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Sample records for interfacial electron transfer

  1. Facile Interfacial Electron Transfer of Hemoglobin

    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

  2. Theory of plasmon enhanced interfacial electron transfer

    Wang, Luxia; May, Volkhard

    2015-04-01

    A particular attempt to improve the efficiency of a dye sensitized solar cell is it's decoration with metal nano-particles (MNP). The MNP-plasmon induced enhancement of the local field enlarges the photoexcitation of the dyes and a subsequent improvement of the charge separation efficiency may result. In a recent work (2014 J. Phys. Chem. C 118 2812) we presented a theory of plasmon enhanced interfacial electron transfer for perylene attached to a TiO2 surface and placed in the proximity of a spherical MNP. These earlier studies are generalized here to the coupling of to up to four MNPs and to the use of somewhat altered molecular parameters. If the MNPs are placed close to each other strong hybridization of plasmon excitations appears and a broad resonance to which molecular excitations are coupled is formed. To investigate this situation the whole charge injection dynamics is described in the framework of the density matrix theory. The approach accounts for optical excitation of the dye coupled to the MNPs and considers subsequent electron injection into the rutile TiO2-cluster. Using a tight-binding model for the TiO2-system with about 105 atoms the electron motion in the cluster is described. We again consider short optical excitation which causes an intermediate steady state with a time-independent overall probability to have the electron injected into the cluster. This probability is used to introduce an enhancement factor which rates the influence of the MNP. Values larger than 500 are obtained.

  3. Electron Transfer Phenomena in Interfacial Bioelectrochemistry

    Baier, Claudia

    2011-01-01

    Biomolecules at the solid-liquid interface have been investigated using electrochemical measurement techniques such as cyclic voltammetry and electrochemical scanning probe microscopies. Structure and function of the biomolecules, depending on the electron transfer and the used electrode material could be studied down to a single molecule level. Besides investigating natural electroactive proteins, e.g. the metalloprotein azurin or the iron storage protein ferritin, a method has been develope...

  4. Interfacial Electron Transfer into Functionalized Crystalline Polyoxotitanate Nanoclusters

    Snoeberger, Robert C.; Young, Karin J.; Tang, Jiji; Allen, Laura J.; Crabtree, Robert H.; Brudvig, Gary W.; Coppens, Philip; Batista, Victor S.; Jason B. Benedict

    2012-01-01

    Interfacial electron transfer (IET) between a chromophore and a semi-conductor nanoparticle is one of the key processes in a dye sensitized solar cell. Theoretical simulations of the electron transfer in polyoxotitanate nanoclusters Ti17O24(OPri)20 (Ti17) functionalized with four para-nitrophenyl acetylacetone (NPA-H) adsorbates, of which the atomic structure has been fully established by X-ray diffraction measurements, are presented. Complementary experimental information showing IET has bee...

  5. Correlated Single Quantum Dot Blinking and Interfacial Electron Transfer Dynamics

    Jin, Shengye; Hsiang, Jung-Cheng; Zhu, Haiming; Song, Nianhui; Dickson, Robert M.; Lian, Tianquan

    2010-01-01

    The electron transfer (ET) dynamics from core/multi-shell (CdSe/CdS3MLZnCdS2MLZnS2ML) quantum dots (QDs) to adsorbed Fluorescein (F27) molecules have been studied by single particle spectroscopy to probe the relationship between single QD interfacial electron transfer and blinking dynamics. Electron transfer from the QD to F27 and the subsequent recombination were directly observed by ensemble-averaged transient absorption spectroscopy. Single QD-F27 complexes show correlated fluctuation of f...

  6. Nanoscale and single-molecule interfacial electron transfer

    Hansen, Allan Glargaard; Wackerbarth, Hainer; Nielsen, Jens Ulrik; Zhang, Jingdong; Kuznetsov, A.M.; Ulstrup, Jens

    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 for...... comprehensive later theoretical work and data interpretation in many areas of chemistry, electrochemistry, and biology. We discuss here some new areas of theoretical electrochemical ET science, with focus on nanoscale electrochemical and bioelectrochemical sciences. Particular attention is given to in situ...

  7. Interfacial electron transfer into functionalized crystalline polyoxotitanate nanoclusters.

    Snoeberger, Robert C; Young, Karin J; Tang, Jiji; Allen, Laura J; Crabtree, Robert H; Brudvig, Gary W; Coppens, Philip; Batista, Victor S; Benedict, Jason B

    2012-05-30

    Interfacial electron transfer (IET) between a chromophore and a semiconductor nanoparticle is one of the key processes in a dye-sensitized solar cell. Theoretical simulations of the electron transfer in polyoxotitanate nanoclusters Ti(17)O(24)(OPr(i))(20) (Ti(17)) functionalized with four p-nitrophenyl acetylacetone (NPA-H) adsorbates, of which the atomic structure has been fully established by X-ray diffraction measurements, are presented. Complementary experimental information showing IET has been obtained by EPR spectroscopy. Evolution of the time-dependent photoexcited electron during the initial 5 fs after instantaneous excitation to the NPA LUMO + 1 has been evaluated. Evidence for delocalization of the excitation over multiple chromophores after excitation to the NPA LUMO + 2 state on a 15 fs time scale is also obtained. While chromophores are generally considered electronically isolated with respect to neighboring sensitizers, our calculations show that this is not necessarily the case. The present work is the most comprehensive study to date of a sensitized semiconductor nanoparticle in which the structure of the surface and the mode of molecular adsorption are precisely defined. PMID:22548416

  8. The microwave-look into the photo electrode: What can we learn about interfacial electron transfer?

    By combining photo-electrochemical and photo-induced microwave conductivity measurements, information on potential dependent minority charge carrier accumulation, on interfacial minority carrier concentration and on interfacial charge transfer rates can be obtained. It suggests a correlation between electron transfer processes and accumulated charge carriers dominated by non-equilibrium conditions. This is inconsistent with the general assumptions leading to the classical Marcus-Gerischer electron transfer at electrodes, conceived for weak interaction, quasi-equilibrium and absence of polarisability effects. It is considered only to be applicable in special situations. A non-linear interfacial electron transfer theory, the properties of which are outlined, will on the other hand open the potential for new phenomena. They include faster (stimulated), and cooperative electron transfer. The latter, which is excluded by the classical theory, requires non linear dynamic feedback polarisability, which will have to be developed on the basis of structural-electronic considerations for semiconductor interfaces to become highly catalytic

  9. Theory of the Control of Ultrafast Interfacial Electron Transfer

    Rasmussen, Andrew Musso

    This dissertation describes the theoretial exploration of electron transfer (ET) processes at the interface between bulk and molecular or nanoscale materials. Analysis of simple model Hamiltonians, those for the two- and three-level electronic systems as well as for a single electronic level coupled to a continuum, inform an understanding of electron transfer in nontrivial systems. A new treatment of the three-level system at an undergraduate level encapsulates the hopping and superexchange mechanisms of electron transfer. The elegance of the behavior of ET from a single-level/continuum system precedes a treatment of the reverse process---quasicontinuum-to-discrete level ET. This reverse process, relevant to ET from a bulk material to a semiconductor quantum dot (QD) offers a handle for the coherent control of ET at an interface: the shape of an electronic wavepacket within the quasicontinuum. An extension of the single-level-to-continuum ET process is the injection of an electron from a QD to a wide-bandgap semiconductor nanoparticle (NP). We construct a minimal model to explain trends in ET rates at the QD/NP interface as a function of QD size. Finally, we propose a scheme to gate ET through a molecular junction via the coherent control of the torsional mode(s) of a linking molecule within the junction.

  10. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    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 to...

  11. Interfacial Electron Transfer and Transient Photoconductivity Studied with Terahertz Spectroscopy

    Milot, Rebecca Lee

    Terahertz spectroscopy is distinguished from other far infrared and millimeter wave spectroscopies by its inherent phase sensitivity and sub-picosecond time resolution making it a versatile technique to study a wide range of physical phenomena. As THz spectroscopy is still a relatively new field, many aspects of THz generation mechanisms have not been fully examined. Using terahertz emission spectroscopy (TES), THz emission from ZnTe(110) was analyzed and found to be limited by two-photon absorption and free-carrier generation at high excitation fluences. Due to concerns about the continued use of fossil fuels, solar energy has been widely investigated as a promising source of renewable energy. Dye-sensitized solar cells (DSSCs) have been developed as a low-cost alternative to conventional photovoltaic solar cells. To solve the issues of the intermittency and inefficient transport associated with solar energy, researchers are attempting to adapt DSSCs for water oxidation and chemical fuel production. Both device designs incorporate sensitizer molecules covalently bound to metal oxide nanoparticles. The sensitizer, which is comprised of a chromophore and anchoring group, absorbs light and transfers an electron from its excited state to the conduction band of the metal oxide, producing an electric current. Using time-resolved THz spectroscopy (TRTS), an optical pump/THz probe technique, the efficiency and dynamics of electron injection from sensitizers to metal oxides was evaluated as a function of the chromophore, its anchoring group, and the metal oxide identity. Experiments for studying fully functioning DSSCs and water oxidation devices are also described. Bio-inspired pentafluorophenyl porphyrin chromophores have been designed and synthesized for use in photoelectrochemical water oxidation cells. Influences on the efficiency and dynamics of electron injection from the chromophores into TiO2 and SnO2 nanoparticles due to changes in both the central substituent to the porphyrin ring and degree of fluorination of ring substituents were analyzed. Due to the high reduction potentials of these sensitizers, injection into TiO2 was generally not observed. Injection timescales from the porphyrins into SnO2 depended strongly on the identity of the central substituent and were affected by competition with excited-state deactivation processes. The carboxylate anchoring group is commonly used to bind DSSC sensitizers to metal oxide surfaces but is typically not stable under the aqueous and oxidative conditions required for water oxidation. Electron injection efficiency and water stability of several alternative anchoring groups, including phosphonic acid, hydroxamic acid, acerylacetone, and boronic acid, were evaluated. While all of the anchoring groups exhibited water stability superior to carboxylate, the hydroxamate anchor had the best combination of ease of handling and electron injection efficiency. The effects on photoconductivity due to metal oxide morphology and the addition of dopants were also analyzed. Mixtures of anatase and rutile TiO 2 nanoparticles are known to exhibit cooperative effects which increase the efficiency of DSSCs and photocatalysis relative to the pure-phase materials. Through analysis of TRTS measurements, the mechanism of this synergistic effect was found to involve electron transfer from the lower-mobility, higher surface area rutile nanoparticles to anatase particles, resulting in a higher charge collection efficiency. In addition to morphology, doping has been investigated as a means of expanding the spectral range of visible absorption of photocatalysts. Doping ZnO nanowires with manganese(II) was found to significantly decrease the electron mobility, and doping with cobalt(II) increased the timescale for electron trapping. These differences can be understood by considering the changes to the band structure of ZnO effected by the dopants. Preliminary analyses of the solvent and electrolyte dependence on the electron injection rate and efficiency suggest that electron injection can be affected by several components of a DSSC or water oxidation cell in addition to the sensitizer and metal oxide. Performing TRTS studies on fully assembled devices will therefore be essential for determining the relationship between electron injection and device efficiency.

  12. Single-molecule interfacial electron transfer dynamics of porphyrin on TiO2 nanoparticles: dissecting the interfacial electric field and electron accepting state density dependent dynamics.

    Rao, Vishal Govind; Dhital, Bharat; Lu, H Peter

    2015-12-01

    Single-molecule photon-stamping spectroscopy correlated with electrochemical techniques was used to dissect complex interfacial electron transfer (ET) dynamics by probing an m-ZnTCPP molecule anchored to a TiO2 NP surface while electrochemically controlling the energetically-accessible surface states of TiO2 NPs. Application of negative potential increases the electron density in TiO2 NPs, resulting in hindered forward ET and enhanced backward ET due to the changes in the interfacial electric field and the occupancy of acceptor states. PMID:26434919

  13. Interfacial electron transfer as a significant step in photoelectrochemical reactions on some semiconductors

    Bockris, J. O'M.; Uosaki, K.; Kita, H.

    1981-02-01

    Photoelectrochemical kinetics at the semiconductor-solution interface has been considered in all treatments in the literature, except one, to be rate controlled by processes inside the semiconductor. Evidence is presented which suggest that, at least for cathodic reactions on p-CdTe, the rate determining step is interfacial electron transfer, and a part of the total potential difference at the interface exists in the Helmholtz layer.

  14. Interfacial electronic charge transfer and density of states in short period Cu/Cr multilayers; TOPICAL

    Nanometer period metallic multilayers are ideal structures to investigate electronic phenomena at interfaces between metal films since interfacial atoms comprise a large atomic fraction of the samples. The Cu/Cr binary pair is especially suited to study the interfaces in metals since these elements are mutually insoluble, thus eliminating mixing effects and compound formation and the lattice mismatch is very small. This allows the fabrication of high structural quality Cu/Cr multilayers that have a structure which can be approximated in calculations based on idealized atomic arrangements. The electronic structure of the Cu and the Cr layers in several samples of thin Cu/Cr multilayers were studied using x-ray absorption spectroscopy (XAS). Total electron yield was measured and used to study the white lines at the Cu L(sub 2) and L(sub 3) absorption edges. The white lines at the Cu absorption edges are strongly related to the unoccupied d-orbitals and are used to calculate the amount of charge transfer between the Cr and Cu atoms in interfaces. Analysis of the Cu white lines show a charge transfer of 0.026 electrons/interfacial Cu atom to the interfacial Cr atoms. In the Cu XAS spectra we also observe a van Hove singularity between the L(sub 2) and L(sub 3) absorption edges as expected from the structural analysis. The absorption spectra are compared to partial density of states obtained from a full-potential linear muffin-tin orbital calculation. The calculations support the presence of charge transfer and indicate that it is localized to the first two interfacial layers in both Cu and Cr

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

    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.

  16. Donor-Dependent Kinetics of Interfacial Proton-Coupled Electron Transfer.

    Jackson, Megan N; Surendranath, Yogesh

    2016-03-01

    The effect of the proton donor on the kinetics of interfacial concerted proton-electron transfer (CPET) to polycrystalline Au was probed indirectly by studying the rate of hydrogen evolution from trialkylammonium donors with different steric profiles, but the same pKa. Detailed kinetic studies point to a mechanism for HER catalysis that involves rate-limiting CPET from the proton donor to the electrode surface, allowing this catalytic reaction to serve as a proxy for the rate of interfacial CPET. In acetonitrile electrolyte, triethylammonium (TEAH(+)) displays up to 20-fold faster CPET kinetics than diisopropylethylammonium (DIPEAH(+)) at all measured potentials. In aqueous electrolyte, this steric constraint is largely lifted, suggesting a key role for water in mediating interfacial CPET. In acetonitrile, TEAH(+) also displays a much larger transfer coefficient (β = 0.7) than DIPEAH(+) (β = 0.4), and TEAH(+) displays a potential-dependent H/D kinetic isotope effect that is not observed for DIPEAH(+). These results demonstrate that proton donor structure strongly impacts the free energy landscape for CPET to extended solid surfaces and highlight the crucial role of the proton donor in the kinetics of electrocatalytic energy conversion reactions. PMID:26862666

  17. Interfacial electron transfer dynamics of ru(II)-polypy6ridine sensitized TiO2

    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.

  18. Interfacial Electron Transfer in TiO2 Surfaces Sensitized with Ru(II)-Polypyridine Complexes

    Jakubikova, Elena; Snoeberger, Robert C., III; Batista, Victor S.; Martin, Richard L.; Batista, Enrique R.

    2009-07-01

    Studies of interfacial electron transfer (IET) in TiO2 surfaces functionalized with (1) pyridine-4-phosphonic acid, (2) [Ru(tpy)(tpy(PO3H2))]2+, and (3) [Ru(tpy)(bpy)(H2O)-Ru(tpy)(tpy(PO3H2))]4+ (tpy = 2,2':6,2''-terpyridine; bpy = 2,2'-bipyridine) are reported. We characterize the electronic excitations, electron injection time scales, and interfacial electron transfer (IET) mechanisms through phosphonate anchoring groups. These are promising alternatives to the classic carboxylates of conventional dye-sensitized solar cells since they bind more strongly to TiO2 surfaces and form stable covalent bonds that are unaffected by humidity. Density functional theory calculations and quantum dynamics simulations of IET indicate that electron injection in 1-TiO2 can be up to 1 order of magnitude faster when 1 is attached to TiO2 in a bidentate mode (? 60 fs) than when attached in a monodentate motif (? 460 fs). The IET time scale also depends strongly on the properties of the sensitizer as well as on the nature of the electronic excitation initially localized in the adsorbate molecule. We show that IET triggered by the visible light excitation of 2-TiO2 takes 1-10 ps when 2 is attached in a bidentate mode, a time comparable to the lifetime of the excited electronic state. IET due to visible-light photoexcitation of 3-TiO2 is slower, since the resulting electronic excitation remains localized in the tpy-tpy bridge that is weakly coupled to the electronic states of the conduction band of TiO2. These results are particularly valuable to elucidate the possible origin of IET efficiency drops during photoconversion in solar cells based on Ru(II)-polypyridine complexes covalently attached to TiO2 thin films with phosphonate linkers.

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

    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.

  20. Interfacial electrochemical electron transfer in biology – Towards the level of the single molecule

    Zhang, Jingdong; Chi, Qijin; Hansen, Allan Glargaard; Jensen, Palle Skovhus; Salvatore, Princia; Ulstrup, Jens

    2012-01-01

    unprecedented resolution, opening a new area of single-molecule bioelectrochemistry. We consider first in situ STM of small redox molecules, followed by in situ STM of thiol-based SAMs as molecular views of bioelectrochemical environments. We then address electron transfer metalloproteins, and multi......Physical electrochemistry has undergone a remarkable evolution over the last few decades, integrating advanced techniques and theory from solid state and surface physics. Single-crystal electrode surfaces have been a core notion, opening for scanning tunnelling microscopy directly in aqueous...... electrolyte (in situ STM). Interfacial electrochemistry of metalloproteins is presently going through a similar transition. Electrochemical surfaces with thiol-based promoter molecular monolayers (SAMs) as biomolecular electrochemical environments and the biomolecules themselves have been mapped with...

  1. Linker dependence of interfacial electron transfer rates in Fe(II)-polypyridine sensitized solar cells

    Bowman, David N.; Mukherjee, Sriparna; Barnes, Lyndsay J.; Jakubikova, Elena

    2015-04-01

    Dye-sensitized solar cells (DSSCs) convert solar energy to electricity employing dye molecules attached to a semiconductor surface. Some of the most efficient DSSCs use Ru-based chromophores. Fe-based dyes represent a cheaper and more environmentally friendly alternative to these expensive and toxic dyes. The photoactive state of Fe-based chromophores responsible for charge-separation at the dye-semiconductor interface is, however, deactivated on a sub-picosecond time scale via the intersystem crossing (ISC) into a manifold of low-lying photo-inactive quintet states. Therefore, development of Fe-based dyes capable of fast interfacial electron transfer (IET) leading to efficient charge separation on a time scale competitive with the ISC events is important. This work investigates how linker groups anchoring a prototypical Fe-based dye [Fe(bpy-L)2(CN)2] (bpy = 2,2‧-bipyridine, L = linker group) onto the TiO2 semiconductor surface influence the IET rates in the dye-semiconductor assemblies. Linker groups investigated include carboxylic acid, phosphonic acid, hydroxamate, catechol, and acetylacetonate. We employ time-dependent density functional theory (TD-DFT) to obtain absorption spectra of [Fe(bpy-L)2(CN)2] with each linker, and quantum dynamics simulations to investigate the IET rates between the dye and the (101) TiO2 anatase surface. For all attachments, TD-DFT calculations show similar absorption spectra with two main bands corresponding to the metal-to-ligand charge transfer transitions. The quantum dynamics simulations predict that the utilization of the hydroxamate linker instead of the commonly used carboxylic acid linker will lead to a more efficient IET and better photon-to-current conversion efficiencies in Fe(II)-polypyridine sensitized solar cells.

  2. Interfacial electron transfer and bioelectrocatalysis of carbonized plant material as effective anode of microbial fuel cell

    ABSTRACT: Effective use of natural materials to fabricate porous carbonaceous structures for anodes of microbial fuel cells (MFCs) has a high potential for substantial cost reduction in MFC. In this study, three kinds of plant materials, i.e. king mushroom, wild mushroom and corn stem, were investigated for fabrication of conductive electrode materials by simple carbonization procedures. Structure–reactivity relationships of these electrodes were systematically studied with electrochemical redox probe ([Fe(CN)6]3−/4−) and biofilm electroactivity. The electrochemical and bioelectrochemical accessibilities of the carbonized electrodes were evaluated by impedance, cyclic voltammetry and chronoamperometry techniques in order to study the electron transfer rate (Kapp), charge transfer resistances, oxidative current density and bioelectroactive moieties. The results showed that the electron transfer resistance (Rct) was 94 Ω for carbonized corn stem electrode with an electron transfer rate (Kapp) of 3.44 × 10−2 cm s−1 for Fe2+/Fe3+ redox probe. Higher bioelectroactivity (9.29 × 10−8 mol cm−2) was found from biofilm on carbonized corn stem (Rbiofilm, 45 Ω) with an electron transfer rate (bacteria-anode) of 63 × 10−5 cm s−1. The maximum bioelectrocatalytic current (imax) of 3.12 mA cm−2 was obtained on carbon electrode derived from corn stem. That is 8 times higher than plain graphite electrode. The porous architecture, high electron transfer rate and high electroactive biofilm growth are attributes that qualify natural-material carbon anodes as low-cost alternative for MFC

  3. Dynamics and mechanisms of interfacial photoinduced electron transfer processes of third generation photovoltaics and photocatalysis

    Bauer, Christophe; Teuscher, Jol; Brauer, Jan Cornelius; Punzi, Angela; Marchioro, Arianna; Ghadiri, Elham; De Jonghe, Jelissa; Wielopolski, Mateusz; Banerji, Natalie; Moser, Jacques-E

    2011-01-01

    Photoinduced electron transfer (PET) across molecular/bulk interfaces has gained attention only recently and is still poorly understood. These interfaces offer an excellent case study, pertinent to a variety of photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices. They play in particular a key role in the emerging fields of third-generation photovoltaic energy converters and artificial photosynthetic syste...

