base-pair level, using the relevant on-site energies of the base-pairs and the hopping parameters between successive base-pairs. A system of $N$ coupled differential equations is solved numerically with the eigenvalue method, allowing the temporal and spatial evolution of electrons or holes along a $N$ base-pair DNA segment to be determined. Useful physical quantities are defined and calculated including the maximum transfer percentage $p$ and the pure maximum transfer rate $\\frac{p}{T}$ for cases where a period $T$ can be defined, as well as the pure mean carrier transfer rate $k$ and the speed of charge transfer $u=kd$, where $d = N \\times$ 3.4 {\\AA} is the charge transfer distance. The inverse decay length $\\beta$ used for the exponential fit $k = k_0 \\exp(-\\beta d)$ and the exponent $\\eta$ used for the power law fit $k = k_0' N^{-\\eta}$ are computed. The electron and hol...

  8. Ultrafast Electron Transfer Between Dye and Catalyst on a Mesoporous NiO Surface.

    Science.gov (United States)

    Brown, Allison M; Antila, Liisa J; Mirmohades, Mohammad; Pullen, Sonja; Ott, Sascha; Hammarström, Leif

    2016-07-01

    The combination of molecular dyes and catalysts with semiconductors into dye-sensitized solar fuel devices (DSSFDs) requires control of efficient interfacial and surface charge transfer between the components. The present study reports on the light-induced electron transfer processes of p-type NiO films cosensitized with coumarin C343 and a bioinspired proton reduction catalyst, [FeFe](mcbdt)(CO)6 (mcbdt = 3-carboxybenzene-1,2-dithiolate). By transient optical spectroscopy we find that ultrafast interfacial electron transfer (τ ≈ 200 fs) from NiO to the excited C343 ("hole injection") is followed by rapid (t1/2 ≈ 10 ps) and efficient surface electron transfer from C343(-) to the coadsorbed [FeFe](mcbdt)(CO)6. The reduced catalyst has a clear spectroscopic signature that persists for several tens of microseconds, before charge recombination with NiO holes occurs. The demonstration of rapid surface electron transfer from dye to catalyst on NiO, and the relatively long lifetime of the resulting charge separated state, suggests the possibility to use these systems for photocathodes on DSSFDs.

  9. Similarity of Heat Transfer on Heat Source Elements in the Entrance Region in Electronic Equipment

    Institute of Scientific and Technical Information of China (English)

    Jane Z. Jiang; Sui Lin

    2001-01-01

    A similarity equation for heat transfer on heat source elements situated in the entrance region in electronic equipment is developed based on the experimental data obtained by Sparrow et al.[4]. The characteristic of the similarity equation is that the ratio of the heat transfer coefficient at the entrance region to that at the fully developed region is independent of the Reynolds number. It depends only on the row number of the elements situated in the entrance region. An example of the usefulness of the similarity equation is presented that determines the heat transfer on heat source elements in a power unit that contains only a small number of the heat source elements.

  10. Controllable Quantum State Transfer Between a Josephson Charge Qubit and an Electronic Spin Ensemble

    Science.gov (United States)

    Yan, Run-Ying; Wang, Hong-Ling; Feng, Zhi-Bo

    2016-01-01

    We propose a theoretical scheme to implement controllable quantum state transfer between a superconducting charge qubit and an electronic spin ensemble of nitrogen-vacancy centers. By an electro-mechanical resonator acting as a quantum data bus, an effective interaction between the charge qubit and the spin ensemble can be achieved in the dispersive regime, by which state transfers are switchable due to the adjustable electrical coupling. With the accessible experimental parameters, we further numerically analyze the feasibility and robustness. The present scheme could provide a potential approach for transferring quantum states controllably with the hybrid system.

  11. Intramolecular electron transfer in cytochrome cd(1) nitrite reductase from Pseudomonas stutzeri; kinetics and thermodynamics

    DEFF Research Database (Denmark)

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

    2002-01-01

    , internal electron transfer between these sites is an inherent element in the catalytic cycle of this enzyme. We have investigated the internal electron transfer reaction employing pulse radiolytically produced N-methyl nicotinamide radicals as reductant which reacts solely with the heme-c in an essentially...... determined over a 277-313 K temperature range and yielded both equilibrium standard enthalpy and entropy changes as well as activation parameters of the specific rate constants. The significance of these parameters obtained at low degree of reduction of the enzyme is discussed and compared with earlier...

  12. Intramolecular electron transfer in ascorbate oxidase is enhanced in the presence of oxygen

    DEFF Research Database (Denmark)

    Farver, O; Wherland, S; Pecht, I

    1994-01-01

    Intramolecular electron transfer from the type 1 copper center to the type 3 copper(II) pair is induced in the multi-copper enzyme, ascorbate oxidase, following pulse radiolytic reduction of the type 1 Cu(II) ion. In the presence of a slight excess of dioxygen over ascorbate oxidase, interaction...... between the trinuclear copper center and O2 is observed even with singly reduced ascorbate oxidase molecules. Under these conditions, the rate constant for intramolecular electron transfer from type 1 Cu(I) to type 3 Cu(II) increases 5-fold to 1100 +/- 300 s-1 (20 degrees C, pH 5.8) as compared...

  13. A Novel Micro-hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between ferro/ferricyanide in aqueous phase (W) and ferrocene in 1, 2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

  14. A Novel Micro—hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    DongPingZHAN; BingLiangWU

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between feero/ferricyanide in aqueous phase(W) and ferrocene in 1,2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

  15. Theoretical Study on the Kinetics of Electron Transfer for Bond-breaking Reaction

    Institute of Scientific and Technical Information of China (English)

    XING,Yu-Mei(邢玉梅); ZHOU,Zheng-Yu(周正宇); GAO,Hong-Wei(高洪伟)

    2002-01-01

    To test the theory of dissociative electron transfer, a simple model describing the kinetics of electron transfer bond-breaking reactions was used. The Hamiltonian of the system was given.The homogeneous and heterogeneous kinetic data fit reasonably well with an activation-driving force relatiobship derived from the Marcus quadratic theory. In the heterogeneous case, there is a good agreement between the theoretical calculation amd the experimental result, while in the homogeneous case, a good a greement is only observed for the tertiary halides. This is due to the stability of tertiary radical resulting from the sterical effect.

  16. Short-lived electron transfer in donor-bridge-acceptor systems

    Science.gov (United States)

    Psiachos, D.

    2016-10-01

    We investigate time-dependent electron transfer (ET) in benchmark donor-bridge-acceptor systems. For the small bridge sizes studied, we obtain results far different from the perturbation theory which underlies scattering-based approaches, notably a lack of destructive interference in the ET for certain arrangements of bridge molecules. We also calculate wavepacket transmission in the non-steady-state regime, finding a featureless spectrum, while for the current we find two types of transmission: sequential and direct, where in the latter, the current transmission increases as a function of the energy of the transferred electron, a regime inaccessible by conventional scattering theory.

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

    Science.gov (United States)

    Yamamoto, Hiromichi

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

  18. Unraveling the electron transfer processes of a nanowire protein from Geobacter sulfurreducens.

    Science.gov (United States)

    Alves, Mónica N; Fernandes, Ana P; Salgueiro, Carlos A; Paquete, Catarina M

    2016-01-01

    The extracellular electron transfer metabolism of Geobacter sulfurreducens is sustained by several multiheme c-type cytochromes. One of these is the dodecaheme cytochrome GSU1996 that belongs to a new sub-class of c-type cytochromes. GSU1996 is composed by four similar triheme domains (A–D). The C-terminal half of the molecule encompasses the domains C and D, which are connected by a small linker and the N-terminal half of the protein contains two domains (A and B) that form one structural unit. It was proposed that this protein works as an electrically conductive device in G. sulfurreducens, transferring electrons within the periplasm or to outer-membrane cytochromes. In this work, a novel strategy was applied to characterize in detail the thermodynamic and kinetic properties of the hexaheme fragment CD of GSU1996. This characterization revealed the electron transfer process of GSU1996 for the first time, showing that a heme at the edge of the C-terminal of the protein is thermodynamic and kinetically competent to receive electrons from physiological redox partners. This information contributes towards understanding how this new sub-class of cytochromes functions as nanowires, and also increases the current knowledge of the extracellular electron transfer mechanisms in G. sulfurreducens.

  19. Ru(II)-diimine functionalized metalloproteins: From electron transfer studies to light-driven biocatalysis.

    Science.gov (United States)

    Lam, Quan; Kato, Mallory; Cheruzel, Lionel

    2016-05-01

    The unique photochemical properties of Ru(II)-diimine complexes have helped initiate a series of seminal electron transfer studies in metalloenzymes. It has thus been possible to experimentally determine rate constants for long-range electron transfers. These studies have laid the foundation for the investigation of reactive intermediates in heme proteins and for the design of light-activated biocatalysts. Various metalloenzymes such as hydrogenase, carbon monoxide dehydrogenase, nitrogenase, laccase and cytochrome P450 BM3 have been functionalized with Ru(II)-diimine complexes. Upon visible light-excitation, these photosensitized metalloproteins are capable of sustaining photocatalytic activity to reduce small molecules such as protons, acetylene, hydrogen cyanide and carbon monoxide or activate molecular dioxygen to produce hydroxylated products. The Ru(II)-diimine photosensitizers are hence able to deliver multiple electrons to metalloenzymes buried active sites, circumventing the need for the natural redox partners. In this review, we will highlight the key achievements of the light-driven biocatalysts, which stem from the extensive electron transfer investigations. 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.

  20. Structural insights into electron transfer in caa 3-type cytochrome oxidase

    OpenAIRE

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

    2012-01-01

    Summary Paragraph Cytochrome c oxidase is a member of the heme copper oxidase superfamily (HCO) 1 . HCOs function as the terminal enzymes in the respiratory chain of mitochondria and aerobic prokaryotes, coupling molecular oxygen reduction to transmembrane proton pumping. Integral to the enzyme’s function is the transfer of electrons from cytochrome c to the oxidase via a transient association of the two proteins. Electron entry and exit are proposed to occur from the same site on cytochrome ...

  1. Long-distance electron transfer by cable bacteria in aquifer sediments

    OpenAIRE

    Müller, Hubert; BOSCH, Julian; Griebler, Christian; Damgaard, Lars Riis; Nielsen, Lars Peter; Lueders, Tillmann; Meckenstock, Rainer U.

    2016-01-01

    The biodegradation of organic pollutants in aquifers is often restricted to the fringes of contaminant plumes where steep countergradients of electron donors and acceptors are separated by limited dispersive mixing. However, long-distance electron transfer (LDET) by filamentous ‘cable bacteria' has recently been discovered in marine sediments to couple spatially separated redox half reactions over centimeter scales. Here we provide primary evidence that such sulfur-oxidizing cable bacteria ca...

  2. Promotion of the Direct Electron Transfer of Hemoglobin by the Carbon Nanotube

    Institute of Scientific and Technical Information of China (English)

    Jing CHEN; Chen Xin CAI

    2004-01-01

    It is reported that the direct electron transfer of hemoglobin (Hb) can be effectively promoted by carbon nanotubes when Hb was immobilized on the surface of the carbon nanotubes modified electrode. The results indicated that the conversion of Hb-Fe(III)/Hb-Fe(II) is a one-electron coupled one-proton reaction process. The method presented can be easily extended to study the direct electrochemistry of other proteins or enzymes.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Adam M Feist

    2014-04-01

    Full Text Available 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.

  5. Electron transfer in N-butylpyridinium tetrafluoroborate ionic liquid by pulse radiolysis

    Institute of Scientific and Technical Information of China (English)

    FU HaiYing; XING ZhaoGuo; CAO XiYan; WU GuoZhong

    2013-01-01

    The radiolysis behavior of neat pyridinium ionic liquids (ILs) and their aqueous solutions was investigated using nanosecond pulse radiolysis techniques.Radiolysis of the ionic liquids,such as N-butylpyridinium tetrafluoroborate (BuPyBF4),resulted in the formation of solvated electrons and organic radicals.Solvated electrons reacted with the pyridinium moiety to produce a pyridinyl radical,which can transfer electrons to various acceptors.The electron-transfer rate constants of the solvent-derived butylpyridinyl radicals in BuPyBF4 and in several compounds (for example,duroquinone,4,4'-pyridine,benzophenone,and 1,1'-dimethyl-4,4'-bypyridinium dichloride) (k of the order 108 L/(mol s) were lower than those measured in water and in i-PrOH but were significantly higher than the diffusion-controlled rate constants estimated based on viscosity.The electron-transfer rate constants in neat BuPyBF4 were one order of magnitude faster than the diffusion-controlled values.This finding suggests that BuPyBF4 acts not only as solvent but also as active solute,such as in solvent-mediated reactions.These reactions result in electrons reaching their final destinations via intervening pyridinium groups without requiring the diffusion of a specific radical.

  6. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul

    2014-01-01

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning we reformulate the method in a computationally e?cient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9-((1-naphthyl)-methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH2-naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety o...

  7. Transfer and reconstruction of the density matrix in off-axis electron holography.

    Science.gov (United States)

    Röder, Falk; Lubk, Axel

    2014-11-01

    The reduced density matrix completely describes the quantum state of an electron scattered by an object in transmission electron microscopy. However, the detection process restricts access to the diagonal elements only. The off-diagonal elements, determining the coherence of the scattered electron, may be obtained from electron holography. In order to extract the influence of the object from the off-diagonals, however, a rigorous consideration of the electron microscope influences like aberrations of the objective lens and the Möllenstedt biprism in the presence of partial coherence is required. Here, we derive a holographic transfer theory based on the generalization of the transmission cross-coefficient including all known holographic phenomena. We furthermore apply a particular simplification of the theory to the experimental analysis of aloof beam electrons scattered by plane silicon surfaces.

  8. The Energy Transfer Processes between Carotenoid and Chlorophyll Regulated by Electron Exchange Mechanism

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The energy transfer efficiency between carotenoids and chlorophyll depend on temperature and viscosity of the media. A 3.5 ps process was detected by the pico-second time-resolved spectra and the process was proved to be regulated by electron exchange mechanism.

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

    Science.gov (United States)

    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.

  10. Modelling microbial fuel cells with suspended cells and added electron transfer mediator

    NARCIS (Netherlands)

    Picoreanu, C.; Katuri, K.P.; Van Loosdrecht, M.C.M.; Head, I.M.; Scott, K.

    2009-01-01

    Derivation of a mathematical model for microbial fuel cells (MFC) with suspended biomass and added electron-transfer mediator is described. The model is based on mass balances for several dissolved chemical species such as substrate, oxidized mediator and reduced mediator. Biological, chemical and e

  11. Flavins mediate extracellular electron transfer in Gram-positive Bacillus megaterium strain LLD-1

    DEFF Research Database (Denmark)

    Xiao, Yong; Liu, Lidan; You, Lexing;

    electrochemically active strain of Bacillus megatherium strain LLD-1, and its extracellular electron transfer mechanism was demonstrated by cyclic voltammetry (CV), differential pulse voltammetry (DPV), HPLC, and chronoamperometric. The CV and DPV showed that a redox peaks ascribing to membrane proteins was found...

  12. Phthalimides as exceptionally efficient single electron transfer acceptors in reductive coupling reactions promoted by samarium diiodide.

    Science.gov (United States)

    Vacas, Tatiana; Alvarez, Eleuterio; Chiara, Jose Luis

    2007-12-20

    Experimental and theoretical evidence shows that phthalimides are highly efficient single electron transfer acceptors in reactions promoted by samarium diiodide, affording ketyl radical anion intermediates, which participate in high-yielding inter- and intramolecular reductive coupling processes with different radicophiles including imides, oxime ethers, nitrones, and Michael acceptors.

  13. Directionality of Ultrafast Electron Transfer in a Hydrogen Evolving Ru-Pd-Based Photocatalyst

    NARCIS (Netherlands)

    Pan, Qing; Mecozzi, Francesco; Korterik, Jeroen P.; Sharma, Divya; Herek, Jennifer L.; Vos, Johannes G.; Browne, Wesley R.; Huijser, Annemarie

    2014-01-01

    Directionality of electron transfer and long-lived charge separation are of key importance for efficient photocatalytic water splitting. Knowledge of the processes that follow photoexcitation is essential for the optimization of supramolecular assembly designs in order to improve the efficiency of p

  14. Bistable switching in supercritical n+-n-n+GaAs transferred electron devices

    DEFF Research Database (Denmark)

    Jøndrup, Peter; Jeppesen, Palle; Jeppson, Bert

    1976-01-01

    Bistable switching in supercritically doped n+-n-n+GaAs transferred electron devices (TED's) is investigated experimentally and interpreted in computer simulations, for which details of the computer program are given. Three switching modes all leading to stable anode domains are discussed, namely...

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

    DEFF Research Database (Denmark)

    Zhu, Nan; Zheng, Kaibo; J. Karki, Khadga

    2015-01-01

    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...

  16. Electron transfer patterns of the di-heme protein cytochrome c(4) from Pseudomonas stutzeri

    DEFF Research Database (Denmark)

    Raffalt, Anders Christer; Schmidt, L.; Christensen, Hans Erik Mølager;

    2009-01-01

    We report kinetic data for the two-step electron transfer (ET) oxidation and reduction of the two-domain di-heme redox protein Pseudomonas stutzeri cytochrome (cyt) c(4) by [Co(bipy)(3)](2- 3-) (bipy = 2,2'-bipyridine). Following earlier reports, the data accord with both bi- and tri-exponential ...

  17. Graphene oxide nanoribbons greatly enhance extracellular electron transfer in bio-electrochemical systems.

    Science.gov (United States)

    Huang, Yu-Xi; Liu, Xian-Wei; Xie, Jia-Fang; Sheng, Guo-Ping; Wang, Guan-Yu; Zhang, Yuan-Yuan; Xu, An-Wu; Yu, Han-Qing

    2011-05-28

    Bridging microbes and electrode to facilitate the extracellular electron transfer (EET) is crucial for bio-electrochemical systems (BESs). Here, a significant enhancement of the EET process was achieved by biomimetically fabricating a network structure of graphene oxide nanoribbons (GONRs) on the electrode. This strategy is universal to enhance the adaptability of GONRs at the bio-nano interface to develop new bioelectronic devices.

  18. Direct Electron Transfer of Enzymes in a Biologically Assembled Conductive Nanomesh Enzyme Platform.

    Science.gov (United States)

    Lee, Seung-Woo; Lee, Ki-Young; Song, Yong-Won; Choi, Won Kook; Chang, Joonyeon; Yi, Hyunjung

    2016-02-24

    Nondestructive assembly of a nanostructured enzyme platform is developed in combination of the specific biomolecular attraction and electrostatic coupling for highly efficient direct electron transfer (DET) of enzymes with unprecedented applicability and versatility. The biologically assembled conductive nanomesh enzyme platform enables DET-based flexible integrated biosensors and DET of eight different enzyme with various catalytic activities.

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

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

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

  20. Electron transfer between a quinohemoprotein alcohol dehydrogenase and an electrode via a redox polymer network

    NARCIS (Netherlands)

    Stigter, E.C.A.; Jong, G.A.H. de; Jongejan, J.A.; Duine, J.A.; Lugt, J.P. van der; Somers, W.A.C.

    1996-01-01

    A quinohemoprotein alcohol dehydrogenase (QH-EDH) from Comamonas testosteroni was immobilized on an electrode in a redox polymer network consisting of a polyvinylpyridine partially N-complexed with osmiumbis-(bipyridine)chloride. The enzyme effectively transfers electrons to the electrode via the po

  1. Role of ligand substitution on long-range electron transfer in azurins

    DEFF Research Database (Denmark)

    Farver, O; Jeuken, L J; Canters, G W

    2000-01-01

    Azurin contains two potential redox sites, a copper centre and, at the opposite end of the molecule, a cystine disulfide (RSSR). Intramolecular electron transfer between a pulse radiolytically produced RSSR- radical anion and the blue Cu(II) ion was studied in a series of azurins in which single-...

  2. 78 FR 6025 - Electronic Fund Transfers (Regulation E) Temporary Delay of Effective Date

    Science.gov (United States)

    2013-01-29

    ... Part 1005 RIN 3170-AA33 Electronic Fund Transfers (Regulation E) Temporary Delay of Effective Date... Financial Protection (Bureau) is issuing this final rule to delay the February 7, 2013, effective date of... delaying the effective date of the 2012 Final Rule pending the finalization of a proposal, published...

  3. Long-range protein electron transfer observed at the single-molecule level

    DEFF Research Database (Denmark)

    Chi, Qijin; Farver, Ole; Ulstrup, Jens

    2005-01-01

    A biomimetic long-range electron transfer (ET) system consisting of the blue copper protein azurin, a tunneling barrier bridge, and a gold single-crystal electrode was designed on the basis of molecular wiring self-assembly principles. This system is sufficiently stable and sensitive in a quasi...

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

    Science.gov (United States)

    Wang, Changhua; Zhang, Xintong; Liu, Yichun

    2015-12-01

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

  5. Electronic Couplings for Resonance Energy Transfer from CCSD Calculations: From Isolated to Solvated Systems.

    Science.gov (United States)

    Caricato, Marco; Curutchet, Carles; Mennucci, Benedetta; Scalmani, Giovanni

    2015-11-10

    Quantum mechanical (QM) calculations of electronic couplings provide great insights for the study of resonance energy transfer (RET). However, most of these calculations rely on approximate QM methods due to the computational limitations imposed by the size of typical donor-acceptor systems. In this work, we present a novel implementation that allows computing electronic couplings at the coupled cluster singles and doubles (CCSD) level of theory. Solvent effects are also taken into account through the polarizable continuum model (PCM). As a test case, we use a dimer of indole, a common model system for tryptophan, which is routinely used as an intrinsic fluorophore in Förster resonance energy transfer studies. We consider two bright π → π* states, one of which has charge transfer character. Lastly, the results are compared with those obtained by applying TD-DFT in combination with one of the most popular density functionals, B3LYP.

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

    Energy Technology Data Exchange (ETDEWEB)

    Feist, AM; Nagarajan, H; Rotaru, AE; Tremblay, PL; Zhang, T; Nevin, KP; Lovley, DR; Zengler, K

    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 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. 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

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

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic...... in the intermediate states. We have furthermore provided criteria for the distinction between direct ET, ET through high-energy (superexchange), and low-energy (''radical'' intermediate mechanism) intermediate states on the basis of experimental rate data and illustrated this with data for organic radical anions...

  8. Electron Transfer in Methylene-Blue-Labeled G3 Dendrimers Tethered to Gold

    DEFF Research Database (Denmark)

    Álvarez-Martos, Isabel; Kartashov, Andrey; Ferapontova, Elena

    2016-01-01

    Redox-modified branched 3D dendrimeric nanostructures are considered a proper tool for the wiring of redox enzymes be-cause they provide both an enzyme-friendly environment and exquisite electron transfer (ET) mediation. ET rates in G3 poly-(amido)amine (PAMAM) dendrimers, covalently attached......,the ET mechanism switched from surface-confined ET (electron tunneling) in dilute monolayers to diffusional ET (electron hopping) at higher surface populations of dendrimers. Structural changes in the positively charged dendrimers electrostatically compressed at negative charges of the electrode surface...

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

    Science.gov (United States)

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

    2013-12-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  10. Resonant electronic excitation energy transfer by Dexter mechanism in the quantum dot system

    Science.gov (United States)

    Samosvat, D. M.; Chikalova-Luzina, O. P.; Vyatkin, V. M.; Zegrya, G. G.

    2016-11-01

    In present work the energy transfer between quantum dots by the exchange (Dexter) mechanism is analysed. The interdot Coulomb interaction is taken into consideration. It is assumed that the quantum dot-donor and the quantum dot-acceptor are made from the same compound A3B5 and embedded in the matrix of other material creating potential barriers for electron and holes. The dependences of the energy transfer rate on the quantum-dot system parameters are found using the Kane model that provides the most adequate description spectra of semiconductors A3B5. Numerical calculations show that the rate of the energy transfer by Dexter mechanism is comparable to the rate of the energy transfer by electrostatic mechanism at the distances approaching to the contact ones.

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

    Directory of Open Access Journals (Sweden)

    Haluk eBeyenal

    2015-09-01

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

  12. Theory of ultrafast photoinduced electron transfer from a bulk semiconductor to a quantum dot

    Energy Technology Data Exchange (ETDEWEB)

    Rasmussen, Andrew M., E-mail: andyras@gmail.com; Ramakrishna, S.; Weiss, Emily A.; Seideman, Tamar, E-mail: t-seideman@northwestern.edu [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113 (United States)

    2014-04-14

    This paper describes analytical and numerical results from a model Hamiltonian method applied to electron transfer (ET) from a quasicontinuum (QC) of states to a set of discrete states, with and without a mediating bridge. Analysis of the factors that determine ET dynamics yields guidelines for achieving high-yield electron transfer in these systems, desired for instance for applications in heterogeneous catalysis. These include the choice of parameters of the laser pulse that excites the initial state into a continuum electronic wavepacket and the design of the coupling between the bridge molecule and the donor and acceptor. The vibrational mode on a bridging molecule between donor and acceptor has an influence on the yield of electron transfer via Franck-Condon factors, even in cases where excited vibrational states are only transiently populated. Laser-induced coherence of the initial state as well as energetic overlap is crucial in determining the ET yield from a QC to a discrete state, whereas the ET time is influenced by competing factors from the coupling strength and the coherence properties of the electronic wavepacket.