  4. Ab Initio Modeling of Fe(II) Adsorption and Interfacial Electron Transfer at Goethite (?-FeOOH) Surfaces

    Alexandrov, Vitali Y.; Rosso, Kevin M.

    2015-01-01

    Goethite (?-FeOOH) surfaces represent one of the most ubiquitous redox-active interfaces in the environment, playing an important role in biogeochemical metal cycling and contaminant residence in the subsurface. Fe(II)-catalyzed recrystallization of goethite is a fundamental process in this context, but the proposed Fe(II)aq-Fe(III)goethite electron and iron atom exchange mechanism of recrystallization remains poorly understood at the atomic level. We examine the adsorption of aqueous Fe(II) and subsequent interfacial electron transfer (ET) between adsorbed Fe(II) and structural Fe(III) at the (110) and (021) goethite surfaces using density functional theory calculations including Hubbard U corrections (DFT+U) aided by ab initio molecular dynamics simulations. We investigate various surface sites for the adsorption of Fe2+(H2O)6 in different coordination environments. Calculated energies for adsorbed complexes at both surfaces favor monodentate complexes with reduced 4- and 5-fold coordination over higher-dentate structures and 6- fold coordination. The hydrolysis of H2O ligands is observed for some pre-ET adsorbed Fe(II) configurations. ET from the adsorbed Fe(II) into the goethite lattice is calculated to be energetically uphill always, but simultaneous proton transfer from H2O ligands of the adsorbed complexes to the surface oxygen species stabilizes post-ET states. We find that surface defects such as oxygen vacancies near the adsorption site also can stabilize post-ET states, enabling the Fe(II)aq-Fe(III)goethite interfacial electron transfer reaction implied from experiments to proceed.

  5. Water-Stable, Hydroxamate Anchors for Functionalization of TiO2 Surfaces with Ultrafast Interfacial Electron Transfer

    McNamara, W.R.; Milot, R.L.; Song, H.; Snoeberger III, R.C.; Batista, Victor S.; Schmuttenmaer, C.A.; Brudvig, Gary W; Crabtree, Robert H

    2010-01-01

    A novel class of derivatized hydroxamic acid linkages for robust sensitization of TiO{sub 2} nanoparticles (NPs) under various aqueous conditions is described. The stability of linkages bound to metal oxides under various conditions is important in developing photocatalytic cells which incorporate transition metal complexes for solar energy conversion. In order to compare the standard carboxylate anchor to hydroxamates, two organic dyes differing only in anchoring groups were synthesized and attached to TiO{sub 2} NPs. At acidic, basic, and close to neutral pH, hydroxamic acid linkages resist detachment compared to the labile carboxylic acids. THz spectroscopy was used to compare ultrafast interfacial electron transfer (IET) into the conduction band of TiO{sub 2} for both linkages and found similar IET characteristics. Observable electron injection and stronger binding suggest that hydroxamates are a suitable class of anchors for designing water stable molecules for functionalizing TiO{sub 2}.

  6. Molecular monolayers and interfacial electron transfer of pseudomonas aeruginosa azurin on Au(111)

    Chi, Qijin; Zhang, Jingdong; Nielsen, Jens Ulrik; Friis, Esben P.; Chorkendorff, Ib; Canters, G. W.; Andersen, Jens Enevold Thaulov; Ulstrup, Jens

    2000-01-01

    disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron...... long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn...

  7. Electron Transfer as a Probe of the Interfacial Quantum Dot-Organic Molecule Interaction

    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.

  8. Gold nanoparticle assisted assembly of a heme protein for enhancement of long-range interfacial electron transfer

    Jensen, Palle Skovhus; Chi, Qijin; Grumsen, Flemming Bjerg; Abad, J.M.; Horsewell, Andy; Schiffrin, D.J.; Ulstrup, Jens

    2007-01-01

    and characterization of water-soluble gold nanoparticles (AuNPs) with core diameter 3-4 nm and their application for the enhancement of long-range interfacial ET of a heme protein. Gold nanoparticles were electrostatically conjugated with cyt c to form nanoparticle-protein hybrid ET systems with well......-defined stoichiometry. The systems were investigated in homogeneous solution and at liquid/solid interface. Conjugation of cyt c results in a small but consistent broadening of the nanoparticle plasmon band. This phenomenon can be explained in terms of long-range electronic interactions between the gold nanoparticle...... bioelectronics. A key challenge in molecular bioelectronics is to improve the efficiency of long-range charge transfer. The present work shows that this can be achieved by nanoparticle (NP) assisted assembly of cytochrome c (cyt c) on macroscopic single-crystalline electrode surfaces. We present the synthesis...

  9. Interfacial Electrochemical Electron Transfer Processes in Bacterial Biofilm Environments on Au(111)

    Hu, Yifan; Zhang, Jingdong; Ulstrup, Jens

    2010-01-01

    We have studied Streptococcus mutans (S. mutans) biolilm growth and growth inhibition on Au(111)-surfaces using atomic force microscopy (AFM) and interfacial electrochemistry of a number of redox probe molecules. AFM of the biofilm growth and growth inhibition on both mica and Au(111)-surfaces was...

  10. Effect of strong coupling on interfacial electron transfer dynamics in dye-sensitized TiO2 semiconductor nanoparticles

    Hirendra N Ghosh

    2007-03-01

    Dynamics of interfacial electron transfer (ET) in ruthenium polypyridyl complex [{bis-(2,2'-bpy)-(4-[2-(4'-methyl-[2,2']bipyridinyl-4-yl)-vinyl]-benzene-1,2-diol)}ruthenium(II) hexafluorophosphate] (Ru-cat) and 5,10,15-tris phenyl-20-(3,4-dihydroxy benzene) porphyrin (TPP-cat)-sensitized TiO2 nanoparticles have been investigated using femtosecond transient absorption spectroscopic detection in the visible and near-infrared region. We have observed that both Ru-cat and TPP-cat are coupled strongly with the TiO2 nanoparticles through their pendant catechol moieties. We have observed a single exponential and pulse-width limited (< 100 fs) electron injection from nonthermalized-excited states of Ru-complex. Here electron injection competes with the singlet-triplet manifold relaxation due to strong coupling of catecholate binding, which is a unique observation. Optical absorption measurements indicate that the catechol moiety interacts with TiO2 nanoparticles showing the characteristic pure catechol-TiO2 charge-transfer (CT) band in the visible region. Transient absorption studies on TPP-cat/TiO2 system exciting both the Soret band at 400 nm and the Q-band at 800 nm have been carried out to determine excitation wavelength-dependence on ET dynamics. The reaction channel for the electron-injection process has been found to be different for both the excitation wavelengths. Excitation at 800 nm, is found directly populate directly the excited CT state from where diffusion of electrons into the conduction band takes place. On the other hand, excitation at 400 nm light excites both the CT band of cat-TiO2 and also Soret band of TPP-cat.

  11. Interfacial electron transfer between the photoexcited porphyrin molecule and TiO2 nanoparticles: effect of catecholate binding.

    Ramakrishna, G; Verma, Sandeep; Jose, D Amilan; Kumar, D Krishna; Das, Amitava; Palit, Dipak K; Ghosh, Hirendra N

    2006-05-11

    Interfacial electron transfer (ET) dynamics of 5,10,15-trisphenyl-20-(3,4-dihydroxybenzene) porphyrin (TPP-cat) adsorbed on TiO2 nanoparticles has been studied by femtosecond transient absorption spectroscopy in the visible and near-IR region exciting at 400 and 800 nm. TPP-cat molecule forms a charge transfer (CT) complex with TiO2 nanoparticles through the catechol moiety with the formation of a five-membered ring. Optical absorption measurements have shown that the Q-band of TPP-cat interacts strongly with TiO2 due to chelation; however, the Soret band is affected very little. Optical absorption measurements indicate that the catechol moiety also interacts with TiO2 nanoparticles showing the characteristic band of pure catechol-TiO2 charge transfer (CT) in the visible region. Electron injection has been confirmed by monitoring the cation radical, instant bleach, and injected electron in the conduction band of TiO2 nanoparticles. Electron injection time has been measured to be < 100 fs and recombination kinetics has been best fitted with a multiexponential function, where the majority of the injected electrons come back to the parent cation radical with a time constant of approximately 800 fs for both excitation wavelengths. However, the reaction channel for the electron injection process has been found to be different for both wavelengths. Excitation at 800 nm, found to populate the CT state of the Q-band, and from the photoexcited CT state electron injection into the conduction band, takes place through diffusion. On the other hand, with excitation at 400 nm, a complicated reaction channel takes place. Excitation with 400 nm light excites both the CT band of Cat-TiO2 and also the Soret band of TPP-cat. We have discussed the reaction path in the TPP-cat/TiO2 system after exciting with both 400 and 800 nm laser light. We have also compared ET dynamics by exciting at both wavelengths. PMID:16671709

  12. Tuning Interfacial Electron Transfer in Nanostructured Cuprous Oxide Photoelectrochemical Cells with Charge-Selective Molecular Coatings.

    Haynes, Keith M; Kratch, Kaci C; Stovall, Sean D; Obondi, Christopher O; Thurber, Casey R; Youngblood, W Justin

    2015-08-01

    The coating of nanostructured films of cuprous oxide with electroactive molecules strongly affects their photoelectrochemical performance in nonaqueous photocells, with photocurrent density increased up to an order of magnitude relative to bare cuprous oxide films or almost completely suppressed, depending on the choice of molecular adsorbant. Among adsorbants that enhance photocurrent, a strong variance of photoelectrochemical behavior is observed with changes in the molecular structure of the sensitizer, associated with differences in the reorganization energy and molecular size, which are interpreted to enhance forward electron transport and impede electrolyte/photocathode recombination, respectively. These results demonstrate that nanostructured cuprous oxide is a promising cathode material for p-type dye-sensitized solar cells. PMID:26075573

  13. Photosensitization of nanoparticulate TiO2 using a Re(I)-polypyridyl complex: studies on interfacial electron transfer in the ultrafast time domain.

    Kar, Prasenjit; Banerjee, Tanmay; Verma, Sandeep; Sen, Anik; Das, Amitava; Ganguly, Bishwajit; Ghosh, Hirendra N

    2012-06-14

    We have synthesized a new photoactive rhenium(i)-complex having a pendant catechol functionality [Re(CO)(3)Cl(L)] (1) (L is 4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) for studying the dynamics of the interfacial electron transfer between nanoparticulate TiO(2) and the photoexcited states of this Re(i)-complex using femtosecond transient absorption spectroscopy. Our steady state absorption studies revealed that complex 1 can bind strongly to TiO(2) surfaces through the catechol functionality with the formation of a charge transfer (CT) complex, which has been confirmed by the appearance of a new red-shifted CT band. The longer wavelength absorption band for 1, bound to TiO(2) through the proposed catecholate functionality, could also be explained based on the DFT calculations. Dynamics of the interfacial electron transfer between 1 and TiO(2) nanoparticles was investigated by studying kinetics at various wavelengths in the visible and near infrared regions. Electron injection into the conduction band of the nanoparticulate TiO(2) was confirmed by detection of the conduction band electron in TiO(2) ([e(-)](TiO(2)(CB))) and the cation radical of the adsorbed dye (1˙(+)) in real time as monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (<100 fs) electron injection was observed. Back electron transfer dynamics was determined by monitoring the decay kinetics of 1˙(+) and . PMID:22549294

  14. Autonomous control of interfacial electron transfer and the activation of DNA machines by an oscillatory pH system.

    Qi, Xiu-Juan; Lu, Chun-Hua; Liu, Xiaoqing; Shimron, Simcha; Yang, Huang-Hao; Willner, Itamar

    2013-10-01

    An oscillatory pH system is implemented to drive oscillatory pH-switchable DNA machines and to control pH-stimulated electron transfer at electrode surfaces. The oscillatory pH system drives the autonomous opening and closure of DNA tweezers and activates a DNA pendulum by the pH-stimulated formation and dissociation of i-motif structures. Also, a sequence-programmed nucleic acid monolayer-functionalized electrode undergoes autonomous oscillatory pH transitions between random coil and i-motif configurations, leading to the control of electron transfer at electrode surfaces. PMID:23988015

  15. Amine-terminated ionic liquid functionalized carbon nanotubes for enhanced interfacial electron transfer of Shewanella putrefaciens anode in microbial fuel cells

    Wei, Huan; Wu, Xiao-Shuai; Zou, Long; Wen, Guo-Yun; Liu, Ding-Yu; Qiao, Yan

    2016-05-01

    An amine-terminated ionic liquid (IL-NH2) is applied to functionalize carbon nanotubes (CNTs) for improving the interfacial electron transfer of Shewanella putrefaciens (S. putrefaciens) anode in Microbial fuel cells (MFCs). The introduction of thin layer of ILs does not change the morphology of CNTs a lot but increases surface positive charges as well as nitrogen functional groups of the CNTs based anode. The CNT-IL composite not only improves the adhesion of S. putrefaciens cells but also promotes both of the flavin-mediated and the direct electron transfer between the S. putrefaciens cells and the anode. It is interesting that the CNT-IL is more favorable for the mediated electron transfer than for the direct electron transfer. The CNT-IL/carbon cloth anode delivers 3-fold higher power density than that of CNT anode and shows great long-term stability in the batch-mode S. putrefaciens MFCs. This CNT-IL could be a promising anode material for high performance MFCs.

  16. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    Zheng, Junwei

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO{sub 2} were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO{sub 2}, large photoelectrocatalytic effect for the reduction of CO{sub 2} was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO{sub 2} in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  17. Exploring the time-scale of photo-initiated interfacial electron transfer through first-principles interpretation of ultrafast X-ray spectroscopy (Presentation Recording)

    Prendergast, David; Pemmaraju, Sri Chaitanya Das

    2015-09-01

    With the advent of X-ray free electron lasers and table-top high-harmonic-generation X-ray sources, we can now explore changes in electronic structure on ultrafast time scales -- at or less than 1ps. Transient X-ray spectroscopy of this kind provides a direct probe of relevant electronic levels related to photoinitiated processes and associated interfacial electron transfer as the initial step in solar energy conversion. However, the interpretation of such spectra is typically fraught with difficulty, especially since we rarely have access to spectral standards for nonequilibrium states. To this end, direct first-principles simulations of X-ray absorption spectra can provide the necessary connection between measurements and reliable models of the atomic and electronic structure. We present examples of modeling excited states of materials interfaces relevant to solar harvesting and their corresponding X-ray spectra in either photoemission or absorption modalities. In this way, we can establish particular electron transfer mechanisms to reveal detailed working principles of materials systems in solar applications and provide insight for improved efficiency.

  18. Impact of Ga-V Codoping on Interfacial Electron Transfer in Dye-Sensitized TiO2.

    Syzgantseva, Olga A; Puska, Martti; Laasonen, Kari

    2015-07-01

    The improvement of charge transfer between an organic molecule and a semiconductor is an important and challenging goal in the fields of photovoltaics and photocatalysis. In this work, we present a time-dependent density functional theory investigation of the impact of Ga-V codoping of TiO2 on the excited-state electron injection from perylene-3-carboxylic acid. The doping is shown to raise the charge-transfer efficiency for the highest possible surface dye uptake by ?16%. The strength of the effect depends on the dopant-pair-dye separation, dopant concentration, and distribution of Ga, V atoms in TiO2. The doping of the superficial level turns out to be more favorable than those in the bulk. The changes in electron injection dynamics are attributed to the modification of accepting semiconductor levels and hybridization profile between molecular and semiconductor states. PMID:26266741

  19. Chemically Driven Interfacial Coupling in Charge-Transfer Mediated Functional Superstructures.

    Xu, Beibei; Li, Huashan; Li, Haoqi; Wilson, Andrew J; Zhang, Lin; Chen, Ke; Willets, Katherine A; Ren, Fei; Grossman, Jeffrey C; Ren, Shenqiang

    2016-04-13

    Organic charge-transfer superstructures are enabling new interfacial electronics, such as organic thermoelectrics, spin-charge converters, and solar cells. These carbon-based materials could also play an important role in spin-based electronics due to their exceptionally long spin lifetime. However, to explore these potentials a coherent design strategy to control interfacial charge-transfer interaction is indispensable. Here we report that the control of organic crystallization and interfacial electron coupling are keys to dictate external stimuli responsive behaviors in organic charge-transfer superstructures. The integrated experimental and computational study reveals the importance of chemically driven interfacial coupling in organic charge-transfer superstructures. Such degree of engineering opens up a new route to develop a new generation of functional charge-transfer materials, enabling important advance in all organic interfacial electronics. PMID:26999430

  20. Disentangling the Physical Processes Responsible for the Kinetic Complexity in Interfacial Electron Transfer of Excited Ru(II) Polypyridyl Dyes on TiO2.

    Zigler, David F; Morseth, Zachary A; Wang, Li; Ashford, Dennis L; Brennaman, M Kyle; Grumstrup, Erik M; Brigham, Erinn C; Gish, Melissa K; Dillon, Robert J; Alibabaei, Leila; Meyer, Gerald J; Meyer, Thomas J; Papanikolas, John M

    2016-04-01

    Interfacial electron transfer at titanium dioxide (TiO2) is investigated for a series of surface bound ruthenium-polypyridyl dyes whose metal-to-ligand charge-transfer state (MLCT) energetics are tuned through chemical modification. The 12 complexes are of the form Ru(II)(bpy-A)(L)2(2+), where bpy-A is a bipyridine ligand functionalized with phosphonate groups for surface attachment to TiO2. Functionalization of ancillary bipyridine ligands (L) enables the potential of the excited state Ru(III/)* couple, E(+/)*, in 0.1 M perchloric acid (HClO4(aq)) to be tuned from -0.69 to -1.03 V vs NHE. Each dye is excited by a 200 fs pulse of light in the visible region of the spectrum and probed with a time-delayed supercontiuum pulse (350-800 nm). Decay of the MLCT excited-state absorption at 376 nm is observed without loss of the ground-state bleach, which is a clear signature of electron injection and formation of the oxidized dye. The dye-dependent decays are biphasic with time constants in the 3-30 and 30-500 ps range. The slower injection rate constant for each dye is exponentially distributed relative to E(+/)*. The correlation between the exponentially diminishing density of TiO2 sub-band acceptor levels and injection rate is well described using Marcus-Gerischer theory, with the slower decay components being assigned to injection from the thermally equilibrated state and the faster components corresponding to injection from higher energy states within the (3)MLCT manifold. These results and detailed analyses incorporating molecular photophysics and semiconductor density of states measurements indicate that the multiexponential behavior that is often observed in interfacial injection studies is not due to sample heterogeneity. Rather, this work shows that the kinetic heterogeneity results from competition between excited-state relaxation and injection as the photoexcited dye relaxes through the (3)MLCT manifold to the thermally equilibrated state, underscoring the potential for a simple kinetic model to reproduce the complex kinetic behavior often observed at the interface of mesoporous metal oxide materials. PMID:26974040

  1. Interfacial area and interfacial transfer in two-phase systems. DOE final report

    Ishii, Mamoru; Hibiki, T.; Revankar, S.T.; Kim, S.; Le Corre, J.M.

    2002-07-01

    In the two-fluid model, the field equations are expressed by the six conservation equations consisting of mass, momentum and energy equations for each phase. The existence of the interfacial transfer terms is one of the most important characteristics of the two-fluid model formulation. The interfacial transfer terms are strongly related to the interfacial area concentration and to the local transfer mechanisms such as the degree of turbulence near interfaces. This study focuses on the development of a closure relation for the interfacial area concentration. A brief summary of several problems of the current closure relation for the interfacial area concentration and a new concept to overcome the problem are given.

  2. Interfacial structures - Thermodynamical and experimental studies of the interfacial mass transfer

    In the first section, we put forward hypotheses concerning the structure of the interfacial regions between two immiscible liquid phases. It appears that the longitudinal structure is comparable with that of a crystallized solid and that the transversal structure is nearest of that of a liquid. In the second section, we present a thermodynamical treatment of the irreversible phenomena in the interfacial region. The equation of evolution of a system consisting of two immiscible liquid phases are deduced. The third part allows an experimental verification of the theoretical relations. We also make clear, in certain cases, the appearance of a great 'interfacial resistance' which slows down the interfacial mass transfer. (author)

  3. Interfacial Charge Transfer States in Condensed Phase Systems.

    Vandewal, Koen

    2016-05-27

    Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified. PMID:26980308

  4. Interfacial electronic structure and charge transfer of hybrid graphene quantum dot and graphitic carbon nitride nanocomposites: insights into high efficiency for photocatalytic solar water splitting.

    Ma, Zuju; Sa, Rongjian; Li, Qiaohong; Wu, Kechen

    2016-01-14

    New metal-free carbon nanodot/carbon nitride (C3N4) nanocomposites have shown to exhibit high efficiency for photocatalytic solar water splitting. (J. Liu, et al., Science, 2015, 347, 970) However, the mechanism underlying the ultrahigh performance of these nanocomposites and consequently the possibilities for further improvements are not at present clear. In this work, we performed hybrid functional calculations and included long-range dispersion corrections to accurately characterize the interfacial electron coupling of the graphene quantum dot-graphitic carbon nitride composites (Gdot/g-C3N4). The results revealed that the band gap of Gdot/g-C3N4 could be engineered by changing the lateral size of Gdots. In particular, the C24H12/g-C3N4 composites present an ideal band gap of 1.92 eV to harvest a large part of solar light. More interestingly, a type-II heterojunction is formed at the interface of the Gdot/g-C3N4 composites, a desirable feature for enhanced photocatalytic activity. The charge redistribution at the interface leads to strong electron depletion above the Gdot sheet and electron accumulation below the g-C3N4 monolayer, potentially facilitating the separation of H2O oxidation and reduction reactions. Furthermore, we suggested that the photocatalytic performance of the Gdot/g-C3N4 nanocomposites can be further improved by decreasing the thickness of Gdots and tuning the size of Gdots. PMID:26659558

  5. Electron donor-acceptor distance dependence of the dynamics of light-induced interfacial charge transfer in the dye-sensitization of nanocrystalline oxide semiconductors

    Wenger, Bernard; Bauer, Christophe; Nazeeruddin, Mohammad K.; Comte, Pascal; Shaik M. Zakeeruddin; Gratzel, Michael; Moser, Jacques-E

    2006-01-01

    The effect of electronic and nuclear factors on the dynamics of dye-to-semiconductor electron transfer was studied employing RuII(terpy)(NCS)3 sensitizers grafted onto transparent films made of titanium dioxide nanoparticles. Various approaches were strived to understand the dependence of the kinetics of charge injection and recombination processes upon the distance separating the dye molecules and the redox active surface. A series of bridged sensitizers containing p- phenylene spacers of va...

  6. Electronic structures of TiO2-TCNE, -TCNQ, and -2,6-TCNAQ surface complexes studied by ionization potential measurements and DFT calculations: Mechanism of the shift of interfacial charge-transfer bands

    Fujisawa, Jun-ichi; Hanaya, Minoru

    2016-06-01

    Interfacial charge-transfer (ICT) transitions between inorganic semiconductors and π-conjugated molecules allow direct charge separation without loss of energy. This feature is potentially useful for efficient photovoltaic conversions. Charge-transferred complexes of TiO2 nanoparticles with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its analogues (TCNX) show strong ICT absorption in the visible region. The ICT band was reported to be significantly red-shifted with extension of the π-conjugated system of TCNX. In order to clarify the mechanism of the red-shift, in this work, we systematically study electronic structures of the TiO2-TCNX surface complexes (TCNX; TCNE, TCNQ, 2,6-TCNAQ) by ionization potential measurements and density functional theory (DFT) calculations.

  7. Pressure transfer functions for interfacial fluid problems

    Chen, Robin Ming; Walsh, Samuel

    2015-01-01

    We make a consistent derivation, from the governing equations, of the pressure transfer function in the small-amplitude Stokes wave regime and the hydrostatic approximation in the small-amplitude solitary water wave regime, in the presence of a background shear flow. The results agree with the well-known formulae in the zero vorticity case,but they incorporate the effects of vorticity through solutions to the Rayleigh equation. We extend the results to permit continuous density stratification and to internal waves between two constant-density fluids. Several examples are discussed.

  8. Investigations on interfacial dynamics with ultrafast electron diffraction

    Murdick, Ryan A.

    An ultrafast electron diffractive voltammetry (UEDV) technique is introduced, extended from ultrafast electron diffraction, to investigate the ultrafast charge transport dynamics at interfaces and in nanostructures. Rooted in Coulomb-induced refraction, formalisms are presented to quantitatively deduce the transient surface voltages (TSVs), caused by photoinduced charge redistributions at interfaces, and are applied to examine a prototypical Si/SiO2 interface, known to be susceptible to photoinduced interfacial charging The ultrafast time resolution and high sensitivity to surface charges of this electron diffractive approach allows direct elucidation of the transient effects of photoinduced hot electron transport at nanometer (˜2 nm) interfaces. Two distinctive regimes are uncovered, characterized by the time scales associated with charge separation. At the low fluence regime, the charge transfer is described by a thermally-mediated process with linear dependence on the excitation fluence. Theoretical analysis of the transient thermal properties of the carriers show that it is well-described by a direct tunneling of the laser heated electrons through the dielectric oxide layer to surface states. At higher fluences, a coherent multiphoton absorption process is invoked to directly inject electrons into the conduction band of SiO2, leading to a more efficient surface charge accumulation. A quadratic fluence dependence on this coherent, 3-photon lead electron injection is characterized by the rapid dephasing of the intermediately generated hot electrons from 2-photon absorption, limiting the yield of the consecutive 1-photon absorption by free carriers. The TSV formalism is extended beyond the simple slab geometry associated with planar surfaces (Si/SiO2), to interfaces with arbitrary geometrical features, by imposing a corrective scheme to the slab model. The validity of this treatment is demonstrated in an investigation of the charge transfer dynamics at a metal nanoparticle/self-assembled monolayer (SAM)/semiconductor interconnected structure, allowing for the elucidation of the photo-initiated charging processes (forward and backward) through the SAM, by monitoring the deflection of the associated Bragg peaks in conjunction with the UEDV extended formalism to interpret the surface voltage. The design, calibration, and implementation of a molecular beam doser (MBD), capable of layer-by-layer coverage is also presented, with preliminary investigations on interfacial ice. With the development of UEDV and implementation of the MBD, continued investigations of charge transfer in more complex interfaces can be explored, such as those pertinent to novel solar-cell device technology, as their quantum efficiencies are usually strongly dependent on an interfacial charge transfer process. As UEDV is inherently capable of probing charge and atomic motion simultaneously, systems that exhibit phenomena that are attributable to strong coupling of the atomic and electronic degrees of freedom are of particular interest for future investigations with UEDV, such as optically induced electronic phase transitions and colossal field switching in functional oxides.

  9. Electron transfer reactions

    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

  10. Interfacial electronic effects control the reaction selectivity of platinum catalysts

    Chen, Guangxu; Xu, Chaofa; Huang, Xiaoqing; Ye, Jinyu; Gu, Lin; Li, Gang; Tang, Zichao; Wu, Binghui; Yang, Huayan; Zhao, Zipeng; Zhou, Zhiyou; Fu, Gang; Zheng, Nanfeng

    2016-05-01

    Tuning the electronic structure of heterogeneous metal catalysts has emerged as an effective strategy to optimize their catalytic activities. By preparing ethylenediamine-coated ultrathin platinum nanowires as a model catalyst, here we demonstrate an interfacial electronic effect induced by simple organic modifications to control the selectivity of metal nanocatalysts during catalytic hydrogenation. This we apply to produce thermodynamically unfavourable but industrially important compounds, with ultrathin platinum nanowires exhibiting an unexpectedly high selectivity for the production of N-hydroxylanilines, through the partial hydrogenation of nitroaromatics. Mechanistic studies reveal that the electron donation from ethylenediamine makes the surface of platinum nanowires highly electron rich. During catalysis, such an interfacial electronic effect makes the catalytic surface favour the adsorption of electron-deficient reactants over electron-rich substrates (that is, N-hydroxylanilines), thus preventing full hydrogenation. More importantly, this interfacial electronic effect, achieved through simple organic modifications, may now be used for the optimization of commercial platinum catalysts.

  11. Multidimensional mechanistic modeling of interfacial heat and mass transfer

    A combined theoretical and computational study in modeling multidimensional, diabatic vapor/liquid flows is presented. Models have been developed governing kinematic aspects of multiphase flow as well as interfacial mass and heat transfer for flows of condensable gas (vapor) and liquids. The modeling formulation is based on the Reynolds averaged Navier-Stokes (RANS) type multi-field approach which utilizes a complete set of conservation equations for each fluid component 1. The modeled interfacial interactions include energy, mass, and momentum transfer. Emphasis in the model development work has been placed on the mechanisms governing coupled interfacial heat and mass transfer between the liquid and vapor fields (condensation and/or boiling). A method for tracking changes in bubble size is presented and tested. Locally based models of multidimensional effects have been analyzed, including distributions of fluid temperatures and volume fractions. The overall model accounts for both kinematic and thermodynamic nonequilibrium between the component fluids including superheated vapor. The model has been implemented in the NPHASE-CMFD computer code. Results from the kinematic model are compared to experimental data and good agreement is demonstrated. The heat and mass transfer model is parametrically tested to show the multidimensional effects on the rate of heat and mass transfer. These effects are explained in terms of local characteristics of the two-phase flow. The model is applied to a scenario of saturated vapor injected into a subcooled flow through a heated, porous wall. This provides a reasonable approximation to subcooled boiling. The results are found to be dependent on the partitioning of the wall heat flux between direct liquid heating and vapor generation. However, the observed dependencies are explained and the modeling is considered consistent. (authors)

  12. Electronic structures of interfacial states formed at polymeric semiconductor heterojunctions

    Huang, Ya-Shih; Westenhoff, Sebastian; Avilov, Igor; Sreearunothai, Paiboon; Hodgkiss, Justin M.; Deleener, Caroline; Friend, Richard H.; Beljonne, David

    2008-06-01

    Heterojunctions between organic semiconductors are central to the operation of light-emitting and photovoltaic diodes, providing respectively for electron-hole capture and separation. However, relatively little is known about the character of electronic excitations stable at the heterojunction. We have developed molecular models to study such interfacial excited electronic excitations that form at the heterojunction between model polymer donor and polymer acceptor systems: poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine) (PFB) with poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), and poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) with F8BT. We find that for stable ground-state geometries the excited state has a strong charge-transfer character. Furthermore, when partly covalent, modelled radiative lifetimes (~10-7s) and off-chain axis polarization (30?) match observed `exciplex' emission. Additionally for the PFB:F8BT blend, geometries with fully ionic character are also found, thus accounting for the low electroluminescence efficiency of this system.

  13. Study of Interfacial Mass Transfer on Vapor Bubbles in Microgravity

    Johannes Straub

    2005-03-01

    Full Text Available The knowledge of interfacial heat and mass transfer is important for environmental and technical applications, especially nowadays for numerical simulations of two phase problems. However, the data available up to now are inconsistent, because most experiments performed on earth suffer under buoyancy and convection, and thus the boundary conditions at the evaluation could not clearly be defined. Therefore, we seized the opportunity to investigate interfacial heat and mass transfer in microgravity environment. In these experiments the growth and collapse in the overall superheated and subcooled bubles, respectively, liquid or free vapor bubbles were observed at various liquid temperature and pressure states and over periods of from a few seconds up to 300 seconds. It was for the first time that such very long periods of bubble growth could be observed. The experimental set-up allowed the control of the liquid supersaturation before the bubbles were initiated by a short heat pulse at a miniaturized heater. Therefore it was possible to perform a systematic parametric study. The measured curves for vapor bubble growth are in good agreement with our numerical simulation. Based on this model the kinetic coefficients for the evaporation and condensation according to Hertz-Knudsen have been derived from the experimental data.

  14. Interfacial charge transfer behavior of conducting polymers as contact electrode for semiconductor devices

    Kawakita, Jin; Fujikawa, Yuki; Nagata, Takahiro; Chikyow, Toyohiro

    2016-04-01

    As an alternative contact electrode material to metals, which is necessary for downsized semiconductor devices in 10 nm processes, an intrinsically conducting polymer was studied in terms of its interfacial charge-transfer behavior with an inorganic semiconductor. Polypyrrole as the conducting polymer was formed using an electrochemical technique on an oxide semiconductor and its electronic properties were evaluated using scanning probe microscopy. The experimental results showed that an ohmic contact was observed dynamically at local positions, although a Schottky barrier was expected in the static electronic state over the measurement area. From this research, the conducting polymer was found to be promising as a contact electrode.

  15. Electron transfer in proteins

    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 to the......-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....

  16. ELECTRON TRANSFER MECHANISM AT THE SOLID-LIQUID INTERFACE OF PHYLLOSILICATES

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

  17. Interfacial heat transfer in countercurrent flows of steam and water

    A study was conducted to examine the departure from equilibrium conditions with respect to direct contact condensation. A simple analytical model, which used an equilibrium factor, K, was derived. The model was structured to represent the physical dimensions of a nuclear reactor downcomer annulus, water subcooling, wall temperature, and water flow rate. In a two step process the model was first used to isolate the average interfacial heat transfer coefficient from vertical countercurrent steam/water data of Cook et al., with the aid of a Stanton number correlation. In the second step the model was assessed by regeneration of measured steam flow rates in the experiments by Cook et al., and an additional experiment of Kim. This report documents the analytical model, the derived Stanton number correlation, and the comparison of the calculated and measured steam flow rates by which the accuracy of the model was assessed

  18. Quantification of interfacial segregation by analytical electron microscopy

    The quantification of interfacial segregation by spatial difference and one-dimensional profiling is presented in general where special attention is given to the random and systematic uncertainties. The method is demonstrated for an example of Al-Al2O3 interfaces in a metal-ceramic composite material investigated by energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in a dedicated scanning transmission electron microscope. The variation of segregation measured at different interfaces by both methods is within the uncertainties, indicating a constant segregation level and interfacial phase formation. The most important random uncertainty is the counting statistics of the impurity signal whereas the specimen thickness introduces systematic uncertainties (via k factor and effective scan width). The latter could be significantly reduced when the specimen thickness is determined explicitly. (orig.)

  19. Quantification of interfacial segregation by analytical electron microscopy

    Muellejans, H

    2003-01-01

    The quantification of interfacial segregation by spatial difference and one-dimensional profiling is presented in general where special attention is given to the random and systematic uncertainties. The method is demonstrated for an example of Al-Al sub 2 O sub 3 interfaces in a metal-ceramic composite material investigated by energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in a dedicated scanning transmission electron microscope. The variation of segregation measured at different interfaces by both methods is within the uncertainties, indicating a constant segregation level and interfacial phase formation. The most important random uncertainty is the counting statistics of the impurity signal whereas the specimen thickness introduces systematic uncertainties (via k factor and effective scan width). The latter could be significantly reduced when the specimen thickness is determined explicitly. (orig.)

  20. Quantum dynamics simulations of interfacial charge-transfer in organic dye-sensitized solar cells

    Rego, Luis G. C.; da Silva, R.; Hoff, D. A.

    2013-03-01

    We describe a novel time-dependent quantum-mechanics/molecular-mechanics method for studying electron transfer in dye sensitized semiconductor interfaces, that takes into account the interacting electron-hole quantum dynamics, the underlying nuclear fluctuations and solvation dynamics. We provide a comprehensive investigation of the quantum dynamics, the electronic and the structural properties of prototypical D- π-A organic dyes sensitizing the TiO2 anatase surface, both in vacuum and solvated by liquid acetonitrile. The organic dyes are comprised of an electron donating moiety and an anchoring acceptor moiety, conjugated by thiophene bridges. Although interfacial electron transfer is very efficient, it is demonstrated that the coupling between the photoexcited electron and the hole delays the electron injection. Simulations demonstrate that the solvent screens the dye from the surface, narrowing the absorption peaks and delaying the electron injection. We have also studied several aspects that are relevant for the recombination process, such as the role played by surface defects and the interaction of redox species with the TiO2 surface, and the effect of additives. J. Phys. Chem. C 116, 21169 (2012). The authors acknowledge support from CNPq and CAPES, Brazil

  1. Relationship Between Casting Distortion, Mold Filling, and Interfacial Heat Transfer in Sand Molds

    J. K. Parker; K. A. Woodbury; T. S. Piwonka; Y. Owusu

    1999-09-30

    This project sought to determine the relationship between casting dimensions and interfacial heat transfer in aluminum alloy sand castings. The program had four parts; measurement of interfacial heat transfer coefficients in resin bonded and green sand molds, the measurement of gap formation in these molds, the analysis of castings made in varying gatings, orientations and thicknesses, and the measurement of residual stresses in castings in the as-cast and gate removed condition. New values for interfacial heat transfer coefficients were measured, a novel method for gap formation was developed, and the variation of casting dimensions with casting method, gating, and casting orientation in the mold was documented.

  2. Quantum Oscillations in an Interfacial 2D Electron Gas.

    Zhang, Bingop [Zhejiang Univ., Hangzhou (China); Lu, Ping [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Liu, Henan [Univ. of North Carolina, Charlotte, NC (United States); Lin, Jiao [Zhejiang Univ., Hangzhou (China); Ye, Zhenyu [Zhejiang Univ., Hangzhou (China); Jaime, Marcelo [Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Balakirev, Fedor F. [Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Yuan, Huiqiu [Zhejiang Univ., Hangzhou (China); Wu, Huizhen [Zhejiang Univ., Hangzhou (China); Pan, Wei [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Zhang, Yong [Univ. of North Carolina, Charlotte, NC (United States)

    2016-01-01

    Recently, it has been predicted that topological crystalline insulators (TCIs) may exist in SnTe and Pb1-xSnxTe thin films [1]. To date, most studies on TCIs were carried out either in bulk crystals or thin films, and no research activity has been explored in heterostructures. We present here the results on electronic transport properties of the 2D electron gas (2DEG) realized at the interfaces of PbTe/ CdTe (111) heterostructures. Evidence of topological state in this interfacial 2DEG was observed.

  3. Contribution to the study of interfacial mass transfers: extraction of U and Pu

    Interfacial mass transfer occuring during the extraction of uranyl and plutonium nitrates by TBP was studied by the single drop method. Limiting step in the chemical interfacial reaction. Order of this reaction is one for neutral species Pu(NO3)4 or UO2(NO3)2, in thermodynamical equilibrium with other metallic species in aqueous phase. Order of the interfacial reaction is two for TBP. The influence of HDBP on interfacial reaction was studied. The following hypothesis (the species TBP-HDBP reacts at the interface with the species UO2(DBP)2(HDBP)2) is substantiated by the experimental results

  4. Advances in electron transfer chemistry

    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

  5. Effect of modification melt treatment on casting/chill interfacial heat transfer and electrical conductivity of Al-13% Si alloy

    For successful modelling of the solidification process, a reliable heat transfer boundary condition data is required. These boundary conditions are significantly influenced by the casting and mould parameters. In the present work, the effect of sodium modification melt treatment on casting/chill interfacial heat transfer during upward solidification of an Al-13% Si alloy against metallic chills is investigated using thermal analysis and inverse modelling techniques. In the presence of chills, modification melt treatment resulted in an increase in the cooling rate of the solidifying casting near the casting/chill interfacial region. The corresponding interfacial heat flux transients and electrical conductivities are also found to be higher. This is attributed to (i) improvement in the casting/chill interfacial thermal contact condition brought about by the decrease in the surface tension of the liquid metal on addition of sodium and (ii) increase in the electronic heat conduction in the initial solidified shell due to change in the morphology of silicon from a acicular type to a fine fibrous structure and increase in the ratio of the modification rating to the secondary dendrite arm spacing

  6. A numerical investigation on the influence of liquid properties and interfacial heat transfer during microdroplet deposition onto a glass substrate

    Bhardwaj, Rajneesh; Attinger, Daniel

    2010-01-01

    This work investigates the impingement of a liquid microdroplet onto a glass substrate at different temperatures. A finite-element model is applied to simulate the transient fluid dynamics and heat transfer during the process. Results for impingement under both isothermal and non-isothermal conditions are presented for four liquids: isopropanol, water, dielectric fluid (FC-72) and eutectic tin-lead solder (63Sn-37Pb). The objective of the work is to select liquids for a combined numerical and experimental study involving a high resolution, laser-based interfacial temperature measurement to measure interfacial heat transfer during microdroplet deposition. Applications include spray cooling, micro-manufacturing and coating processes, and electronics packaging. The initial droplet diameter and impact velocity are 80 {\\mu}m and 5 m/s, respectively. For isothermal impact, our simulations with water and isopropanol show very good agreement with experiments. The magnitude and rates of spreading for all four liquids ...

  7. Implementation of a new interfacial mass and energy transfer model in RETRAN-3D

    The RETRAN-3D MOD002.0 best estimate code includes a five-equation flow field model developed to deal with situations in which thermodynamic non-equilibrium phenomena are important. Several applications of this model to depressurization and pressurization transients showed serious convergence problems. An analysis of the causes for the numerical instabilities identified the models for interfacial heat and mass transfer as the source of the problems. A new interfacial mass and energy transfer model has thus been developed and implemented in RETRAN-3D. The heat transfer for each phase is equal to the product of the interfacial area density, a heat transfer coefficient and the temperature difference between the interface at saturation and the bulk temperature of the respective phase. However, in the context of RETRAN-3D, the vapor remains saturated in a two-phase volume, and no vapor heat transfer is thus calculated. The values of interfacial area density and heat transfer coefficient are obtained based on correlations appropriate for different flow regimes. A flow regime map, based on the work of Taitel and Dukler, with void fraction and mixture mass flux as map coordinates, is used to identify the flow regime present in a given volume. The new model has performed well when assessed against data from four experimental facilities covering depressurization, condensation and steady state void distribution. The results also demonstrate the viability of the approach followed to develop the new model for a five-equation based code. (author)

  8. Study on heat transfer and interfacial stability in supersonic steam injector

    Supersonic steam injector is one of the most possible devices for Next-generation nuclear systems to achieve more simplified system and to enhance the safety and credibility of the systems. Supersonic steam injector has dual functions that are passive jet pump and high efficient heat exchanger. In order to design the supersonic steam injector, it is important to clarify the heat transfer and flow behavior of high-speed water jet in supersonic steam flow. However, thermal-hydraulic behaviors in the steam injector including the interfacial heat transfer behavior due to the direct contact condensation and interfacial stability of water jet are not clarified in detail yet. The purpose of the present study is to investigate the interfacial heat transfer behavior of high-speed water jet. The interface of water jet is observed by using high-speed video camera. From the observation results obtained, wave propagation on the interface is identified. The velocity of the wave propagation is estimated from the visual information. Radial distribution of the pressure and the temperature in the supersonic steam injector are also measured experimentally in order to investigate the dynamic behavior and the heat transfer due to the condensation. From the results, the interaction between the interfacial dynamic behavior and the heat transfer due to the condensation are discussed. (author)

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

    Samec, Zdeněk

    2009-01-01

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

  10. Proton-Coupled Electron Transfer

    Weinberg, Dave; Gagliardi, Christopher J.; Hull, Jonathan F; Murphy, Christine Fecenko; Kent, Caleb A.; Westlake, Brittany C.; Paul, Amit; Ess, Daniel H; McCafferty, Dewey Granville; Meyer, Thomas J

    2012-07-11

    Proton-Coupled Electron Transfer (PCET) describes reactions in which there is a change in both electron and proton content between reactants and products. It originates from the influence of changes in electron content on acid-base properties and provides a molecular-level basis for energy transduction between proton transfer and electron transfer. Coupled electron-proton transfer or EPT is defined as an elementary step in which electrons and protons transfer from different orbitals on the donor to different orbitals on the acceptor. There is (usually) a clear distinction between EPT and H-atom transfer (HAT) or hydride transfer, in which the transferring electrons and proton come from the same bond. Hybrid mechanisms exist in which the elementary steps are different for the reaction partners. EPT pathways such as PhO•/PhOH exchange have much in common with HAT pathways in that electronic coupling is significant, comparable to the reorganization energy with H{sub DA} ~ λ. Multiple-Site Electron-Proton Transfer (MS-EPT) is an elementary step in which an electron-proton donor transfers electrons and protons to different acceptors, or an electron-proton acceptor accepts electrons and protons from different donors. It exploits the long-range nature of electron transfer while providing for the short-range nature of proton transfer. A variety of EPT pathways exist, creating a taxonomy based on what is transferred, e.g., 1e-/2H+ MS-EPT. PCET achieves “redox potential leveling” between sequential couples and the buildup of multiple redox equivalents, which is of importance in multielectron catalysis. There are many examples of PCET and pH-dependent redox behavior in metal complexes, in organic and biological molecules, in excited states, and on surfaces. Changes in pH can be used to induce electron transfer through films and over long distances in molecules. Changes in pH, induced by local electron transfer, create pH gradients and a driving force for long-range proton transfer in Photosysem II and through other biological membranes. In EPT, simultaneous transfer of electrons and protons occurs on time scales short compared to the periods of coupled vibrations and solvent modes. A theory for EPT has been developed which rationalizes rate constants and activation barriers, includes temperature- and driving force (ΔG)-dependences implicitly, and explains kinetic isotope effects. The distance-dependence of EPT is dominated by the short-range nature of proton transfer, with electron transfer being far less demanding.Changes in external pH do not affect an EPT elementary step. Solvent molecules or buffer components can act as proton donor acceptors, but individual H2O molecules are neither good bases (pKa(H3O+) = -1.74) nor good acids (pKa(H2O) = 15.7). There are many examples of mechanisms in chemistry, in biology, on surfaces, and in the gas phase which utilize EPT. PCET and EPT play critical roles in the oxygen evolving complex (OEC) of Photosystem II and other biological reactions by decreasing driving force and avoiding high-energy intermediates.