  13. Direct Measurement of Electron Transfer in Nanoscale Host-Guest Systems: Metallocenes in Carbon Nanotubes.

    Science.gov (United States)

    McSweeney, Robert L; Chamberlain, Thomas W; Baldoni, Matteo; Lebedeva, Maria A; Davies, E Stephen; Besley, Elena; Khlobystov, Andrei N

    2016-09-12

    Electron-transfer processes play a significant role in host-guest interactions and determine physicochemical phenomena emerging at the nanoscale that can be harnessed in electronic or optical devices, as well as biochemical and catalytic systems. A novel method for qualifying and quantifying the electronic doping of single walled carbon nanotubes (SWNTs) using electrochemistry has been developed that establishes a direct link between these experimental measurements and ab initio DFT calculations. Metallocenes such as cobaltocene and methylated ferrocene derivatives were encapsulated inside SWNTs (1.4 nm diameter) and cyclic voltammetry (CV) was performed on the resultant host-guest systems. The electron transfer between the guest molecules and the host SWNTs is measured as a function of shift in the redox potential (E1/2 ) of Co(II) /Co(I) , Co(III) /Co(II) and Fe(III) /Fe(II) . Furthermore, the shift in E1/2 is inversely proportional to the nanotube diameter. To quantify the amount of electron transfer from the guest molecules to the SWNTs, a novel method using coulometry was developed, allowing the mapping of the density of states and the Fermi level of the SWNTs. Correlated with theoretical calculations, coulometry provides an accurate indication of n/p-doping of the SWNTs.

  14. Status of the proton and electron transfer lines for the AWAKE Experiment at CERN

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, J.S., E-mail: janet.schmidt@cern.ch [CERN, Geneva (Switzerland); Bauche, J. [CERN, Geneva (Switzerland); Biskup, B. [CERN, Geneva (Switzerland); Czech Technical University, Prague (Czech Republic); Bracco, C.; Doebert, S.; Goddard, B.; Gschwendtner, E.; Jensen, L.K.; Jones, O.R.; Mazzoni, S.; Meddahi, M.; Pepitone, K.; Petrenko, A.; Velotti, F.M.; Vorozhtsov, A. [CERN, Geneva (Switzerland)

    2016-09-01

    The AWAKE project at CERN is planned to study proton driven plasma wakefield acceleration with an externally injected electron beam. Therefore two transfer lines are being designed in order to provide the proton beam from the SPS and the electron beam from an RF gun to the plasma cell. The commissioning of the proton line will take place in 2016 for the first phase of the experiment, which is focused on the self-modulation of a 12 cm long proton bunch in the plasma. The electron line will be added for the second phase of AWAKE in 2017, when the wakefield will be probed with an electron beam of 10–20 MeV/c. The challenge for these transfer lines lies in the parallel operation of the proton, electron and laser beam used to ionize the plasma and seed the self-modulation. These beams, of different characteristics, need to be synchronized and positioned for optimized injection conditions into the wakefield. This task requires great flexibility in the transfer line optics. The status of these designs will be presented in this paper.

  15. Status of the proton and electron transfer lines for the AWAKE Experiment at CERN

    Science.gov (United States)

    Schmidt, J. S.; Bauche, J.; Biskup, B.; Bracco, C.; Doebert, S.; Goddard, B.; Gschwendtner, E.; Jensen, L. K.; Jones, O. R.; Mazzoni, S.; Meddahi, M.; Pepitone, K.; Petrenko, A.; Velotti, F. M.; Vorozhtsov, A.

    2016-09-01

    The AWAKE project at CERN is planned to study proton driven plasma wakefield acceleration with an externally injected electron beam. Therefore two transfer lines are being designed in order to provide the proton beam from the SPS and the electron beam from an RF gun to the plasma cell. The commissioning of the proton line will take place in 2016 for the first phase of the experiment, which is focused on the self-modulation of a 12 cm long proton bunch in the plasma. The electron line will be added for the second phase of AWAKE in 2017, when the wakefield will be probed with an electron beam of 10-20 MeV/c. The challenge for these transfer lines lies in the parallel operation of the proton, electron and laser beam used to ionize the plasma and seed the self-modulation. These beams, of different characteristics, need to be synchronized and positioned for optimized injection conditions into the wakefield. This task requires great flexibility in the transfer line optics. The status of these designs will be presented in this paper.

  16. Large work function difference driven electron transfer from electrides to single-walled carbon nanotubes.

    Science.gov (United States)

    Menamparambath, Mini Mol; Park, Jong-Ho; Yoo, Ho-Sung; Patole, Shashikant P; Yoo, Ji-Beom; Kim, Sung Wng; Baik, Seunghyun

    2014-08-07

    A difference in work function plays a key role in charge transfer between two materials. Inorganic electrides provide a unique opportunity for electron transfer since interstitial anionic electrons result in a very low work function of 2.4-2.6 eV. Here we investigated charge transfer between two different types of electrides, [Ca(2)N](+)·e(-) and [Ca(24)Al(28)O(64)](4+)·4e(-), and single-walled carbon nanotubes (SWNTs) with a work function of 4.73-5.05 eV. [Ca(2)N](+) · e(-) with open 2-dimensional electron layers was more effective in donating electrons to SWNTs than closed cage structured [Ca(24)Al(28)O(64)](4+) · 4e(-) due to the higher electron concentration (1.3 × 10(22) cm(-3)) and mobility (∼ 200 cm(2) V(-1) s(-1) at RT). A non-covalent conjugation enhanced near-infrared fluorescence of SWNTs as high as 52%. The field emission current density of electride-SWNT-silver paste dramatically increased by a factor of 46,000 (14.8 mA cm(-2)) at 2 V μm(-1) (3.5 wt% [Ca(2)N](+) · e(-)) with a turn-on voltage of 0.85 V μm(-1).

  17. Influence of chemical and structural evolution of dissolved organic matter on electron transfer capacity during composting

    Energy Technology Data Exchange (ETDEWEB)

    He, Xiao-Song [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Xi, Bei-Dou, E-mail: hexs82@126.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Cui, Dong-Yu [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Liu, Yong [Guangdong Key Laboratory of Agro-Environmental Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Tan, Wen-Bin; Pan, Hong-Wei; Li, Dan [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China)

    2014-03-01

    Highlights: • Electron transfer capability (ETC) of compost-derived DOM was investigated. • Composting treatment increased the ETC of DOM from municipal solid wastes. • The ETC increase related to humic matter, and molecule weight, and N and S content. - Abstract: Dissolved organic matter (DOM) can mediate electron transfer and change chemical speciation of heavy metals. In this study, the electron transfer capability (ETC) of compost-derived DOM was investigated through electrochemical approaches, and the factors influencing the ETC were studied using spectral and elemental analysis. The results showed that the electron accepting capacity (EAC) and electron donating capacity (EDC) of compost-derived DOM were 3.29–40.14 μmol{sub e−} (g C){sup −1} and 57.1– 346.07 μmol{sub e−} (g C){sup −1}, respectively. Composting treatment increased the fulvic- and humic-like substance content, oxygenated aliphatic carbon content, lignin-derived aromatic carbon content, molecule weight, and N and S content of DOM, but decreased the aliphatic carbon content and the C and H content. This conversion increased the EDC and EAC of the DOM during composting.

  18. Large work function difference driven electron transfer from electrides to single-walled carbon nanotubes

    KAUST Repository

    Menamparambath, Mini Mol

    2014-06-23

    A difference in work function plays a key role in charge transfer between two materials. Inorganic electrides provide a unique opportunity for electron transfer since interstitial anionic electrons result in a very low work function of 2.4-2.6 eV. Here we investigated charge transfer between two different types of electrides, [Ca2N]+·e- and [Ca 24Al28O64]4+·4e-, and single-walled carbon nanotubes (SWNTs) with a work function of 4.73-5.05 eV. [Ca2N]+·e- with open 2-dimensional electron layers was more effective in donating electrons to SWNTs than closed cage structured [Ca24Al28O64] 4+·4e- due to the higher electron concentration (1.3 × 1022 cm-3) and mobility (∼200 cm 2 V-1 s-1 at RT). A non-covalent conjugation enhanced near-infrared fluorescence of SWNTs as high as 52%. The field emission current density of electride-SWNT-silver paste dramatically increased by a factor of 46000 (14.8 mA cm-2) at 2 V μm-1 (3.5 wt% [Ca2N]+·e-) with a turn-on voltage of 0.85 V μm-1. This journal is © the Partner Organisations 2014.

  19. Characterizing the Locality of Diabatic States for Electronic Excitation Transfer by Decomposing the Diabatic Coupling

    Energy Technology Data Exchange (ETDEWEB)

    Vura-Weis, Josh; Newton, M. D.; Wasielewski, Michael R; Subotnik, J.E.

    2010-12-09

    A common strategy to calculate electronic coupling matrix elements for charge or energy transfer is to take the adiabatic states generated by electronic structure computations and rotate them to form localized diabatic states. In this paper, we show that, for intermolecular transfer of singlet electronic excitation, usually we cannot fully localize the electronic excitations in this way. Instead, we calculate putative initial and final states with small excitation tails caused by weak interactions with high energy excited states in the electronic manifold. These tails do not lead to substantial changes in the total diabatic coupling between states, but they do lead to a different partitioning of the total coupling between Coulomb (Förster), exchange (Dexter), and one-electron components. The tails may be reduced by using a multistate diabatic model or eliminated entirely by truncation (denoted as “chopping”). Without more information, we are unable to conclude with certainty whether the observed diabatic tails are a physical reality or a computational artifact. This research suggests that decomposition of the diabatic coupling between chromophores into Coulomb, exchange, and one-electron components may depend strongly on the number of states considered, and such results should be treated with caution.

  20. First Observation of Electron Transfer Mediated Decay in Aqueous Solutions: A Novel Probe of Ion Pairing

    CERN Document Server

    Unger, I; Thürmer, S; Aziz, E F; Cederbaum, L S; Muchová, E; Slavíček, P; Winter, B; Kryzhevoi, N V

    2016-01-01

    A major goal of many spectroscopic techniques is to provide comprehensive information on the local chemical environment. Electron transfer mediated decay (ETMD) is a sensitive probe of the environment since it is actively involved in this non-local radiationless decay process through electron and energy transfer steps. We report the first experimental observation of ETMD in the liquid phase. Using liquid-jet X-ray photoelectron spectroscopy we explore LiCl aqueous solution, and detect low-energy electrons unambiguously emerging from the ETMD processes of core-ionized Li+. We interpret the experimental results with molecular dynamics and high-level ab initio calculations. By considering various solvation-structure models we show that both water molecules and Cl- anions can participate in ETMD, with each process having its characteristic spectral fingerprint. Different ion associations lead to different spectral shapes. The potential application of the unique sensitivity of the ETMD spectroscopy to the local hy...

  1. Investigation of liquid-liquid interfacial electron transfer kinetics using multicenter ferrocenyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Xiang Debo [Department of Chemistry, Faculty of Science, Beijing Institute of Technology, Beijing 100081 (China); Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Merbouh, Nabyl [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Shao Huibo [Department of Chemistry, Faculty of Science, Beijing Institute of Technology, Beijing 100081 (China); Yu Huazhong, E-mail: hogan_yu@sfu.ca [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada)

    2011-06-30

    The redox behavior of two novel multicenter redox molecules (triferrocenylmethane and triferrocenylmethanol) has been studied in a thin film of nitrobenzene (NB) imposed between a graphite electrode and an aqueous electrolyte. The well separated three sets of redox peaks indicate strong intramolecular electronic communications between the three ferrocene centers in each molecule. They were adapted as model compounds for the study of electron transfer kinetics across the liquid/liquid interface with varied overall driving force using only one-type redox couples in the organic and aqueous phase, respectively. It has been shown that in both cases the dependence of interfacial electron transfer rate on the increased overall driving force across the nitrobenzene/water interface is not monotonic.

  2. Simulation study of the ferrous ferric electron transfer at a metal--aqueous electrolyte interface

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.B.; Halley, J.W. (School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States))

    1994-12-15

    We report a new simulation study of the rate of ferrous--ferric electron transfer at a metal electrolyte interface. In contrast with earlier work, new features in our study include a detailed account of the effects of the field associated with the charging of the electrode, inclusion of entropic effects in the calculated free energy barriers, and a study of the dependence of the relevant free energy surfaces on the distance of the ion from the electrode. The qualitative picture of the reaction mechanism which emerges is significantly more detailed than that in earlier work. The dominant factors in determining the rate and mechanisms of electron transfer are the distance dependence of the work function of the metal, the redox species concentration profile, and the electronic matrix element. Calculated free energy barriers are consistent with experimentally measured ones. We also estimate the equilibrium potential for this reaction from the model, and find it to be consistent with the experimental equilibrium potential.

  3. On the theory of electron transfer reactions at semiconductor electrode/liquid interfaces

    Science.gov (United States)

    Gao, Yi Qin; Georgievskii, Yuri; Marcus, R. A.

    2000-02-01

    Electron transfer reaction rate constants at semiconductor/liquid interfaces are calculated using the Fermi Golden Rule and a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the electronic structures of semiconductors with surfaces and are compared. The maximum electron transfer rate constants at Si/viologen2+/+ and InP/Me2Fc+/0 interfaces are computed using the tight-binding type calculations for the solid and the extended-Hückel for the coupling to the redox agent at the interface. These results for the bulk states are compared with the experimentally measured values of Lewis and co-workers, and are in reasonable agreement, without adjusting parameters. In the case of InP/liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

  4. Nitrogen doped carbon nanoparticles enhanced extracellular electron transfer for high-performance microbial fuel cells anode.

    Science.gov (United States)

    Yu, Yang-Yang; Guo, Chun Xian; Yong, Yang-Chun; Li, Chang Ming; Song, Hao

    2015-12-01

    Nitrogen doped carbon nanoparticles (NDCN) were applied to modify the carbon cloth anodes of microbial fuel cells (MFCs) inoculated with Shewanella oneidensis MR-1, one of the most well-studied exoelectrogens. Experimental results demonstrated that the use of NDCN increased anodic absorption of flavins (i.e., the soluble electron mediator secreted by S. oneidensis MR-1), facilitating shuttle-mediated extracellular electron transfer. In addition, we also found that NDCN enabled enhanced contact-based direct electron transfer via outer-membrane c-type cytochromes. Taken together, the performance of MFCs with the NDCN-modified anode was enormously enhanced, delivering a maximum power density 3.5 times' higher than that of the MFCs without the modification of carbon cloth anodes.

  5. Intraprotein electron transfer between tyrosine and tryptophan in DNA photolyase from Anacystis nidulans.

    Science.gov (United States)

    Aubert, C; Mathis, P; Eker, A P; Brettel, K

    1999-05-11

    Light-induced electron transfer reactions leading to the fully reduced, catalytically competent state of the flavin adenine dinucleotide (FAD) cofactor have been studied by flash absorption spectroscopy in DNA photolyase from Anacystis nidulans. The protein, overproduced in Escherichia coli, was devoid of the antenna cofactor, and the FAD chromophore was present in the semireduced form, FADH., which is inactive for DNA repair. We show that after selective excitation of FADH. by a 7-ns laser flash, fully reduced FAD (FADH-) is formed in less than 500 ns by electron abstraction from a tryptophan residue. Subsequently, a tyrosine residue is oxidized by the tryptophanyl radical with t(1)/(2) = 50 microseconds. The amino acid radicals were identified by their characteristic absorption spectra, with maxima at 520 nm for Trp. and 410 nm for TyrO. The newly discovered electron transfer between tyrosine and tryptophan occurred for approximately 40% of the tryptophanyl radicals, whereas 60% decayed by charge recombination with FADH- (t(1)/(2) = 1 ms). The tyrosyl radical can also recombine with FADH- but at a much slower rate (t(1)/(2) = 76 ms) than Trp. In the presence of an external electron donor, however, TyrO. is rereduced efficiently in a bimolecular reaction that leaves FAD in the fully reduced state FADH-. These results show that electron transfer from tyrosine to Trp. is an essential step in the process leading to the active form of photolyase. They provide direct evidence that electron transfer between tyrosine and tryptophan occurs in a native biological reaction.

  6. Electron velocity saturation and intervalley transfer in monolayer MoS2

    Science.gov (United States)

    Ferry, D. K.

    2016-11-01

    Monolayer MoS2 is a material with a rich history and that is being suggested for many applications in electronics, including novel electron devices. Recent experiments has shown that it has a saturation velocity at high electric fields well below other electronic materials such as Si. This is a very important property that is crucial to high performance electron devices. Here, we study this property with ensemble Monte Carlo simulations of the electron transport. We find that the velocity at high electric fields is larger than the experiments, and does not show a saturation up to 100 kV cm-1. In addition, the transport at high fields is dominated by inter-valley transfer to the T valleys.

  7. Photoinduced electron transfer in some photosensitive molecules-incorporated semiconductor/zeolites: New photocatalytic systems

    Indian Academy of Sciences (India)

    Minjoong Yoon; Devendra P S Negi

    2002-12-01

    An intramolecular charge transfer (ICT) molecule, -N,N-dimethylaminobenzoic acid (DMABA) has been studied in zeolite and colloidal media. The ratio of ICT to normal emission (ICT/LE) is greatly enhanced in zeolites compared to that in polar solvents. The ICT emission of DMABA was quenched by increasing the concentration of TiO2 colloids, while the normal emission was slightly enhanced. Upon illumination of the heteropoly acid (HPA) incorporated TiO2 colloids, interfacial electron transfer takes place from the conduction band of TiO2 to the incorporated HPA which is also excited to catalyze the photoreduction of Methyl Orange. It is found that the interfacial electron transfer mechanism of HPA/TiO2 is quite analogous to the Z-scheme mechanism for plant photosynthetic systems. In DMABA-adsorbed TiO2/Y-zeolite the ICT/LE ratio of DMABA is quite small implying that electron transfer takes place from DMABA to the conduction band of TiO2. This results in drastic enhancement in the photocatalytic activity of DMABA-adsorbed TiO2/Y-zeolite compared to free TiO2/Y-zeolite.

  8. Quantum chemical calculations of tryptophan → heme electron and excitation energy transfer rates in myoglobin.

    Science.gov (United States)

    Suess, Christian J; Hirst, Jonathan D; Besley, Nicholas A

    2017-04-01

    The development of optical multidimensional spectroscopic techniques has opened up new possibilities for the study of biological processes. Recently, ultrafast two-dimensional ultraviolet spectroscopy experiments have determined the rates of tryptophan → heme electron transfer and excitation energy transfer for the two tryptophan residues in myoglobin (Consani et al., Science, 2013, 339, 1586). Here, we show that accurate prediction of these rates can be achieved using Marcus theory in conjunction with time-dependent density functional theory. Key intermediate residues between the donor and acceptor are identified, and in particular the residues Val68 and Ile75 play a critical role in calculations of the electron coupling matrix elements. Our calculations demonstrate how small changes in structure can have a large effect on the rates, and show that the different rates of electron transfer are dictated by the distance between the heme and tryptophan residues, while for excitation energy transfer the orientation of the tryptophan residues relative to the heme is important. © 2017 The Authors Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

  9. Temperature and detection-wavelength dependence of the electron transfer rates in initial stages of photosynthesis.

    Science.gov (United States)

    Kurzynski, Michal; Chelminiak, Przemyslaw

    2013-10-17

    Unusual temperature behavior, observed in the initial electron transfer stages in the photosynthetic reaction centers of the purple bacteria, and a strong probing pulse wavelength dependence of transfer rates, determined in transient absorption spectroscopy, can easily be explained on assuming that the transfer takes place from dynamically unrelaxed states of protein environment. The transitions from the primary special pair (P) to a single bacteriochlorophyll (B) and next to a bacteriopheophytin (H) are controlled by diffusion down the energy value of underdamped vibrational modes of frequency 200 K, probably determining distances between the succeeding cofactors. The subsequent transition to the quinone A (Q) is controlled by diffusion in the position value of an overdamped conformational mode, probably corresponding to the local polarization. From the fit of available experimental data to simple theoretical formulas, the important physical conclusion arises that the very electronic transitions are fast as compared to the relaxation processes and, in the first approximation, only the latter contribute to the overall times of the initial electron transfer stages in photosynthesis.

  10. Spectral Properties and Energy Transfer between Ce(3+) and Yb(3+) in the Ca3Sc2Si3O12 Host: Is It an Electron Transfer Mechanism?

    Science.gov (United States)

    Zhou, Lei; Tanner, Peter A; Ning, Lixin; Zhou, Weijie; Liang, Hongbin; Zheng, Lirong

    2016-07-21

    The downshifting from Ce(3+) blue emission to Yb(3+) near-infrared emission has been studied in the garnet host Ca2.8-2xCe0.1YbxNa0.1+xSc2Si3O12 (x = 0-0.36). The downshifting does not involve quantum cutting, but one incident blue photon is transferred from Ce(3+) to Yb(3+) with an energy transfer efficiency up to 90% when x = 0.36 for the Yb(3+) dopant ion. For x ≤ 0.15, a multiphonon-assisted electric dipole-electric quadrupole mechanism of energy transfer dominates, while for the highest concentration of Yb(3+) employed, the electron transfer mechanism is confirmed. A temperature-dependent increase of the Ce(3+) → Yb(3+) energy transfer rate does not exclusively indicate the electron transfer mechanism. The application of the material to solar energy conversion is indicated.

  11. Two-Dimensional Electronic Spectroscopies for Probing Electronic Structure and Charge Transfer: Applications to Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Ogilvie, Jennifer P. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Physics

    2016-11-22

    Photosystem II (PSII) is the only known natural enzyme that uses solar energy to split water, making the elucidation of its design principles critical for our fundamental understanding of photosynthesis and for our ability to mimic PSII’s remarkable properties. This report discusses progress towards addressing key open questions about the PSII RC. It describes new spectroscopic methods that were developed to answer these questions, and summarizes the outcomes of applying these methods to study the PSII RC. Using 2D electronic spectroscopy and 2D electronic Stark spectroscopy, models for the PSII RC were tested and refined. Work is ongoing to use the collected data to elucidate the charge separation mechanism in the PSII RC. Coherent dynamics were also observed in the PSII RC for the first time. Through extensive characterization and modeling we have assigned these coherences as vibronic in nature, and believe that they reflect resonances between key vibrational pigment modes and electronic energy gaps that may facilitate charge separation. Work is ongoing to definitively test the functional relevance of electronic-vibrational resonances.

  12. Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers: volume change, enthalpy, and entropy of electron-transfer reactions in manganese-depleted photosystem II core complexes.

    Science.gov (United States)

    Hou, J M; Boichenko, V A; Diner, B A; Mauzerall, D

    2001-06-19

    We have previously reported the thermodynamic data of electron transfer in photosystem I using pulsed time-resolved photoacoustics [Hou et al. (2001) Biochemistry 40, 7109-7116]. In the present work, using preparations of purified manganese-depleted photosystem II (PS II) core complexes from Synechocystis sp. PCC 6803, we have measured the DeltaV, DeltaH, and estimated TDeltaS of electron transfer on the time scale of 1 micros. At pH 6.0, the volume contraction of PS II was determined to be -9 +/- 1 A3. The thermal efficiency was found to be 52 +/- 5%, which corresponds to an enthalpy change of -0.9 +/- 0.1 eV for the formation of the state P680+Q(A-) from P680*. An unexpected volume expansion on pulse saturation of PS II was observed, which is reversible in the dark. At pH 9.0, the volume contraction, the thermal efficiency, and the enthalpy change were -3.4 +/- 0.5 A3, 37 +/- 7%, and -1.15 +/- 0.13 eV, respectively. The DeltaV of PS II, smaller than that of PS I and bacterial centers, is assigned to electrostriction and analyzed using the Drude-Nernst equation. To explain the small DeltaV for the formation of P680+Q(A-) or Y(Z*)Q(A-), we propose that fast proton transfer into a polar region is involved in this reaction. Taking the free energy of charge separation of PS II as the difference between the energy of the excited-state P680* and the difference in the redox potentials of the donor and acceptor, the apparent entropy change (TDeltaS) for charge separation of PS II is calculated to be negative, -0.1 +/- 0.1 eV at pH 6.0 (P680+Q(A-)) and -0.2 +/- 0.15 eV at pH 9.0 (Y(Z*)Q(A-)). The thermodynamic properties of electron transfer in PS II core reaction centers thus differ considerably from those of bacterial and PS I reaction centers, which have DeltaV of approximately -27 A3, DeltaH of approximately -0.4 eV, and TDeltaS of approximately +0.4 eV.

  13. Probing Electron Transfer Mechanisms in Shewanella oneidensis MR-1 using a Nanoelectrode Platform and Single-Cell Imaging

    Science.gov (United States)

    2010-01-01

    nanowires The capability of bacteria, such as Shewanella and Geobacter ,to transfer electrons from metabolism of organic sources to electrodes without...filamentous pili growth from Shewanella and Geobacter cells report a third mechanism for extracellular electron transfer through biological nanowires (12

  14. 48 CFR 52.232-35 - Designation of Office for Government Receipt of Electronic Funds Transfer Information.