  11. Core-concrete molten pool dynamics and interfacial heat transfer

    Theoretical models are derived for the heat transfer from molten oxide pools to an underlying concrete surface and from molten steel pools to a general concrete containment. To accomplish this, two separate effects models are first developed, one emphasizing the vigorous agitation of the molten pool by gases evolving from the concrete and the other considering the insulating effect of a slag layer produced by concrete melting. The resulting algebraic expressions, combined into a general core-concrete heat transfer representation, are shown to provide very good agreement with experiments involving molten steel pours into concrete crucibles

  12. Interfacial condensation heat transfer for countercurrent steam-water wavy flow in a horizontal circular pipe

    An experimental study of interfacial condensation heat transfer has been performed for countercurrent steam-water wavy flow in a horizontal circular pipe. A total of 105 local interfacial condensation heat transfer coefficients have been obtained for various combinations of test parameters. Two empirical Nusselt number correlations were developed and parametric effects of steam and water flow rates and the degree of water subcooling on the condensation heat transfer were examined. For the wavy interface condition, the local Nusselt number is more strongly sensitive to the steam Reynolds number than water Reynolds number as opposed to the case of smooth interface condition. Comparisons of the present circular pipe data with existing correlations showed that existing correlations developed for rectangular channels are not directly applicable to a horizontal circular pipe flow

  13. Modeling and database for melt-water interfacial heat transfer

    A mechanistic model (CORQUENCH=Corium Quenching) has been developed to predict the transition superficial gas velocity between bulk cooldown and crust-limited heat transfer regimes in a sparged molten pool with a coolant overlayer. The model has direct applications in the analysis of ex-vessel severe accidents, where molten corium interacts with concrete, thereby producing sparging concrete decomposition gases. The analysis approach embodies thermal, mechanical, and hydrodynamic aspects associated with incipient crust formation at the melt/coolant interface. To validate the model, benchtop experiments were performed which employed water (melt) and liquid nitrogen (coolant) simulants; decomposition gases were simulated using argon gas. The results confirm the existence of distinct crust limited and bulk cooldown heat transfer regimes. The transition between the two regimes occurred gradually between j=2 to 4 cm/s, with onset of bulk cooling occurring at j=2 cm/s. The model predicts a transition gas velocity of j=2.5 cm/s without empirical adjustment. Application of the model to the case of oxidic corium over concrete indicates that efficient bulk cooling of melt will occur as long as the concrete decomposition gas velocity lies above 6 cm/s. When the gas velocity falls below this value, an interstitial crust is predicted to form. Thereafter, heat transfer from the MCCI zone to the coolant will be crust-limited. (orig./HP)

  14. Modeling and database for melt-water interfacial heat transfer

    A mechanistic model is developed to predict the transition superficial gas velocity between bulk cooldown and crust-limited heat transfer regimes in a sparged molten pool with a coolant overlayer. The model has direct applications in the analysis of ex-vessel severe accidents, where molten corium interacts with concrete, thereby producing sparging concrete decomposition gases. The analysis approach embodies thermal, mechanical, and hydrodynamic aspects associated with incipient crust formation at the melt/coolant interface. The model is validated against experiment data obtained with water (melt) and liquid nitrogen (coolant) simulants. Predictions are then made for the critical gas velocity at which crust formation will occur for core material interacting with concrete in the presence of water

  15. Marcus Electron Transfer Reactions with Bulk Metallic Catalysis

    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.

  16. Advances in electron transfer chemistry

    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

  17. Near-infrared fluorescent single walled carbon nanotube-chitosan composite: Interfacial strain transfer efficiency assessment

    Mol Menamparambath, Mini; Arabale, Girish; Nikolaev, Pavel; Baik, Seunghyun; Arepalli, Sivaram

    2013-04-01

    Effective load transfer at the single walled carbon nanotube (SWCNT)-polymer interface is most desirable for mechanically reinforced polymer composites. Versatile layer-by-layer assembly technique achieved dispersion and uniform distribution of sodium carboxymethylcellulose (CMC)-solubilized SWCNTs within the polymer matrix. Electrostatic interaction between positively charged chitosan and negatively charged CMC facilitates design of an optically active biocompatible nanocomposite. Interfacial strain transfer efficiency of SWCNT-chitosan nanocomposite was assessed via SWCNT Raman and photoluminescence band shifts under uniaxial strain. Photoluminescence peak shift rates of individual semiconducting SWCNTs were investigated and compared with tight binding model calculations.

  18. The role of interfacial heat and mechanical energy transfers in a liquid-metal MHD generator

    A brief description of the two-phase liquid-metal MHD power generation cycle and its advantages is provided. The importance of good interfacial liquid to gas heat transfer is discussed, and data confirming that satisfactory heat transfer is indeed achieved in an experimental generator are presented. An expression for the effect of the velocity difference between the gas and the liquid on generator performance is derived. An equivalent turbine efficiency is defined to characterize the generator as part of a heat engine and related to experimental data. (author)

  19. Interfacial condensation heat transfer of steam-water countercurrent flow in a circular pipe

    The interfacial heat transfer in a steam-water countercurrent stratified horizontal pipe was experimentally investigated for smooth and rough interfaces, with emphasis on the temperature and velocity distribution within the thick water layer (0.0175 ∼ 0.0345m). Although there are several existing experimental studies on this subject, most of the existing studies were performed using a rectangular channel having large aspect ratio. Due to the great difference in flow channel geometry there is a difficulty in applying existing correlations to the flow in NPP (Nuclear Power Plant) directly. When the cross sectional area of a wide rectangular channel and that of a circular pipe are the same, the water layer of the circular channel will be much thicker than that of the wide rectangular channel for given flow rates of steam and water. In particular, when the water layer thickness is increased, the characteristics of heat, mass and momentum transport, such as the turbulent intensity and the efficiency of turbulent mixing in the interface between the steam and water which play a dominant role in the interfacial condensation heat transfer, would be changed. The present experiments have been carried out using a nearly horizontal pipe (0.02 .deg.) that has a length of 2.2m and inner diameter of 0.083m. It is shown that the velocity and temperature profiles in the water layer are different between smooth and rough interface. The velocity profile nearby the interface has been obtained by a Hot Film Anemometer. The interfacial condensation heat transfer coefficients with interfacial velocity were higher than that without interfacial velocity. Based on the present experimental data, two Nusselt number correlations were developed in terms of steam and water Reynolds numbers, and the water Jacob number; one for smooth and the other for rough interfaces. The present experimental data agree with the calculated values within ±30% for the smooth interface and ±25% for the rough interface. Comparisons of the present data with existing correlations showed that the present heat transfer coefficients were significantly lower than the values predicted by existing correlations

  20. Interfacial Area and Interfacial Transfer in Two-Phase Flow Systems (Volume IV. Chapters 15-19)

    Guo, T.; Park, J.; Kojasoy, G.

    2003-03-15

    Experiments were performed on horizontal air-water bubbly two-phase flow, axial flow, stratified wavy flow, and annular flow. Theoretical studies were also undertaken on interfacial parameters for a horizontal two-phase flow.

  1. Interfacial Area and Interfacial Transfer in Two-Phase Flow Systems (Volume II. Chapters 6-10)

    Guo, T.; Park, J.; Kojasoy, G.

    2003-03-15

    Experiments were performed on horizontal air-water bubbly two-phase flow, axial flow, stratified wavy flow, and annular flow. Theoretical studies were also undertaken on interfacial parameters for a horizontal two-phase flow.

  2. Interfacial Area and Interfacial Transfer in Two-Phase Flow Systems (Volume III. Chapters 11-14)

    Guo, T.; Park, J.; Kojasoy, G.

    2003-03-15

    Experiments were performed on horizontal air-water bubbly two-phase flow, axial flow, stratified wavy flow, and annular flow. Theoretical studies were also undertaken on interfacial parameters for a horizontal two-phase flow.

  3. Interfacial Area and Interfacial Transfer in Two-Phase Flow Systems (Volume I. Chapters 1-5)

    Guo, T.; Park, J.; Kojasoy, G.

    2003-03-15

    Experiments were performed on horizontal air-water bubbly two-phase flow, axial flow, stratified wavy flow, and annular flow. Theoretical studies were also undertaken on interfacial parameters for a horizontal two-phase flow.

  4. A layer-by-layer ZnO nanoparticle-PbS quantum dot self-assembly platform for ultrafast interfacial electron injection

    Eita, Mohamed Samir

    2014-08-28

    Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low-cost, high-performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by-layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic-energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Direct correlation of charge transfer absorption with molecular donor:acceptor interfacial area via photothermal deflection spectroscopy

    Domingo, Ester

    2015-04-09

    We show that the Charge Transfer (CT) absorption signal in bulk-heterojunction (BHJ) solar cell blends, measured by photothermal deflection spectroscopy (PDS), is directly proportional to the density of molecular donor/acceptor interfaces. Since the optical transitions from ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer-fullerene interface. The latter is ~100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment (0.3 D) and the electronic coupling between ground state and CT state to be on the order of 30 meV.

  6. Detrimental effect of interfacial Dzyaloshinskii-Moriya interaction on perpendicular spin-transfer-torque magnetic random access memory

    Interfacial Dzyaloshinskii-Moriya interaction in ferromagnet/heavy metal bilayers is recently of considerable interest as it offers an efficient control of domain walls and the stabilization of magnetic skyrmions. However, its effect on the performance of perpendicular spin transfer torque memory has not been explored yet. We show based on numerical studies that the interfacial Dzyaloshinskii-Moriya interaction decreases the thermal energy barrier while increases the switching current. As high thermal energy barrier as well as low switching current is required for the commercialization of spin torque memory, our results suggest that the interfacial Dzyaloshinskii-Moriya interaction should be minimized for spin torque memory applications

  7. An experimental investigation of the interfacial condensation heat transfer in steam/water countercurrent stratified flow in a horizontal pipe

    Chu, In Cheol; Yu, Seon Oh; Chun, Moon Hyun [Korea Advanced Institute of Science and Technology, Taejon (Korea, Republic of); Kim, Byong Sup; Kim, Yang Seok; Kim, In Hwan; Lee, Sang Won [Korea Electric Power Research Institute, Taejon (Korea, Republic of)

    1998-12-31

    An interfacial condensation heat transfer phenomenon in a steam/water countercurrent stratified flow in a nearly horizontal pipe has been experimentally investigated. The present study has been focused on the measurement of the temperature and velocity distributions within the water layer. In particular, the water layer thickness used in the present work is large enough so that the turbulent mixing is limited and the thermal stratification is established. As a result, the thermal resistance of the water layer to the condensation heat transfer is increased significantly. An empirical correlation of the interfacial condensation heat transfer has been developed. The present correlation agrees with the data within {+-} 15%. 5 refs., 6 figs. (Author)

  8. An experimental investigation o the interfacial condensation heat transfer in steam/water countercurrent stratified flow in a horizontal pipe

    An interfacial condensation heat transfer phenomenon in a steam/water countercurrent stratified flow in a nearly horizontal pipe has been experimentally investigated. The present study has been focused on the measurement of the temperature and velocity distributions within the water layer. In particular, the water layer thickness used in the present work is large enough so that the turbulent mixing is limited and the thermal stratification is established. As a result, the thermal resistance of the water layer to the condensation heat transfer is increased significantly. An empirical correlation of the interfacial condensation heat transfer has been developed. The present correlation agrees with the data within ±15%

  9. Electron Transfer to Vinylaromatic Polymers

    Aromatic polymers accept electrons from alkali metals to form polyradicalanions. These undergo chain scission as a result of electronic interaction between aromatic rings. Spectrophotometric and chemical evidence led to the conclusion that during the chain-breaking process polymeric fragments were formed which had the properties of ''living polymers'', i.e. the characteristic visible spectra and the capability of initiating the polymerization of a number of vinyl monomers. It was possible to follow the rate of chain scission in the case of poly (4-vinyl biphenyl) and poly(α-vinyl naphthalene) by means of viscosity and spectrophotometric measurements. The postulated mechanism was found to be consistent with the slow decrease in free spin concentration measured by means of the electron spin resonance technique. Chain scission in polyacenaphthalene takes place at a much faster rate than in poly (4-vinyl biphenyl) and this fact is in good agreement with simple LCAO MO calculations. Preliminary experiments indicate that electron transfer to poly-N-vinyl carbazole produces little if any degradation. These investigations led to the examination of the temperature effect on the electron-transfer reaction from sodium to some substituted aromatic hydrocarbons. The details of this effect are discussed. (author)

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

    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-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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04942c

  11. Electron transfer in helical polyaromatics

    Pospíšil, Lubomír; Gál, Miroslav; Horáček, Michal; Teplý, Filip; Adriaenssens, Louis; Severa, Lukáš

    Xi´an : International Society of Electrochemistry , 2009. O06-O06. [International Symposium on Frontiers of Electrochemical Science and Technology. 12.08.2009-15.08.2009, Xi´an] R&D Projects: GA ČR GA203/08/1157; GA MŠk OC 140; GA ČR GA203/09/0705; GA ČR GP203/09/P502; GA MŠk ME09114 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : electron transfer * helical polyaromatics Subject RIV: CG - Electrochemistry

  12. Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

    Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

    2015-11-28

    Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings. PMID:26486297

  13. Electron transfer reactions. Pt. 1

    The oxidation of the substituted ethylenes, 2,3-dimethylbutene-2 (1), 2-methylbutene-2 (8), and ?-methylstyrene (13), by ferriin or lead dioxide in water and/or methanol has been studied. Product analyses of the reactions, which lead to kinetically controlled product distributions, showed that lead dioxide, just as ferriin, reacts as a one-electron-oxidant. The product distributions, which arise from further reactions of the primary intermediates, i.e. the radical cations formed via one-electron transfer, were found to depend on substituents, acidity and solvent. The results are consistent with three separate reaction paths of the radical cation, each of which leads to specific products. The radical cation can either deprotonate, be nucleophilicly attacked by solvent, or lead to dimeric products. (orig.)

  14. An experimental investigation on the interfacial condensation heat transfer in steam-water counter current stratified horizontal pipe flow

    The present study has been carried out to increase the understanding of the phenomenon of condensation heat transfer at the steam-water interface in countercurrent stratified horizontal pipe that has a length of 2m and inner diameter of 83mm. The method of measuring the increase of the bulk temperature in the water flow layer and then deducing the interfacial condensation heat transfer coefficient has been used to obtain the information of the thermal resistance of the water flow. In the present experiments the water layer was thick enough for the thermal stratification to be established, and that increased the thermal resistance of the water layer to the condensation heat transfer significantly. As a result, the interfacial condensation heat transfer coefficient becomes very small. In the present study, two types of correlations that can predict the interfacial condensation heat transfer coefficient in the countercurrent stratified horizontal pipe flow were developed.It is shown here that the correlation involving interfacial turbulence property gives a better agreement with the present experimental data than the correlation involving bulk flow properties

  15. Comparison of the methods for calculating the interfacial heat transfer coefficient in hot stamping

    This paper presents a hot stamping experimentation and three methods for calculating the Interfacial Heat Transfer Coefficient (IHTC) of 22MnB5 boron steel. Comparison of the calculation results shows an average error of 7.5% for the heat balance method, 3.7% for the Beck's nonlinear inverse estimation method (the Beck's method), and 10.3% for the finite-element-analysis-based optimization method (the FEA method). The Beck's method is a robust and accurate method for identifying the IHTC in hot stamping applications. The numerical simulation using the IHTC identified by the Beck's method can predict the temperature field with a high accuracy. - Highlights: • A theoretical formula was derived for direct calculation of IHTC. • The Beck's method is a robust and accurate method for identifying IHTC. • Finite element method can be used to identify an overall equivalent IHTC

  16. Section thickness-dependant interfacial heat transfer in squeeze casting of aluminum alloy A443

    Five-step castings of aluminum alloy A443 with different section thicknesses (2, 6, 8, 10, 20 mm) were squeezed under a hydraulic pressure of 60 MPa. Temperatures inside the P20 steel die mold and at the casting surface were recorded by fine type-K thermocouples. A numerical solution, i.e. inverse method was employed to determine the casting-die interfacial heat transfer coefficients (IHTCs). The results show the IHTCs initially reached a maximum peak value followed by a gradually decline to a lower level. With the applied pressure of 60MPa, the peak IHTC values from steps 1 to 5 varied from 5629 W/m2K to 9419 W/m2K. The section thickness affected IHTC peak values significantly. Compared to the thin steps at upper cavity, the lower thick steps obtained higher peak IHTCs and heat flux values due to high local pressures and high melt temperature.

  17. Interfacial electron transfer dynamics of photosensitized zinc oxide nanoclusters

    Murakoshi, Kei; Yanagida, Shozo [Osaka Univ. (Japan). Graduate School of Engineering; Capel, M. [Brookhaven National Lab., Upton, NY (United States)] [and others

    1997-06-01

    The authors have prepared and characterized photosensitized zinc oxide (ZnO) nanoclusters, dispersed in methanol, using carboxylated coumarin dyes for surface adsorption. Femtosecond time-resolved emission spectroscopy allows the authors to measure the photo-induced charge carrier injection rate constant from the adsorbed photosensitizer to the n-type semiconductor nanocluster. These results are compared with other photosensitized semiconductors.

  18. Solar energy conversion dynamics of interfacial electron and excitation transfer

    Piotrowiak, Piotr

    2013-01-01

    The importance of developing new, clean and renewable sources of energy will continue to grow in the foreseeable future and so will the need for the education of researchers in this field of research. The interest and challenges of the field continue to shift from simple homogeneous solutions to increasingly more complex heterogeneous systems and interfaces. Over the past decade there have been numerous theoretical and experimental breakthroughs many of which still exist only in the primary literature. The aim of this book is to gather in one volume the description of modern, sometimes explora

  19. Experimental measurement of the interfacial heat transfer coefficients of subcooled flow boiling using micro-thermocouple and double directional images

    Full text of publication follows: Models or correlations for phase interface are needed to analyze the multi-phase flow. Interfacial heat transfer coefficients are important to constitute energy equation of multi-phase flow, specially. In subcooled boiling flow, bubble condensation at the bubble-liquid interface is a major mechanism of heat transfer within bulk subcooled liquid. Bubble collapse rates and temperatures of each phase are needed to determine the interfacial heat transfer coefficient for bubble condensation. Bubble collapse rates were calculated through image processing in single direction, generally. And in case of liquid bulk temperature, which has been obtained by general temperature sensor such as thermocouple, was used. However, multi-directional images are needed to analyze images due to limitations of single directional image processing. Also, temperature sensor, which has a fast response time, must be used to obtain more accurate interfacial heat transfer coefficient. Low pressure subcooled water flow experiments using micro-thermocouple and double directional image processing with mirrors were conducted to investigate bubble condensation phenomena and to modify interfacial heat transfer correlation. Experiments were performed in a vertical subcooled boiling flow of a rectangular channel. Bubble condensing traces with respect to time were recorded by high speed camera in double direction and bubble collapse rates were calculated by processing recorded digital images. Temperatures were measured by micro-thermocouple, which is a K-type with a 12.7 ?m diameter. The liquid temperature was estimated by the developed algorithm to discriminate phases and find each phase temperature in the measured temperature including both liquid and bubble temperature. The interfacial heat transfer coefficient for bubble condensation was calculated from the bubble collapse rates and the estimated liquid temperature, and its correlation was modified. The modified correlation has been compared with other correlations. (authors)

  20. Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

    Smieja, Jonathan M.; Benson, Eric E.; Kumar, Bhupendra; Grice, Kyle A.; Seu, Candace; Miller, Alexander J.; Mayer, James M.; Kubiak, Cliff

    2012-09-25

    The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Re(bipy-tBu) (CO)3(L) catalyst for the reduction of CO2 to CO. A remarkable selectivity for CO2 over Hþ was observed by stopped-flow UV-vis spectroscopy of [Re(bipy-tBu)3]-1. The reaction with CO2 is about 25 times faster than the reaction with water or methanol at the same concentrations. X-ray crystallography and DFT studies of the doubly reduced anionic species suggest that the highest occupied molecular orbital (HOMO) has mixed metal-ligand character rather than being purely doubly occupied dz2, which is believed to determine selectivity by favoring CO2 (σ+π) over H+ (σ only) binding. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of protons to Re-CO2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed current densities for catalysis more than threefold, indicating that the properties of the electrode surface need to be addressed when developing a homogeneous artificial photosynthetic system.

  1. The effect of molecular aggregates over the interfacial charge transfer processes on dye sensitized solar cells

    The electron transfer reaction between the photoinjected electrons in the nanocrystalline TiO2 mesoporous sensitized films and the oxidized electrolyte in dye sensitized solar cells (DSSC) plays a major role on the device efficiency. In this communication we show that, although the presence of molecular aggregates on the free base porphyrin DSSC limits the device photocurrent response under illumination, they form an effective hydrophobic barrier against the oxidized electrolyte impeding fast back-electron transfer kinetics. Therefore, their drawback can be overcome by designing dyes with peripheral moieties that prevent the formation of the aggregates and are able to achieve efficiencies as high as 3.2% under full sun

  2. Determination of the metal/die interfacial heat transfer coefficient of high pressure die cast B390 alloy

    High-pressure die cast B390 alloy was prepared on a 350 ton cold chamber die casting machine. The metal/die interfacial heat transfer coefficient of the alloy was investigated. Considering the filling process, a 'finger'-shaped casting was designed for the experiments. This casting consisted of five plates with different thicknesses (0.05 inch or 1.27 mm to 0.25 inch or 6.35 mm) as well as individual ingates and overflows. Experiments under various operation conditions were conducted, and temperatures were measured at various specific locations inside the die. Based on the results, the interfacial heat transfer coefficient and heat flux were determined by solving the inverse heat transfer problem. The influence of the mold-filling sequence, sensor locations, as well as processing parameters including the casting pressure, die temperature, and fast/slow shot speeds on the heat transfer coefficient were discussed.

  3. Interfacial electron and phonon scattering processes in high-powered nanoscale applications.

    Hopkins, Patrick E.

    2011-10-01

    The overarching goal of this Truman LDRD project was to explore mechanisms of thermal transport at interfaces of nanomaterials, specifically linking the thermal conductivity and thermal boundary conductance to the structures and geometries of interfaces and boundaries. Deposition, fabrication, and post possessing procedures of nanocomposites and devices can give rise to interatomic mixing around interfaces of materials leading to stresses and imperfections that could affect heat transfer. An understanding of the physics of energy carrier scattering processes and their response to interfacial disorder will elucidate the potentials of applying these novel materials to next-generation high powered nanodevices and energy conversion applications. An additional goal of this project was to use the knowledge gained from linking interfacial structure to thermal transport in order to develop avenues to control, or 'tune' the thermal transport in nanosystems.

  4. Relationship between casting distortion, mold filling, and interfacial heat transfer. Annual technical report, September 1997 - September 1998

    Woodbury, K.A.; Parker, J.K.; Piwonka, T.S.; Owusu, Y.

    1998-10-22

    In the third year of this program, the final castings necessary to evaluate the effect of casting orientation and gating in silica sand lost foam were poured and measured using a CMM machine. Interfacial heat transfer and gap formation measurements continued. However, significant problems were encountered in making accurate measurements. No consistent evidence of gap formation was found in aluminum sand casting. Initial analysis yields heat transfer values below those previously reported in the literature. The program in continuing.

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

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

    2016-01-14

    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. PMID:26505730

  6. Interfacial condensation heat transfer for countercurrent steam-water stratified flow in a circular pipe

    An experimental study of steam condensation on a subcooled thick water layer (0.018 ∼ 0.031 m) in a countercurrent stratified flow has been performed using a nearly horizontal circular pipe. A total of 103 average interfacial condensation heat transfer coefficients were obtained and parametric effects of steam and water flow rates and the degree of subcooling on condensation heat transfer were examined. The measured local temperature and velocity distributions in the thick water layer revealed that there was a thermal stratification due to the lack of full turbulent thermal mixing in the lower region of the water layer. Two empirical Nusselt number correlations, one in items of average steam and water Reynolds numbers, and the water Prandtl number, and the other in terms of the Jacob number in place of the Prandtl number, which agree with most of the data within ±25 percent were developed based on the bulk flow properties. Comparisons of the present data with existing correlations showed that the present data were significantly lower than the values predicted by existing correlations. (author)

  7. Interfacial condensation heat transfer for countercurrent steam-water stratified flow in a horizontal circular pipe

    An experimental study of steam condensation on subcooled thick water layer (0.018-0.032 m) in a countercurrent stratified flow has been performed using a nearly horizontal circular pipe. A total of 104 average interfacial condensation heat transfer coefficients were obtained and parametric effects of steam and water flow rates and the degree of subcooling on the condensation heat transfer were examined. The measured local temperature and velocity distributions in the thick water layer revealed that there was a thermal stratification due to the lack of full turbulent thermal mixing in the lower region of the water layer. Two empirical Nusselt number correlations, one in terms of average steam and water Reynolds numbers, and the water Prandtl number, and the other in terms of the Jakob number in place of the Prandtl number, which agree with the data within ± 25 % were developed based on the bulk flow properties. Comparisons of the present data with existing correlations showed that the present data were singificantly lower than the values predicted by existing correlations

  8. Metal/dielectric thermal interfacial transport considering cross-interface electron-phonon coupling: Theory, two-temperature molecular dynamics, and thermal circuit

    Lu, Zexi; Wang, Yan; Ruan, Xiulin

    2016-02-01

    The standard two-temperature equations for electron-phonon coupled thermal transport across metal/nonmetal interfaces are modified to include the possible coupling between metal electrons with substrate phonons. The previous two-temperature molecular dynamics (TT-MD) approach is then extended to solve these equations numerically at the atomic scale, and the method is demonstrated using Cu/Si interface as an example. A key parameter in TT-MD is the nonlocal coupling distance of metal electrons and nonmetal phonons, and here we use two different approximations. The first is based on Overhauser's "joint-modes" concept, while we use an interfacial reconstruction region as the length scale of joint region rather than the phonon mean-free path as in Overhauser's original model. In this region, the metal electrons can couple to the joint phonon modes. The second approximation is the "phonon wavelength" concept where electrons couple to phonons nonlocally within the range of one phonon wavelength. Compared with the original TT-MD, including the cross-interface electron-phonon coupling can slightly reduce the total thermal boundary resistance. Whether the electron-phonon coupling within the metal block is nonlocal or not does not make an obvious difference in the heat transfer process. Based on the temperature profiles from TT-MD, we construct a new mixed series-parallel thermal circuit. We show that such a thermal circuit is essential for understanding metal/nonmetal interfacial transport, while calculating a single resistance without solving temperature profiles as done in most previous studies is generally incomplete. As a comparison, the simple series circuit that neglects the cross-interface electron-phonon coupling could overestimate the interfacial resistance, while the simple parallel circuit in the original Overhauser's model underestimates the total interfacial resistance.

  9. Absolute electron transfer efficiency of GEM

    We report on the absolute single-electron transfer efficiency of a Gas Electron Multiplier (GEM). It is shown that the electron transfer and thus the detection efficiency, depend not only on the GEM geometry and gain but mostly on the electric field and electron diffusion in the gas volume preceding the GEM. We have demonstrated that conditions can be found, including pre-amplification of the single electrons in the gap preceding the GEM, in which full detection efficiency is obtained. The experimental electron transfer efficiency results are confirmed by Monte Carlo simulations

  10. Electron transfer at semiconducting metal dichalcogenide/liquid electrolyte interfaces

    Howard, J.N.

    1992-01-01

    Charge transfer at semiconductor/electrolyte interfaces is the critical process in photoelectrochemical systems. Many aspects of the theory for these interfaces have yet to be experimentally verified. There are few reliable measurements of the fundamental electron transfer rate at nonilluminated semiconductors. This situation stems from experimental limitations imposed by most semiconductor electrode surfaces. Layered metal dichalcogenide semiconductors have excellent properties as semiconductor electrodes, but edge sites and crystal defects must be masked so only the defect-free basal plane of the two-dimensional material is exposed to solution. Conventional epoxy encapsulation of the crystal epoxy can introduce deleterious effects. A minielectrochemical cell was developed to perform experiments in a single drop of electrolyte held against the working electrode. The electrochemical behavior and operational considerations of the cell for aqueous and nonaqueous systems were investigated. Spatially-resolved electrochemistry was demonstrated for n-WSe[sub 2] and highly ordered pyrolytic graphite. The minicell was used to investigate electron transfer at nonilluminated n-WSe[sub 2]/dimethylferrocene[sup +/0] interfaces. This semiconductor is resistant to corrosion and has stable interfacial energetics. Interfaces with excellent diode behavior could be obtained by probing different regions of the surface. Electron transfer at these high quality surfaces was studied over an extensive solution concentration range. The rate of electron transfer was independent of solution acceptor concentration from 5 [mu]M to 0.25 M. The electron transfer data can be explained by assuming a surface-state mediate mechanism. A second metal dichalcogenide, n-SnS[sub 2], was investigated to compare the behavior of this wide band gap material to the narrow band gap n-WSe[sub 2]. The n-SnS[sub 2] electrodes displayed undesirable electrochemical effects in several solvent systems.

  11. Effect of binder polymer structures used in composite cathodes on interfacial charge transfer processes in lithium polymer batteries

    The effect of binder polymer structures used in composite cathodes on the interfacial charge transfer processes in lithium polymer batteries (LPB) has been studied in detail. A cross-linked comb-copolymer, consisting of ethylene oxide (EO), 2-(2-methoxyethoxy)ethyl glycidyl ether (MEEGE), and allyl glycidyl ether (AGE), was used as a solid polymer electrolyte (SPE). LiCoO2 composite cathodes were fabricated using binder comb-copolymers, consisting of EO and MEEGE with different compositions. Ionic conductivity of the SPE, and the interfacial charge transfer processes between the SPE and metallic lithium and between the SPE and the composite cathode at several cathode potentials versus Li/Li+, were electrochemically explored. With increasing MEEGE composition in the binder copolymers, the interfacial resistances between the SPE and the composite cathode appreciably decreased. As the result, discharge capacity of the LPB also enhanced with increasing the MEEGE composition. The introduction of the branched-side-chains to the polymer backbone to the binder polymers for the composite cathodes caused to facilitate the interfacial charge transport processes, while the introduction had also been found to be very effective in terms of the enhancement of ionic conductivity of SPE

  12. Surfactant transfer across a water/oil interface: A diffusion/kinetics model for the interfacial tension evolution

    The transfer of amphiphilic solutes through an interface between water and an organic solvent has been studied numerically by simulations based on a general diffusion/reaction model. This description predicts the evolution of the solute concentrations and the transfer across the liquid/liquid interface. It especially focuses on the dynamic interfacial tension evolution that can be measured by a pendant drop tensiometer. Both the bulk diffusion and the adsorption/desorption rate on both sides of the liquid interface are assumed to contribute to the global transfer kinetic. The calculations provide an understanding on how kinetic exchange at the interface and diffusion transport through the bulk determine the dynamic interfacial tension evolution. In particular, complex interfacial tension evolutions with a non-trivial behavior are predicted in some special cases when diffusion and kinetic exchange are of the same order of magnitude. Finally, this model is used to re-interpret experimental data about Triton X-100 transfer at a water-oil interface. (authors)

  13. Effect of solute transfer and interfacial instabilities on scalar and velocity field around a drop rising in quiescent liquid channel

    Khanwale, Makrand A.; Khadamkar, Hrushikesh P.; Mathpati, Channamallikarjun S.

    2015-11-01

    Physics of development of flow structures around the drop rising with solute transfer is highly influenced by the interfacial behaviour and is remarkably different than a particle rising under the same conditions. We report on the use of simultaneous particle image velocimetry-planar laser induced fluorescence technique to measure scalar and velocity fields around a drop rising in a quiescent liquid channel. The selected continuous phase is glycerol, and the drop consists of a mixture of toluene, acetone, and a dye rhodamine-6G, with acetone working as a interfacial tension depressant. The drop lies in the spherical region with Eötvös number, Eo = 1.95, Morton number, M = 78.20 and the particle Reynolds number being, Rep = 0.053. With Rep approaching that of creeping flow, we analyse the effect of interfacial instabilities solely, contrary to other investigations [M. Wegener et al., "Impact of Marangoni instabilities on the fluid dynamic behaviour of organic droplets," Int. J. Heat Mass Transfer 52, 2543-2551 (2009); S. Burghoff and E. Y. Kenig, "A CFD model for mass transfer and interfacial phenomena on single droplets," AIChE J. 52, 4071-4078 (2006); J. Wang et al., "Numerical simulation of the Marangoni effect on transient mass transfer from single moving deformable drops," AIChE J. 57, 2670-2683 (2011); R. F. Engberg, M. Wegener, and E. Y. Kenig, "The impact of Marangoni convection on fluid dynamics and mass transfer at deformable single rising droplets—A numerical study," Chem. Eng. Sci. 116, 208-222 (2014)] which account for turbulence as well as interfacial instabilities with Rep in the turbulent range. The velocity and concentration fields obtained are subjected to scale-wise energy decomposition using continuous wavelet transform. Scale-wise probability distribution functions of wavelet coefficients are calculated to check intermittent non-Gaussian behaviour for simultaneous velocity and scalar statistics. Multi-fractal singularity spectra for scalar and velocity fields are calculated using wavelet transform modulus maxima methodology to analyse the distribution of non-Gaussian flow structures and their effect on scalar transport. Further, Fourier spectra based on velocity and concentration are also reported. We found that vorticity and concentration fields became progressively non-Gaussian, as one moved from large scales to small scales. This turbulence like behaviour is attributed to interfacial instabilities developed because of the non-uniform shear at the interface. The multi-fractal singularity spectra had their Hurst exponent H > 0.5, which showed high correlation in the hierarchy of the flow structures. A strong correlation between concentration and velocity multi-fractal spectra was also seen.

  14. Interfacial valence electron localization and the corrosion resistance of Al-SiC nanocomposite

    Mosleh-Shirazi, Sareh; Hua, Guomin; Akhlaghi, Farshad; Yan, Xianguo; Li, Dongyang

    2015-12-01

    Microstructural inhomogeneity generally deteriorates the corrosion resistance of materials due to the galvanic effect and interfacial issues. However, the situation may change for nanostructured materials. This article reports our studies on the corrosion behavior of SiC nanoparticle-reinforced Al6061 matrix composite. It was observed that the corrosion resistance of Al6061 increased when SiC nanoparticles were added. Overall electron work function (EWF) of the Al-SiC nanocomposite increased, along with an increase in the corrosion potential. The electron localization function of the Al-SiC nanocomposite was calculated and the results revealed that valence electrons were localized in the region of SiC-Al interface, resulting in an increase in the overall work function and thus building a higher barrier to hinder electrons in the nano-composite to participate in corrosion reactions.

  15. Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

    Smieja, Jonathan M.; Benson, Eric E.; Kumar, Bhupendra; Grice, Kyle A.; Seu, Candace; Miller, Alexander J.; Mayer, James M.; Kubiak, Cliff

    2012-09-25

    The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-Vis spectroscopy, X-ray crystallography, DFT, and electrochemical kinetic studies of the Re(bipy-tBu)(CO)3(L) catalyst system. A remarkable selectivity for CO2 over H+ was observed by stopped-flow UV-Vis spectroscopy of [Re(bipy-tBu)(CO)3]-. The pseudo-first order rate constant for the reaction with 10 mM CO2 in THF is 35 s-1. This is ca. 15-20 times faster than the reactions with water or methanol at the same concentration in THF. X-ray crystallography and DFT studies of the doubly-reduced anionic species suggest that the HOMO has mixed metal-ligand character rather than being purely dz 2, which is thought to aid catalytic selectivity by favoring binding of CO2 over H+. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of protons to Re-CO2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed catalytic rates up to seven-fold, indicating that the properties of the electrode surface should not be overlooked when developing a homogeneous artificial photosynthetic system. This research was supported at the University of Washington, Seattle by the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry (for a fellowship to A. J. M. M.), and, for funds to purchase the stopped-flow instrument, the U.S. National Institutes of Health 13 (Grant GM-50422 to JMM), and 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.

  16. An expression for the bridge-mediated electron transfer rate in dye-sensitized solar cells.

    Maggio, Emanuele; Troisi, Alessandro

    2014-04-13

    We have derived an expression for the rate of electron transfer between a semiconductor and a redox centre connected to the semiconductor via a molecular bridge. This model is particularly useful to study the charge recombination (CR) process in dye-sensitized solar cells, where the dye is often connected to the semiconductor by a conjugated bridge. This formalism, designed to be coupled with density functional theory electronic structure calculations, can be used to explore the effect of changing the bridge on the rate of interfacial electron transfer. As an example, we have evaluated the CR rate for a series of systems that differ in the bridge length. PMID:24615149

  17. Activating "Invisible" Glue: Using Electron Beam for Enhancement of Interfacial Properties of Graphene-Metal Contact.

    Kim, Songkil; Russell, Michael; Kulkarni, Dhaval D; Henry, Mathias; Kim, Steve; Naik, Rajesh R; Voevodin, Andrey A; Jang, Seung Soon; Tsukruk, Vladimir V; Fedorov, Andrei G

    2016-01-26

    Interfacial contact of two-dimensional graphene with three-dimensional metal electrodes is crucial to engineering high-performance graphene-based nanodevices with superior performance. Here, we report on the development of a rapid "nanowelding" method for enhancing properties of interface to graphene buried under metal electrodes using a focused electron beam induced deposition (FEBID). High energy electron irradiation activates two-dimensional graphene structure by generation of structural defects at the interface to metal contacts with subsequent strong bonding via FEBID of an atomically thin graphitic interlayer formed by low energy secondary electron-assisted dissociation of entrapped hydrocarbon contaminants. Comprehensive investigation is conducted to demonstrate formation of the FEBID graphitic interlayer and its impact on contact properties of graphene devices achieved via strong electromechanical coupling at graphene-metal interfaces. Reduction of the device electrical resistance by ∼50% at a Dirac point and by ∼30% at the gate voltage far from the Dirac point is obtained with concurrent improvement in thermomechanical reliability of the contact interface. Importantly, the process is rapid and has an excellent insertion potential into a conventional fabrication workflow of graphene-based nanodevices through single-step postprocessing modification of interfacial properties at the buried heterogeneous contact. PMID:26741645

  18. Electron-electron Thomas peak in fast transfer ionization

    ''Thomas process'' is a name used for a family of singular two-step processes that can lead to electron transfer. The Thomas process of the ''second kind,'' occurring in reactions with both transfer and ionization, utilizes the e-e scattering in the second step, so this Thomas process requires the dynamics of the electron-electron interaction. We calculate numerically the second order element of an S matrix and corresponding cross sections for the transfer ionization process. We find that the position and shape of the Thomas peak depend on both electron-electron and the electron-nucleus interaction. Also the direct and exchange amplitudes are equal at the peak position. We test the peaking approximation used for transfer ionization. Our results can be compared to experimental results for p++He?H+He2++e-. (c) 2000 The American Physical Society

  19. Interfacial Engineering for Enhanced Light Absorption and Charge Transfer of a Solution-Processed Bulk Heterojunction Based on Heptazole as a Small Molecule Type of Donor.

    Lim, Iseul; Bui, Hoa Thi; Shrestha, Nabeen K; Lee, Joong Kee; Han, Sung-Hwan

    2016-04-01

    In the present study, a solution-processed organic semiconductor based on indolocarbazole derivative (heptazole) is introduced as a p-type donor material for a bulk-heterojunction photovoltaic device. The heptazole has an optical band gap of 2.97 eV, and its highest occupied molecular orbital-lowest unoccupied molecular orbital energy levels are compactable with the PC60BM to construct a donor-acceptor heterojuction for energy harvesting and transfer. When the bulk-heterojunction photovoltaic devices consisting of ITO/PEDOT:PSS/heptazole:PC60BM/Al with different blending ratio of heptazole:PC60BM were constructed, the cell with 1:1 blending ratio exhibited the best power conversion efficiency. Further, when an indoline organic dye (D149) was introduced as an interfacial modifier to the above donor/acceptor bulk heterojunction, the device demonstrated an enhanced overall power conversion efficiency from 1.26% to 2.51% hence demonstrating enhancement by the factor of 100%. The device was further characterized using electronic absorption spectroscopy, photoluminescence spectroscopy, electrochemical impedance spectroscopy, and the photovoltage decay kinetics. These studies reveal that the enhanced power conversion efficiency of the device is due to the enhanced charge transfer with the complementary light absorption feature of the interfacial D149 dye molecules. PMID:26999287

  20. Effects of interfacial Fe electronic structures on magnetic and electronic transport properties in oxide/NiFe/oxide heterostructures

    Liu, Qianqian; Chen, Xi; Zhang, Jing-Yan [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Yang, Meiyin [SKLSM, Institute of Semiconductors, CAS, P.O. Box 912, Beijing 100083 (China); Li, Xu-Jing; Jiang, Shao-Long; Liu, Yi-Wei; Cao, Yi [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Wu, Zheng-Long [Analytical and Testing Center, Beijing Normal University, Beijing 100875 (China); Feng, Chun [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Ding, Lei [School of Materials and Chemical Engineering, Hainan University, Haikou 570228 (China); Yu, Guang-Hua, E-mail: ghyu@mater.ustb.edu.cn [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China)

    2015-09-15

    Highlights: • The magnetic and transport properties of oxide/NiFe/oxide films were studied. • The oxide (SiO{sub 2}, MgO and HfO{sub 2}) has different elemental electronegativity. • Redox reaction at different NiFe/oxide interface is dependent on the oxide layer. • Different interfacial electronic structures shown by XPS influence the properties. - Abstract: We report that the magnetic and electronic transport properties in oxide/NiFe(2 nm)/oxide film (oxide = SiO{sub 2}, MgO or HfO{sub 2}) are strongly influenced by the electronic structure of NiFe/oxide interface. Magnetic measurements show that there exist magnetic dead layers in the SiO{sub 2} sandwiched film and MgO sandwiched film, whereas there is no magnetic dead layer in the HfO{sub 2} sandwiched film. Furthermore, in the ultrathin SiO{sub 2} sandwiched film no magnetoresistance (MR) is detected, while in the ultrathin MgO sandwiched film and HfO{sub 2} sandwiched film the MR ratios reach 0.35% and 0.88%, respectively. The investigation by X-ray photoelectron spectroscopy reveals that the distinct interfacial redox reactions, which are dependent on the oxide layers, lead to the variation of magnetic and transport properties in different oxide/NiFe/oxide heterostructures.