    Science.gov (United States)

    2010-10-01

    ... Government Receipt of Electronic Funds Transfer Information. 52.232-35 Section 52.232-35 Federal Acquisition... of Office for Government Receipt of Electronic Funds Transfer Information (MAY 1999) (a) As provided... CONTRACT CLAUSES Text of Provisions and Clauses 52.232-35 Designation of Office for Government Receipt...

  15. Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report, [March 1992--March 1993

    Energy Technology Data Exchange (ETDEWEB)

    Neta, P.

    1993-04-01

    Electron transfer and other reactions of various short-lived intermediates have been studied by pulse radiolysis and laser flash photolysis. Highlights of results during the past year are summarized under two main sections: Metalloporphyrin electron transfer and associated reactions, and solvent effects on reactions of inorganic radicals and organic peroxyl radicals.

  16. The two-photon exchange contribution to elastic electron-nucleon scattering at large momentum transfer

    Energy Technology Data Exchange (ETDEWEB)

    Andrei V. Afanasev; Stanley J. Brodsky; Carl E. Carlson; Yu-Chun Chen; Marc Vanderhaeghen

    2005-01-01

    We estimate the two-photon exchange contribution to elastic electron-proton scattering at large momentum transfer by using a quark-parton representation of virtual Compton scattering. We thus can relate the two-photon exchange amplitude to the generalized parton distributions which also enter in other wide angle scattering processes. We find that the interference of one- and two-photon exchange contribution is able to substantially resolve the difference between electric form factor measurements from Rosenbluth and polarization transfer experiments.

  17. Long-distance electronic energy transfer in light-harvesting supramolecular polymers.

    Science.gov (United States)

    Winiger, Christian B; Li, Shaoguang; Kumar, Ganesh R; Langenegger, Simon M; Häner, Robert

    2014-12-01

    The efficient collection of solar energy relies on the design and construction of well-organized light-harvesting systems. Herein we report that supramolecular phenanthrene polymers doped with pyrene are effective collectors of light energy. The linear polymers are formed through the assembly of short amphiphilic oligomers in water. Absorption of light by phenanthrene residues is followed by electronic energy transfer along the polymer over long distances (>100 nm) to the accepting pyrene molecules. The high efficiency of the energy transfer, which is documented by large fluorescence quantum yields, suggests a quantum coherent process.

  18. Proton-coupled electron transfer promotes the reduction of ferrylmyoglobin by uric acid under physiological conditions

    DEFF Research Database (Denmark)

    de Zawadzki, Andressa; Cardoso, Daniel R.; Skibsted, Leif Horsfelt

    2017-01-01

    The hypervalent muscle pigment ferrylmyoglobin, MbFe(IV)]O, is not reduced by urate monoanions at physiological conditions despite a strong driving force of around 30 kJ mol1 while for low pH, uric acid was found to reduce protonated ferrylmyoglobin, MbFe(IV)]O,H+, efficiently in a bimolecular...... for reduction of hypervalent heme iron, where initial proton transfer to oxo-iron initiates the intermolecular electron transfer from urate to ferrylmyoglobin. The concentration of the powerful prooxidant ferrylmyoglobin increases strongly during digestion of red meat in the stomach. A concomitant increase...

  19. DFT study of electronic transfer properties of carboxyl and nitro substituted benzene

    Energy Technology Data Exchange (ETDEWEB)

    Megala, M.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in [PG and Research Department of Physics, Lady Doak College, Madurai – 625002 (India)

    2015-06-24

    The electronic and optical transfer properties of Benzene, Benzoic Acid (BA), Nitrobenzene (NB) and Para Nitro Benzoic Acid (PNBA) at ground and first excited state has been investigated by the Density functional theory (DFT)and Time Dependent Density Functional Theory (TDDFT) using SVWN functional/3-21G basis set respectively. Possible intra-molecular charge transfer and n to π* transitions in the ground and the first excitation states have been predicted by the molecular orbitals and the Natural Bond Orbital (NBO) analysis. The simulated absorption spectra have been generated and the result compared with existing experimental results.

  20. Nonadiabatic dynamics of photoinduced proton-coupled electron transfer in a solvated phenol-amine complex.

    Science.gov (United States)

    Goyal, Puja; Schwerdtfeger, Christine A; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-02-12

    Photoinduced concerted electron-proton transfer (EPT), denoted photo-EPT, is important for a wide range of energy conversion processes. Transient absorption and Raman spectroscopy experiments on the hydrogen-bonded p-nitrophenylphenol-t-butylamine complex, solvated in 1,2-dichloroethane, suggested that this complex may undergo photo-EPT. The experiments probed two excited electronic states that were interpreted as an intramolecular charge transfer (ICT) state and an EPT state. Herein mixed quantum mechanical/molecular mechanical nonadiabatic surface hopping dynamics is used to investigate the relaxation pathways following photoexcitation. The potential energy surface is generated on the fly with a semiempirical floating occupation molecular orbital complete active space configuration interaction method for the solute molecule and a molecular mechanical force field for the explicit solvent molecules. The free energy curves along the proton transfer coordinate illustrate that proton transfer is thermodynamically and kinetically favorable on the lower-energy excited state but not on the higher-energy excited state, supporting the characterization of these states as EPT and ICT, respectively. The nonadiabatic dynamics simulations indicate that the population decays from the ICT state to the EPT state in ∼100 fs and from the EPT state to the ground state on the slower time scale of ∼1 ps, qualitatively consistent with the experimental measurements. For ∼54% of the trajectories, the proton transfers from the phenol to the amine in ∼400 fs on the EPT state and then transfers back to the phenol rapidly upon decay to the ground state. Thus, these calculations augment the original interpretation of the experimental data by providing evidence of proton transfer on the EPT state prior to decay to the ground state. The fundamental insights obtained from these simulations are also relevant to other photo-EPT processes.

  1. Beyond vibrationally mediated electron transfer: interfacial charge injection on a sub-10-fs time scale

    Science.gov (United States)

    Huber, Robert; Moser, Jacques E.; Gratzel, Michael; Wachtveitl, Josef L.

    2003-12-01

    The electron transfer (ET) from organic dye molecules to semiconductor-colloidal systems is characterized by a special energetic situation with a charge transfer reaction from a system of discrete donor levels to a continuum of acceptor states. If these systems show a strong electronic coupling they are amongst the fastest known ET systems with transfer times of less than 10 fs. In the first part a detailed discussion of the direct observation of an ET reaction with a time constant of about 6 fs will be given, with an accompanying argumentation concerning possible artifacts or other interfering signal contributions. In a second part we will try to give a simple picture for the scenario of such superfast ET reactions and one main focus will be the discussion of electronic dephasing and its consequences for the ET reaction. The actual ET process can be understood as a kind of dispersion process of the initially located electron into the colloid representing a real motion of charge density from the alizarin to the colloid.

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

    Science.gov (United States)

    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

    2015-05-21

    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 × 10(9) 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.

  3. Electron transfer from sulfate-reducing bacteria biofilm promoted by reduced graphene sheets

    Institute of Scientific and Technical Information of China (English)

    WAN Yi; ZHANG Dun; WANG Yi; WU Jiajia

    2012-01-01

    Reduced graphene sheets (RGSs) mediate electron transfer between sulfate-reducing bacteria (SRB) and solid electrodes,and promote the development of microbial fuelcells (MFC).We have investigated RSG-promoted electron transfer between SRB and a glassy carbon (GC) electrode.The RGSs were produced at high yield by a chemical sequence involving graphite oxidation,ultrasonic exfoliation of nanosheets,and N2H4 reduction.Cyclic voltammetric testing showed that the characteristic anodic peaks (around 0.3 V)might arise from the combination of bacterial membrane surface cytochrome c3 and the metabolic products of SRB.After 6 d,another anodic wave gradually increased to a maximum current peak and a third anodic signal became visible at around 0 V.The enhancements of two characteristic anodic peaks suggest that RSGs mediate electron-transfer kinetics between bacteria and the solid electrode.Manipulation of these recentlydiscovered electron-transport mechanisms will lead to significant advances in MFC engineering.

  4. Excited state electron transfer from aminopyrene to graphene: a combined experimental and theoretical study.

    Science.gov (United States)

    Chakraborti, Himadri; Bramhaiah, Kommula; John, Neena Susan; Pal, Suman Kalyan

    2013-12-01

    The quenching of the fluorescence of 1-aminopyrene (1-Ap) by reduced graphene oxide (rGO) has been investigated using spectroscopic techniques. In spite of the upward curvature in the Stern-Volmer plot, the unchanged spectral signature of the absorption of 1-Ap in the presence of rGO and the decrease in fluorescence lifetime with increasing rGO concentration point toward the dynamic nature of the quenching. Detailed analysis of steady state and time-resolved spectroscopic data has shown that the quenching arises due to the photoinduced electron transfer from 1-Ap to rGO. This is again supported by estimating the Gibb's free energy change for the ground as well as excited state electron transfer. Ab initio calculations under the density functional theory (DFT) formalism reveal that the possibility of π-π stacking is very slim in the 1-Ap-rGO system and the electron density resides completely on 1-Ap in the highest occupied molecular orbital (HOMO) and on graphene in the lowest unoccupied molecular orbital (LUMO), supporting the experimental findings of the intermolecular electron transfer between 1-Ap and rGO in the excited state.

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

    Science.gov (United States)

    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.

  6. Endocrine disruptive estrogens role in electron transfer: bio-electrochemical remediation with microbial mediated electrogenesis.

    Science.gov (United States)

    Kumar, A Kiran; Reddy, M Venkateswar; Chandrasekhar, K; Srikanth, S; Mohan, S Venkata

    2012-01-01

    Bioremediation of selected endocrine disrupting compounds (EDCs)/estrogens viz. estriol (E3) and ethynylestradiol (EE2) was evaluated in bio-electrochemical treatment (BET) system with simultaneous power generation. Estrogens supplementation along with wastewater documented enhanced electrogenic activity indicating their function in electron transfer between biocatalyst and anode as electron shuttler. EE2 addition showed more positive impact on the electrogenic activity compared to E3 supplementation. Higher estrogen concentration showed inhibitory effect on the BET performance. Poising potential during start up phase showed a marginal influence on the power output. The electrons generated during substrate degradation might have been utilized for the EDCs break down. Fuel cell behavior and anodic oxidation potential supported the observed electrogenic activity with the function of estrogens removal. Voltammetric profiles, dehydrogenase and phosphatase enzyme activities were also found to be in agreement with the power generation, electron discharge and estrogens removal.

  7. Extended Electron-Transfer in Animal Cryptochromes Mediated by a Tetrad of Aromatic Amino Acids.

    Science.gov (United States)

    Nohr, Daniel; Franz, Sophie; Rodriguez, Ryan; Paulus, Bernd; Essen, Lars-Oliver; Weber, Stefan; Schleicher, Erik

    2016-07-26

    The cryptochrome/photolyase protein family possesses a conserved triad of tryptophans that may act as a molecular wire to transport electrons from the protein surface to the FAD cofactor for activation and/or signaling-state formation. Members from the animal (and animal-like) cryptochrome subclade use this process in a light-induced fashion in a number of exciting responses, such as the (re-)setting of circadian rhythms or magnetoreception; however, electron-transfer pathways have not been explored in detail yet. Therefore, we present an in-depth time-resolved optical and electron-paramagnetic resonance spectroscopic study of two cryptochromes from Chlamydomonas reinhardtii and Drosophila melanogaster. The results do not only reveal the existence of a fourth, more distant aromatic amino acid that serves as a terminal electron donor in both proteins, but also show that a tyrosine is able to fulfill this very role in Chlamydomonas reinhardtii cryptochrome. Additionally, exchange of the respective fourth aromatic amino acid to redox-inactive phenylalanines still leads to light-induced radical pair formation; however, the lifetimes of these species are drastically reduced from the ms- to the μs-range. The results presented in this study open up a new chapter, to our knowledge, in the diversity of electron-transfer pathways in cryptochromes. Moreover, they could explain unique functions of animal cryptochromes, in particular their potential roles in magnetoreception because magnetic-field effects of light-induced radical pairs strongly depend on distance and orientation parameters.

  8. 3-Coil resonance-based wireless power transfer system for implantable electronic

    KAUST Repository

    Yi, Ying

    2013-05-01

    This paper presents a 3-coil resonance-based wireless power transfer (R-WPT) system using a single layer of inductor coil windings, in a pancake configuration, in order to obtain a compact system for implantable electronic applications. A theoretical analysis and experimental measurements in terms of quality factor Q and power transfer efficiency (PTE), was done. Our proposed 3-coil scheme can achieve a high PTE with a resonance frequency of 2.46 MHz over a transfer distance of up to 30 mm, by using two 15-mm radius implant coils. The achieved experimental PTE is more than 85%at a 5 mm separation distance, and about 50% PTE at a distance of 20 mm. © 2013 IEEE.

  9. Measurement of Tensor Polarization in Elastic Electron-Deuteron Scattering at Large Momentum Transfer

    Energy Technology Data Exchange (ETDEWEB)

    David Abbott; Abdellah Ahmidouch; Heinz Anklin; Francois Arvieux; Jacques Ball; S. Beedoe; Elizabeth Beise; Louis Bimbot; Werner Boeglin; Herbert Breuer; Roger Carlini; Nicholas Chant; Samuel Danagoulian; K. Dow; Jean-Eric Ducret; James Dunne; Lars Ewell; Laurent Eyraud; Christophe Furget; Michel Garcon; Ronald Gilman; Charles Glashausser; Paul Gueye; Kenneth Gustafsson; Kawtar Hafidi; Adrian Honegger; Juerg Jourdan; Serge Kox; Gerfried Kumbartzki; L. Lu; Allison Lung; David Mack; Pete Markowitz; Justin McIntyre; David Meekins; Fernand Merchez; Joseph Mitchell; R. Mohring; Sekazi Mtingwa; Hamlet Mkrtchyan; David Pitz; Liming Qin; Ronald Ransome; Jean-Sebastien Real; Philip Roos; Paul Rutt; Reyad Sawafta; Samuel Stepanyan; Raphael Tieulent; Egle Tomasi-Gustafsson; William Turchinetz; Kelley Vansyoc; Jochen Volmer; Eric Voutier; William Vulcan; Claude Williamson; Stephen Wood; Chen Yan; Jie Zhao; Wenxia Zhao

    2000-05-01

    Tensor polarization observables (t20, t21 and t22) have been measured in elastic electron-deuteron scattering for six values of momentum transfer between 0.66 and 1.7 (GeV/c){sup 2}. The experiment was performed at the Jefferson Laboratory in Hall C using the electron HMS Spectrometer, a specially designed deuteron magnetic channel and the recoil deuteron polarimeter POLDER. The new data determine to much larger Q{sup 2} the deuteron charge form factors G{sub C} and G{sub Q}. They are in good agreement with relativistic calculations and disagree with pQCD predictions.

  10. Vectorial electron transfer in spatially ordered arrays. Progress report, January 1991--January 1994

    Energy Technology Data Exchange (ETDEWEB)

    Fox, M.A.

    1994-01-01

    Objective was to find methods for rapid, controlled placement of light absorbers, relays, and multi-electron catalysts at defined sites with respect to a semiconductor or metal surface and thus to develop methods for preparing chemically modified photoactive surfaces as artificial photosynthetic units. Progress has been made in four areas: synthesis of new materials for directional electron transfer, preparation and characterization of anisotropic composites containing organic and inorganic components, elaboration of mechanisms of electrocatalysis, and development of new methods for surface modification of metals and semiconductors.

  11. Photoinduced Electron Transfer in Ordered Macromolecular Assemblies. Final report for May 1, 1988 - June 30, 2002

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G.

    2005-02-11

    The final report describes studies over a 13 year period having to do with photoinduced electron transfer for active chromophores and redox agents, including assembly of the components in water soluble polymers or polypeptides. The findings include observation of long range charge separation and electron transport using laser phototransient spectroscopy. The systems targeted in these studies include peptide assemblies for which helical conformations and aggregation are documented. Oligomeric peptides modified with non-native redox active groups were also selected for investigation. Highly charged polymers or peptides were investigated as host agents that resemble proteins. The overall goal of these investigations focused on the design and characterization of systems capable of artificial photosynthesis.

  12. Electron transfer and redox metalloenzyme catalysis at the single-molecule level

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Zhang, Jingdong; Christensen, Hans Erik Mølager

    2004-01-01

    transfer (ET). Image interpretation requires, however, theoretical support, as STM represents both electronic and topographic features. Molecules with accessible redox levels offer other insight into electron tunneling mechanisms, addressed in detail for ET metalloproteins. We present here in situ STM...... concentrations where most of the enzyme is in the enzyme-substrate bound state. Molecular resolution for both cysteamine/Au(111) and AxCuNiR/cysteamine/ Au(111) electrode surfaces was achieved. The enzyme coverage is about 1.5 x 10(-13) Mol cm(-2), which is low compared with an ideal close-packed monolayer...

  13. Mechanism of organophosphates (nerve gases and pesticides) and antidotes: electron transfer and oxidative stress.

    Science.gov (United States)

    Kovacic, Peter

    2003-12-01

    Evidence indicates that nerve gas toxins operate in ways in addition to inhibition of acetylcholine esterase. Alternative bioactivities are discussed with focus on electron transfer. The main class, including pralidoxime (2-PAM), incorporates conjugated iminium and oxime moieties that are electron affinic. Various physiological properties of iminium and oxime species are reviewed. The organophosphates encompass both nerve gases and insecticides, possessing similar properties, but different activities. Toxic manifestations are apparently due, in part, to oxidative stress. Alkylation of DNA takes place which may lead to generation of reactive oxygen species. Structure-activity relationships are examined, including reduction potentials and the captodative effect.

  14. Preferred sites and pathways for electron transfer in blue copper proteins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1988-01-01

    Long-range electron transfer reactions proceed within and between metalloproteins at relatively fast rates and with marked specificities. The blue single copper proteins are well known electron carriers with their redox center being of limited accessibility to solvent and solutes. The question......, E.T. proceeds via an extended imidazole ring system, and in plastocyanin and stellacyanin via a weakly coupled pi-system. Therefore, a case emerges for suggesting that this is the common feature of the long-distance intramolecular E.T. in this class of metalloproteins. These pathways are most...

  15. Cathodic Aromatic C,C Cross-Coupling Reaction via Single Electron Transfer Pathway.

    Science.gov (United States)

    Qu, Yang; Tateno, Hiroyuki; Matsumura, Yoshimasa; Kashiwagi, Tsuneo; Atobe, Mahito

    2017-03-07

    We have successfully developed a novel cathodic cross-coupling reaction of aryl halides with arenes. Utilization of the cathodic single electron transfer (SET) mechanism for activation of aryl halides enables the cross-coupling reaction to proceed without the need for any transition metal catalysts or single electron donors in a mild condition. The SET from a cathode to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle also consists entirely of anion radical intermediates.

  16. Cathodic Aromatic C,C Cross-Coupling Reaction via Single Electron Transfer Pathway

    Directory of Open Access Journals (Sweden)

    Yang Qu

    2017-03-01

    Full Text Available We have successfully developed a novel cathodic cross-coupling reaction of aryl halides with arenes. Utilization of the cathodic single electron transfer (SET mechanism for activation of aryl halides enables the cross-coupling reaction to proceed without the need for any transition metal catalysts or single electron donors in a mild condition. The SET from a cathode to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle also consists entirely of anion radical intermediates.

  17. Ultrafast static and diffusion-controlled electron transfer at Ag 29 nanocluster/molecular acceptor interfaces

    KAUST Repository

    Aly, Shawkat Mohammede

    2015-10-29

    Efficient absorption of visible light and a long-lived excited state lifetime of silver nanoclusters (Ag29 NCs) are integral properties for these new clusters to serve as light-harvesting materials. Upon optical excitation, electron injection at Ag29 NC/methyl viologen (MV2+) interfaces is very efficient and ultrafast. Interestingly, our femto- and nanosecond time-resolved results demonstrate clearly that both dynamic and static electron transfer mechanisms are involved in photoluminescence quenching of Ag29 NCs. © 2016 The Royal Society of Chemistry.

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

    Science.gov (United States)

    Riesen, Hans

    2011-06-02

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

  19. Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit

    Science.gov (United States)

    Richardson, Jeremy O.; Bauer, Rainer; Thoss, Michael

    2015-10-01

    We present semiclassical approximations to Green's functions of multidimensional systems, extending Gutzwiller's work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton method for computing the rate of nonadiabatic reactions, such as electron transfer, in the weak-coupling limit, where Fermi's golden-rule can be employed. This generalizes Marcus theory to systems for which the environment free-energy curves are not harmonic and where nuclear tunnelling plays a role. The derivation avoids using the Im F method or short-time approximations to real-time correlation functions. A clear physical interpretation of the nuclear tunnelling processes involved in an electron-transfer reaction is thus provided. In Paper II [J. O. Richardson, J. Chem. Phys. 143, 134116 (2015)], we discuss numerical evaluation of the formulae.

  20. Diagnostic criteria for the characterization of quasireversible electron transfer reactions by cyclic square wave voltammetry.

    Science.gov (United States)

    Mann, Megan A; Helfrick, John C; Bottomley, Lawrence A

    2014-08-19

    Theory for cyclic square wave voltammetry of quasireversible electron transfer reactions is presented and experimentally verified. The impact of empirical parameters on the shape of the current-voltage curve is examined. From the trends, diagnostic criteria enabling the use of this waveform as a tool for mechanistic analysis of electrode reaction processes are presented. These criteria were experimentally confirmed using Eu(3+)/Eu(2+), a well-established quasireversible analyte. Using cyclic square wave voltammetry, both the electron transfer coefficient and rate were calculated for this analyte and found to be in excellent agreement with literature. When properly applied, these criteria will enable nonexperts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

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

    DEFF Research Database (Denmark)

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

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...... entropy difference and to compensate for the different temperature dependencies of E-0'. Thus, differences in driving force and thermal expansion appear as the most straightforward rationale for the observed isotope effect....

  2. Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities.

    Science.gov (United States)

    Miller, David C; Tarantino, Kyle T; Knowles, Robert R

    2016-06-01

    Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter, we aim to highlight the origins, development, and evolution of the PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups.

  3. Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids

    Science.gov (United States)

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Velayudham, Murugesan; Rajagopal, Seenivasan

    2016-07-01

    Three [Os(NN)3]2+ complexes (NN = polypyridine) with ligands of varying hydrophobicity were synthesized and characterized by NMR spectral techniques. The geometry of the molecules are optimized by DFT calculations. The interaction between [Os(NN)3]2+ complexes and phenolate ion in ground state is confirmed by absorption spectral study and the binding constant values are in the range of 3-740 M-1. The photoinduced electron transfer reaction of these [Os(NN)3]2+ complexes with phenols and phenolic acids at pH 12.5 leads to the formation of phenoxyl radical confirmed through transient absorption spectral study. Binding constants and electron transfer rate constants within the [Os(NN)3]2+-phenolate ion adduct account for the change for the overall quenching constant with the change of structure of reactants.

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

    Science.gov (United States)

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

    2012-08-01

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

  5. Theoretical Study on the NO2 + NO2- Electron Transfer Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Zheng-Yu(周正宇); GAO,Hong-Wei(高洪伟); XING,Yu-Mei(邢玉梅); GUO,Li(郭丽); QU,Yu-Hui(曲玉辉)

    2002-01-01

    The NO2 + NO2- electron transfer reaction was studied with DFT-B3LYP method at 6-311 + G* basis set level for the eight selected structures: four species favor the strucure of "head to head". The geometry of transition state was obtained by the linear coordinate method. Three parameters, non-adiahatic activation energy (Ead), coupling matrix element (Hif) and reorganization energy (λ) for electron transfer reaction can be calculated. According to the reorganization energy of the ET reaction, the values obtained from George-Griffith-Marcus (GGM) method (the contribution only from diagonal elements of force constant matrix) are larger than those obtained from Hessian matrix method (including the contribution from both diagonal and off-diagonal elements), which suggests that the coupling interactions between different vibrational modes are important to the inner-sphere reogrganization energy for the ET reactions in gaseous phase. The value of rate constant was obtained by using above three activation parameters.

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

    DEFF Research Database (Denmark)

    Morita, Masahiko; Malvankar, Nikhil S; Franks, Ashley E;

    2011-01-01

    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 r......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...... 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...

  7. Phosphate mediated adsorption and electron transfer of cytochrome c. A time-resolved SERR spectroelectrochemical study.

    Science.gov (United States)

    Capdevila, Daiana A; Marmisollé, Waldemar A; Williams, Federico J; Murgida, Daniel H

    2013-04-21

    The study of proteins immobilized on biomimetic or biocompatible electrodes represents an active field of research as it pursues both fundamental and technological interests. In this context, adsorption and redox properties of cytochrome c (Cyt) on different electrode surfaces have been extensively reported, although in some cases with contradictory results. Here we report a SERR spectroelectrochemical study of the adsorption and electron transfer behaviour of the basic protein Cyt on electrodes coated with amino-terminated monolayers. The obtained results show that inorganic phosphate (Pi) and ATP anions are able to mediate high affinity binding of the protein with preservation of the native structure and rendering an average orientation that guarantees efficient pathways for direct electron transfer. These findings aid the design of Cyt-based bioelectronic devices and understanding the modulation by Pi and ATP of physiological functions of Cyt.