  1. Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

    Pan, Shanlin [Univ. of Alabama, Tuscaloosa, AL (United States)

    2014-11-16

    Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an electrochemical cell. For example, we are able to use this technique to track electroluminescence of single Au NPs, and the electrodeposition of individual Ag NPs in-situ. These metallic NPs are useful to enhance light harvesting in organic photovoltaic systems. The scattering at the surface of an indium tin oxide (ITO) working electrode was measured during a potential sweep. Utilizing Mie scattering theory and high resolution scanning electron microscopy (SEM), the scattering data were used to calculate current-potential curves depicting the electrodeposition of individual Ag NPs. The oxidation of individual presynthesized and electrodeposited Ag NPs was also investigated using fluorescence and DFS microscopies. Our work has produced 1 US provisional patent, 15 published manuscripts, 1 submitted and two additional in-writing manuscripts. 5 graduate students, 1 postdoctoral student, 1 visiting professor, and two undergraduate students have received research training in the area of electrochemistry and optical spectroscopy under support of this award.

  2. Advances in electron transfer chemistry, v.6

    Mariano, PS

    1999-01-01

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

  3. Biotechnological Aspects of Microbial Extracellular Electron Transfer

    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 appli...

  4. Electron Transfer for Large Molecules through Delocalization

    Neuhauser, D.; Reslan, R.; Hernandez, S.; Arnsen, C.; Lopata, K.; Govind, N.; Gao, Y.; Tolbert, S.; Schwartz, B.; Rubin, Y.; Nardes, A.; Kopidakis, N.

    2012-01-01

    Electron transfer for large molecules lies in between a Marcus-Theory two-state transfer and a Landauer description. We discuss a delocalization formalism which,through the introduction of artificial electric fields which emulate bulk dipole fields, allows calculation between a pair of identical molecules (A+A- (R)A-+A) with several open states. Dynamical electron polarization effects can be inserted with TDDFT and are crucial for large separations.

  5. Heat Transfer Augmentation for Electronic Cooling

    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.

  6. Quantifying electron transfer reactions in biological systems

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

    2015-01-01

    which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between...... quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to...... deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe...

  7. Water-mediated electron transfer between protein redox centers.

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

    2007-04-12

    Recent experimental and theoretical investigations show that water molecules between or near redox partners can significantly affect their electron-transfer (ET) properties. Here we study the effects of intervening water molecules on the electron self-exchange reaction of azurin (Az), by performing a conformational sampling on the water medium and by using a newly developed ab initio method to calculate transfer integrals between molecular redox sites. We show that the insertion of water molecules at the interface between the copper active sites of Az dimers slightly increases the overall ET rate, while some favorable water conformations can considerably enhance the ET kinetics. These features are traced back to the interplay of two competing factors: the electrostatic interaction between the water and protein subsystems (mainly opposing the ET process for the water arrangements drawn from MD simulations) and the effectiveness of water in mediating ET coupling pathways. Such an interplay provides a physical basis for the found absence of correlation between the electronic couplings derived through ab initio electronic structure calculations and the related quantities obtained through the Empirical Pathways (EP) method. In fact, the latter does not account for electrostatic effects on the transfer integrals. Thus, we conclude that the water-mediated electron tunneling is not controlled by the geometry of a single physical pathway. We discuss the results in terms of the interplay between different ET pathways controlled by the conformational changes of one of the water molecules via its electrostatic influence. Finally, we examine the dynamical effects of the interfacial water and check the validity of the Condon approximation. PMID:17388538

  8. The effect of interfacial charge transfer on ferromagnetism in perovskite oxide superlattices

    The structural, magnetic, and electrical properties of superlattices composed of the ferromagnetic/metal La0.7Sr0.3MnO3 and non-magnetic/metal La0.5Sr0.5TiO3 grown on (001)-oriented SrTiO3 substrates have been investigated. Using a combination of bulk magnetometry, soft x-ray magnetic spectroscopy, and scanning transmission electron microscopy, we demonstrate that robust ferromagnetic properties can be maintained in this superlattice system where charge transfer at the interfaces is minimized. Therefore, ferromagnetism can be controlled effectively through the chemical identity and the thickness of the individual superlattice layers.

  9. Medium effects in photoinduced electron transfer reactions

    The transfer of an electron between two molecules is a fundamental chemical process of great significance in biochemistry as well as in general chemistry. Electron transfer reactions can be induced by the absorption of light - as in photosynthesis - so that one of the molecules reacts through an electronically excited state; a net storage of chemical energy may then take place. When electron transfer involves molecules in condensed phase, the role of the liquid or solid medium must be considered. In the first place, a polar solvent may promote electron transfer through the stabilization of ion pairs and the separation of ions; but if the polar solvent must reorganize prior to the reaction, then an activation barrier will exist against electron transfer in polar solvents. This article gives a citical review of this field, with some novel ideas concerning the role of the medium (liquid solvent or solid matrix) in the overall energy balance of electron transfer, in the kinetics of the reaction, and in the further process of charge separation. It is suggested in particular that no dielectric screening by a polar solvent can exist when ions are formed in direct contact; and that the extensive reorganization of the solvent prior to electron transfer is so unlikely as to be discounted. In these respects the model presented in this article diverges from the commonly accepted model of Weller and of Marcus and Hush. In the Conclusion section some areas of particular importance for further research in this field are outlined. (author) 28 refs., 20 figs., 2 tabs

  10. Magneto-controlled Quantized Electron Transfer to Surface-confined Redox Units and Metal Nanoparticles

    Itamar Willner; Eugenii Katz

    2006-01-01

    Hydrophobic magnetic nanoparticles (NPs) consisting of undecanoate-capped magnetite (Fe3O4, average diameter ca. 5 nm) are used to control quantized electron transfer to surface-confined redox units and metal NPs. A two-phase system consisting of an aqueous electrolyte solution and a toluene phase that includes the suspended undecanoate-capped magnetic NPs is used to control the interfacial properties of the electrode surface. The attracted magnetic NPs form a hydrophobic layer on the electro...

  11. Molecular Choreography of Isomerization and Electron Transfer Using One and Two Dimensional Femtosecond Stimulated Raman Spectroscopy

    Hoffman, David Paul

    2014-01-01

    Chemical reactions are defined by the change in the relative positions and bonding of nuclei in molecules. I have used femtosecond stimulated Raman spectroscopy (FSRS) to probe these transformations with structural specificity and high time precision revealing the mechanisms of two important classes of reactions; isomerization about an N=N bond and interfacial/intermolecular electron transfer.Isomerization about a double bond is one of the simplest, yet most important, photochemical reactions...

  12. Imaging the electrons from transfer ionization collisions

    The electrons emitted into the continuum in transfer ionization of He2+ on helium collisions in the energy range of 75 - 400 keV were imaged using reaction microscope. The electron emission patterns show big difference for projectile velocity lower and upper than 1 a.u. in the present studies.

  13. Electron transfer induced fragmentation of acetic acid

    We present negative ion formation driven by electron transfer in atom (K) molecule (acetic acid) collisions. Acetic acid has been found in the interstellar medium, is also considered a biological related compound and as such studying low energy electron interactions will bring new insights as far as induced chemistry is concerned.

  14. Single Molecule Spectroscopy of Electron Transfer

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

  15. Interfacial bonding and electronic structure of GaN/GaAs interface: A first-principles study

    Cao, Ruyue; Zhang, Zhaofu; Wang, Changhong; Li, Haobo; Dong, Hong; Liu, Hui; Wang, Weichao, E-mail: weichaowang@nankai.edu.cn [College of Electronic Information and Optical Engineering, Nankai University, Tianjin 300071 (China); Xie, Xinjian [College of Materials Science, Hebei Technology University, Tianjin 300401 (China)

    2015-04-07

    Understanding of GaN interfacing with GaAs is crucial for GaN to be an effective interfacial layer between high-k oxides and III-V materials with the application in high-mobility metal-oxide-semiconductor field effect transistor (MOSFET) devices. Utilizing first principles calculations, here, we investigate the structural and electronic properties of the GaN/GaAs interface with respect to the interfacial nitrogen contents. The decrease of interfacial N contents leads to more Ga dangling bonds and As-As dimers. At the N-rich limit, the interface with N concentration of 87.5% shows the most stability. Furthermore, a strong band offsets dependence on the interfacial N concentration is also observed. The valance band offset of N7 with hybrid functional calculation is 0.51 eV. The electronic structure analysis shows that significant interface states exist in all the GaN/GaAs models with various N contents, which originate from the interfacial dangling bonds and some unsaturated Ga and N atoms. These large amounts of gap states result in Fermi level pinning and essentially degrade the device performance.

  16. Enhanced electrochemistry of nanoparticle-embedded polyelectrolyte films: Interfacial electronic coupling and distance dependence

    Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte-nanoparticle (PE-NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN)63-/4-) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-L-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE-NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between particles (interparticle coupling) as well as at the electrode-film interface. The cumulative results observed at these films suggest that, while distance dependence prevails in nearly every case and interparticle coupling can contribute to facilitating the Fe(CN)63-/4- electrochemistry, interfacial electronic coupling of the PE-NP films is of critical importance and decoupling is easily achieved by disengaging NP-electrode interactions.

  17. Enhanced electrochemistry of nanoparticle-embedded polyelectrolyte films: Interfacial electronic coupling and distance dependence

    Dowdy, Callie E.; Leopold, Michael C., E-mail: mleopold@richmond.ed

    2010-11-01

    Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte-nanoparticle (PE-NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN){sub 6}{sup 3-/4-}) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-L-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE-NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between particles (interparticle coupling) as well as at the electrode-film interface. The cumulative results observed at these films suggest that, while distance dependence prevails in nearly every case and interparticle coupling can contribute to facilitating the Fe(CN){sub 6}{sup 3-/4-} electrochemistry, interfacial electronic coupling of the PE-NP films is of critical importance and decoupling is easily achieved by disengaging NP-electrode interactions.

  18. Interfacial electronic structure at the CH3NH3PbI3/MoOx interface

    Liu, Peng; Liu, Xiaoliang; Lyu, Lu; Xie, Haipeng; Zhang, Hong; Niu, Dongmei; Huang, Han; Bi, Cheng; Xiao, Zhengguo; Huang, Jinsong; Gao, Yongli

    2015-05-01

    Interfacial electronic properties of the CH3NH3PbI3 (MAPbI3)/MoOx interface are investigated using ultraviolet photoemission spectroscopy and X-ray photoemission spectroscopy. It is found that the pristine MAPbI3 film coated onto the substrate of poly (3,4-ethylenedioxythiophene) poly(styrenesulfonate)/indium tin oxide by two-step method behaves as an n-type semiconductor, with a band gap of 1.7 eV and a valence band edge of 1.40 eV below the Fermi energy (EF). With the MoOx deposition of 64 upon MAPbI3, the energy levels of MAPbI3 shift toward higher binding energy by 0.25 eV due to electron transfer from MAPbI3 to MoOx. Its conduction band edge is observed to almost pin to the EF, indicating a significant enhancement of conductivity. Meanwhile, the energy levels of MoOx shift toward lower binding energy by 0.30 eV, and an interface dipole of 2.13 eV is observed at the interface of MAPbI3/MoOx. Most importantly, the chemical reaction taking place at this interface results in unfavorable interface energy level alignment for hole extraction. A potential barrier of 1.36 eV observed for hole transport will impede the hole extraction from MAPbI3 to MoOx. On the other hand, a potential barrier of 0.14 eV for electron extraction is too small to efficiently suppress electrons extracted from MAPbI3 to MoOx. Therefore, such an interface is not an ideal choice for hole extraction in organic photovoltaic devices.

  19. Decoupling interfacial reactions between plasmas and liquids: charge transfer vs plasma neutral reactions.

    Rumbach, Paul; Witzke, Megan; Sankaran, R Mohan; Go, David B

    2013-11-01

    Plasmas (gas discharges) formed at the surface of liquids can promote a complex mixture of reactions in solution. Here, we decouple two classes of reactions, those initiated by electrons (electrolysis) and those initiated by gaseous neutral species, by examining an atmospheric-pressure microplasma formed in different ambients at the surface of aqueous saline (NaCl) solutions. Electrolytic reactions between plasma electrons and aqueous ions yield an excess of hydroxide ions (OH(-)), making the solution more basic, while reactions between reactive neutral species formed in the plasma phase and the solution lead to nitrous acid (HNO2), nitric acid (HNO3), and hydrogen peroxide (H2O2), making the solution more acidic. The relative importance of either reaction path is quantified by pH measurements, and we find that it depends directly on the composition of the ambient background gas. With a background gas of oxygen or argon, electron transfer reactions yielding excess OH(-) dominate, while HNO2 and HNO3 formed in the plasma and by the dissolution of nitrogen oxide (NOx) species dominate in the case of air and nitrogen. For pure nitrogen (N2) gas, we observe a unique coupling between both reactions, where oxygen (O2) gas formed via water electrolysis reacts in the bulk of the plasma to form NOx, HNO2, and HNO3. PMID:24144120

  20. Correlating Interfacial Structure and Magnetism in Thin-Film Oxide Heterostructures Using Transmission Electron Microscopy and Polarized Neutron Reflectometry

    Spurgeon, Steven Richard

    Oxide thin-films have attracted considerable attention for a new generation of spintronics devices, where both electron charge and spin are used to transport information. However, a poor understanding of the local features that mediate magnetization and coupling in these materials has greatly limited their deployment into new information and communication technologies. This thesis describes direct, local measurements of structure-property relationships in ferrous thin-films and La1--xSrxMnO3 (LSMO) / Pb(ZrxTi1--x)O3 (PZT) thin-film heterostructures using spatially-resolved characterization techniques. In the first part of this thesis we explore the properties of ferrous spintronic thin-films. These films serve as a model system to establish a suite of interfacial characterization techniques for subsequent studies. We then study the static behavior of LSMO / PZT devices with polarization set by the underlying substrate. Using transmission electron microscopy and geometric phase analysis we reveal the presence of significant local strain gradients in these films for the first time. Electron energy loss spectroscopy mapping of the LSMO / PZT interface reveals Mn valence changes induced by charge-transfer screening. Bulk magnetometry and polarized neutron reflectometry indicate that these chemical and strain changes are associated with a graded magnetization across the LSMO layer. Density functional theory calculations are presented, which show that strain and charge-transfer screening act locally to suppress magnetization in the LSMO by changing the Mn orbital polarization. In the second half of this thesis, we explore asymmetric screening effects on magnetization LSMO / PZT composites. We find that the local ferroelectric polarization can vary widely and that this may be responsible for reduced charge-transfer effects, as well as magnetic phase gradients at interfaces. From this information and electron energy loss spectroscopy, we construct a map of the magnetic phases at the interface. Collectively these results show that we must move toward high-resolution local probes of structure and magnetism to achieve deterministic control of functional thin-film oxides.

  1. Controlling Interfacial Reactions and Intermetallic Compound Growth at the Interface of a Lead-free Solder Joint with Layer-by-Layer Transferred Graphene.

    Ko, Yong-Ho; Lee, Jong-Dae; Yoon, Taeshik; Lee, Chang-Woo; Kim, Taek-Soo

    2016-03-01

    The immoderate growth of intermetallic compounds (IMCs) formed at the interface of a solder metal and the substrate during soldering can degrade the mechanical properties and reliability of a solder joint in electronic packaging. Therefore, it is critical to control IMC growth at the solder joints between the solder and the substrate. In this study, we investigated the control of interfacial reactions and IMC growth by the layer-by-layer transfer of graphene during the reflow process at the interface between Sn-3.0Ag-0.5Cu (in wt %) lead-free solder and Cu. As the number of graphene layers transferred onto the surface of the Cu substrate increased, the thickness of the total IMC (Cu6Sn5 and Cu3Sn) layer decreased. After 10 repetitions of the reflow process for 50 s above 217 °C, the melting temperature of Sn-3.0Ag-0.5Cu, with a peak temperature of 250 °C, the increase in thickness of the total IMC layer at the interface with multiple layers of graphene was decreased by more than 20% compared to that at the interface of bare Cu without graphene. Furthermore, the average diameter of the Cu6Sn5 scallops at the interface with multiple layers of graphene was smaller than that at the interface without graphene. Despite 10 repetitions of the reflow process, the growth of Cu3Sn at the interface with multiple layers of graphene was suppressed by more than 20% compared with that at the interface without graphene. The multiple layers of graphene at the interface between the solder metal and the Cu substrate hindered the diffusion of Cu atoms from the Cu substrate and suppressed the reactions between Cu and Sn in the solder. Thus, the multiple layers of graphene transferred at the interface between dissimilar metals can control the interfacial reaction and IMC growth occurring at the joining interface. PMID:26856638

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

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

    2015-01-01

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

  3. Surface Chemically Switchable Ultraviolet Luminescence from Interfacial Two-Dimensional Electron Gas.

    Islam, Mohammad A; Saldana-Greco, Diomedes; Gu, Zongquan; Wang, Fenggong; Breckenfeld, Eric; Lei, Qingyu; Xu, Ruijuan; Hawley, Christopher J; Xi, X X; Martin, Lane W; Rappe, Andrew M; Spanier, Jonathan E

    2016-01-13

    We report intense, narrow line-width, surface chemisorption-activated and reversible ultraviolet (UV) photoluminescence from radiative recombination of the two-dimensional electron gas (2DEG) with photoexcited holes at LaAlO3/SrTiO3. The switchable luminescence arises from an electron transfer-driven modification of the electronic structure via H-chemisorption onto the AlO2-terminated surface of LaAlO3, at least 2 nm away from the interface. The control of the onset of emission and its intensity are functionalities that go beyond the luminescence of compound semiconductor quantum wells. Connections between reversible chemisorption, fast electron transfer, and quantum-well luminescence suggest a new model for surface chemically reconfigurable solid-state UV optoelectronics and molecular sensing. PMID:26675987

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

    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 activated kinetics, which extends the transition-state theory to dynamically dispersive media. Releasing the grip of thermodynamics in kinetic calculations through nonergodicity provides the mechanism for an efficient optimization between reaction rates and the spectrum of relaxation times of the protein-water thermal bath. Bath dynamics, it appears, play as important role as the free energy in optimizing biology’s performance.

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

    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 activated kinetics, which extends the transition-state theory to dynamically dispersive media. Releasing the grip of thermodynamics in kinetic calculations through nonergodicity provides the mechanism for an efficient optimization between reaction rates and the spectrum of relaxation times of the protein-water thermal bath. Bath dynamics, it appears, play as important role as the free energy in optimizing biology's performance. PMID:26558324

  6. Interfacial spin-filter assisted spin transfer torque effect in Co/BeO/Co magnetic tunnel junction

    Tang, Y.-H., E-mail: yhtang@cc.ncu.edu.tw; Chu, F.-C. [Department of Physics, National Central University, Jung-Li 32001, Taiwan (China)

    2015-03-07

    The first-principles calculation is employed to demonstrate the spin-selective transport properties and the non-collinear spin-transfer torque (STT) effect in the newly proposed Co/BeO/Co magnetic tunnel junction. The subtle spin-polarized charge transfer solely at O/Co interface gives rise to the interfacial spin-filter (ISF) effect, which can be simulated within the tight binding model to verify the general expression of STT. This allows us to predict the asymmetric bias behavior of non-collinear STT directly via the interplay between the first-principles calculated spin current densities in collinear magnetic configurations. We believe that the ISF effect, introduced by the combination between wurtzite-BeO barrier and the fcc-Co electrode, may open a new and promising route in semiconductor-based spintronics applications.

  7. Interfacial spin-filter assisted spin transfer torque effect in Co/BeO/Co magnetic tunnel junction

    Tang, Y.-H.; Chu, F.-C.

    2015-03-01

    The first-principles calculation is employed to demonstrate the spin-selective transport properties and the non-collinear spin-transfer torque (STT) effect in the newly proposed Co/BeO/Co magnetic tunnel junction. The subtle spin-polarized charge transfer solely at O/Co interface gives rise to the interfacial spin-filter (ISF) effect, which can be simulated within the tight binding model to verify the general expression of STT. This allows us to predict the asymmetric bias behavior of non-collinear STT directly via the interplay between the first-principles calculated spin current densities in collinear magnetic configurations. We believe that the ISF effect, introduced by the combination between wurtzite-BeO barrier and the fcc-Co electrode, may open a new and promising route in semiconductor-based spintronics applications.

  8. Theory of Ultrafast Photoinduced Heterogeneous Electron Transfer

    May, Volkhard

    2006-01-01

    Abstract Ultrafast heterogeneous electron transfer (HET) between a molecule attached to a semiconductor surface and the conduction band of the semiconductor is discussed theoretically with emphasis on the perylene TiO_2 system. The used description accounts for the specialty of the molecule i.e. its particular electronic level scheme together with its vibrational degrees of freedom. The band continuum of the semiconductor is included and the approach is ready to describe different...

  9. Resonant electron transfer between quantum dots

    Openov, Leonid A.

    1999-01-01

    An interaction of electromagnetic field with a nanostructure composed of two quantum dots is studied theoretically. An effect of a resonant electron transfer between the localized low-lying states of quantum dots is predicted. A necessary condition for such an effect is the existence of an excited bound state whose energy lies close to the top of the barrier separating the quantum dots. This effect may be used to realize the reversible quantum logic gate NOT if the superposition of electron s...

  10. Facilitating electron transfer in bioelectrocatalytic systems

    Sekretaryova, Alina

    2016-01-01

    Bioelectrocatalytic systems are based on biological entities, such as enzymes, whole cells, parts of cells or tissues, which catalyse electrochemical processes that involve the interaction between chemical change and electrical energy. In all cases, biocatalysis is implemented by enzymes, isolated or residing inside cells or part of cells. Electron transfer (ET) phenomena, within the protein molecules and between biological redox systems and electronics, enable the development of various bioe...

  11. Role of surface stoichiometry on the interfacial electron behavior at Ni/TiO{sub 2}(0 0 1) interfaces

    Tao Junguang, E-mail: junguangtao@usf.edu [Department of Physics, University of South Florida, Tampa, FL 33620 (United States); Division of Physics and Applied Physics, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Pan, J.S.; Chiam, S.Y. [Institute of Materials Research and Engineering, A-STAR, 3 Research Link, Singapore 117602 (Singapore); Huan, C.H.A. [Division of Physics and Applied Physics, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore)

    2012-04-16

    Highlights: Black-Right-Pointing-Pointer Surface stoichiometry affects the interfacial charge re-distribution. Black-Right-Pointing-Pointer Separation of electron-hole pairs depends on surface stoichiometry. Black-Right-Pointing-Pointer Oxidization state of Ni depends on the initial conditions of the TiO{sub 2} surface. Black-Right-Pointing-Pointer Insulator-to-metal transition affects the binding energies. - Abstract: The interfacial properties of Ni clusters grown on the stoichiometric and reduced rutile TiO{sub 2}(0 0 1) surfaces were investigated by means of X-ray photoelectron spectroscopy (XPS). The binding energies (BE's) of elements from both overlayers and substrates were found to be affected by the formation of interfacial dipole. Regardless of the TiO{sub 2} surface stoichiometry, the Ni 2p{sub 3/2} BE's move monotonically toward lower value with the increase of Ni thickness due to the cluster size effect. However, the Ni 2p{sub 3/2} BE shift is much smaller on reduced TiO{sub 2}(0 0 1) surfaces compared to that on the annealed stoichiometric surface. For stoichiometric and lightly reduced TiO{sub 2} surfaces, O 1s BE's exhibit an unexpected upward shift with increasing Ni thickness below 2 Angstrom-Sign , and then downward shift to lower BE's when the Ni thickness increases further. This opposite tendency is attributed to the insulator-to-metal transition. On heavily reduced surface, only monotonically downward shift of the O 1s BE's was observed with the increase of Ni thickness. The different behaviors are well elucidated by collective contributions of interfacial charge transfer and image charge effect.

  12. Electron transfer in dinucleoside phosphate anions

    The electron transfer reaction within various dinucleoside phosphate radical anions has been investigated by ESR spectroscopy and pulse radiolysis. In the ESR work electrons are produced by photolysis of K4Fe(CN)6 in a 12 M LiCl glass at 770K. Upon photobleaching the electrons react with the dinucleoside phosphate to form the anion radical. The anions of the four DNA nucleosides were also produced and their ESR spectra were appropriately weighted and summed by computer to simulate the spectra found for the dinucleoside phosphate anions. From the analysis the relative amounts of each of the nucleoside anions in the dinucleoside phosphate anion were determined. Evidence suggests the electron affinity of the pyrimidine bases are greater than the purine bases; however, the results are not sufficient to distinguish between the individual purine or pyrimidine. When dinucleoside phosphate anions containing thymidine are warmed, protonation occurs only on thymine to produce the well known ''thymyl'' spectrum. Pulse radiolysis experiments on individual nucleotides (TMP, dAMP), mixtures of these nucleotides and the dinucleoside phosphate, TdA, in aqueous solution at room temperature show that in the TdA anion electron transfer occurs from adenine to thymine, whereas no electron transfer is found for mixtures of individual nucleotides. Protonation is found to occur only on thymine in the TdA anion in agreement with the ESR results

  13. Quantum effects in biological electron transfer

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

    2012-01-01

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

  14. Electron transfer and bond breaking: Recent advances

    After a reminder of concerted/stepwise mechanistic dichotomy and other basic concepts and facts in the field, a series of recent advances is discussed. Particular emphasis is laid on the interactions between the fragments formed upon bond cleavage. These interactions may persist even in polar solvents and have important consequences on dissociative electron transfer kinetics and on the competition between concerted and stepwise pathways. Cleavage of ion radicals and its reverse reaction are examples of single electron transfer reactions concerted with bond cleavage and bond formation, respectively. The case of aromatic carbon-heteroatom bonds is particularly worth examination since symmetry restrictions impose circumventing a conical intersection. Reductive dehalogenases are involved in 'dehalorespiration' of anaerobic bacteria in which the role of dioxygen in aerobic organisms is played by major polychloride pollutants such as tetrachloroethylene. They offer an interesting illustration of how the coupling of electron transfer with bond breaking may be an important issue in natural processes. Applications of dissociative electron transfer concepts and models to mechanistic analysis in this class of enzymes will be discussed

  15. Electrochemical fabrication and interfacial charge-transfer process of Ni/GaN(0001) electrodes.

    Qin, Shuang-Jiao; Peng, Fei; Chen, Xue-Qing; Pan, Ge-Bo

    2016-02-17

    The electrodeposition of Ni on single-crystal n-GaN(0001) film from acetate solution was investigated using scanning electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, atomic force microscopy, and electrochemical techniques. The as-deposited Ni/n-GaN(0001) had a flat band potential of Ufb = -1.0 V vs. Ag/AgCl, which was much lower than that of bare GaN(0001). That is, a more feasible charge-transfer process occurred at the Ni/n-Ga(0001) interface. On the basis of a Tafel plot, an exchange current density of ?1.66 10(-4) mA cm(-2) was calculated. The nuclei density increased when the applied potential was varied from -0.9 V to -1.2 V and, eventually the whole substrate was covered. In addition, the current transient measurements revealed that the Ni deposition process followed instantaneous nucleation in 5 mM Ni(CH3COO)2 + 0.5 M H3BO3. PMID:26841153

  16. Oscillatory Non-collinear Magnetism Induced by Interfacial Charge Transfer in Metallic Oxide Superlattices

    Hoffman, Jason

    2015-03-01

    Non-collinear magnetic textures give rise to interesting charge and spin transport properties, and allow for control of magnetism using small electric currents. While these textures have been observed in a number of bulk materials and in thin films, realizing non-collinear magnetism in heterostructures presents new avenues to control their properties using tailored interfaces and gate electric fields. We have discovered a non-collinear magnetic coupling in superlattices comprised of two metallic perovskites, La2/3Sr1/3MnO3 (LSMO) and LaNiO3 (LNO). The superlattices are synthesized using oxide molecular beam epitaxy, and characterized with a variety of means, including x-ray and neutron scattering. We find that the angle between the magnetization of the LSMO layers varies in an oscillatory manner with the thickness of the intervening LNO. The magnetic field and temperature dependence of this coupling angle cannot be explained using models that incorporate bilinear and biquadratic coupling, which are commonly used to describe non-collinear magnetism in conventional metallic heterostructures. Furthermore, we observe substantial electron transfer from the LSMO into the LNO layer, causing the Ni sites in the vicinity of interfaces to be in approximately a 2+ oxidation state. We propose a model where these localized Ni2+ spins in the LNO couple to a momentum dependent spin susceptibility, giving rise to a spiral magnetic structure within the LNO.

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

    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.

  18. An approach to long-range electron transfer mechanisms in metalloproteins: In situ scanning tunneling microscopy with submolecular resolution

    Friis, Esben P.; Jens E. T. Andersen; Kharkats, Yu. I.; Kuznetsov, A. M.; Nichols, R.J.; Zhang, J.-D.; Ulstrup, Jens

    1999-01-01

    In situ scanning tunneling microscopy (STM) of redox molecules, in aqueous solution, shows interesting analogies and differences compared with interfacial electrochemical electron transfer (ET) and ET in homogeneous solution. This is because the redox level represents a deep indentation in the tunnel barrier, with possible temporary electronic population. Particular perspectives are that both the bias voltage and the overvoltage relative to a reference electrode ca...

  19. Tailoring liquid/solid interfacial energy transfer: fabrication and application of multiscale metallic surfaces with engineered heat transfer and electrolysis properties via femtosecond laser surface processing techniques

    Anderson, Troy P.; Wilson, Chris; Zuhlke, Craig A.; Kruse, Corey; Hassebrook, Anton; Somanas, Isra; Ndao, Sidy; Gogos, George; Alexander, Dennis

    2014-03-01

    Femtosecond Laser Surface Processing (FLSP) is a powerful technique for the fabrication of self-organized multiscale surface structures on metals that are critical for advanced control over energy transfer at a liquid/solid interface in applications such as electrolysis. The efficiency of the hydrogen evolution reaction on stainless steel 316 electrodes in a 1 molar potassium hydroxide solution is used to analyze the role of surface geometry to facilitate the phase conversion of the liquid to a gaseous state in the vicinity of the interface. It is found that the efficiency of the electrolysis process is directly related to the separation of micro-scale features on an electrode surface. The enhancement is attributed to the size of the valleys between microstructures controlling the contact between an evolving vapor bubble and the electrode surface. The results suggest an alternative pathway for the tailoring of interfacial energy transfer on structured surfaces separate from traditional benchmarks such as surface area and contact angle.

  20. Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells.

    Zhou, Nanjia; Kim, Myung-Gil; Loser, Stephen; Smith, Jeremy; Yoshida, Hiroyuki; Guo, Xugang; Song, Charles; Jin, Hosub; Chen, Zhihua; Yoon, Seok Min; Freeman, Arthur J; Chang, Robert P H; Facchetti, Antonio; Marks, Tobin J

    2015-06-30

    In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor-inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance. PMID:26080437

  1. Extracellular electron transfer from cathode to microbes: application for biofuel production.

    Choi, Okkyoung; Sang, Byoung-In

    2016-01-01

    Extracellular electron transfer in microorganisms has been applied for bioelectrochemical synthesis utilizing microbes to catalyze anodic and/or cathodic biochemical reactions. Anodic reactions (electron transfer from microbe to anode) are used for current production and cathodic reactions (electron transfer from cathode to microbe) have recently been applied for current consumption for valuable biochemical production. The extensively studied exoelectrogenic bacteria Shewanella and Geobacter showed that both directions for electron transfer would be possible. It was proposed that gram-positive bacteria, in the absence of cytochrome C, would accept electrons using a cascade of membrane-bound complexes such as membrane-bound Fe-S proteins, oxidoreductase, and periplasmic enzymes. Modification of the cathode with the addition of positive charged species such as chitosan or with an increase of the interfacial area using a porous three-dimensional scaffold electrode led to increased current consumption. The extracellular electron transfer from the cathode to the microbe could catalyze various bioelectrochemical reductions. Electrofermentation used electrons from the cathode as reducing power to produce more reduced compounds such as alcohols than acids, shifting the metabolic pathway. Electrofuel could be generated through artificial photosynthesis using electrical energy instead of solar energy in the process of carbon fixation. PMID:26788124

  2. Biotechnological Aspects of Microbial Extracellular Electron Transfer.

    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

  3. Electron Transfer Dissociation Mass Spectrometry in Proteomics

    Kim, Min-Sik; Pandey, Akhilesh

    2012-01-01

    Mass spectrometry has rapidly evolved to become the platform of choice for proteomic analysis. While CID remains the major fragmentation method for peptide sequencing, electron transfer dissociation (ETD) is emerging as a complementary method for characterization of peptides and post-translational modifications (PTMs). Here, we review the evolution of ETD and some of its newer applications including characterization of PTMs, non-tryptic peptides and intact proteins. We will also discuss some ...

  4. Promoting Interspecies Electron Transfer with Biochar

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

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with...

  5. Promoting interspecies electron transfer with biochar

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

    2014-01-01

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

  6. Education and solar conversion. Demonstrating electron transfer

    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

  7. The comparison of steam-water interfacial condensation heat transfer correlation in vertical channel

    Safety injection water is injected into the reactor vessel downcomer directly in Korean Next Generation Reactor(KNGR). Due to the adoption of direct vessel injection(DVI) method, thermal hydraulic phenomena different from existing cold leg injection plants can be occurred during large break loss of coolant accidents (LBLOCAs). Therefore, safety evaluation against LBLOCA has been performed for KNGR using TRAC-M/F77 code. One of the important phenomena is steam-water condensation in the upper downcomer. In the paper, heat transfer correlation of TRAC code is evaluated through the comparison between the correlation and the experiment results for steam-water heat transfer in vertical rectangular channel. As a result, TRAC code predicts the heat transfer coefficient larger than those of experiment results. Therefore, in LBLOCA analysis using TRAC code, the sensitivity studies for heat transfer in upper downcomer should be performed to evaluate the uncertainty

  8. Finite difference method for computer study of the interfacial heat transfer coefficient during rapid solidification of spherical samples on a metallic substrate

    Nikolić Z.S.

    2007-01-01

    Full Text Available In this paper a numerical model will be adopted to analyze the heat transfer process during rapid solidification of a spherical sample placed on a metallic substrate cooled by water. The interfacial heat transfer coefficient between the sample and the substrate will be evaluated by matching model calculations with the surface temperature history recorded by a digital camera during solidification of a sample melted in an Arc-image furnace. .

  9. Finite difference method for computer study of the interfacial heat transfer coefficient during rapid solidification of spherical samples on a metallic substrate

    Nikolić Z.S.; Yoshimura M.; Araki S.; Fujiwara T.

    2007-01-01

    In this paper a numerical model will be adopted to analyze the heat transfer process during rapid solidification of a spherical sample placed on a metallic substrate cooled by water. The interfacial heat transfer coefficient between the sample and the substrate will be evaluated by matching model calculations with the surface temperature history recorded by a digital camera during solidification of a sample melted in an Arc-image furnace. .

  10. Interfacial mass transfer to a cylinder endwall during spin-up/spin-down

    Larrousse, Mark F.; Wilcox, William R.

    1990-01-01

    The local rate of mass transfer to the bottom endwall of a large aspect ratio cylinder was measured during spin-up/spin-down. The local mass transfer rate was a strong function radial position along the endwall. At the center during spin-up from rest, the maximum enhancement in mass transfer occurred after the Ekman time scale and before the viscous time scale. At the center during spin-down to rest, a stagnation vortex formed, causing the mass transfer rate to decay and then increase back to the original value of the order of the viscous time scale. Away from the center a much more complicated pattern was observed, but spin-up and spin-down were similar. Two peaks in mass transfer rate occurred for an Ekman number over 0.0074. Alternating spin-up and spin-down with a short period caused the center of the endwall to experience a nearly sinusoidal variation in mass transfer with the frequency equal to the forcing frequency. Near the edge the frequency was twice the forcing frequency.

  11. An investigation of the effects of interfacial shear between the gas and turbulent falling liquid film on the heat transfer coefficient

    An improved method is presented for the prediction of heat transfer coefficients in turbulent falling liquid films with or without interfacial shear for both heating or condensation. A modified Mudawwar and El-Masri's semiempirical turbulence model, particularly to extend its use for the turbulent falling film with high interfacial shear, is used to replace the eddy viscosity model incorporated in the unified approach proposed by Yih and Liu. The liquid film thickness and asymptotic heat transfer coefficients against the film Reynolds number for wide range of interfacial shear predicted by both present and existing methods are compared with experimental data. The results show that, in general, predictions of the modified model agree more closely with experimental data than that of existing models. Comparisons of the predictions of the present model with that of existing models and the experimental data show that agreement is fairly good and consistent. A brief summary of the results are as follows: (1) As opposed to the previous model, present model utilizes a continuous linear variation of eddy viscosity near the interfacial surface. For freely falling liquid film, the present model reduce to the Mudawwar and El-Masri's model. (2) The curves of the present model for the heat transfer coefficients with liquid film Reynolds number have positive slopes in turbulent regime while the curves obtained by other models have negative slopes particularly for condensation. (3) The two criteria for transition from laminar to turbulent film flow, one for low interfacial shear and the other for high interfacial shear, respectively are shown to give the best agreement with the data for the present method

  12. Summary of Interfacial Heat Transfer Model and Correlations in SPACE Code

    Bae, Sung Won; Lee, Seung Wook; Kim, Kyung Du [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-10-15

    The first stage of development program for a nuclear reactor safety analysis code named as SPACE which will be used by utility bodies has been finished at last April 2010. During the first stage, main logic and conceptual sculpture have been established successfully under the support of Korea Ministry of Knowledge and Economy. The code, named as SPACE, has been designed to solve the multi-dimensional 3-field 2 phase equations. From the beginning of second stage of development, KNF has moved to concentrate on the methodology evaluation by using he SPACE code. Thus, KAERI, KOPEC, KEPRI have been remained as the major development organizations. In the second stage, it is focused to assess the physical models and correlations of SPACE code by using the well known SET problems. For the successful SET assessment procedure, a problem selection process has been performed under the leading of KEPRI. KEPRI has listed suitable SET problems according to the individual assessment purpose. For the interfacial area concentration, the models and correlations are continuously modified and verified

  13. Electronic Structure and Ferromagnetism Modulation in Cu/Cu2O Interface: Impact of Interfacial Cu Vacancy and Its Diffusion

    Li, Hao-Bo; Wang, Weichao; Xie, Xinjian; Cheng, Yahui; Zhang, Zhaofu; Dong, Hong; Zheng, Rongkun; Wang, Wei-Hua; Lu, Feng; Liu, Hui

    2015-10-01

    Cu/Cu2O composite structures have been discovered to show sizable ferromagnetism (FM) with the potential applications in spintronic devices. To date, there is no consensus on the FM origin in Cu/Cu2O systems. Here, first principles calculations are performed on the interface structure to explore the microscopic mechanism of the FM. It is found that only the Cu vacancy (VCu) adjacent to the outermost Cu2O layer induces a considerable magnetic moment, mostly contributed by 2p orbitals of the nearest-neighbor oxygen atom (ONN) with two dangling bonds and 3d orbitals of the Cu atoms bonding with the ONN. Meanwhile, the charge transfer from Cu to Cu2O creates higher density of states at the Fermi level and subsequently leads to the spontaneous FM. Furthermore, the FM could be modulated by the amount of interfacial VCu, governed by the interfacial Cu diffusion with a moderate energy barrier (~1.2 eV). These findings provide insights into the FM mechanism and tuning the FM via interfacial cation diffusion in the Cu/Cu2O contact.

  14. Interfacial electronic structure of Na deposited on rubrene thin film studied by synchrotron radiation photoemission

    Wei, Ching-Hsuan; Cheng, Chiu-Ping; Lin, Hong-Cheu; Pi, Tun-Wen

    2015-12-01

    The electronic structure of rubrene doped with various concentrations of Na was studied by synchrotron-radiation photoemission. Three stages of development were found with increasing Na concentration; Na penetrating deep into the organic film, followed by development of gap states, and ended with a metallic Na film. The charge transfer from Na to rubrene resulted in a vacuum-level shift. By doping Na into rubrene, we could control the IP of the organic molecule, which is favorable for application in organic semiconductor devices.

  15. Analysis of anodic current transient measured on Pd electrode with fractal surface: Hydrogen diffusion coupled with interfacial charge transfer

    Hydrogen transport through Pd electrode with fractally rough surface was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. The Pd electrode surfaces were electrochemically modified to be rough by redox cycling in 1 M H2SO4 solution. From the triangulation analysis of the atomic force microscopy images, it was found that the modified electrode surfaces exhibited self-similar scaling properties with different fractal dimensions, depending upon the number of redox cycles. The anodic current transient measured on the surface-modified fractal electrode subjected to the hydrogen discharging potentials of 0.3-0.7 V reversible hydrogen electrode (RHE) showed the non-generalised Cottrell behaviour, which resulted from the constraint of hydrogen diffusion mixed with interfacial charge transfer during hydrogen transport. Especially, it displayed an inflexion point at the time that corresponds to the temporal outer cut-off of fractality, i.e. the crossover time required for the fractal to flat transition. In addition, the temporal outer cut-off under the constraint of mixed control was observed to be shortened with increasing hydrogen discharging potential, which could be accounted for by the increased growth rate of diffusion layer in the electrode accompanying the facilitated charge transfer kinetics at the electrode/electrolyte interface

  16. Interfacial Heat Transfer during Die Casting of an Al-Si-Cu Alloy

    Hamasaiid, A.; Wang, G.; Davidson, C.; Dour, G.; Dargusch, M. S.

    2009-12-01

    The relationship between in-cavity pressure, heat flux, and heat-transfer coefficient during high-pressure die casting of an Al-9 pct Si-3 pct Cu alloy was investigated. Detailed measurements were performed using infrared probes and thermocouple arrays that accurately determine both casting and die surface temperatures during the pressure die casting of an aluminum A380 alloy. Concurrent in-cavity pressure measurements were also performed. These measurements enabled the correlation between in-cavity pressure and accurate heat-transfer coefficients in high-pressure die-casting operations.

  17. Nonlinear quantum effects on electron transfer reactions

    Yoshimori, A.

    1995-03-01

    An approximate expression is developed for a nonadiabatic electron transfer rate to estimate quantum effects of nuclear rearrangements. The time-dependent formula for Fermi's golden rule is expanded by Plank's constant to the second order, using the Wigner transformation. The method of h̵- expansion is applicable to systems with nonlinear potentials or many degrees of freedom. Using a continuum approximation, from the expansion, a rate expression is obtained, including sizes of reactants and a distance between reactants explicitly. The ratio of the obtained rate to the classical rate agrees well with a ratio by a quantum Monte Carlo simulation.

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

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

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

    Bruning, H.; Helm, H.; Briggs, J. S.

    2007-11-01

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

  20. Computational Approach to Electron Charge Transfer Reactions

    Jónsson, Elvar Örn

    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 to...... 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 to...... structure modes. This is for a large iridium-iridium dimer complex which shows a dramatic structural (and vibrational) change upon electronic excitation....