  8. Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit

    CERN Document Server

    Richardson, Jeremy O; Thoss, Michael

    2015-01-01

    We present semiclassical approximations to Green's functions of multidimensional systems, extending Gutzwiller's work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton method for computing the rate of nonadiabatic reactions, such as electron transfer, in the weak-coupling limit, where Fermi's golden-rule can be employed. This generalizes Marcus theory to systems for which the environment free-energy curves are not harmonic and where nuclear tunnelling plays a role. The derivation avoids using the Im F method or short-time approximations to real-time correlation functions. A clear physical interpretation of the nuclear tunnelling processes involved in an electron-transfer reaction is thus provided. In the following paper, we discuss numerical evaluation of the formulae.

  9. Electron-transfer processes in dendrimers and their implication in biology, catalysis, sensing and nanotechnology

    Science.gov (United States)

    Astruc, Didier

    2012-04-01

    The extraordinary development of the design and synthesis of dendrimers has allowed scientists to locate redox sites at precise positions (core, focal points, branching points, termini, cavities) of these perfectly defined macromolecules, which have generation-controlled sizes and topologies matching those of biomolecules. Redox-dendrimer engineering has led to fine modelling studies of electron-transfer metalloproteins, in which the branches of the dendrimers hinder access to the active site in a manner reminiscent of that of the protein. It has also enabled the construction of remarkable catalysts, sensors and printboards, including by sophisticated design of the interface between redox dendrimers and solid-state devices -- for example by functionalizing electrodes and other surfaces. Electron-transfer processes between dendrimers and a variety of other molecules hold promising applications in diverse areas that range from bio-engineering to sensing, catalysis and energy materials.

  10. Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

    Institute of Scientific and Technical Information of China (English)

    Yinxi YU; Haobin WANG

    2011-01-01

    The constrained density functional theory (CDFT) was used to investigate the topological effects on intramolecular electron transfer processes that have been reported in previous experimental work [Inorg.Chem.,1997,36 (22),pp 5037-50491.The computation mainly focused on three isomers of diferrocenylbenzenes (ortho,para,and meta) and 5-substituted derivatives of m-diferrocencylbenzenes with R =NH2,Cl,CH3,CN,NO2,N(CH3)3+3,and N+2.The influence of a third group R' (R' =NH2 and N+2) was introduced to the ortho and para isomers.The calculations were compared with the experimental results.The relation between the substituted functional groups and the effectiveness of intramolecular electron transfer was discussed on the basis of CDFT computational results.

  11. The Alternative complex III: properties and possible mechanisms for electron transfer and energy conservation.

    Science.gov (United States)

    Refojo, Patrícia N; Teixeira, Miguel; Pereira, Manuela M

    2012-10-01

    Alternative complexes III (ACIII) are recently identified membrane-bound enzymes that replace functionally the cytochrome bc(1/)b(6)f complexes. In general, ACIII are composed of four transmembrane proteins and three peripheral subunits that contain iron-sulfur centers and C-type hemes. ACIII are built by a combination of modules present in different enzyme families, namely the complex iron-sulfur molybdenum containing enzymes. In this article a historical perspective on the investigation of ACIII is presented, followed by an overview of the present knowledge on these enzymes. Electron transfer pathways within the protein are discussed taking into account possible different locations (cytoplasmatic or periplasmatic) of the iron-sulfur containing protein and their contribution to energy conservation. In this way several hypotheses for energy conservation modes are raised including linear and bifurcating electron transfer pathways. This article is part of a Special Issue entitled: 17th European Bioenergetics Conference (EBEC 2012).

  12. Hybrid bio-organic interfaces with matchable nanoscale topography for durable high extracellular electron transfer activity.

    Science.gov (United States)

    Ding, Chunmei; Liu, Huan; Lv, Meiling; Zhao, Tianyi; Zhu, Ying; Jiang, Lei

    2014-07-21

    Here, we developed a novel hybrid bio-organic interface with matchable nano-scale topography between a polypyrrole nanowire array (PPy-NA) and the bacterium Shewanella, which enabled a remarkably increased extracellular electron transfer (EET) current from genus Shewanella over a rather long period. PPy-NA thus exhibited outstanding performance in mediating bacterial EET, which was superior to normal electrodes such as carbon plates, Au and tin-doped In₂O₃. It was proposed that the combined effect of the inherent electrochemical nature of PPy and the porous structured bacterial network that was generated on the PPy-NA enabled long-term stability, while the high efficiency was attributed to the enhanced electron transfer rate between PPy-NA and microbes caused by the enhanced local topological interactions.

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

    CERN Document Server

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

    2016-01-01

    During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is understood in terms of exciton quasiparticles which move on a grid of biomolecular sites on typical time scales less than 100 femtoseconds (fs). Since the early days of quantum mechanics, this energy transfer is described as an incoherent Forster hopping with classical site occupation probabilities, but with quantum mechanically determined rate constants. This orthodox picture has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein in which interference oscillatory signals up to 1.5 picoseconds were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidenc...

  14. RNA with iron(II) as a cofactor catalyses electron transfer

    Science.gov (United States)

    Hsiao, Chiaolong; Chou, I.-Chun; Okafor, C. Denise; Bowman, Jessica C.; O'Neill, Eric B.; Athavale, Shreyas S.; Petrov, Anton S.; Hud, Nicholas V.; Wartell, Roger M.; Harvey, Stephen C.; Williams, Loren Dean

    2013-06-01

    Mg2+ is essential for RNA folding and catalysis. However, for the first 1.5 billion years of life on Earth RNA inhabited an anoxic Earth with abundant and benign Fe2+. We hypothesize that Fe2+ was an RNA cofactor when iron was abundant, and was substantially replaced by Mg2+ during a period known as the ‘great oxidation’, brought on by photosynthesis. Here, we demonstrate that reversing this putative metal substitution in an anoxic environment, by removing Mg2+ and replacing it with Fe2+, expands the catalytic repertoire of RNA. Fe2+ can confer on some RNAs a previously uncharacterized ability to catalyse single-electron transfer. We propose that RNA function, in analogy with protein function, can be understood fully only in the context of association with a range of possible metals. The catalysis of electron transfer, requisite for metabolic activity, may have been attenuated in RNA by photosynthesis and the rise of O2.

  15. Photoinitiated electron transfer in multichromophoric species: Synthetic tetrads and pentads featuring diquinone moieties

    Energy Technology Data Exchange (ETDEWEB)

    1992-04-30

    This project involves the design, synthesis and photophysical study of complex molecular systems engineered to achieve long lived charge separated states by a biomimetic, photoinitiated multistep electron transfer process. The use of these artificial systems to investigate different electron and energy transfer strategies will allow the evolution of more efficient molecular devices for the gathering of light energy and its transformation into chemical potential energy. The three major aspects of the work emphasized in the initial proposal are: design and synthesis of molecular devices incorporating new quinone moieties, synthesis and spectroscopic studies of molecular tetrads and pentads featuring modified porphyrin-diquinone linkages, and new photochemical and photophysical investigations of tetrads and pentads, including the development of methods for harvesting the energy stored in long-lived charge separated states.

  16. Modulation of electron transfer kinetics by protein conformational fluctuations during early-stage photosynthesis.

    Science.gov (United States)

    Chaudhury, Srabanti; Cherayil, Binny J

    2007-10-14

    The kinetics of electron transfer during the early stages of the photosynthetic reaction cycle has recently been shown in transient absorption experiments carried out by Wang et al. [Science 316, 747 (2007)] to be strongly influenced by fluctuations in the conformation of the surrounding protein. A model of electron transfer rates in polar solvents developed by Sumi and Marcus using a reaction-diffusion formalism [J. Chem. Phys. 84, 4894 (1986)] was found to be successful in fitting the experimental absorption curves over a roughly 200 ps time interval. The fits were achieved using an empirically determined time-dependent function that described protein conformational relaxation. In the present paper, a microscopic model of this function is suggested, and it is shown that the function can be identified with the dynamic autocorrelation function of intersegment distance fluctuations that occur in a harmonic potential of mean force under the action of fractional Gaussian noise.

  17. Subphthalocyanines: tuneable molecular scaffolds for intramolecular electron and energy transfer processes.

    Science.gov (United States)

    González-Rodríguez, David; Torres, Tomás; Guldi, Dirk M; Rivera, José; Herranz, Maria Angeles; Echegoyen, Luis

    2004-05-26

    A series of four subphthalocyanine-C(60) fullerene dyads have been prepared through axial functionalization of the macrocycle with m-hydroxybenzaldehyde and a subsequent dipolar cycloaddition reaction. The subphthalocyanine moiety has been peripherally functionalized with substituents of different electronic character, namely fluorine or iodine atoms and ether or amino groups, thus reaching a control over its electron-donating properties. This is evidenced in cyclic voltammetry experiments by a progressive shift to lower potentials, by ca. 200 mV, of the first oxidation event of the SubPc unit in the dyads. As a consequence, the energy level of the SubPc(*)(+)-C(60)(*)(-) charge-transfer state may be tuned so as to compete with energy transfer deactivation pathways upon selective excitation of the SubPc component. For instance, excitation of those systems where the level of the radical pair lies high in energy triggers a sequence of exergonic photophysical events that comprise (i) nearly quantitative singlet-singlet energy transfer to the C(60) moiety, (ii) fullerene intersystem crossing, and (iii) triplet-triplet energy transfer back to the SubPc. On the contrary, the stabilization of the SubPc(*)(+)-C(60)(*)(-) radical pair state by increasing the polarity of the medium or by lowering the donor-acceptor redox gap causes charge transfer to dominate. In the case of 1c in benzonitrile, the thus formed radical pair has a lifetime of 0.65 ns and decays via the energetically lower lying triplet excited state. Further stabilization is achieved for dyad 1d, whose charge-transfer state would lie now below both triplets. The radical pair lifetime consequently increases in more than 2 orders of magnitude with respect to 1c and presents a significant stabilization in less polar solvents, revealing a low reorganization energy for this kind of SubPc-C(60) systems.

  18. Evidence for resonance electron transfer in photon excited X-ray satellite spectra of fluorine compounds

    Indian Academy of Sciences (India)

    K Ram Narayana; B Seetharami Reddy; S S Raju; T Seshi Reddy; S Lakshmi Narayana; K Premachand; B M Rao; M V R Murti; L S Mombasawala

    2005-08-01

    The KL1/KL0 intensity ratio of fluorine is measured in five fluorine compounds with a crystal spectrometer. An anomalous reduction of this intensity ratio was observed in KF and SrF2, which is attributed to resonance electron transfer from the metal ion to the spectator vacancy in the fluorine ion. KL2/KL0 intensity ratio of fluorine is also measured. The measured relative intensities are compared with the theoretical estimates of Aberg.

  19. Solvent Effects on Simple Electron Transfer Reactions. A Comparison of Results for Homogeneous and Heterogeneous Systems

    Science.gov (United States)

    1989-05-01

    Electroanalytical Chemistry Department of Chemistry University of California . Davis, CA 95616 \\ JUN2 0 1989 May 1, 1989 C2 E Reproduction in whole or in...0541 Davis, CA 95616 . O 0 Office of Naval Research 800 N. Quincy Arlington, VA 22217-5000 Prepared for Publication in: Journal of Electroanalytical ... Chemistry 1& A (U fm M Solvent effects on the rate constants for both homogeneous and hetero- geneous electron transfer reactions have been analyzed on

  20. Analysis of proteins and peptides on a chromatographic timescale by electron-transfer dissociation MS

    OpenAIRE

    Udeshi, Namrata D.; Shabanowitz, Jeffrey; Hunt, Donald F.; Rose, Kristie L

    2007-01-01

    Peptide and protein sequence analysis using a combination of gas-phase ion–ion chemistry and tandem MS is described. Samples are converted to multiply charged ions by ESI and then allowed to react with fluoranthene radical anions in a quadrupole linear ion trap mass spectrometer. Electron transfer from the radical anion to the multiply charged peptide or protein promotes random fragmentation along the amide backbone that is independent of peptide or protein size, sequence, or the presence of ...

  1. Bibliography of electron transfer in heavy particle collisions, 1950--1975

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, S.W.; Barnett, C.F.; Crandall, D.H.; Gilbody, H.B.; Kirkpatrick, M.I.; McDaniel, E.; Phaneuf, R.A.; Thomas, E.W. (eds.)

    1979-02-01

    This annotated bibliography lists published work on electron transfer in heavy particle collisions for the period 1950 to 1975. Sources include scientific journals, abstract compilations, conference proceedings, books, and reports. The bibliography is arranged alphabetically by author. Each entry indicates whether the work was experimental or theoretical, what energy range was covered, and what reactants were investigated. Following the bibliographical listing are indexes of reactants and authors.

  2. Mechanism of Anesthetic Toxicity: Metabolism, Reactive Oxygen Species, Oxidative Stress, and Electron Transfer

    OpenAIRE

    2011-01-01

    There is much literature on the toxic effects of anesthetics. This paper deals with both the volatiles and locals. Adverse effects appear to be multifaceted, with the focus on radicals, oxidative stress (OS), and electron transfer (ET). ET functionalities involved are quinone, iminoquinone, conjugated iminium, and nitrone. The non-ET routes involving radicals and OS apparently pertain to haloalkanes and ethers. Beneficial effects of antioxidants, evidently countering OS, are reported. Knowled...

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

    Energy Technology Data Exchange (ETDEWEB)

    Tawara, H.

    1997-04-01

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

  4. Biocatalytic anode for glucose oxidation utilizing carbon nanotubes for direct electron transfer with glucose oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Vaze, Abhay; Hussain, Nighat; Tang, Chi [Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060 (United States); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland); Rusling, James [Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060 (United States); Department of Cell Biology, University of Connecticut Health Center, Farmington, CT 06032 (United States); School of Chemistry, National University of Ireland, Galway (Ireland)

    2009-10-15

    Covalently linked layers of glucose oxidase, single-wall carbon nanotubes and poly-L-lysine on pyrolytic graphite resulted in a stable biofuel cell anode featuring direct electron transfer from the enzyme. Catalytic response observed upon addition of glucose was due to electrochemical oxidation of FADH{sub 2} under aerobic conditions. The electrode potential depended on glucose concentration. This system has essential attributes of an anode in a mediator-free biocatalytic fuel cell. (author)

  5. Ultrafast energy and electron transfers in structurally well addressable BODIPY-porphyrin-fullerene polyads.

    Science.gov (United States)

    Gao, Di; Aly, Shawkat M; Karsenti, Paul-Ludovic; Brisard, Gessie; Harvey, Pierre D

    2017-01-25

    Two electron transfer polyads built upon [C60]-[ZnP]-[BODIPY] (1) and [ZnP]-[ZnP](-[BODIPY])(-[C60]) (2), where [C60] = N-methyl-2-phenyl-3,4-fulleropyrrolidine, [BODIPY] = boron dipyrromethane, and [ZnP] = zinc(ii) porphyrin, were synthesized along with their corresponding energy transfer polyads [ZnP]-[BODIPY] (1a) and [ZnP]-[ZnP]-[BODIPY] (2a) as well as relevant models. These polyads were studied using cyclic voltammetry, DFT computations, steady state and time-resolved fluorescence spectroscopy, and fs transient absorption spectroscopy. The rates for energy transfer, kET, [BODIPY]* → [ZnP] are ∼2.8 × 10(10) s(-1) for both 1a and 2a, with an efficiency of 99%. Concurrently, the fast appearance of the [C60](-)˙ anion for 1 and 2 indicates that the charge separation occurs on the 20-30 ps timescale with the rates of electron transfer, ket, [ZnP]*/[C60] → [ZnP](+)˙/[C60](-)˙ of ∼0.9 × 10(10) to ∼3.8 × 10(10) s(-1). The latter value is among the fastest for these types of polyads. Conversely, the charge recombination operates on the ns timescale. These rates are comparable to or faster than those reported for other more flexible [C60]-[ZnP]-[BODIPY] polyads, which can be rationalized by the donor-acceptor separations.

  6. Coupled electron and proton transfer processes in 4-dimethylamino-2-hydroxy-benzaldehyde.

    Science.gov (United States)

    Zgierski, Marek Z; Fujiwara, Takashige; Lim, Edward C

    2011-09-08

    TDDFT calculations, picosecond transient absorption, and time-resolved fluorescence studies of 4-dimethylamino-2-hydroxy-benzaldehyde (DMAHBA) have been carried out to study the electron and proton transfer processes in polar (acetonitrile) and nonpolar (n-hexane) solvents. In n-hexane, the transient absorption (TA) as well as the fluorescence originate from the ππ* state of the keto form (with the carbonyl group in the benzaldehyde ring), which is produced by an intramolecular proton transfer from the initially excited ππ* state of the enol form (OH group in the ring). The decay rate of TA and fluorescence are essentially identical in n-hexane. In acetonitrile, on the other hand, the TA exhibits features that can be assigned to the highly polar twisted intramolecular charge transfer (TICT) states of enol forms, as evidenced by the similarity of the absorption to the TICT-state absorption spectra of the closely related 4-dimethylaminobenzaldehyde (DMABA). As expected, the decay rate of the TICT-state of DMAHBA is different from the fluorescence lifetime of the ππ* state of the keto form. The occurrence of the proton and electron transfers in acetonitrile is in good agreement with the predictions of the TDDFT calculations. The very short-lived (∼1 ps) fluorescence from the ππ* state of the enol form has been observed at about 380 nm in n-hexane and at about 400 nm in acetonitrile.

  7. Activity-stability relationships revisited in blue oxidases catalyzing electron transfer at extreme temperatures.

    Science.gov (United States)

    Roulling, Frédéric; Godin, Amandine; Cipolla, Alexandre; Collins, Tony; Miyazaki, Kentaro; Feller, Georges

    2016-09-01

    Cuproxidases are a subset of the blue multicopper oxidases that catalyze the oxidation of toxic Cu(I) ions into less harmful Cu(II) in the bacterial periplasm. Cuproxidases from psychrophilic, mesophilic, and thermophilic bacteria display the canonical features of temperature adaptation, such as increases in structural stability and apparent optimal temperature for activity with environmental temperature as well as increases in the binding affinity for catalytic and substrate copper ions. In contrast, the oxidative activities at 25 °C for both the psychrophilic and thermophilic enzymes are similar, suggesting that the nearly temperature-independent electron transfer rate does not require peculiar adjustments. Furthermore, the structural flexibilities of both the psychrophilic and thermophilic enzymes are also similar, indicating that the firm and precise bindings of the four catalytic copper ions are essential for the oxidase function. These results show that the requirements for enzymatic electron transfer, in the absence of the selective pressure of temperature on electron transfer rates, produce a specific adaptive pattern, which is distinct from that observed in enzymes possessing a well-defined active site and relying on conformational changes such as for the induced fit mechanism.

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

    Energy Technology Data Exchange (ETDEWEB)

    Balgley, Renata; de Ruiter, Graham; Evmenenko, Guennadi; Bendikov, Tatyana; Lahav, Michal; van der Boom, Milko E.

    2016-12-21

    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 the 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.

  9. Proton-coupled electron transfers: pH-dependent driving forces? Fundamentals and artifacts.

    Science.gov (United States)

    Bonin, Julien; Costentin, Cyrille; Robert, Marc; Routier, Mathilde; Savéant, Jean-Michel

    2013-09-25

    Besides its own interest, tryptophan oxidation by photogenerated Ru complexes is one of the several examples where concerted proton-electron transfer (CPET) to water as proton acceptor endowed with a pH-dependent driving force has been invoked to explain the data. Since this notion is contrary to the very basic principles of chemical physics, it was interesting to attempt uncovering the source of this contradiction with an easily accessible substrate. Careful examination of the oxidation of the tryptophan (ethyl ester derivative) bearing a NH3(+)/NH2 group showed that there is no trace of such an unconventional H2O-CPET with a pH-dependent driving force. The reaction mechanism simply consists, with both the NH3(+) acid and NH2 basic forms of the tryptophan derivative, in a rate-determining electron-transfer step followed by deprotonation steps. The same is true with the ethyl ester-methyl amide derivative of tryptophan, whose behavior is even simpler since the molecule does not bear an acid-base group. No such unconventional H2O-CPET was found with phenol, another easily accessible substrate. It may thus be inferred that the same applies to less easily available systems in which electron transfer occurs intramolecularly. These observations help to rid the road of such artificial obstacles and improve present models of H2O-CPET reactions, a landmark towards the understanding of the role of water chains in natural systems.

  10. Electron transfer behavior at polyoxometalate-adsorbed alkanethiol self-assembled monolayers

    Science.gov (United States)

    Chu, Yeonyi; Kim, Jandee; Choi, Suhee; Rhee, Choong Kyun; Kim, Jongwon

    2011-09-01

    The interaction between polyoxometalate (POM) anions, SiMo 12O 404-, and a self-assembled monolayer (SAM) of dodecanethiol (DT) on Au surfaces was investigated using electrochemical methods, X-ray photoelectron spectroscopy, and scanning probe microscopy. The SiMo 12O 404- ions adsorb on the SAM of DT on Au to form a composite organic-inorganic hybrid layer. The adsorbed SiMo 12O 404- ion on the SAM layer shows its characteristic redox waves with an electron transfer rate slower than that on a bare Au electrode. The electron transfer behavior at DT-SAM could be regulated by the adsorption of SiMo 12O 404- depending on the charge of the investigated electroactive species: a significant increase toward a positively charged Ru(NH 3) 63+ ion, a moderate increase toward a neutral 1,1'-ferrocenedimethanol molecule and a slight decrease toward a negatively charged Fe(CN) 63- ion. The effect of the chain length of alkanethiols on the adsorption of SiMo 12O 404- ion was also investigated: as the chain length decreases, the amount of the adsorbed POM increases and the electron transfer rate through the composite layers increases. The nature of SiMo 12O 404- ions adsorbed on the SAMs of alkanethiols on Au is discussed in detail.

  11. The electron-transfer reaction between azurin and the cytochrome c oxidase from Pseudomonas aeruginosa.

    Science.gov (United States)

    Parr, S R; Barber, D; Greenwood, C; Brunori, M

    1977-11-01

    A stopped-flow investigation of the electron-transfer reaction between oxidized azurin and reduced Pseudomonas aeruginosa cytochrome c-551 oxidase and between reduced azurin and oxidized Ps. aeruginosa cytochrome c-551 oxidase was performed. Electrons leave and enter the oxidase molecule via its haem c component, with the oxidation and reduction of the haem d1 occurring by internal electron transfer. The reaction mechanism in both directions is complex. In the direction of oxidase oxidation, two phases assigned on the basis of difference spectra to haem c proceed with rate constants of 3.2 X 10(5)M-1-S-1 and 2.0 X 10(4)M-1-S-1, whereas the haem d1 oxidation occurs at 0.35 +/- 0.1S-1. Addition of CO to the reduced enzyme profoundly modifies the rate of haem c oxidation, with the faster process tending towards a rate limit of 200S-1. Reduction of the oxidase was similarly complex, with a fast haem c phase tending to a rate limit of 120S-1, and a slower phase with a second-order rate of 1.5 X 10(4)M-1-S-1; the internal transfer rate in this direction was o.25 +/- 0.1S-1. These results have been applied to a kinetic model originally developed from temperature-jump studies.

  12. Intermolecular electron transfer from naphthalene derivatives in the higher triplet excited states.

    Science.gov (United States)

    Sakamoto, Masanori; Cai, Xichen; Hara, Michihiro; Fujitsuka, Mamoru; Majima, Tetsuro

    2004-08-11

    Intermolecular electron transfer (ELT) from a series of naphthalene derivatives (NpD) in the higher triplet excited states (T(n)) to carbon tetrachloride (CCl(4)) in Ar-saturated acetonitrile was observed using the two-color two-laser flash photolysis method. The ELT efficiency depended on the driving force of ELT. Since the ELT from the T(n) state occurred competitively with the internal conversion (IC, T(n) --> T(1)) and the triplet energy transfer (ENT), the ELT became apparent only when sufficient free energy change of ELT was attained. On the other hand, ELT from the T(1) state was not observed, although ELT from the T(1) state with sufficiently long lifetime has a slightly exothermic driving force. The fast ELT from the T(n) state and lack of the reactivity of the T(1) state were explained well by the "sticky" dissociative electron-transfer model based on one-electron reductive attachment to CCl(4) leading to the C-Cl bond cleavage.

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

    Science.gov (United States)

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

    2016-07-27

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

  14. Analysis of the role of intraprotein electron transfer in photoreactivation by DNA photolyase in vivo.

    Science.gov (United States)

    Kavakli, I Halil; Sancar, Aziz

    2004-12-07

    Escherichia coli DNA photolyase contains FADH(-) as the catalytic cofactor. The cofactor becomes oxidized to the FADH(*) blue neutral radical during purification. The E-FADH(*) form of the enzyme is catalytically inert but can be converted to the active E-FADH(-) form by a photoreduction reaction that involves intraprotein electron transfer from Trp306. It is thought that the E-FADH(*) form is also transiently generated during pyrimidine dimer repair by photoinduced electron transfer, and it has been suggested that the FADH(*) that is generated after each round of catalysis must be photoreduced before the enzyme can engage in subsequent rounds of repair. In this study, we introduced the Trp306Phe mutation into the chromosomal gene and tested the non-photoreducible W306F mutant for photorepair in vivo. We find that both wild-type and W306F mutant photolyases carry out at least 25 rounds of photorepair at the same rate. We conclude that photoreduction by intraprotein electron transfer is not part of the photolyase photocycle under physiological conditions.

  15. Proton coupled electron transfer from the excited state of a ruthenium(II) pyridylimidazole complex.

    Science.gov (United States)

    Pannwitz, Andrea; Wenger, Oliver S

    2016-04-28

    Proton coupled electron transfer (PCET) from the excited state of [Ru(bpy)2pyimH](2+) (bpy = 2,2'-bipyridine; pyimH = 2-(2'-pyridyl)imidazole) to N-methyl-4,4'-bipyridinium (monoquat, MQ(+)) was studied. While this complex has been investigated previously, our study is the first to show that the formal bond dissociation free energy (BDFE) of the imidazole-N-H bond decreases from (91 ± 1) kcal mol(-1) in the electronic ground state to (43 ± 5) kcal mol(-1) in the lowest-energetic (3)MLCT excited state. This makes the [Ru(bpy)2pyimH](2+) complex a very strong (formal) hydrogen atom donor even when compared to metal hydride complexes, and this is interesting for light-driven (formal) hydrogen atom transfer (HAT) reactions with a variety of different substrates. Mechanistically, formal HAT between (3)MLCT excited [Ru(bpy)2pyimH](2+) and monoquat in buffered 1 : 1 (v : v) CH3CN/H2O was found to occur via a sequence of reaction steps involving electron transfer from Ru(ii) to MQ(+) coupled to release of the N-H proton to buffer base, followed by protonation of reduced MQ(+) by buffer acid. Our study is relevant in the larger contexts of photoredox catalysis and light-to-chemical energy conversion.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-12-21

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

  17. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    Energy Technology Data Exchange (ETDEWEB)

    Nagesh, Jayashree; Brumer, Paul [Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada); Izmaylov, Artur F. [Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada); Department of Physical and Environmental Sciences, University of Toronto, Scarborough, Toronto, Ontario M1C 1A4 (Canada)

    2015-02-28

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning, we reformulate the method in a computationally efficient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9 − ((1 − naphthyl) − methyl) − anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH{sub 2} − naphthyl groups as subsystems and examine their electronic energies and populations for several excited states using configuration interaction singles method. The implemented approach shows a wide variety of different behaviors amongst the excited electronic states.

  18. Electrostatic models of electron-driven proton transfer across a lipid membrane

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, Anatoly Yu; Nori, Franco [Advanced Science Institute, RIKEN, Wako-shi, Saitama, 351-0198 (Japan); Mourokh, Lev G [Department of Physics, Queens College, The City University of New York, Flushing, NY 11367 (United States)

    2011-06-15

    We present two models for electron-driven uphill proton transport across lipid membranes, with the electron energy converted to the proton gradient via the electrostatic interaction. In the first model, associated with the cytochrome c oxidase complex in the inner mitochondria membranes, the electrostatic coupling to the site occupied by an electron lowers the energy level of the proton-binding site, making proton transfer possible. In the second model, roughly describing the redox loop in a nitrate respiration of E. coli bacteria, an electron displaces a proton from the negative side of the membrane to a shuttle, which subsequently diffuses across the membrane and unloads the proton to its positive side. We show that both models can be described by the same approach, which can be significantly simplified if the system is separated into several clusters, with strong Coulomb interaction inside each cluster and weak transfer couplings between them. We derive and solve the equations of motion for the electron and proton creation/annihilation operators, taking into account the appropriate Coulomb terms, tunnel couplings, and the interaction with the environment. For the second model, these equations of motion are solved jointly with a Langevin-type equation for the shuttle position. We obtain expressions for the electron and proton currents and determine their dependence on the electron and proton voltage build-ups, on-site charging energies, reorganization energies, temperature, and other system parameters. We show that the quantum yield in our models can be up to 100% and the power-conversion efficiency can reach 35%.

  19. A Langevin equation approach to electron transfer reactions in the diabatic basis.

    Science.gov (United States)

    Song, XiaoGeng; Wang, Haobin; Van Voorhis, Troy

    2008-10-14

    A linear Langevin equation that governs the population dynamics of electron transfer reactions is derived. The noise in the Langevin equation is eliminated by treating the diabatic population fluctuations as the relevant variables, leaving only the memory kernel responsible for the population relaxation. Within the memory kernel, the diabatic coupling is treated perturbatively and a second order expansion is found to give a simple closed form expression for the kernel. The accuracy of the second order truncation is maximized by performing a fixed rotation of the diabatic electronic states that minimizes the first order free energy of the system and thus minimizes the effect of the perturbation on the thermodynamics. The resulting two-hop Langevin equation (THLE) is then validated by applying it to a simple spin-boson model, where exact results exist. Excellent agreement is found in a wide parameter range, even where the perturbation is moderately strong. Results obtained in the rotated electronic basis are found to be consistently more accurate than those from the unrotated basis. These benchmark calculations also allow us to demonstrate the advantage of treating the population fluctuations instead of the populations as the relevant variables, as only the former lead to reliable results at long time. Thus, the THLE appears to provide a viable alternative to established methods--such as Ehrenfest dynamics or surface hopping--for the treatment of nonadiabatic effects in electron transfer simulations.

  20. Interfacial electron transfer dynamics of ru(II)-polypy6ridine sensitized TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Jakubikova, Elena [Los Alamos National Laboratory; Martin, Richard L [Los Alamos National Laboratory; Batista, Enrique R [Los Alamos National Laboratory; Snoeberger, Robert C [YALE UNIV.; Batista, Victor S [YALE UNIV.

    2009-01-01

    Quantum dynamics simulations combined with density functional theory calculations are applied to study interfacial electron transfer (IET) from pyridine-4-phosphonic acid, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} and [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} into the (101) surface of anatase TiO{sub 2}. IET rate from pyridine-4-phosphonic acid attached to the nanoparticle in bidentate mode ({tau} {approx} 100 fs) is an order of magnitude faster than the IET rate of the adsorbate attached in the monodentate mode ({tau} {approx} 1 ps). Upon excitation with visible light, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} attached to TiO{sub 2} in bidentate binding mode will undergo IET with the rate of {approx} 1-10 ps, which is competitive with the excited state decay into the ground state. The probability of electron injection from [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} is rather low, as the excitation with visible light localizes the excited electron in the tpy-tpy bridge, which does not have favorable coupling with the TiO{sub 2} nanoparticle. The results are relevant to better understanding of the adsorbate features important for promoting efficient interfacial electron transfer into the semiconductor.

  1. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films

    CERN Document Server

    Gibbard, Jemma A

    2016-01-01

    Thin metallic films have a 1D quantum well along the surface normal direction, which yields particle-in-a-box style electronic quantum states. However the quantum well is not infinitely deep and the wavefunctions of these states penetrate outside the surface where the electron is bound by its own image-charge attraction. Therefore a series of discrete, vacant states reach out from the thin film into the vacuum increasing the probability of electron transfer from an external atom or molecule to the thin film, especially for the resonant case where the quantum well energy matches that of the Rydberg atom. We show that `handshake' electron transfer from a highly excited Rydberg atom to these thin-film states is experimentally measurable. Thicker films, have a wider 1D box, changing the energetic distribution and image-state contribution to the thin film wavefunctions, resulting in more resonances. Calculations successfully predict the number of resonances and the nature of the thin-film wavefunctions for a given...

  2. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    Science.gov (United States)

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.

  3. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films.

    Science.gov (United States)

    Gibbard, J A; Softley, T P

    2016-06-21

    Thin metallic films have a 1D quantum well along the surface normal direction, which yields particle-in-a-box style electronic quantum states. However the quantum well is not infinitely deep and the wavefunctions of these states penetrate outside the surface where the electron is bound by its own image-charge attraction. Therefore a series of discrete, vacant states reach out from the thin film into the vacuum increasing the probability of electron transfer from an external atom or molecule to the thin film, especially for the resonant case where the quantum well energy matches that of the atom. We show that "handshake" electron transfer from a highly excited Rydberg atom to these thin-film states is experimentally measurable. Thicker films have a wider 1D box, changing the energetic distribution and image-state contribution to the thin film wavefunctions, resulting in more resonances. Calculations successfully predict the number of resonances and the nature of the thin-film wavefunctions for a given film thickness.

  4. Photoinduced electron and energy transfer in a new porphyrin-phthalocyanine triad

    Energy Technology Data Exchange (ETDEWEB)

    Ermilov, Eugeny A. [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany)], E-mail: ermilov@physik.hu-berlin.de; Tannert, Sebastian [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany); Werncke, Thomas [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany); Choi, Michael T.M. [Department of Chemistry, Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China); Ng, Dennis K.P. [Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China)], E-mail: dkpn@cuhk.edu.hk; Roeder, Beate [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany)

    2006-09-29

    Complexes of porphyrins, phthalocyanines, and chlorophylls are well suited for modelling both the electron and energy transfer processes in photosynthetic reaction centers and natural chlorophyll complexes. In the present paper, we report the synthesis and photophysical characterization of a novel tetraphenylporphyrin-silicon(IV) phthalocyanine triad, where two porphyrins are linked to the central silicon atom of a phthalocyanine moiety. It has been found that the photophysical properties of the triad (Tr) are strongly affected by two different types of interactions between the porphyrin (P) and the phthalocyanine (Pc) parts of Tr, namely excitation energy transfer (EET) and photoinduced electron transfer (ET). The first one results in appearance of the Pc fluorescence when the P-part was initially excited and plays dominant role in fast depopulation of the first excited singlet state of the P moiety. Another competitive process in quenching of P-part fluorescence is electron transfer, but the probability of it is six times less compared to that of EET. If the first excited singlet state of the Pc-part is populated (directly or via EET), it undergoes fast depopulation via ET to the charge-separated state. As a result, the fluorescence quantum yield of the Pc-part of Tr is approximately three orders of magnitude less compared to that of silicon(IV) phthalocyanine with two axial poly(ethylene glycol) chains (SiPc) used as a reference. Analysis of transient absorption data has shown that charge-recombination occurs with a decay time of 30 ps directly to the ground state.

  5. Impact of speciation on the electron charge transfer properties of nanodiamond drug carriers

    Science.gov (United States)

    Sun, Baichuan; Barnard, Amanda S.

    2016-07-01

    Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove useful in designing drug delivery systems where the release of (selected) drugs needs to be sensitive to specific conditions at the point of delivery.Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove

  6. Noise-Assisted Quantum Electron Transfer in Multi-Level Donor-Acceptor System

    CERN Document Server

    Gurvitz, Shmuel; Berman, Gennady P

    2014-01-01

    We analytically and numerically study noise-assisted quantum electron transfer (ET) in bio-complexes consisting of a single-level electron donor and an acceptor which is modeled by many electron energy levels. Interactions are included between the donor and the acceptor energy levels and with the protein environment, which is modeled by a diagonal classical noise acting on all donor and acceptor energy levels. Different regions of parameters characterizing (i) the number of the acceptor levels, (ii) the acceptor "band-width", and (iii) the amplitude of noise and its correlation time are considered. Under some conditions, we derive analytical expressions for the ET rate and efficiency, which reveal the coarse-grain features. We obtain equal occupation of all levels at large times, independently of the structure of the acceptor band. We discuss the multi-scale regime of the acceptor population, and the accompanying effect of quantum coherent oscillations, which are analogous to those observed in experiments on ...

  7. Spin Entangling Effects of Electron and Nucleus on Hopping Transfer in Organic Semiconductors

    Science.gov (United States)

    Zhao, Jun-Qing; Sun, Ling-Ling; Wang, Ting

    2016-05-01

    To study the spin entangling effects on organic magneto-resistance in organic semiconductors, we focused on the entanglement-related hopping transfer of electrons on the basis of the Miller-Abrahams hopping rate. Considering spin entanglement of localized electron with the nucleus in the hopping process, we deduced an attempt hopping rate of electrons as a function of the applied magnetic field and the localized hyperfine interaction, and thus established a model to calculate the organic magneto-resistance. The calculated results show that the magneto-resistance has a maximum in the lower magnetic field, and the corresponding magnetic field Bmax increases with the hyperfine interaction. In the higher magnetic field, the magneto-resistance tends to a negative saturation value. This analysis will be an valuable reference for deep understanding of the organic magneto-resistance.

  8. Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

    Science.gov (United States)

    Lee, Mi Kyung; Coker, David F

    2016-08-18

    An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation.

  9. Surface residues dynamically organize water bridges to enhance electron transfer between proteins

    CERN Document Server

    de la Lande, Aurélien; Řezáč, Jan; Sanders, Barry C; Salahub, Dennis R; 10.1073/pnas.0914457107

    2010-01-01

    Cellular energy production depends on electron transfer (ET) between proteins. In this theoretical study, we investigate the impact of structural and conformational variations on the electronic coupling between the redox proteins methylamine dehydrogenase and amicyanin from Paracoccus denitrificans. We used molecular dynamics simulations to generate configurations over a duration of 40ns (sampled at 100fs intervals) in conjunction with an ET pathway analysis to estimate the ET coupling strength of each configuration. In the wild type complex, we find that the most frequently occurring molecular configurations afford superior electronic coupling due to the consistent presence of a water molecule hydrogen-bonded between the donor and acceptor sites. We attribute the persistence of this water bridge to a "molecular breakwater" composed of several hydrophobic residues surrounding the acceptor site. The breakwater supports the function of nearby solvent-organizing residues by limiting the exchange of water molecul...

  10. Electron transfer, ionization, and excitation in atomic collisions. Progress report, June 15, 1989--June 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-08-01

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

  11. A bioelectrochemical approach to characterize extracellular electron transfer by Synechocystis sp. PCC6803.

    Directory of Open Access Journals (Sweden)

    Angelo Cereda

    Full Text Available Biophotovoltaic devices employ photosynthetic organisms at the anode of a microbial fuel cell to generate electrical power. Although a range of cyanobacteria and algae have been shown to generate photocurrent in devices of a multitude of architectures, mechanistic understanding of extracellular electron transfer by phototrophs remains minimal. Here we describe a mediatorless bioelectrochemical device to measure the electrogenic output of a planktonically grown cyanobacterium, Synechocystis sp. PCC6803. Light dependent production of current is measured, and its magnitude is shown to scale with microbial cell concentration and light intensity. Bioelectrochemical characterization of a Synechocystis mutant lacking Photosystem II demonstrates conclusively that production of the majority of photocurrent requires a functional water splitting aparatus and electrons are likely ultimately derived from water. This shows the potential of the device to rapidly and quantitatively characterize photocurrent production by genetically modified strains, an approach that can be used in future studies to delineate the mechanisms of cyanobacterial extracellular electron transport.

  12. C-type cytochromes in the photosynthetic electron transfer pathways in green sulfur bacteria and heliobacteria.

    Science.gov (United States)

    Azai, Chihiro; Tsukatani, Yusuke; Itoh, Shigeru; Oh-oka, Hirozo

    2010-06-01

    Green sulfur bacteria and heliobacteria are strictly anaerobic phototrophs that have homodimeric type 1 reaction center complexes. Within these complexes, highly reducing substances are produced through an initial charge separation followed by electron transfer reactions driven by light energy absorption. In order to attain efficient energy conversion, it is important for the photooxidized reaction center to be rapidly rereduced. Green sulfur bacteria utilize reduced inorganic sulfur compounds (sulfide, thiosulfate, and/or sulfur) as electron sources for their anoxygenic photosynthetic growth. Membrane-bound and soluble cytochromes c play essential roles in the supply of electrons from sulfur oxidation pathways to the P840 reaction center. In the case of gram-positive heliobacteria, the photooxidized P800 reaction center is rereduced by cytochrome c-553 (PetJ) whose N-terminal cysteine residue is modified with fatty acid chains anchored to the cytoplasmic membrane.

  13. Electron Transfer as a Probe of the Interfacial Quantum Dot-Organic Molecule Interaction

    Science.gov (United States)

    Peterson, Mark D.

    This dissertation describes a set of experimental and theoretical studies of the interaction between small organic molecules and the surfaces of semiconductor nanoparticles, also called quantum dots (QDs). Chapter 1 reviews the literature on the influence of ligands on exciton relaxation dynamics following photoexcitation of semiconductor QDs, and describes how ligands promote or inhibit processes such as emission, nonradiative relaxation, and charge transfer to redox active adsorbates. Chapter 2 investigates the specific interaction of alkylcarboxylated viologen derivatives with CdS QDs, and shows how a combination of steady-state photoluminescence (PL) and transient absorption (TA) experiments can be used to reveal the specific binding geometry of redox active organic molecules on QD surfaces. Chapter 3 expands on Chapter 2 by using PL and TA to provide information about the mechanisms through which methyl viologen (MV 2+) associates with CdS QDs to form a stable QD/MV2+ complex, suggesting two chemically distinct reactions. We use our understanding of the QD/molecule interaction to design a drug delivery system in Chapter 4, which employs PL and TA experiments to show that conformational changes in a redox active adsorbate may follow electron transfer, "activating" a biologically inert Schiff base to a protein inhibitor form. The protein inhibitor limits cell motility and may be used to prevent tumor metastasis in cancer patients. Chapter 5 discusses future applications of QD/molecule redox couples with an emphasis on efficient multiple charge-transfer reactions -- a process facilitated by the high degeneracy of band-edge states in QDs. These multiple charge-transfer reactions may potentially increase the thermodynamic efficiency of solar cells, and may also facilitate the splitting of water into fuel. Multiple exciton generation procedures, multi-electron transfer experiments, and future directions are discussed.

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

    Science.gov (United States)

    Xiao, Tiejun; 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.

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

    Science.gov (United States)

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

    2017-02-01

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

  16. Photoinduced reductive repair of thymine glycol: implications for excess electron transfer through DNA containing modified bases.

    Science.gov (United States)

    Ito, Takeo; Kondo, Akiko; Terada, Satoru; Nishimoto, Sei-Ichi

    2006-08-23

    Photoinduced reduction of thymine glycol in oligodeoxynucleotides was investigated using either a reduced form of flavin adenine dinucleotide (FADH(-)) as an intermolecular electron donor or covalently linked phenothiazine (PTZ) as an intramolecular electron donor. Intermolecular electron donation from photoexcited flavin (FADH(-)) to free thymidine glycol generated thymidine in high yield, along with a small amount of 6-hydroxy-5,6-dihydrothymidine. In the case of photoreduction of 4-mer long single-stranded oligodeoxynucleotides containing thymine glycol by *FADH(-), the restoration yield of thymine was varied depending on the sequence of oligodeoxynucleotides. Time-resolved spectroscopic study on the photoreduction by laser-excited N,N-dimethylaniline (DMA) suggested elimination of a hydroxyl ion from the radical anion of thymidine glycol with a rate constant of approximately 10(4) s(-1) generates 6-hydroxy-5,6-dihydrothymidine (6-HOT(*)) as a key intermediate, followed by further reduction of 6-HOT(*) to thymidine or 6-hydroxy-5,6-dihydrothymdine (6-HOT). On the other hand, an excess electron injected into double-stranded DNA containing thymine glycol was not trapped at the lesion but was further transported along the duplex. Considering redox properties of the nucleobases and PTZ, competitive excess electron trapping at pyrimidine bases (thymine, T and cytosine, C) which leads to protonation of the radical anion (T(-)(*), C(-)(*)) or rapid back electron transfer to the radical cation of PTZ (PTZ(+)(*)), is presumably faster than elimination of the hydroxyl ion from the radical anion of thymine glycol in DNA.

  17. Enhanced rate of intramolecular electron transfer in an engineered purple CuA azurin.

    Science.gov (United States)

    Farver, O; Lu, Y; Ang, M C; Pecht, I

    1999-02-02

    The recent expression of an azurin mutant where the blue type 1 copper site is replaced by the purple CuA site of Paracoccus denitrificans cytochrome c oxidase has yielded an optimal system for examining the unique electron mediation properties of the binuclear CuA center, because both type 1 and CuA centers are placed in the same location in the protein while all other structural elements remain the same. Long-range electron transfer is induced between the disulfide radical anion, produced pulse radiolytically, and the oxidized binuclear CuA center in the purple azurin mutant. The rate constant of this intramolecular process, kET = 650 +/- 60 s-1 at 298 K and pH 5.1, is almost 3-fold faster than for the same process in the wild-type single blue copper azurin from Pseudomonas aeruginosa (250 +/- 20 s-1), in spite of a smaller driving force (0.69 eV for purple CuA azurin vs. 0.76 eV for blue copper azurin). The reorganization energy of the CuA center is calculated to be 0.4 eV, which is only 50% of that found for the wild-type azurin. These results represent a direct comparison of electron transfer properties of the blue and purple CuA sites in the same protein framework and provide support for the notion that the binuclear purple CuA center is a more efficient electron transfer agent than the blue single copper center because reactivity of the former involves a lower reorganization energy.

  18. A new model for electron flow during anaerobic digestion: direct interspecies electron transfer to Methanosaeta for the reduction of carbon dioxide to methane

    DEFF Research Database (Denmark)

    Rotaru, Amelia-Elena; Shrestha, Pravin M.; Liu, Fanghua

    2013-01-01

    Anaerobic conversion of organic wastes and biomass to methane is an important bioenergy strategy, which depends on poorly understood mechanisms of interspecies electron transfer to methanogenic microorganisms. Metatranscriptomic analysis of methanogenic aggregates from a brewery wastewater digester......, coupled with fluorescence in situ hybridization with specific 16S rRNA probes, revealed that Methanosaeta species were the most abundant and metabolically active methanogens. Methanogens known to reduce carbon dioxide with H2 or formate as the electron donor were rare. Although Methanosaeta have......, the most abundant bacteria in the aggregates, highly expressed genes for ethanol metabolism and for extracellular electron transfer via electrically conductive pili, suggesting that Geobacter and Methanosaeta species were exchanging electrons via direct interspecies electron transfer (DIET...

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

    Science.gov (United States)

    Chang, Hao

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

  20. Modified Current Differencing Unit and its Application for Electronically Reconfigurable Simple First-order Transfer Function

    Directory of Open Access Journals (Sweden)

    SOTNER, R.

    2015-02-01

    Full Text Available Modified current differencing unit (MCDU and its simple filtering application are introduced in this paper. Modification of the well-known current differencing unit consists in weighted difference of both input currents controlled by adjustable current gain, controllable intrinsic resistance of both current input terminals, and availability of additional voltage terminal(s. Definition of MCDU therefore requires four adjustable parameters (B1, B2, Rp, Rn. A presented active element offers and combines benefits of electronically controllable current conveyor of second generation and current differencing unit and allows synthesis of interesting adjustable applications, which are not available by classical approaches based on simple elements. MCDU brings variability of the transfer function into the structure. It provides several transfer types without necessity of input or output node change by simple electronic tuning. A presented structure represents so-called reconnection-less reconfigurable current-mode filter for realization of all-pass, inverting high-pass, low-pass and direct transfer response. Behavioral model of the MCDU was prepared and carefully tested in filtering application. Spice simulations and measurements confirmed theoretical assumptions.

  1. Structure and electronic spectra of purine-methyl viologen charge transfer complexes.

    Science.gov (United States)

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

    2014-01-01

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

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

    Science.gov (United States)

    Andrés, Juan; Berski, Sławomir; Silvi, Bernard

    2016-07-07

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

  3. A severe reduction in the cytochrome C content of Geobacter sulfurreducens eliminates its capacity for extracellular electron transfer.

    Science.gov (United States)

    Estevez-Canales, Marta; Kuzume, Akiyoshi; Borjas, Zulema; Füeg, Michael; Lovley, Derek; Wandlowski, Thomas; Esteve-Núñez, Abraham

    2015-04-01

    The ability of Geobacter species to transfer electrons outside the cell enables them to play an important role in a number of biogeochemical and bioenergy processes. Gene deletion studies have implicated periplasmic and outer-surface c-type cytochromes in this extracellular electron transfer. However, even when as many as five c-type cytochrome genes have been deleted, some capacity for extracellular electron transfer remains. In order to evaluate the role of c-type cytochromes in extracellular electron transfer, Geobacter sulfurreducens was grown in a low-iron medium that included the iron chelator (2,2'-bipyridine) to further sequester iron. Haem-staining revealed that the cytochrome content of cells grown in this manner was 15-fold lower than in cells exposed to a standard iron-containing medium. The low cytochrome abundance was confirmed by in situ nanoparticle-enhanced Raman spectroscopy (NERS). The cytochrome-depleted cells reduced fumarate to succinate as well as the cytochrome-replete cells do, but were unable to reduce Fe(III) citrate or to exchange electrons with a graphite electrode. These results demonstrate that c-type cytochromes are essential for extracellular electron transfer by G. sulfurreducens. The strategy for growing cytochrome-depleted G. sulfurreducens will also greatly aid future physiological studies of Geobacter species and other microorganisms capable of extracellular electron transfer.

  4. Coronenetetraimide-centered cruciform pentamers containing multiporphyrin units: synthesis and sequential photoinduced energy- and electron-transfer dynamics.

    Science.gov (United States)

    Hasobe, Taku; Ida, Koichi; Sakai, Hayato; Ohkubo, Kei; Fukuzumi, Shunichi

    2015-07-27

    A series of coronenetetraimide (CorTIm)-centered cruciform pentamers containing multiporphyrin units, in which four porphyrin units are covalently linked to a CorTIm core through benzyl linkages, were designed and synthesized to investigate their structural, spectroscopic, and electrochemical properties as well as photoinduced electron- and energy-transfer dynamics. These systems afforded the first synthetic case of coroneneimide derivatives covalently linked with dye molecules. The steady-state absorption and electrochemical results indicate that a CorTIm and four porphyrin units were successfully characterized by the corresponding reference monomers. In contrast, the steady-state fluorescence measurements demonstrated that strong fluorescence quenching relative to the corresponding monomer units was observed in these pentamers. Nanosecond laser flash photolysis measurements revealed the occurrence of intermolecular electron transfer from triplet excited state of zinc porphyrins to CorTIm. Femtosecond laser-induced transient absorption measurements for excitation of the CorTIm unit clearly demonstrate the sequential photoinduced energy and electron transfer between CorTIm and porphyrins, that is, occurrence of the initial energy transfer from CorTIm (energy donor) to porphyrins (energy acceptor) and subsequent electron transfer from porphyrins (electron donor) to CorTIm (electron acceptor) in these pentamers, whereas only the electron-transfer process from porphyrins to CorTIm was observed when we mainly excite porphyrin units. Finally, construction of high-order supramolecular patterning of these pentamers was performed by utilizing self-assembly and physical dewetting during the evaporation of solvent.

  5. Electron Transport, Energy Transfer, and Optical Response in Single Molecule Junctions

    Science.gov (United States)

    White, Alexander James

    The last decade has seen incredible growth in the quality of experiments being done on single molecule junctions. Contemporary experimental measurements have expanded far beyond simple electron transport. Measurement of vibronic eects, quantum interference and decoherence eects, molecular optical response (Raman spectroscopy), and molecular spintronics are just some of the continuing areas of research in single molecule junctions. Experimental advancements demand advanced theoretical treatments, which can be used accurately within appropriate physical regimes, in order to understand measured phenomena and predict interesting directions for future study. In this dissertation we will study systems with strong intra-system interactions using a many-body states based approach. We will be focused on three related processes in molecular junctions: electron transport, electronic energy transfer, and molecular excitation. Inelastic electron transport in the regime of strong and nonlinear electron-vibration coupling within and outside of the Born-Oppenheimer regime will be investigated. To understand their appropriateness, we will compare simple semi-classical approximations in molecular redox junctions and electron-counting devices to fully quantum calculations based on many-body system states. The role of coherence and quantum interference in energy and electron transfer in molecular junctions is explored. Experiments that simultaneously measure surface enhanced Raman scattering and electron conduction have revealed a strong interaction between conducting electrons and molecular excitation. We investigate the role of the molecular response to a classical surface plasmon enhanced electric eld considering the back action of the oscillating molecular dipole. Raman scattering is quantum mechanical by nature and involves strong interaction between surface plasmons in the contacts and the molecular excitation. We develop a scheme for treating strong plasmon-molecular excitation

  6. Density matrix treatment of non-adiabatic photoinduced electron transfer at a semiconductor surface.

    Science.gov (United States)

    Micha, David A

    2012-12-14

    Photoinduced electron transfer at a nanostructured surface leads to localized transitions and involves three different types of non-adiabatic couplings: vertical electronic transitions induced by light absorption emission, coupling of electronic states by the momentum of atomic motions, and their coupling due to interactions with electronic density fluctuations and vibrational motions in the substrate. These phenomena are described in a unified way by a reduced density matrix (RDM) satisfying an equation of motion that contains dissipative rates. The RDM treatment is used here to distinguish non-adiabatic phenomena that are localized from those due to interaction with a medium. The fast decay of localized state populations due to electronic density fluctuations in the medium has been treated within the Lindblad formulation of rates. The formulation is developed introducing vibronic states constructed from electron orbitals available from density functional calculations, and from vibrational states describing local atomic displacements. Related ab initio molecular dynamics calculations have provided diabatic momentum couplings between excited electronic states. This has been done in detail for an indirect photoexcitation mechanism of the surface Ag(3)Si(111):H, which leads to long lasting electronic charge separation. The resulting coupled density matrix equations are solved numerically to obtain the population of the final charge-separated state as it changes over time, for several values of the diabatic momentum coupling. New insight and unexpected results are presented here which can be understood in terms of photoinduced non-adiabatic transitions involving many vibronic states. It is found that the population of long lasting charge separation states is larger for smaller momentum coupling, and that their population grows faster for smaller coupling.

  7. Electron transfer flavoprotein domain II orientation monitored using double electron-electron resonance between an enzymatically reduced, native FAD cofactor, and spin labels.

    Science.gov (United States)

    Swanson, Michael A; Kathirvelu, Velavan; Majtan, Tomas; Frerman, Frank E; Eaton, Gareth R; Eaton, Sandra S

    2011-03-01

    Human electron transfer flavoprotein (ETF) is a soluble mitochondrial heterodimeric flavoprotein that links fatty acid β-oxidation to the main respiratory chain. The crystal structure of human ETF bound to medium chain acyl-CoA dehydrogenase indicates that the flavin adenine dinucleotide (FAD) domain (αII) is mobile, which permits more rapid electron transfer with donors and acceptors by providing closer access to the flavin and allows ETF to accept electrons from at least 10 different flavoprotein dehydrogenases. Sequence homology is high and low-angle X-ray scattering is identical for Paracoccus denitrificans (P. denitrificans) and human ETF. To characterize the orientations of the αII domain of P. denitrificans ETF, distances between enzymatically reduced FAD and spin labels in the three structural domains were measured by double electron-electron resonance (DEER) at X- and Q-bands. An FAD to spin label distance of 2.8 ± 0.15 nm for the label in the FAD-containing αII domain (A210C) agreed with estimates from the crystal structure (3.0 nm), molecular dynamics simulations (2.7 nm), and rotamer library analysis (2.8 nm). Distances between the reduced FAD and labels in αI (A43C) were between 4.0 and 4.5 ± 0.35 nm and for βIII (A111C) the distance was 4.3 ± 0.15 nm. These values were intermediate between estimates from the crystal structure of P. denitrificans ETF and a homology model based on substrate-bound human ETF. These distances suggest that the αII domain adopts orientations in solution that are intermediate between those which are observed in the crystal structures of free ETF (closed) and ETF bound to a dehydrogenase (open).

  8. Diving into the redox properties of Geobacter sulfurreducens cytochromes: a model for extracellular electron transfer.

    Science.gov (United States)

    Santos, Telma C; Silva, Marta A; Morgado, Leonor; Dantas, Joana M; Salgueiro, Carlos A

    2015-05-28

    Geobacter bacteria have a remarkable respiratory versatility that includes the dissimilatory reduction of insoluble metal oxides in natural habitats and electron transfer to electrode surfaces from which electricity can be harvested. In both cases, electrons need to be exported from the cell interior to the exterior via a mechanism designated as extracellular electron transfer (EET). Several c-type cytochromes from G. sulfurreducens (Gs) were identified as key players in this process. Biochemical and biophysical data have been obtained for ten Gs cytochromes, including inner-membrane associated (MacA), periplasmic (PpcA, PpcB, PpcC, PpcD, PpcE and GSU1996) and outer membrane-associated (OmcF, OmcS and OmcZ). The redox properties of these cytochromes have been determined, except for PpcC and GSU1996. In this perspective, the reduction potentials of these two cytochromes were determined by potentiometric redox titrations followed by visible spectroscopy. The data obtained are taken together with those available for other key cytochromes to present a thorough overview of the current knowledge of Gs EET mechanisms and provide a possible rationalization for the existence of several multiheme cytochromes involved in the same respiratory pathways.

  9. Unraveling the structure of membrane proteins in situ by transfer function corrected cryo-electron tomography.

    Science.gov (United States)

    Eibauer, Matthias; Hoffmann, Christian; Plitzko, Jürgen M; Baumeister, Wolfgang; Nickell, Stephan; Engelhardt, Harald

    2012-12-01

    Cryo-electron tomography in combination with subtomogram averaging allows to investigate the structure of protein assemblies in their natural environment in a close to live state. To make full use of the structural information contained in tomograms it is necessary to analyze the contrast transfer function (CTF) of projections and to restore the phases of higher spatial frequencies. CTF correction is however hampered by the difficulty of determining the actual defocus values from tilt series data, which is due to the low signal-to-noise ratio of electron micrographs. In this study, an extended acquisition scheme is introduced that enables an independent CTF determination. Two high-dose images are recorded along the tilt axis on both sides of each projection, which allow an accurate determination of the defocus values of these images. These values are used to calculate the CTF for each image of the tilt series. We applied this scheme to the mycobacterial outer membrane protein MspA reconstituted in lipid vesicles and tested several variants of CTF estimation in combination with subtomogram averaging and correction of the modulation transfer function (MTF). The 3D electron density map of MspA was compared with a structure previously determined by X-ray crystallography. We were able to demonstrate that structural information up to a resolution of 16.8Å can be recovered using our CTF correction approach, whereas the uncorrected 3D map had a resolution of only 26.2Å.

  10. Long-distance electron transfer by cable bacteria in aquifer sediments.

    Science.gov (United States)

    Müller, Hubert; Bosch, Julian; Griebler, Christian; Damgaard, Lars Riis; Nielsen, Lars Peter; Lueders, Tillmann; Meckenstock, Rainer U

    2016-08-01

    The biodegradation of organic pollutants in aquifers is often restricted to the fringes of contaminant plumes where steep countergradients of electron donors and acceptors are separated by limited dispersive mixing. However, long-distance electron transfer (LDET) by filamentous 'cable bacteria' has recently been discovered in marine sediments to couple spatially separated redox half reactions over centimeter scales. Here we provide primary evidence that such sulfur-oxidizing cable bacteria can also be found at oxic-anoxic interfaces in aquifer sediments, where they provide a means for the direct recycling of sulfate by electron transfer over 1-2-cm distance. Sediments were taken from a hydrocarbon-contaminated aquifer, amended with iron sulfide and saturated with water, leaving the sediment surface exposed to air. Steep geochemical gradients developed in the upper 3 cm, showing a spatial separation of oxygen and sulfide by 9 mm together with a pH profile characteristic for sulfur oxidation by LDET. Bacterial filaments, which were highly abundant in the suboxic zone, were identified by sequencing of 16S rRNA genes and fluorescence in situ hybridization (FISH) as cable bacteria belonging to the Desulfobulbaceae. The detection of similar Desulfobulbaceae at the oxic-anoxic interface of fresh sediment cores taken at a contaminated aquifer suggests that LDET may indeed be active at the capillary fringe in situ.

  11. An experimental investigation of convective heat transfer enhancement in electronic module using curved deflector

    Science.gov (United States)

    Rosas, A. S.; Ali, R. K.; Abdel-Aziz, A. A.; Elshazly, K. M.

    2016-07-01

    This work investigated experimentally the heat transfer and pressure drop in electronic module using a curved deflector to direct the flow towards the recirculation zone enclosed between the two heat sources. The experiments were carried out to investigate the effect of deflector dimensionless radius (R r ) and both horizontal and vertical distances (R x , R y ) within a range of Reynolds number from 5223 to 11,380. The results show that larger deflector at small vertical distance enhances the heat transfer for upstream and downstream heat sources while the horizontal distance has a contrast effect. Correlations are obtained for the average Nusselt number of both upstream and downstream heat sources utilizing the present measurements within 5223 ≤ Re L ≤ 11,380, 0.02 ≤ R x ≤ 0.4, 0.3 ≤ R y ≤ 0.5 and 0.15 ≤ R r ≤ 0.35.

  12. Population of highly excited intermediate resonance states by electron transfer and excitation

    Energy Technology Data Exchange (ETDEWEB)

    Schuch, R. (Manne Siegbahn Institute of Physics, S-104 05 Stockholm, Sweden (SE)); Justiniano, E. (Department of Physics, East Carolina University, Greenville, North Carolina 27858-4353 (USA)); Schulz, M.; Datz, S.; Dittner, P.F.; Giese, J.P.; Krause, H.F.; Schoene, H.; Vane, R. (Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6377 (USA)); Shafroth, S. (Department of Physics, North Carolina University, Chapel Hill, North Carolina 27599-3255 (USA))

    1991-05-01

    Coincidences between two sulfur {ital K} x rays were detected from collisions of hydrogenlike S ions with H{sub 2} gas in the projectile energy range between 150 and 225 MeV. These {ital K} x rays are emitted in the decay of doubly excited states formed in the collisions via transfer and excitation. The excitation function for two coincident {ital K}{beta} transitions peaks at about 175 MeV, slightly above the expected {ital KMM} resonance energy for resonant transfer and excitation (RTE). This demonstrates the occurrence of {Delta}{ital N}{ge}2 transitions (i.e., {ital KMM} and higher resonances) in the RTE process. The cross sections for the population of the very highly excited states are higher than those predicted by theoretical calculations that use dielectronic recombination rates folded with the Compton profile for the bound electrons.

  13. An experimental investigation of convective heat transfer enhancement in electronic module using curved deflector

    Science.gov (United States)

    Rosas, A. S.; Ali, R. K.; Abdel-Aziz, A. A.; Elshazly, K. M.

    2017-03-01

    This work investigated experimentally the heat transfer and pressure drop in electronic module using a curved deflector to direct the flow towards the recirculation zone enclosed between the two heat sources. The experiments were carried out to investigate the effect of deflector dimensionless radius ( R r ) and both horizontal and vertical distances ( R x , R y ) within a range of Reynolds number from 5223 to 11,380. The results show that larger deflector at small vertical distance enhances the heat transfer for upstream and downstream heat sources while the horizontal distance has a contrast effect. Correlations are obtained for the average Nusselt number of both upstream and downstream heat sources utilizing the present measurements within 5223 ≤ Re L ≤ 11,380, 0.02 ≤ R x ≤ 0.4, 0.3 ≤ R y ≤ 0.5 and 0.15 ≤ R r ≤ 0.35.

  14. Biofuel Cells Select for Microbial Consortia That Self-Mediate Electron Transfer

    Science.gov (United States)

    Rabaey, Korneel; Boon, Nico; Siciliano, Steven D.; Verhaege, Marc; Verstraete, Willy

    2004-01-01

    Microbial fuel cells hold great promise as a sustainable biotechnological solution to future energy needs. Current efforts to improve the efficiency of such fuel cells are limited by the lack of knowledge about the microbial ecology of these systems. The purposes of this study were (i) to elucidate whether a bacterial community, either suspended or attached to an electrode, can evolve in a microbial fuel cell to bring about higher power output, and (ii) to identify species responsible for the electricity generation. Enrichment by repeated transfer of a bacterial consortium harvested from the anode compartment of a biofuel cell in which glucose was used increased the output from an initial level of 0.6 W m−2 of electrode surface to a maximal level of 4.31 W m−2 (664 mV, 30.9 mA) when plain graphite electrodes were used. This result was obtained with an average loading rate of 1 g of glucose liter−1 day−1 and corresponded to 81% efficiency for electron transfer from glucose to electricity. Cyclic voltammetry indicated that the enhanced microbial consortium had either membrane-bound or excreted redox components that were not initially detected in the community. Dominant species of the enhanced culture were identified by denaturing gradient gel electrophoresis and culturing. The community consisted mainly of facultative anaerobic bacteria, such as Alcaligenes faecalis and Enterococcus gallinarum, which are capable of hydrogen production. Pseudomonas aeruginosa and other Pseudomonas species were also isolated. For several isolates, electrochemical activity was mainly due to excreted redox mediators, and one of these mediators, pyocyanin produced by P. aeruginosa, could be characterized. Overall, the enrichment procedure, irrespective of whether only attached or suspended bacteria were examined, selected for organisms capable of mediating the electron transfer either by direct bacterial transfer or by excretion of redox components. PMID:15345423

  15. Photoinduced electron-transfer processes involving covalently linked ruthenium and cobalt polypyridyl complexes. Comparison of electronic coupling in bridged and nonbridged ruthenium and cobalt complexes

    Energy Technology Data Exchange (ETDEWEB)

    Song, Xiaoqing; Lei, Yabin; Endicott, J.F. (Wayne State Univ., Detroit, MI (United States)); Van Wallendal, S.; Jackman, D.C.; Rillema, D.P. (Univ. of North Carolina, Charlotte (United States)); Perkovic, M.W. (Wayne State Univ., Detroit, MI (United States) Univ. of North Carolina, Charlotte (United States))

    1993-04-01

    Photoinduced electron-transfer processes have been examined in a heterobimetallic coordination complex with polypyridyl ligands. Three relaxation processes were observed to follow light absorption by (bpy)[sub 2]Ru(bb)Co(bpy)[sub 2][sup 5+] (where bpy = 2,2'-bipyridine and bb 1,2-bis(2,2'-bipyridyl-4'-yl)ethane) with lifetimes in water at 25[degrees]C of 0.18, 1, and 6 ns determined using picosecond flash photolysis techniques. These nearly solvent independent relaxation rates are ascribed to forward electron transfer from ([sup 3]MLCT)Ru(bpy)[sub 2][sup 2+] to Co(bpy)[sub 2][sup 3+], spin relaxation at the Co(II) center and back electron transfer from ([sup 4]T[sub 1])Co(bpy)[sub 2][sub 2+] to Ru(bpy)[sub 2][sup 3+]. Luminescence decay of ([sup 3]MLCT)Ru(bpy)[sub 2][sup 2+] has also been used to monitor the electron-transfer quenching step from 77-150 K, and the quenching rate extrapolated to 25[degrees]C (activation energy of 2.2 [times] 10[sup 3] cm[sup [minus]1]) was compatible with the 180-ps lifetime. It is inferred that the back electron transfer rate is retarded by poor donor-acceptor electronic coupling (k[sub el] [congruent] 10[sup [minus]3]). A Mulliken type of perturbational model is proposed to describe the weak electronic coupling in this complex. Spectroscopic parameters are combined with the perturbational expressions to give a plausible account of the electronic coupling in the back-electron-transfer process. 84 refs., 9 figs., 5 tabs.

  16. Extracellular electron transfer mechanism in Shewanella loihica PV- 4 biofilms formed at indium tin oxide and graphite electrodes

    OpenAIRE

    2013-01-01

    Electroactive biofilms are capable of extracellular electron transfer to insoluble metal oxides and electrodes; such biofilms are relevant to biogeochemistry, bioremediation, and bioelectricity production. We investigated the extracellular electron transfer mechanisms in Shewanella loihica PV-4 viable biofilms grown at indium tin oxide (ITO) and graphite electrodes in potentiostat-controlled electrochemical cells poised at 0.2 V vs. Ag/AgCl. Chronoamperometry and confocal microscopy showed hi...

  17. Electron transfer-induced four-membered cyclic intermediate formation: Olefin cross-coupling vs. olefin cross-metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Yohei [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan); Chiba, Kazuhiro, E-mail: chiba@cc.tuat.ac.j [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan)

    2011-01-01

    An electron transfer-induced four-membered cyclic intermediate, formed between a radical cation of an enol ether and an unactivated olefin, played a key role in the pathway toward either cross-coupling or cross-metathesis. The presence of an alkoxy group on the phenyl ring of the olefin entirely determined the synthetic outcome of the reaction, which mirrored the efficiency of the intramolecular electron transfer.

  18. Sensing lymphoma cells based on a cell-penetrating/apoptosis-inducing/electron-transfer peptide probe

    Energy Technology Data Exchange (ETDEWEB)

    Sugawara, Kazuharu, E-mail: kzsuga@maebashi-it.ac.jp [Maebashi Institute of Technology, Gunma 371-0816 (Japan); Shinohara, Hiroki; Kadoya, Toshihiko [Maebashi Institute of Technology, Gunma 371-0816 (Japan); Kuramitz, Hideki [Department of Environmental Biology and Chemistry, Graduate School of Science and Engineering for Research, University of Toyama, Toyama 930-8555 (Japan)

    2016-06-14

    To electrochemically sense lymphoma cells (U937), we fabricated a multifunctional peptide probe that consists of cell-penetrating/apoptosis-inducing/electron-transfer peptides. Electron-transfer peptides derive from cysteine residue combined with the C-terminals of four tyrosine residues (Y{sub 4}). A peptide whereby Y{sub 4}C is bound to the C-terminals of protegrin 1 (RGGRLCYCRRRFCVCVGR-NH{sub 2}) is known to be an apoptosis-inducing agent against U937 cells, and is referred to as a peptide-1 probe. An oxidation response of the peptide-1 probe has been observed due to a phenolic hydroxyl group, and this response is decreased by the uptake of the peptide probe into the cells. To improve the cell membrane permeability against U937 cells, the RGGR at the N-terminals of the peptide-1 probe was replaced by RRRR (peptide-2 probe). In contrast, RNRCKGTDVQAWY{sub 4}C (peptide-3 probe), which recognizes ovalbumin, was constructed as a control. Compared with the other probes, the change in the peak current of the peptide-2 probe was the greatest at low concentrations and occurred in a short amount of time. Therefore, the cell membrane permeability of the peptide-2 probe was increased based on the arginine residues and the apoptosis-inducing peptides. The peak current was linear and ranged from 100 to 1000 cells/ml. The relative standard deviation of 600 cells/ml was 5.0% (n = 5). Furthermore, the membrane permeability of the peptide probes was confirmed using fluorescent dye. - Highlights: • We constructed a multifunctional peptide probe for the electrochemical sensing of lymphoma cells. • The peptide probe consists of cell-penetrating/apoptosis-inducing/electron-transfer peptides. • The electrode response of the peptide probe changes due to selective uptake into the cells.

  19. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

    Science.gov (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

    2016-11-01

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

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

    Energy Technology Data Exchange (ETDEWEB)

    Slavov, Chavdar Lyubomirov

    2009-07-09

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

  1. Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations.

    Science.gov (United States)

    Romańczyk, Piotr P; Rotko, Grzegorz; Kurek, Stefan S

    2016-08-10

    Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures.

  2. Charge-dependent dissociation of insulin cations via ion/ion electron transfer

    Science.gov (United States)

    Liu, Jian; Gunawardena, Harsha P.; Huang, Teng-Yi; McLuckey, Scott A.

    2008-10-01

    The dissociation reactions of various charge states of insulin cations obtained directly from nano-electrospray were investigated as a result of ion/ion electron transfer from azobenzene anions. Data were collected with and without simultaneous ion trap collisional excitation of the first generation charge-reduced product during the ion/ion reaction period. Neither separation of the two constituent chains nor cleavages within the loop defined by the disulfide bridges were observed under normal electron transfer dissociation (ETD) conditions for any of the charge states studied. However, substantial sequence coverage (exocyclic region: 82.6%; entire protein: 38.8%) outside the ring structure was obtained for insulin +6, while only limited coverage (exocyclic: 43.5%; entire protein: 20.4%) was observed for insulin +5 and no dissociation, aside from low abundance side-chain losses, was noted for insulin +4 and +3 in the normal ETD spectra. When the first generation charge-reduced precursor ions were subjected to collisional activation during the ion/ion reaction period, higher sequence coverages were obtained for both insulin +5 (entire protein: 34.7%) and +4 (entire protein: 20.4%) with backbone cleavages occurring within the loop defined by the disulfide bonds. Dissociation of insulin +3 was not significantly improved by the additional activation. Separation of the two constituent chains resulting from cleavages of both of the two disulfide bridges that link the chains was observed for insulin +6, +5, and +4 when the charge-reduced species were activated. The dissociation of disulfide linkages in this study suggests that as the charge state decreases, disulfide bond cleavages dominate over N-C[alpha] bond cleavages in the electron transfer dissociation process.

  3. The Relationship between Organizational Factors and the Transfer of Training in the Electronics Industry in Shenzhen, China.

    Science.gov (United States)

    Xiao, Jin

    1996-01-01

    A transfer model was applied to data from a survey of workers in four Chinese electronics firms. Results showed that transfer of training depends on organizational factors that facilitate use of knowledge, skills, and attitudes acquired. Supervision and other human factors were most influential. (SK)

  4. Designed azurins show lower reorganization free energies for intraprotein electron transfer

    DEFF Research Database (Denmark)

    Farver, Ole; Marshall, Nicholas M; Wherland, Scot;

    2013-01-01

    Low reorganization free energies are necessary for fast electron transfer (ET) reactions. Hence, rational design of redox proteins with lower reorganization free energies has been a long-standing challenge, promising to yield a deeper understanding of the underlying principles of ET reactivity...... and to enable potential applications in different energy conversion systems. Herein we report studies of the intramolecular ET from pulse radiolytically produced disulfide radicals to Cu(II) in rationally designed azurin mutants. In these mutants, the copper coordination sphere has been fine-tuned to span...

  5. In situ scanning tunnelling microscopy of redox molecules. Coherent electron transfer at large bias voltages

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Kuznetsov, A.M.; Ulstrup, Jens

    2003-01-01

    Theories of in situ scanning tunnelling microscopy (STM) of molecules with redox levels near the substrate and tip Fermi levels point to 'spectroscopic' current-overpotential features. Prominent features require a narrow 'probing tip', i.e. a small bias voltage, eV(bias), compared...... and tip Fermi levels. STM here involves coherent two-step interfacial electron transfer between the redox level and the enclosing substrate and tip. We have also extended previous experimental in situ STM studies of the blue copper protein Pseudomonas aeruginosa azurin, adsorbed on Au(111), to cover...

  6. GaN based transfer electron and avalanche transit time devices

    Institute of Scientific and Technical Information of China (English)

    R.K.Parida; A.K.Panda

    2012-01-01

    A new model is developed to study the microwave/mm wave characteristics of two-terminal GaN- based transfer electron devices (TEDs),namely a Gunn diode and an impact avalanche transit time (IMPATT) device.Microwave characteristics such as device efficiency and the microwave power generated are computed and compared at D-band (140 GHz center frequency) to see the potentiality of each device under the same operating conditions.It is seen that GaN-based IMPATT devices surpass the Gunn diode in the said frequency region.

  7. GaN based transfer electron and avalanche transit time devices

    Science.gov (United States)

    Parida, R. K.; Panda, A. K.

    2012-05-01

    A new model is developed to study the microwave/mm wave characteristics of two-terminal GaN-based transfer electron devices (TEDs), namely a Gunn diode and an impact avalanche transit time (IMPATT) device. Microwave characteristics such as device efficiency and the microwave power generated are computed and compared at D-band (140 GHz center frequency) to see the potentiality of each device under the same operating conditions. It is seen that GaN-based IMPATT devices surpass the Gunn diode in the said frequency region.

  8. Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy

    Science.gov (United States)

    Guo, Zhenkun; Giokas, Paul G.; Cheshire, Thomas P.; Williams, Olivia F.; Dirkes, David J.; You, Wei; Moran, Andrew M.

    2016-09-01

    Analogues of 2D photon echo methods in which two population times are sampled have recently been used to expose heterogeneity in chemical kinetics. In this work, the two population times sampled for a transition metal complex are transformed into a 2D rate spectrum using the maximum entropy method. The 2D rate spectrum suggests heterogeneity in the vibrational cooling (VC) rate within the ensemble. In addition, a cross peak associated with VC and back electron transfer (BET) dynamics reveals correlation between the two processes. We hypothesize that an increase in the strength of solute-solvent interactions, which accelerates VC, drives the system toward the activationless regime of BET.

  9. Tensor polarization in elastic electron-deuteron scattering to the highest possible momentum transfers

    CERN Document Server

    Garçon, M; Ahmidouch, A; Anklin, H; Arvieux, J; Ball, J; Beedoe, S; Beise, E J; Bimbot, L; Böglin, W; Breuer, H; Carlini, R; Chant, N S; Danagulyan, S; Dow, K; Ducret, J E; Dunne, J; Ewell, L A; Eyraud, L; Furget, C; Gilman, R; Glashausser, C; Gueye, P; Gustafsson, K K; Hafidi, K; Honegger, A; Jourdan, J; Kox, S; Kumbartzki, G; Lü, L; Lung, A; Mack, D; Markowitz, P; McIntyre, J; Meekins, D; Merchez, F; Mitchell, J; Möhring, R H; Mtingwa, S; Mrktchyan, H; Pitz, D; Qin, L; Ransome, R; Real, J S; Roos, P G; Rutt, P; Schmidt, W; Sawafta, R; Stepanyan, S; Stephenson, E J; Tieulent, R; Tomasi-Gustafsson, E; Turchinetz, W E; Vansyoc, K; Volmer, J; Voutier, E; Vulcan, W; Williamson, C; Wood, S A; Yan, C; Zhao, J; Zhao, W

    1999-01-01

    In elastic electron-deuteron scattering, the tensor polarization moments t sub 2 sub 0 , t sub 2 sub 1 and t sub 2 sub 2 , together with the unpolarized cross-sections, have been measured up to a momentum transfer of 1.8 (GeV/c) sup 2 , or 6.8 fm sup - sup 1. The experiment was performed at Jefferson Laboratory using the recoil deuteron polarimeter POLDER. Preliminary results are presented and discussed, especially in view of their significance concerning the applicability of perturbative QCD to this exclusive process.

  10. Extracellular polymeric substances play roles in extracellular electron transfer of Shewanella oneidensis MR-1

    DEFF Research Database (Denmark)

    Xiao, Yong; Zhang, En-Hua; Christensen, Hans Erik Mølager

    It is well known that microorganism is surrounded by extracellular polymeric substances (EPS) which include polysaccharides, proteins, glycoproteins, nucleic acids, phospholipids, and humic acids. However, previous studies on microbial extracellular electron transfer (EET) are conducted on cells...... the extraction (Figure 1.a and 1.b). Comparing to cells in control group, MR-1 treated at 38 °C for EPS extraction showed different electrochemical characterizations as revealed by differential pulse voltammetry (Figure 1.c). EPS extracted from MR-1 also was proved to be electrochemically active. The present...

  11. Resonant electron transfer in slow collisions of protons with Rydberg hydrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Joachain, C.J.; Nedeljkovic, N.N.

    1984-05-01

    The resonant charge-transfer reaction of protons on highly excited hydrogen atoms is considered by taking into account both the tunneling (under-barrier) and the over-barrier (classically allowed) electron transitions. It is demonstrated that in a wide range of variation of the reduced ve- locity v = vn, the classical transition mechanism is predominant. Cross-section calculations for principal quantum numbers n between 10 and 50 are presented. The results for 45< or =n< or =50 are compared with the available experimental data and with other theoretical calculations.

  12. Electron Transfer Mediators for Photoelectrochemical Cells Based on Cu(I Metal Complexes

    Directory of Open Access Journals (Sweden)

    Michele Brugnati

    2007-01-01

    Full Text Available The preparation and the photoelectrochemical characterization of a series of bipyridine and pyridyl-quinoline Cu(I complexes, used as electron transfer mediators in regenerative photoelectrochemical cells, are reported. The best performing mediators produced maximum IPCEs of the order of 35–40%. The J-V curves recorded under monochromatic light showed that the selected Cu(I/(II couples generated higher Vocs and fill factors compared to an equivalent I-/I3- cell, due to a decreased dark current.

  13. Fast electron transfer through a single molecule natively structured redox protein

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Macdonald, J. Emyr;

    2012-01-01

    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...

  14. Global proteomic profiling of phosphopeptides using electron transfer dissociation tandem mass spectrometry

    DEFF Research Database (Denmark)

    Molina, Henrik; Horn, David M; Tang, Ning;

    2007-01-01

    Electron transfer dissociation (ETD) is a recently introduced mass spectrometric technique that provides a more comprehensive coverage of peptide sequences and posttranslational modifications. Here, we evaluated the use of ETD for a global phosphoproteome analysis. In all, we identified a total...... fragment ions that facilitated localization of phosphorylation sites. Although our data indicate that ETD is superior to CID for phosphorylation analysis, the two methods can be effectively combined in alternating ETD and CID modes for a more comprehensive analysis. Combining ETD and CID, from this single...

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

    Directory of Open Access Journals (Sweden)

    Karen J. Brewer

    2010-08-01

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

  16. DNA repair mechanism by photolyase: electron transfer path from the photolyase catalytic cofactor FADH(-) to DNA thymine dimer.

    Science.gov (United States)

    Medvedev, D; Stuchebrukhov, A A

    2001-05-21

    Photolyase is an enzyme that catalyses photorepair of thymine dimers in UV damaged DNA by electron transfer reaction. The structure of the photolyase/DNA complex is unknown at present. Using crystal structure coordinates of the substrate-free enzyme from E. coli, we have recently built a computer molecular model of a thymine dimer docked to photolyase catalytic site and studied molecular dynamics of the system. In this paper, we present analysis of the electronic coupling and electron transfer pathway between the catalytic cofactor FADH(-) and the pyrimidine dimer by the method of interatomic tunneling currents. Electronic structure is treated in the extended Hückel approximation. The root mean square transfer matrix element is about 6 cm(-1), which is consistent with the experimentally determined rate of transfer. We find that electron transfer mechanism responsible for the repair utilizes an unusual folded conformation of FADH(-) in photolyases, in which the isoalloxazine ring of the flavin and the adenine are in close proximity, and the peculiar features of the docked orientation of the dimer. The tunneling currents show explicitly that despite of the close proximity between the donor and acceptor complexes, the electron transfer mechanism between the flavin and the thymine bases is not direct, but indirect, with the adenine acting as an intermediate. These calculations confirm the previously made conclusion based on an indirect evidence for such mechanism.

  17. Marked detergents effects on safranine T-mediated photo-induced electron transfer in cytochrome P-450 1A2.

    Science.gov (United States)

    Nakano, R; Konami, H; Sato, H; Ito, O; Shimizu, T

    1995-10-25

    Cytochrome P-450 accepts electrons from electron transfer proteins to facilitate monooxidation reactions. It is suggested that basic amino acids such as Lys and Arg on the P-450 molecular surface interact with acidic amino acids such as Glu and Asp of the electron transfer protein. Safranine T is a basic compound which mediates electron transfer with illumination. It was found with flash photolysis that an electron from photo-reduced safranine T quickly reaches the heme iron of cytochrome P-450 1A2 (P-450 1A2). The photo-induced reduction kinetics of P-450 1A2 were analyzed by the Runge-Kutta method on the second order assumption. The electron-transfer rate constant from safranine T to P-450 1A2 was 2.1 x 10(6) M-1s-1. The rate constant was remarkably increased up to 3.1 x 10(8) M-1s-1 by adding cholic acid, while that was drastically reduced down to 3.5 x 10(4) M-1s-1 by adding Emulgen 913. The electron-transfer rate of a His163-Glu mutant, which has a 40 mV lower redox potential than that of the wild type, was the same as that of the wild type in the absence of the detergents, although the reduced fraction of the mutant was 30% lower than that of the wild type. The electron-transfer rate of the mutant also changed significantly by adding the detergents in the same way as the wild type. Based on these results, together with optical absorbance and fluorescence data, we discuss the inter- and intramolecular electron-transfer mechanism of P-450 1A2.

  18. A review of electron-capture and electron-transfer dissociation tandem mass spectrometry in polymer chemistry.

    Science.gov (United States)

    Hart-Smith, Gene

    2014-01-15

    Mass spectrometry (MS)-based studies of synthetic polymers often characterise detected polymer components using mass data alone. However when mass-based characterisations are ambiguous, tandem MS (MS/MS) offers a means by which additional analytical information may be collected. This review provides a synopsis of two particularly promising methods of dissociating polymer ions during MS/MS: electron-capture and electron-transfer dissociation (ECD and ETD, respectively). The article opens with a summary of the basic characteristics and operating principles of ECD and ETD, and relates these techniques to other methods of dissociating gas-phase ions, such as collision-induced dissociation (CID). Insights into ECD- and ETD-based MS/MS, gained from studies into proteins and peptides, are then discussed in relation to polymer chemistry. Finally, ECD- and ETD-based studies into various classes of polymer are summarised; for each polymer class, ECD- and ETD-derived data are compared to CID-derived data. These discussions identify ECD and ETD as powerful means by which unique and diagnostically useful polymer ion fragmentation data may be generated, and techniques worthy of increased utilisation by the polymer chemistry community.

  19. Evaluating Electronic Couplings for Excited State Charge Transfer Based on Maximum Occupation Method ΔSCF Quasi-Adiabatic States.

    Science.gov (United States)

    Liu, Junzi; Zhang, Yong; Bao, Peng; Yi, Yuanping

    2017-02-14

    Electronic couplings of charge-transfer states with the ground state and localized excited states at the donor/acceptor interface are crucial parameters for controlling the dynamics of exciton dissociation and charge recombination processes in organic solar cells. Here we propose a quasi-adiabatic state approach to evaluate electronic couplings through combining maximum occupation method (mom)-ΔSCF and state diabatization schemes. Compared with time-dependent density functional theory (TDDFT) using global hybrid functional, mom-ΔSCF is superior to estimate the excitation energies of charge-transfer states; moreover it can also provide good excited electronic state for property calculation. Our approach is hence reliable to evaluate electronic couplings for excited state electron transfer processes, which is demonstrated by calculations on a typical organic photovoltaic system, oligothiophene/perylenediimide complex.

  20. Ultrafast spectroscopic investigations of cadmium chalcogenides: Nanoscale electronic relaxation and transfer

    Science.gov (United States)

    Spann, Bryan Thomas

    Harnessing solar energy more effectively remains one of the most important scientific challenges in recent history. Various strategies have been developed to capture the sun's energy to generate usable electricity. Recently, advances in chemistry have allowed researchers to synthesize semiconducting nanocrystals which show great promise in capturing and converting solar energy in a cheap and efficient way. In this dissertation, aspects of energy conversion processes in semiconducting nanocrystals are explored to elucidate their potential for photovoltaic applications. Various forms of linear and non-linear optical spectroscopy techniques were employed to explore electronic relaxation and transfer phenomena in nanoscale cadmium chalcogenide materials and heterojunctions. Ultrafast transient absorption studies were performed on various sizes of CdSe quantum dots (QDs) and quantum rods (QRs) with similar bandedge energies. These studies reviled that QRs have increased intraband relaxation times when compared with QDs as a result of an ultrafast formation of a 1D exciton along the elongated axis of the QR. The formation of the 1D exciton reduces the electron-to-hole scattering potential, consequently reducing the Auger thermalization mechanism. Furthermore, QD samples made in film form showed increased intraband relaxation times as a result of a hydrazine treatment which removed (in part) the organic ligands attached to the surface. As a result of removing the ligands, the ligand based relaxation pathway for the holes was also reduced, causing longer intraband relaxation. In addition to the studies on CdSe nanocrystals (NCs), ultrafast spectroscopy was used to study aspects of charge transfer in CdS -- TiO2 NC heterojunctions. This study revealed a means of increasing photo-induced ultrafast charge transfer in successive ionic layer adsorption and reaction (SILAR) CdS--TiO2 NC heterojunctions using pulsed laser sintering of TiO2 nanocrystals. The enhanced charge

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

    Science.gov (United States)

    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

    2016-06-01

    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.

  2. Optically monitoring voltage in neurons by photo-induced electron transfer through molecular wires.

    Science.gov (United States)

    Miller, Evan W; Lin, John Y; Frady, E Paxon; Steinbach, Paul A; Kristan, William B; Tsien, Roger Y

    2012-02-07

    Fluorescence imaging is an attractive method for monitoring neuronal activity. A key challenge for optically monitoring voltage is development of sensors that can give large and fast responses to changes in transmembrane potential. We now present fluorescent sensors that detect voltage changes in neurons by modulation of photo-induced electron transfer (PeT) from an electron donor through a synthetic molecular wire to a fluorophore. These dyes give bigger responses to voltage than electrochromic dyes, yet have much faster kinetics and much less added capacitance than existing sensors based on hydrophobic anions or voltage-sensitive ion channels. These features enable single-trial detection of synaptic and action potentials in cultured hippocampal neurons and intact leech ganglia. Voltage-dependent PeT should be amenable to much further optimization, but the existing probes are already valuable indicators of neuronal activity.

  3. Vibrational to electronic energy transfer from CO to C 2 molecules

    Science.gov (United States)

    Grigorian, G.; Cenian, A.

    2009-02-01

    The paper discusses the experimental results pointing to the efficient channel of the CO vibrational to the C 2 electronic energy transfer. The radiation spectra of the d 3П g, e 3П g, C 1П g electronic states of C 2 molecule are investigated and the relation of their kinetics to a vibrational excitation of CO molecules in the He-CO-O 2 plasma is discussed. The changes of CO vibrational energy distribution (VED) were imposed by an application of a laser resonator to the discharge tube under investigation. It was found that the modulation of laser radiation (and VED) led to a similar changes of the spontaneous radiation from d 3П g, e 3П g and C 1П g states of C 2 molecules.

  4. Interaction between in vivo bioluminescence and extracellular electron transfer in Shewanella woodyi via charge and discharge.

    Science.gov (United States)

    Tian, Xiaochun; Zhao, Feng; You, Lexing; Wu, Xuee; Zheng, Zhiyong; Wu, Ranran; Jiang, Yanxia; Sun, Shigang

    2017-01-18

    Extracellular electron transfer (EET) and bioluminescence are both important for microbial growth and metabolism, but the mechanism of interaction between EET and bioluminescence is poorly understood. Herein, we demonstrate an exclusively respiratory luminous bacterium, Shewanella woodyi, which possesses EET ability and electron communication at the interface of S. woodyi and solid substrates via charge and discharge methods. Using an electro-chemiluminescence apparatus, our results confirmed that the FMN/FMNH2 content and the redox status of cytochrome c conjointly regulated the bioluminescence intensity when the potential of an indium-tin oxide electrode was changed. More importantly, this work revealed that there is an interaction between the redox reaction of single cells and bioluminescence of group communication via the EET pathway.

  5. Ultrafast Electron Transfer at Organic Semiconductor Interfaces: Importance of Molecular Orientation

    KAUST Repository

    Ayzner, Alexander L.

    2015-01-02

    © 2014 American Chemical Society. 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 C60 acceptor yields a rate that is 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.

  6. Photo-induced electron transfer processes in doped conjugated polymer films (Presentation Recording)

    Science.gov (United States)

    Rumbles, Garry; Reid, Obadiah G.; Park, Jaehong; Ramirez, Jessica; Marsh, Hilary; Clikeman, Tyler T.

    2015-08-01

    With increasing knowledge of the role of the different phases in the bulk heterojunction organic solar cell, the primary site for charge generation is now considered to be the mixed phase, and not the clean interface between neat polymer and neat fullerene. To gain a better understanding of the primary charge generating and recombination steps in this region of the system, we focus our studies on the role of the solid-state microstructure of neat polymers and light-doping of these polymers with a variety of electron-accepting dopants at low concentration. This presentation will describe some recent work on the doping of polythiophene and polyfluorene derivatives with fullerenes, phthalocyanines and perylenes, which provide a range of reduction potentials that serve to control the driving force for electron transfer processes. Results from flash photolysis, time-resolved microwave conductivity (fp-TRMC), femtosecond transient absorption spectroscopy (fTA) and photoluminescence spectroscopy will be presented.

  7. Graphene oxide-facilitated electron transfer of metalloproteins at electrode surfaces.

    Science.gov (United States)

    Zuo, Xiaolei; He, Shijiang; Li, Di; Peng, Cheng; Huang, Qing; Song, Shiping; Fan, Chunhai

    2010-02-02

    Graphene is a particularly useful nanomaterial that has shown great promise in nanoelectronics. Because of the ultrahigh electron mobility of graphene and its unique surface properties such as one-atom thickness and irreversible protein adsorption at surfaces, graphene-based materials might serve as an ideal platform for accommodating proteins and facilitating protein electron transfer. In this work, we demonstrate that graphene oxide (GO) supports the efficient electrical wiring the redox centers of several heme-containing metalloproteins (cytochrome c, myoglobin, and horseradish peroxidase) to the electrode. Importantly, proteins retain their structural intactness and biological activity upon forming mixtures with GO. These important features imply the promising applications of GO/protein complexes in the development of biosensors and biofuel cells.

  8. The Role of Microbial Electron Transfer in the Coevolution of the Biosphere and Geosphere.

    Science.gov (United States)

    Jelen, Benjamin I; Giovannelli, Donato; Falkowski, Paul G

    2016-09-01

    All life on Earth is dependent on biologically mediated electron transfer (i.e., redox) reactions that are far from thermodynamic equilibrium. Biological redox reactions originally evolved in prokaryotes and ultimately, over the first ∼2.5 billion years of Earth's history, formed a global electronic circuit. To maintain the circuit on a global scale requires that oxidants and reductants be transported; the two major planetary wires that connect global metabolism are geophysical fluids-the atmosphere and the oceans. Because all organisms exchange gases with the environment, the evolution of redox reactions has been a major force in modifying the chemistry at Earth's surface. Here we briefly review the discovery and consequences of redox reactions in microbes with a specific focus on the coevolution of life and geochemical phenomena.

  9. l-distributions of the first electron transferred to multiply charged ions interacting with solid surfaces

    Science.gov (United States)

    Mirkovic, M. A.; Nedeljkovic, N. N.

    2008-07-01

    We analyze the angular momentum distributions of the electron transferred into the Rydberg states of multiply charged ions escaping the solid surfaces. The population probabilities are calculated within the framework of two-state-vector model; in the case of large values of the angular momentum quantum numbers l the model takes into account an importance of a wide space region around the projectile trajectory. The reionization of the previously populated states is also taken into account. The corresponding ionization rates are obtained by the appropriate etalon equation method; in the large-l case the radial electronic coordinate rho is treated as variational parameter. The theoretical predictions based on the proposed population-reionization mechanism fit the available beam-foil experimental data; the obtained large-l distributions are also used to elucidate the recent experimental data concerning the multiply charged Rydberg ions interacting with micro-capillary foil.

  10. Long-distance electron transfer by cable bacteria in aquifer sediments

    DEFF Research Database (Denmark)

    Damgaard, Lars Riis; Nielsen, Lars Peter

    2016-01-01

    The biodegradation of organic pollutants in aquifers is often restricted to the fringes of contaminant plumes where steep countergradients of electron donors and acceptors are separated by limited dispersive mixing. However, long-distance electron transfer (LDET) by filamentous ‘cable bacteria’ has...... recently been discovered in marine sediments to couple spatially separated redox half reactions over centimeter scales. Here we provide primary evidence that such sulfur-oxidizing cable bacteria can also be found at oxic–anoxic interfaces in aquifer sediments, where they provide a means for the direct...... of oxygen and sulfide by 9 mm together with a pH profile characteristic for sulfur oxidation by LDET. Bacterial filaments, which were highly abundant in the suboxic zone, were identified by sequencing of 16S rRNA genes and fluorescence in situ hybridization (FISH) as cable bacteria belonging...

  11. Electron Transfer in D-B-A Model Systems and Dye-Sensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Wiberg, Joanna

    2010-01-15

    This Thesis presents a thorough study of the electron transfer (ET) processes, both inter-molecular - between dyes for dye-sensitized solar cells (DSSCs), and intra-molecular - in porphyrin based electron donor-bridge-electron acceptor model systems. The focus has been on charge separation and subsequent re-combination in the femtosecond-nanosecond range in both systems. Studying these processes on nanocrystalline mesoporous films in rather heterogeneous systems for solar cell application is quite a challenge. Therefore, the knowledge gained by studying the same type of processes in designed model systems is in-valuable. To this end, ET has been verified and studied in a series of donor-bridge-acceptor (D-B-A) model systems using femtosecond transient absorption. The D-B-A series show photo-induced ET with exponential distance dependence via superexchange interactions. The attenuation factor of the ET rate, beta, was shown to be direction specific, which is in accordance with the McConnell model. A parallel study of the influence of the barrier height showed that the decrease in electronic coupling for the charge recombination (CR) reaction could be correlated to the impact of charge location. The importance of charge location was also used to explain the large differences in energy conversion efficiency found for two solar cell dyes with differently conjugated anchoring groups adsorbed on TiO{sub 2}. The disparity in energy conversion efficiency for these two dyes was ascribed to the effect of differences in electron density on the binding oxygens, rather than efficiency variations in the injection process. An exponential distance dependence for CR was found also for dyes adsorbed on TiO{sub 2}, with attenuation factors similar to those found for the D-B-A system. In addition, the hole transfer to and from NiO films was studied for two p-type dyes that had shown great differences in current generation. The CR was found to be slower for the dye with the strongest

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-09

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H., E-mail: millerwh@berkeley.edu [Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2014-08-28

    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.

  14. Charge separation distance for flexible donor-bridge-acceptor systems after electron-transfer quenching.

    Science.gov (United States)

    Zhou, Jinwei; Lukin, Leonid V; Braun, Charles L

    2008-08-21

    Photoinduced transient dipole experiments are used to measure the effective charge separation distance, which is equivalent to the photoinduced change in dipole moment divided by the electron charge of flexible electron-donor/acceptor systems, D-(CH2)n-A, where D is 4- N,N-dimethylaniline, A is 9-anthryl, and n = 3, 4. We find that the dipole moments increase strongly with solvent polarity. For the compound with n = 4 (DBA4), analysis of dipole signals indicates that the effective charge separation distances in toluene, 1,4-dioxane, ethyl acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 2-methylpentanone-3, 3-pentanone, and benzonitrile are 2.2, 2.5, 4.5, 4.7, 5.5, 5.5, 4.8, and 6.3 A, respectively. These values can be understood as the root-mean-square charge separation distance in the solutions of different solvents. We assume that the folded contact configuration has a separation distance of 3.5 A, the extended, solvent-separated configuration has a separation distance of 8.0 A, and that they are the only two stable species after electron-transfer quenching. The formation efficiencies of contact radical ion pairs (CRIPs) and solvent-separated radical ion pairs (SSRIPs) are estimated in different solvents. The results indicate that a significant fraction of the ion pairs exist as solvent-separated ion pairs when the dielectric constant of the solvent is larger than 10. These results indicate that electron-transfer quenching can indeed happen at large separations in polar solvents. They also reveal that there is a barrier for ion pairs formed at large separations, hindering collapse to a contact separation of around 3.5 A.

  15. Marine phototrophic consortia transfer electrons to electrodes in response to reductive stress.

    Science.gov (United States)

    Darus, Libertus; Ledezma, Pablo; Keller, Jürg; Freguia, Stefano

    2016-03-01

    This work studies how extracellular electron transfer (EET) from cyanobacteria-dominated marine microbial biofilms to solid electrodes is affected by the availability of inorganic carbon (Ci). The EET was recorded chronoamperometrically in the form of electrical current by a potentiostat in two identical photo-electrochemical cells using carbon electrodes poised at a potential of +0.6 V versus standard hydrogen electrode under 12/12 h illumination/dark cycles. The Ci was supplied by the addition of NaHCO3 to the medium and/or by sparging CO2 gas. At high Ci conditions, EET from the microbial biofilm to the electrodes was observed only during the dark phase, indicating the occurrence of a form of night-time respiration that can use insoluble electrodes as the terminal electron acceptor. At low or no Ci conditions, however, EET also occurred during illumination suggesting that, in the absence of their natural electron acceptor, some cyanobacteria are able to utilise solid electrodes as an electron sink. This may be a natural survival mechanism for cyanobacteria to maintain redox balance in environments with limiting CO2 and/or high light intensity.

  16. Electronic coupling effects and charge transfer between organic molecules and metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Forker, Roman

    2010-07-01

    We employ a variant of optical absorption spectroscopy, namely in situ differential reflectance spectroscopy (DRS), for an analysis of the structure-properties relations of thin epitaxial organic films. Clear correlations between the spectra and the differently intense coupling to the respective substrates are found. While rather broad and almost structureless spectra are obtained for a quaterrylene (QT) monolayer on Au(111), the spectral shape resembles that of isolated molecules when QT is grown on graphite. We even achieve an efficient electronic decoupling from the subjacent Au(111) by inserting an atomically thin organic spacer layer consisting of hexa-peri-hexabenzocoronene (HBC) with a noticeably dissimilar electronic behavior. These observations are further consolidated by a systematic variation of the metal substrate (Au, Ag, and Al), ranging from inert to rather reactive. For this purpose, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is chosen to ensure comparability of the molecular film structures on the different metals, and also because its electronic alignment on various metal surfaces has previously been studied with great intensity. We present evidence for ionized PTCDA at several interfaces and propose the charge transfer to be related to the electronic level alignment governed by interface dipole formation on the respective metals. (orig.)

  17. Promotion of iron oxide reduction and extracellular electron transfer in Shewanella oneidensis by DMSO.

    Directory of Open Access Journals (Sweden)

    Yuan-Yuan Cheng

    Full Text Available The dissimilatory metal reducing bacterium Shewanella oneidensis MR-1, known for its capacity of reducing iron and manganese oxides, has great environmental impacts. The iron oxides reducing process is affected by the coexistence of alternative electron acceptors in the environment, while investigation into it is limited so far. In this work, the impact of dimethyl sulphoxide (DMSO, a ubiquitous chemical in marine environment, on the reduction of hydrous ferric oxide (HFO by S. oneidensis MR-1 was investigated. Results show that DMSO promoted HFO reduction by both wild type and ΔdmsE, but had no effect on the HFO reduction by ΔdmsB, indicating that such a promotion was dependent on the DMSO respiration. With the DMSO dosing, the levels of extracellular flavins and omcA expression were significantly increased in WT and further increased in ΔdmsE. Bioelectrochemical analysis show that DMSO also promoted the extracellular electron transfer of WT and ΔdmsE. These results demonstrate that DMSO could stimulate the HFO reduction through metabolic and genetic regulation in S. oneidensis MR-1, rather than compete for electrons with HFO. This may provide a potential respiratory pathway to enhance the microbial electron flows for environmental and engineering applications.

  18. Conformational changes of the NADPH-dependent cytochrome P450 reductase in the course of electron transfer to cytochromes P450

    DEFF Research Database (Denmark)

    Laursen, Tomas; Jensen, Kenneth; Møller, Birger Lindberg

    2011-01-01

    The NADPH-dependent cytochrome P450 reductase (CPR) is a key electron donor to eucaryotic cytochromes P450 (CYPs). CPR shuttles electrons from NADPH through the FAD and FMN-coenzymes into the iron of the prosthetic heme-group of the CYP. In the course of these electron transfer reactions, CPR...... to serve as an effective electron transferring "nano-machine"....

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer...... reactions of trHb-Bs were electrochemically studied in solution and at graphite electrodes. Spectrophotometrical potentiometric titration and direct electrochemical measurements gave a heme iron redox potential of −103 ± 4 mV and −108 ± 2 mV vs. NHE, at pH 7, respectively. The redox potential of the heme...... in trHb-Bs shifted −59 mV per pH unit at pH higher than 7, consistently with a 1e−/1 H+ – transfer reaction. The heterogeneous rate constant ks for a quasi-reversible 1e− – 1H+ – transfer reaction between graphite and trHb-Bs was 10.1 ± 2.3 s−1. Upon reversible cyanide binding the ks doubled, while...

  20. Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

    KAUST Repository

    Alsam, Amani Abdu

    2016-09-21

    Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

  1. The kinetics of electron transfer reaction of methylene green and titanium trichloride in different solvents

    Science.gov (United States)

    Saeed, Rehana; Nadeem, Syed Muhammad Saqib

    2016-06-01

    The kinetics of the electron transfer reaction of methylene green and titanium trichloride was investigated in different solvents by spectrophotometry at different temperatures. The the reaction rate was determined by monitoring the absorbance as a function of time at λmax 655 nm. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of methylene green. The effect of an aqueous alcoholic solvent was studied in the acidic range of pH from 4 to 7. It was observed that the reaction rate increased with an increase in polarity of the reaction medium. The the reaction rate was high in acidic conditions and decreased with a further increase in acidity. The increase in temperature increased the rate of the electron transfer reaction of methylene green and titanium trichloride. The activation energy ( E a) was calculated by the Arrhenius relation. The absence of any reaction intermediate was confirmed by spectroscopic and kinetic investigations. A plausible mechanism for the reaction in line with outer-sphere reaction pathway has been proposed. Thermodynamic parameters such as the activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G), and entropy change (Δ S) were also evaluated

  2. Solvent Reorganization Energy of Intramolecular Electron Transfer in Peptides Involving Tryptophan and Tyrosine

    Institute of Scientific and Technical Information of China (English)

    ZHAO Ying-Yi; MA Jian-Yi; ZHAO Xiao-Jun; LI Xiang-Yuan

    2008-01-01

    Intramolecular electron transfer(ET)from tyrosine to tryptophan within peptide Trp-(Pro),-Tyr(n=1,2)has been investigated by ab initio calculation associated with a proper consideration of solvent effect by a continuum model.After geometry optimizations of the charge-localized reactant and product,double-well potentials have been constructed by adopting the linear reaction coordinate.The transition state has been determined by finding the crossing point of the potential energy curves.The realistic ET reaction was found complicated in polar solvent,hence the solvent reorganization energy of the electron transfer has received especial attention in this work.Apply-ing the nonequilibrium solvation procedure implemented based on the polarizable continuum model by the authors,the solvent reorganization energy was estimated to be 87.36 kJ/mol for the ET in Trp-Pro-Tyr system and 105.80 kJ/mol for Trp-(Pro)2-Tyr.

  3. Mechanism of electron transfer reaction of ternary dipicolinatochromium(III) complex involving oxalate as secondary ligand

    Indian Academy of Sciences (India)

    Hassan Amroun Ewais; Iqbal Mohamed Ibrhium Ismail

    2013-09-01

    Mechanism of electron transfer reaction of ternary Mechanism of the oxidation of [CrIII(DPA)(OX)(H2O)]− (DPA = dipicolinate and OX = oxalate) by periodate in aqueous acidic medium has been studied spectrophotometrically over the pH range of 4.45-5.57 at different temperatures. The reaction is first order with respect to both [IO$^{−}_{4}$] and the complex concentration, and it obeys the following rate law: $$d[{\\text Cr}^{\\text{VI}}]/dt = k_6K_4K_6[{\\text IO}^−_4][{\\text{Cr}}^{\\text{III}}]_{\\text{T}}/\\{([H^+] + K_4) + (K_5[H+] + K_6K_4)[{\\text{IO}}^{−}_{4}]\\}.$$ The rate of the reaction increases with increasing pH due to the deprotonation equilibria of the complex. The experimental rate law is consistent with a mechanism in which the deprotonated form [CrIII(DPA)(OX)(OH)]2− is more reactive than the conjugated acid. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO$^{−}_{4}$ to chromium(III). Thermodynamic activation parameters were calculated using the transition state theory equation.dipicolinatochromium(III) complex involving oxalate as secondary ligand

  4. Metabolic transistor strategy for controlling electron transfer chain activity in Escherichia coli.

    Science.gov (United States)

    Wu, Hui; Tuli, Leepika; Bennett, George N; San, Ka-Yiu

    2015-03-01

    A novel strategy to finely control a large metabolic flux by using a "metabolic transistor" approach was established. In this approach a small change in the level or availability of an essential component for the process is controlled by adding a competitive reaction that affects a precursor or an intermediate in its biosynthetic pathway. The change of the basal level of the essential component, considered as a base current in a transistor, has a large effect on the flux through the major pathway. In this way, the fine-tuning of a large flux can be accomplished. The "metabolic transistor" strategy was applied to control electron transfer chain function by manipulation of the quinone synthesis pathway in Escherichia coli. The achievement of a theoretical yield of lactate production under aerobic conditions via this strategy upon manipulation of the biosynthetic pathway of the key participant, ubiquinone-8 (Q8), in an E. coli strain provides an in vivo, genetically tunable means to control the activity of the electron transfer chain and manipulate the production of reduced products while limiting consumption of oxygen to a defined amount.

  5. Kinetics study of ultrafast electron transfer from sensitized dyes to silver halide microcrystals

    Institute of Scientific and Technical Information of China (English)

    Yang Shao-Peng; Fan Guo-Zhi; Fan Shan-Shan; Cao Ning; Li Xiao-Wei; Jiang Xiao-Li; Fu Guang-Sheng

    2006-01-01

    Spectral sensitization micromechanism of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr microcrystals with different dye concentrations is studied by using picosecond time-resolved fluorescence spectroscopy,and the dependences of electron transfer and spectral efficiency sensitization on different conditions are analysed in detail. With the steady spectroscopy, the wavelengths of absorption and fluorescence of J-aggregate adsorbed on AgBr microcrystals are found to shift to red relative to dye monomer. The spectrum of fluorescence has a red shift relative to the absorption peak. With the time-resolved fluorescence spectroscopy, the fluorescence decay curves of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr grains are found to be fitted well by a double-exponential decay function. The fitting curves consist of a fast and a slow component. Because of the large amplitude of the fast component, this fast decay should be attributable mainly to the electron transfer from J-aggregate of dye to a conduction band of AgBr.

  6. Late-onset form of beta-electron transfer flavoprotein deficiency

    DEFF Research Database (Denmark)

    Curcoy, A; Olsen, R K J; Ribes, A;

    2003-01-01

    Multiple acyl-CoA-dehydrogenase deficiency (MADD) or glutaric aciduria type II (GAII) are a group of metabolic disorders due to deficiency of either electron transfer flavoprotein (ETF) or electron transfer flavoprotein ubiquinone oxidoreductase (ETF-QO). We report the clinical features...... and biochemical and molecular genetic analyses of a patient with a mild late-onset form of GAII due to beta-ETF deficiency. Biochemical data showed an abnormal urine organic acid profile, low levels of free carnitine, increased levels of C(10:1n-6), and C(14:1n-9) in plasma, and decreased oxidation of [9,10-3H......]palmitate and [9,10-3H]myristate in fibroblasts, suggesting MAD deficiency. In agreement with these findings, mutational analysis of the ETF/ETFDH genes demonstrated an ETFB missense mutation 124T>C in exon 2 leading to replacement of cysteine-42 with arginine (C42R), and a 604_606AAG deletion in exon 6...

  7. Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

    Institute of Scientific and Technical Information of China (English)

    Kun-hui Liu; Li-dan Wu; Xiao-ran Zou; Wen Yang; Qian Du; Hong-mei Su

    2011-01-01

    Pentachlorophenol,a widespread environmental pollutant that is possibly carcinogenic to humans,is metabolically oxidized to tetrachloroquinone (TCBQ) which can result in DNA damage.We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases (thymine and uracil) upon UVA (355 nm) excitation using the technique of nanosecond time-resolved laser flash photolysis.It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ*,which are highly reactive towards thymine or uracil and undergo two parallel reactions,the hydrogen abstraction and electron transfer,leading to the observed photoproducts of TCBQH.and TCBQ.- in transient absorption spectra.The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards.By characterizing the photochemical hydrogen abstraction and electron transfer reactions,our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

  8. Design and fine-tuning redox potentials of metalloproteins involved in electron transfer in bioenergetics.

    Science.gov (United States)

    Hosseinzadeh, Parisa; Lu, Yi

    2016-05-01

    Redox potentials are a major contributor in controlling the electron transfer (ET) rates and thus regulating the ET processes in the bioenergetics. To maximize the efficiency of the ET process, one needs to master the art of tuning the redox potential, especially in metalloproteins, as they represent major classes of ET proteins. In this review, we first describe the importance of tuning the redox potential of ET centers and its role in regulating the ET in bioenergetic processes including photosynthesis and respiration. The main focus of this review is to summarize recent work in designing the ET centers, namely cupredoxins, cytochromes, and iron-sulfur proteins, and examples in design of protein networks involved these ET centers. We then discuss the factors that affect redox potentials of these ET centers including metal ion, the ligands to metal center and interactions beyond the primary ligand, especially non-covalent secondary coordination sphere interactions. We provide examples of strategies to fine-tune the redox potential using both natural and unnatural amino acids and native and nonnative cofactors. Several case studies are used to illustrate recent successes in this area. Outlooks for future endeavors are also provided. 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.

  9. Monitoring Chemical and Biological Electron Transfer Reactions with a Fluorogenic Vitamin K Analogue Probe.

    Science.gov (United States)

    Belzile, Mei-Ni; Godin, Robert; Durantini, Andrés M; Cosa, Gonzalo

    2016-12-21

    We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of vitamin K, B-VKQ, prepared by coupling vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.

  10. Revealing various coupling of electron transfer and proton pumping in mitochondrial respiratory chain.

    Science.gov (United States)

    Sun, Fei; Zhou, Qiangjun; Pang, Xiaoyun; Xu, Yingzhi; Rao, Zihe

    2013-08-01

    Cellular respiration is the process that releases energy from food and supplies energy for life processes. The mitochondrial respiratory chain is the final and most important step for cellular respiration and is located on the inner membrane of mitochondrion and comprises four large trans-membrane protein complexes (respiratory chain Complexes I, II, III and IV) as well as ubiquinone between Complexes I/II and III and cytochrome c between Complexes III and IV. The function of mitochondrial respiratory chain is biological oxidation by transferring electrons from NADH and succinate to oxygen and then generating proton gradient across the inner membrane. Such proton gradient is utilized by ATP synthase (ATPase, also called as Complex V) to produce energy molecules ATP. Structural studies of mitochondrial respiratory membrane protein complexes are important to understand the mechanism of electron transfer and the redox-coupled proton translocation across the inner membrane. Here, according to the time line, we reviewed the great achievements on structural studies of mitochondrial respiratory complexes in the past twenty years as well as the recent research progresses on the structures of mitochondrial respiratory supra-complexes.

  11. Late-onset form of beta-electron transfer flavoprotein deficiency.

    Science.gov (United States)

    Curcoy, A; Olsen, R K J; Ribes, A; Trenchs, V; Vilaseca, M A; Campistol, J; Osorio, J H; Andresen, B S; Gregersen, N

    2003-04-01

    Multiple acyl-CoA-dehydrogenase deficiency (MADD) or glutaric aciduria type II (GAII) are a group of metabolic disorders due to deficiency of either electron transfer flavoprotein (ETF) or electron transfer flavoprotein ubiquinone oxidoreductase (ETF-QO). We report the clinical features and biochemical and molecular genetic analyses of a patient with a mild late-onset form of GAII due to beta-ETF deficiency. Biochemical data showed an abnormal urine organic acid profile, low levels of free carnitine, increased levels of C(10:1n-6), and C(14:1n-9) in plasma, and decreased oxidation of [9,10-3H]palmitate and [9,10-3H]myristate in fibroblasts, suggesting MAD deficiency. In agreement with these findings, mutational analysis of the ETF/ETFDH genes demonstrated an ETFB missense mutation 124T>C in exon 2 leading to replacement of cysteine-42 with arginine (C42R), and a 604_606AAG deletion in exon 6 in the ETFB gene resulting in the deletion of lysine-202 (K202del). The present report delineates further the phenotype of mild beta-ETF deficiency and illustrates that the differential diagnosis of GAII is readily achieved by mutational analysis.

  12. Photosynthetical electron transfer and biomass formation in selected evolutionary wheat types

    Energy Technology Data Exchange (ETDEWEB)

    Klein, H.

    1980-01-01

    The primary photosynthetical reactions, which are responsible for the absorption of light energy and its fixing as chemical energy, represent the first part of a chain of metabolic processes occurring in the green plant, which ends with the production of organic material. In principle, the synthesis of reserve substances and their deposition in economically profitable storage organs also bases on the supply with energy and reduction equivalents due to the photosynthetical electron transfer, although this production is also determined and influenced by other processes, whose regulative connections are not yet completely known. The formation of biomasses (vegetative organs) however, has a close connection with the capacity of the photosynthetic electron transfer, because there are numerous possibilities of an indirect usage of ATP and NADPH/sub 2/ in the protein and lipid metabolisms besides the synthesis of carbohydrates, which is limited by the CO/sub 2/ supply at the carboxylation site. Consequently, a high degree of functional capacity should correlate with the capacity of intensive growth and result to be a selective advantage in evolution. It was the intention of this study to examine the above-mentioned suppositions on selected species of the genera triticum and aegilops, each of which represents a certain step in the evolution from wild grasses to cultured wheat.

  13. Fundamental studies of energy-and hole/electron- transfer in hydroporphyrin architectures

    Energy Technology Data Exchange (ETDEWEB)

    Bocian, David F. [University of California, Riverside, CA (United States)

    2014-08-20

    The long-term objective of the Bocian/Holten/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten group), and electrochemical, electron paramagnetic resonance, and resonance Raman studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (1) Determination of the rates of ground-state hole/electron transfer between (hydro)porphyrins in multipigment arrays as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (2) Examination of excited-state energy transfer among hydroporphyrins in multipigment arrrays, including both pairwise and non-adjacent transfer, with a chief aim to identify the relative contributions of through-space (Förster) and through-bond (Dexter) mechanisms of energy transfer, including the roles of site of linker connection and frontier molecular orbital composition. (3) Elucidation of the role of substituents in tuning the spectral and electronic properties of bacteriochlorins, with a primary aim of learning how to shift the long-wavelength absorption band deeper into the near-infrared region. (4) Continued development of the software package PhotochemCAD for spectral manipulations and calculations through the compilation of a database

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

    CERN Document Server

    Fujihashi, Yuta; Ishizaki, Akihito

    2015-01-01

    Recently, nuclear vibrational contribution signatures in 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 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 e...

  15. Proximal FAD histidine residue influences interflavin electron transfer in cytochrome P450 reductase and methionine synthase reductase.

    Science.gov (United States)

    Meints, Carla E; Parke, Sarah M; Wolthers, Kirsten R

    2014-04-01

    Cytochrome P450 reductase (CPR) and methionine synthase reductase (MSR) transfer reducing equivalents from NADPH to FAD to FMN. In CPR, hydride transfer and interflavin electron transfer are kinetically coupled steps, but in MSR the two catalytic steps are represented by two distinct kinetic phases leading to transient formation of the FAD hydroquinone. In human CPR, His(322) forms a hydrogen-bond with the highly conserved Asp(677), a member of the catalytic triad. The catalytic triad is present in MSR, but Ala(312) replaces the histidine residue. To examine if this structural variation accounts for differences in their kinetic behavior, reciprocal substitutions were created. Substitution of His(322) for Ala in CPR does not affect the rate of NADPH hydride transfer or the FAD redox potentials, but does impede interflavin electron transfer. For MSR, swapping Ala(312) for a histidine residue resulted in the kinetic coupling of hydride and interflavin electron transfer, and eliminated the formation of the FAD hydroquinone intermediate. For both enzymes, placement of the His residue in the active site weakens coenzyme binding affinity. The data suggest that the proximal FAD histidine residue accelerates proton-coupled electron transfer from FADH2 to the higher potential FMN; a mechanism for this catalytic role is discussed.

  16. Model system-bath Hamiltonian and nonadiabatic rate constants for proton-coupled electron transfer at electrode-solution interfaces.

    Science.gov (United States)

    Navrotskaya, Irina; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2008-06-28

    An extension of the Anderson-Newns-Schmickler model for electrochemical proton-coupled electron transfer (PCET) is presented. This model describes reactions in which electron transfer between a solute complex in solution and an electrode is coupled to proton transfer within the solute complex. The model Hamiltonian is derived in a basis of electron-proton vibronic states defined within a double adiabatic approximation for the electrons, transferring proton, and bath modes. The interaction term responsible for electronic transitions between the solute complex and the electrode depends on the proton donor-acceptor vibrational mode within the solute complex. This model Hamiltonian is used to derive the anodic and cathodic rate constants for nonadiabatic electrochemical PCET. The derivation is based on the master equations for the reduced density matrix of the electron-proton subsystem, which includes the electrons of the solute complex and the electrode, as well as the transferring proton. The rate constant expressions differ from analogous expressions for electrochemical electron transfer because of the summation over electron-proton vibronic states and the dependence of the couplings on the proton donor-acceptor vibrational motion. These differences lead to additional contributions to the total reorganization energy, an additional exponential temperature-dependent prefactor, and a temperature-dependent term in the effective activation energy that has different signs for the anodic and cathodic processes. This model can be generalized to describe both nonadiabatic and adiabatic electrochemical PCET reactions and provides the framework for the inclusion of additional effects, such as the breaking and forming of other chemical bonds.

  17. Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion

    Science.gov (United States)

    Fredin, Lisa A.; Persson, Petter

    2016-09-01

    The rapidly growing interest in photocatalytic systems for direct solar fuel production such as hydrogen generation from water splitting is grounded in the unique opportunity to achieve charge separation in molecular systems provided by electron transfer processes. In general, both photoinduced and catalytic processes involve complicated dynamics that depend on both structural and electronic effects. Here the excited state landscape of metal centered light harvester-catalyst pairs is explored using density functional theory calculations. In weakly bound systems, the interplay between structural and electronic factors involved can be constructed from the various mononuclear relaxed excited states. For this study, supramolecular states of electron transfer and excitation energy transfer character have been constructed from constituent full optimizations of multiple charge/spin states for a set of three Ru-based light harvesters and nine transition metal catalysts (based on Ru, Rh, Re, Pd, and Co) in terms of energy, structure, and electronic properties. The complete set of combined charge-spin states for each donor-acceptor system provides information about the competition of excited state energy transfer states with the catalytically active electron transfer states, enabling the identification of the most promising candidates for photocatalytic applications from this perspective.

  18. Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion.

    Science.gov (United States)

    Fredin, Lisa A; Persson, Petter

    2016-09-14

    The rapidly growing interest in photocatalytic systems for direct solar fuel production such as hydrogen generation from water splitting is grounded in the unique opportunity to achieve charge separation in molecular systems provided by electron transfer processes. In general, both photoinduced and catalytic processes involve complicated dynamics that depend on both structural and electronic effects. Here the excited state landscape of metal centered light harvester-catalyst pairs is explored using density functional theory calculations. In weakly bound systems, the interplay between structural and electronic factors involved can be constructed from the various mononuclear relaxed excited states. For this study, supramolecular states of electron transfer and excitation energy transfer character have been constructed from constituent full optimizations of multiple charge/spin states for a set of three Ru-based light harvesters and nine transition metal catalysts (based on Ru, Rh, Re, Pd, and Co) in terms of energy, structure, and electronic properties. The complete set of combined charge-spin states for each donor-acceptor system provides information about the competition of excited state energy transfer states with the catalytically active electron transfer states, enabling the identification of the most promising candidates for photocatalytic applications from this perspective.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jolley, Greg; Dehdashti Akhavan, Nima; Umana-Membreno, Gilberto; Antoszewski, Jarek; Faraone, Lorenzo [School of Electrical, Electronic and Computer Engineering, University of Western Australia, Perth, Western Australia 6009 (Australia)

    2013-11-21

    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 the 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.

  20. The role of protein dynamics and thermal fluctuations in regulating cytochrome c/cytochrome c oxidase electron transfer.

    Science.gov (United States)

    Alvarez-Paggi, Damian; Zitare, Ulises; Murgida, Daniel H

    2014-07-01

    In this overview we present recent combined electrochemical, spectroelectrochemical, spectroscopic and computational studies from our group on the electron transfer reactions of cytochrome c and of the primary electron acceptor of cytochrome c oxidase, the CuA site, in biomimetic complexes. Based on these results, we discuss how protein dynamics and thermal fluctuations may impact on protein ET reactions, comment on the possible physiological relevance of these results, and finally propose a regulatory mechanism that may operate in the Cyt/CcO electron transfer reaction in vivo. This article is part of a Special Issue entitled: 18th European Bioenergetic Conference.