  1. Electron transfer in branched expanded pyridinium molecules

    Hromadová, Magdaléna; Lachmanová, Štěpánka; Pospíšil, Lubomír; Fortage, J.; Dupeyre, G.; Perruchot, Ch.; Lainé, P. P.

    Aveiro : DEMAC - Universidade de Aveiro, 2014. s. 99-99. [Meeting of the Portuguese Electrochemical Society /19./. Iberian Meeting of Electrochemistry /16./. 30.06.2014-02.07.2014, Aveiro] R&D Projects: GA ČR(CZ) GA14-05180S Grant ostatní: Rada Programu interní porpory projektů mezinárodní spolupráce AV ČR M200401202 Institutional support: RVO:61388955 Keywords : electron transfer * electrochemistry * pyridinium Subject RIV: CG - Electrochemistry

  2. Electronic Energy Transfer in Polarizable Heterogeneous Environments

    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...... embedding model has been suggested (C. Curutchet, A. Muoz-Losa, S. Monti, J. Kongsted, G. D. Scholes, and B. Mennucci, J. Chem. Theory Comput., 2009 5 (7), 1838-1848). In this work, we further develop this computational model by extending it with an ab initio derived polarizable force field including...

  3. Computational micromechanics analysis of electron hopping and interfacial damage induced piezoresistive response in carbon nanotube-polymer nanocomposites

    Carbon nanotube (CNT)-polymer nanocomposites have been observed to exhibit an effective macroscale piezoresistive response, i.e., change in macroscale resistivity when subjected to applied deformation. The macroscale piezoresistive response of CNT-polymer nanocomposites leads to deformation/strain sensing capabilities. It is believed that the nanoscale phenomenon of electron hopping is the major driving force behind the observed macroscale piezoresistivity of such nanocomposites. Additionally, CNT-polymer nanocomposites provide damage sensing capabilities because of local changes in electron hopping pathways at the nanoscale because of initiation/evolution of damage. The primary focus of the current work is to explore the effect of interfacial separation and damage at the nanoscale CNT-polymer interface on the effective macroscale piezoresistive response. Interfacial separation and damage are allowed to evolve at the CNT-polymer interface through coupled electromechanical cohesive zones, within a finite element based computational micromechanics framework, resulting in electron hopping based current density across the separated CNT-polymer interface. The macroscale effective material properties and gauge factors are evaluated using micromechanics techniques based on electrostatic energy equivalence. The impact of the electron hopping mechanism, nanoscale interface separation and damage evolution on the effective nanocomposite electrostatic and piezoresistive response is studied in comparison with the perfectly bonded interface. The effective electrostatic/piezoresistive response for the perfectly bonded interface is obtained based on a computational micromechanics model developed in the authors’ earlier work. It is observed that the macroscale effective gauge factors are highly sensitive to strain induced formation/disruption of electron hopping pathways, interface separation and the initiation/evolution of interfacial damage. (paper)

  4. Role of surface stoichiometry on the interfacial electron behavior at Ni/TiO2(0 0 1) interfaces

    Highlights: ► Surface stoichiometry affects the interfacial charge re-distribution. ► Separation of electron–hole pairs depends on surface stoichiometry. ► Oxidization state of Ni depends on the initial conditions of the TiO2 surface. ► Insulator-to-metal transition affects the binding energies. - Abstract: The interfacial properties of Ni clusters grown on the stoichiometric and reduced rutile TiO2(0 0 1) surfaces were investigated by means of X-ray photoelectron spectroscopy (XPS). The binding energies (BE's) of elements from both overlayers and substrates were found to be affected by the formation of interfacial dipole. Regardless of the TiO2 surface stoichiometry, the Ni 2p3/2 BE's move monotonically toward lower value with the increase of Ni thickness due to the cluster size effect. However, the Ni 2p3/2 BE shift is much smaller on reduced TiO2(0 0 1) surfaces compared to that on the annealed stoichiometric surface. For stoichiometric and lightly reduced TiO2 surfaces, O 1s BE's exhibit an unexpected upward shift with increasing Ni thickness below 2 Å, and then downward shift to lower BE's when the Ni thickness increases further. This opposite tendency is attributed to the insulator-to-metal transition. On heavily reduced surface, only monotonically downward shift of the O 1s BE's was observed with the increase of Ni thickness. The different behaviors are well elucidated by collective contributions of interfacial charge transfer and image charge effect.

  5. In situ scanning tunnelling microscopy of redox molecules. Coherent electron transfer at large bias voltages

    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 with the...... substrate 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...

  6. Electron transfer pathways in microbial oxygen biocathodes

    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 O2 reduction by heme compounds. Here we showed that 1 μM 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 O2 reduction to H2O2 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.

  7. Mediated Electron Transfer at Redox Active Monolayers

    Michael E.G. Lyons

    2001-12-01

    Full Text Available A theoretical model describing the transport and kinetic processes involved in heterogeneous redox catalysis of solution phase reactants at electrode surfaces coated with redox active monolayers is presented. Although the analysis presented has quite general applicability, a specific focus of the paper is concerned with the idea that redox active monolayers can be used to model an ensemble of individual molecular nanoelectrodes. Three possible rate determining steps are considered: heterogeneous electron transfer between immobilized mediator and support electrode ; bimolecular chemical reaction between redox mediator and reactant species in the solution phase, and diffusional mass transport of reactant in solution. A general expression for the steady state reaction flux is derived which is valid for any degree of reversibility of both the heterogeneous electron transfer reaction involving immobilized mediator species and of the bimolecular cross exchange reaction between immobilized mediator and solution phase reactant. The influence of reactant transport in solution is also specifically considered. Simplified analytical expressions for the net reaction flux are derived for experimentally reasonable situations and a kinetic case diagram is constructed outlining the relationships between the various approximate solutions. The theory enables simple diagnostic plots to be constructed which can be used to analyse experimental data.

  8. Electron transfer pathways in microbial oxygen biocathodes

    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.

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

    Zhu, Nan; Hao, Xian; Ulstrup, Jens; Chi, Qijin

    2016-01-01

    Long-range electron transfer (LRET) is a core elementary step in a wealth of processes central to chemistry and biology, including photosynthesis, respiration, and catalysis. In nature, biological catalysis is performed by enzymes. However, enzymes are structurally fragile and have limited...... correlation between electrocatalytic efficiency and distance-dependent interfacial ET kinetics. Given their high stability and low cost, such enzyme-mimicking nanoparticles could offer new perspectives in the fields of catalysis, sensors, and electrochemical energy conversion....

  10. Electronic excitation transfer in concentrated micelle solutions

    Electronic excitation transport among interacting clusters of chromophores is investigated as a function of chromophores is investigated as a function of chromophore and cluster concentration. The technique of time-correlated single photon counting is employed to obtain time-resolved fluorescence depolarization data on aqueous octadecylrhodamine B/triton X-100 micelle solutions. The time-dependent fluorescence anisotropy, the energy transport observable, is directly compared to a theory developed to model this system. The theory is based on a first-order cumulant approximation to the solution of the transport master equation. The model depicts the micelles as monodisperse hard spheres with chromophores (octadecylrhodamine B) distributed about their surfaces. At low micelle concentration, the dynamics of excitation transfer depend only on internal micelle structure. At high micelle concentration excitation transfer occurs among chromophores on different micelles in addition to intramicelle transfer. The theoretical treatment provides nearly quantitative descriptions of the time and concentration dependence of the excitation transport. It correctly predicts the concentration at which intermicelle transfer becomes significant. In the low micelle concentration limit (energy transport confined to isolated micelles) the model having a Poisson distribution of chromophores works well for small ? ([chromophores]/[micelle]), but progressively worse as ? is increased. Following the literature, a chromophere interaction parameter (in the form of a two dimensional second virial coefficient) is used to skew the probe distribution. This enables the transport theory to reproduce the data for all the values of ? investigated and provides a determination of the second virial coefficient. 34 refs., 4 figs., 2 tabs

  11. A test for interfacial effects and stress transfer in ceramic matrix composites

    Bascom, Willard D.; Lee, Ilzoo

    1988-01-01

    The efforts to fabricate single embedded filament specimens of carbon and SiC fibers were unsuccessful largely due to the thermal stresses resulting from differences in thermal coefficient of expansion. Other factors appear to have been involved including embrittlement of the metal substrate by the H2 gas in the chemical vapor deposition flow stream and reaction layers formed between the silicon carbide and the metal substrate. The carbon fiber may have been attacked by the CVD reactant. It is concluded that these differential stresses are so large as to make the embedded fiber test impractical for the study of interphase effects and stress transfer in fiber ceramic matrix systems.

  12. Electron transfer in gas surface collisions

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

  13. Photoinduced electron transfer in model systems of photosynthesis.

    Hofstra, U.

    1988-01-01

    This Thesis describes Investigations on photoinduced electron transfer (ET) for several compounds, serving as model systems of the natural photosynthesis. In addition, the properties of the systems, e.g. the conformation in solution and the electronic properties of the photoexcited states are treated.Chapter 2 discusses present theories of photoinduced electron transfer. The following factors appear to effect the electron transfer rate constants:- donor-acceptor distance- nature of the linkin...

  14. Activation entropy of electron transfer reactions

    Milischuk, A A; Newton, M D; Milischuk, Anatoli A.; Matyushov, Dmitry V.; Newton, Marshall D.

    2005-01-01

    We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by conti...

  15. GPU-accelerated computation of electron transfer.

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

    2012-11-01

    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. PMID:22847673

  16. Interfacial electronic transport phenomena in single crystalline Fe-MgO-Fe thin barrier junctions

    Gangineni, R. B., E-mail: rameshg.phy@pondiuni.edu.in [Department of Physics, School of Physical, Chemical and Applied Sciences, Pondicherry University, R. V. Nagar, Kalapet, Pondicherry 605 014 (India); SPINTEC, UMR 8191 CEA/CNRS/UJF-Grenoble 1/Grenoble INP, INAC, 17 rue des Martyrs, F-38054 Grenoble Cedex (France); Bellouard, C., E-mail: christine.bellouard@ijl.nancy-universite.fr; Duluard, A. [Institut Jean Lamour, UMR 7198, CNRS-Université de Lorraine, BP 239, 54506 Vandoeuvre (France); Negulescu, B. [Institut Jean Lamour, UMR 7198, CNRS-Université de Lorraine, BP 239, 54506 Vandoeuvre (France); UFR de Sciences et Techniques, Matériaux, microélectronique, acoustique, nanotechnologies (GREMAN), University François Rabelais, Parc de Grandmont, 37200 Tours (France); Baraduc, C.; Gaudin, G. [SPINTEC, UMR 8191 CEA/CNRS/UJF-Grenoble 1/Grenoble INP, INAC, 17 rue des Martyrs, F-38054 Grenoble Cedex (France); Tiusan, C., E-mail: coriolan.tiusan@phys.utcluj.ro [Institut Jean Lamour, UMR 7198, CNRS-Université de Lorraine, BP 239, 54506 Vandoeuvre (France); Department of Physics and Chemistry, Center of Superconductivity, Spintronics and Surface Science, Technical University of Cluj Napoca, Str. Memorandumului No. 28, RO-400114 Cluj-Napoca (Romania)

    2014-05-05

    Spin filtering effects in nano-pillars of Fe-MgO-Fe single crystalline magnetic tunnel junctions are explored with two different sample architectures and thin MgO barriers (thickness: 3–8 monolayers). The two architectures, with different growth and annealing conditions of the bottom electrode, allow tuning the quality of the bottom Fe/MgO interface. As a result, an interfacial resonance states (IRS) is observed or not depending on this interface quality. The IRS contribution, observed by spin polarized tunnel spectroscopy, is analyzed as a function of the MgO barrier thickness. Our experimental findings agree with theoretical predictions concerning the symmetry of the low energy (0.2 eV) interfacial resonance states: a mixture of Δ{sub 1}-like and Δ{sub 5}-like symmetries.

  17. Study on interfacial heat transfer coefficient at metal/die interface during high pressure die casting process of AZ91D alloy

    GUO Zhi-peng

    2007-02-01

    Full Text Available The high pressure die casting (HPDC process is one of the fastest growing and most efficient methods for the production of complex shape castings of magnesium and aluminum alloys in today’s manufacturing industry.In this study, a high pressure die casting experiment using AZ91D magnesium alloy was conducted, and the temperature profiles inside the die were Measured. By using a computer program based on solving the inverse heat problem, the metal/die interfacial heat transfer coefficient (IHTC was calculated and studied. The results show that the IHTC between the metal and die increases right after the liquid metal is brought into the cavity by the plunger,and decreases as the solidification process of the liquid metal proceeds until the liquid metal is completely solidified,when the IHTC tends to be stable. The interfacial heat transfer coefficient shows different characteristics under different casting wall thicknesses and varies with the change of solidification behavior.

  18. Study on interfacial heat transfer coefficient at metal/die interface during high pressure die casting process of AZ91D alloy

    GUO Zhi-peng; XIONG Shou-mei

    2007-01-01

    The high pressure die casting (HPDC) process is one of the fastest growing and most efficient methods for the production of complex shape castings of magnesium and aluminum alloys in today’s manufacturing industry.In this study, a high pressure die casting experiment using AZ91D magnesium alloy was conducted, and the temperature profiles inside the die were Measured. By using a computer program based on solving the inverse heat problem, the metal/die interfacial heat transfer coefficient (IHT...

  19. Reactions involving electron transfer at semiconductor surfaces

    Rapid isotopic equilibration was observed upon contacting an equimolar mixture of (16O2 + 18O2) at 295 or 77 K with oxygen-deficient surfaces of pure and doped zinc oxides from which light was excluded at all stages. Kinetic expressions for opposing second-order reactions accurately described variations in mole fraction of 16O2, 16O18O and 18O2 in the gas phase during the approach to full isotopic equilibration at 295 or 77 K. Rate constants thereby derived for this R0-type exchange did not correlate with reported concentrations of conduction-band electrons for the zinc oxides, indicating that the rate-determining process for exchange was not collective-electron type charge transfer at the oxygen-deficient surfaces in the absence of illumination. Surfaces could be rendered inactive by extensive preoxidation in 16O2 at 650 K in the dark, but heating for 2 h periods in the dark under continuous evacuation restored activity to a progressively increasing extent at temperatures of 400 to 650 K. Preadsorption of H2O, H2 or (CH3)2CHOH at 295 K strongly inhibited activity. An explanation of the observed results is developed. (author)

  20. Electron transfer processes in photosynthetics biological systems

    This seminar presents a conceptual model of the sequence of primary light induced electron transfer (ET) steps in photosynthetic bacteria. The temperature dependence of some of these redox reactions, like ET process between cytochrome and bacteriochlorophyll in Chromatium, is characterized by a temperature-independent rate at low temperatures and exhibits the Arrhenius-type dependence at high temperatures. The other primary ET processes, like an ET reaction between bacteriopheophytin and Fe-quinone complex in Rps. spheroides, are temperature-independent in the broad range of 4-300K. The third type of ET processes, exemplified by back ET reactions between Fe-quinone and bacteriochlorophyll in Rhs. rubrum, exhibits negative activation energy at high temperatures. The theoretical approach, describing the primary ET processes in photosynthesis, is based on the non-adiabatic multiphonon ET theory, which incorporates both a continuous distribution of optical phonons in a polar solvent and discrete intramolecular vibrational modes. The last two types of the redox reactions are attributed to activationless ET processes which play an essential role in highly efficient charge separation in primary photosynthetic processes. The transition temperature, separating the tunneling region from the activated region indicates the range of phonon frequencies involved in the ET process. Comparing the low-temperature rates with calculated Franck-Condon factors one can determine the value of the electron-exchange matrix element, which in turn provides a rough estimate of the distance scale between a donor and an acceptor in the primary ET events

  1. Photoreduction of polyhalogenated anthraquinones by direct electron transfer from alcohol

    Inoue, Haruo; Ikeda, Kenji; Mihara, Hayao; Hida, Mitsuhiko

    1983-02-01

    Polyhalogenated anthraquinones such as perfluoroanthraquinone, 1,2,3,4-tetrafluoroanthraquinone, and 1,2,3,4-tetrachloroanthraquinone are photoreduced in ethanol via direct electron transfer from ethanol. A dramatic switch-over from hydrogen-atom abstraction to electron transfer is induced by mixing of?? with n? * states in their T 1 state and the enhanced electron-accepting character of polyhalogenated anthraquinones.

  2. Electronic and Nuclear Factors in Charge and Excitation Transfer

    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.

  3. Soliton-like Solutions and Electron Transfer in DNA

    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.

  4. Transcriptomic and genetic analysis of direct interspecies electron transfer

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Summers, Zarath M; Shrestha, Minita; Liu, Fanghua; Lovley, Derek R

    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...

  5. Theory of interrelated electron and proton transfer processes

    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 and...

  6. Electrons cross transfer in multislit electromagnetic trap 'Jupiter 2M'

    The researches of cross electrons transfer in the central and parts of a trap are carried out. It is shown, that increased electrons transfer in a face part is connected to presence here toroidal area of the superseded magnetic field. The change of a magnetic configuration has resulted in reduction of a cross electrons transfer in a face part, increase of density and negative potential of plasma

  7. Imaging interfacial electrical transport in graphene–MoS{sub 2} heterostructures with electron-beam-induced-currents

    White, E. R., E-mail: ewhite@physics.ucla.edu; Kerelsky, Alexander; Hubbard, William A.; Regan, B. C., E-mail: regan@physics.ucla.edu [Department of Physics and Astronomy and California NanoSystems Institute, University of California, Los Angeles, California 90095 (United States); Dhall, Rohan; Cronin, Stephen B. [Department of Electrical Engineering, University of Southern California, Los Angeles, California 90089 (United States); Mecklenburg, Matthew [Center for Electron Microscopy and Microanalysis, University of Southern California, Los Angeles, California 90089 (United States)

    2015-11-30

    Heterostructure devices with specific and extraordinary properties can be fabricated by stacking two-dimensional crystals. Cleanliness at the inter-crystal interfaces within a heterostructure is crucial for maximizing device performance. However, because these interfaces are buried, characterizing their impact on device function is challenging. Here, we show that electron-beam induced current (EBIC) mapping can be used to image interfacial contamination and to characterize the quality of buried heterostructure interfaces with nanometer-scale spatial resolution. We applied EBIC and photocurrent imaging to map photo-sensitive graphene-MoS{sub 2} heterostructures. The EBIC maps, together with concurrently acquired scanning transmission electron microscopy images, reveal how a device's photocurrent collection efficiency is adversely affected by nanoscale debris invisible to optical-resolution photocurrent mapping.

  8. Imaging interfacial electrical transport in graphene–MoS2 heterostructures with electron-beam-induced-currents

    Heterostructure devices with specific and extraordinary properties can be fabricated by stacking two-dimensional crystals. Cleanliness at the inter-crystal interfaces within a heterostructure is crucial for maximizing device performance. However, because these interfaces are buried, characterizing their impact on device function is challenging. Here, we show that electron-beam induced current (EBIC) mapping can be used to image interfacial contamination and to characterize the quality of buried heterostructure interfaces with nanometer-scale spatial resolution. We applied EBIC and photocurrent imaging to map photo-sensitive graphene-MoS2 heterostructures. The EBIC maps, together with concurrently acquired scanning transmission electron microscopy images, reveal how a device's photocurrent collection efficiency is adversely affected by nanoscale debris invisible to optical-resolution photocurrent mapping

  9. Oxide/Electrolyte interface: Electron transfer phenomena

    Fernndez-Ibez, P.

    2000-08-01

    Full Text Available Electron transfer on a titanium dioxide/electrolyte solution interface has been studied. As observed by other researchers on similar interfaces (TiO2- and ZnO- electrolyte solution, slow consumption of OH- ions was found. A theoretical model has been developed for calculating the change in Fermi energy levels of both electrolyte solution and semiconductor, showing that ion consumption from the solution is favoured by a decreased difference in their Fermi energies. A kinetic constant (? is found to characterise the consumption process, its value increasing with electrolyte and semiconductor mass concentrations. Furthermore, this process may be used to estimate the point of zero charge of a titanium dioxide colloidal dispersion.

    En este trabajo se ha estudiado un proceso de transferencia de electrones en la interfase dixido de titanio/electrolito acuoso. Tal y como han observado otros investigadores en interfases similares (TiO2- y ZnO- electrolito, se ha detectado un consumo lento de iones OH-. Para dar explicacin a este proceso, se ha desarrollado un modelo terico basado en el clculo de las energas de Fermi en el semiconductor y en el electrolito. De este modo, se demuestra que dicho consumo de iones est favorecido por una disminucin de la diferencia entre ambos niveles de Fermi. Para caracterizar el proceso de consumo lento de OH- se define una constante cintica (?, cuyo valor aumenta a medida que crece la concentracin msica de semiconductor y de electrolito en la suspensin. Adicionalmente, este fenmeno proporciona una herramienta para determinar experimentalmente el punto de carga nula de la suspensin de dixido de titanio en el medio acuoso.

  10. Electron Transfer Dissociation of Milk Oligosaccharides

    Han, Liang; Costello, Catherine E.

    2011-06-01

    For structural identification of glycans, the classic collision-induced dissociation (CID) spectra are dominated by product ions that derived from glycosidic cleavages, which provide only sequence information. The peaks from cross-ring fragmentation are often absent or have very low abundances in such spectra. Electron transfer dissociation (ETD) is being applied to structural identification of carbohydrates for the first time, and results in some new and detailed information for glycan structural studies. A series of linear milk sugars was analyzed by a variety of fragmentation techniques such as MS/MS by CID and ETD, and MS3 by sequential CID/CID, CID/ETD, and ETD/CID. In CID spectra, the detected peaks were mainly generated via glycosidic cleavages. By comparison, ETD generated various types of abundant cross-ring cleavage ions. These complementary cross-ring cleavages clarified the different linkage types and branching patterns of the representative milk sugar samples. The utilization of different MS3 techniques made it possible to verify initial assignments and to detect the presence of multiple components in isobaric peaks. Fragment ion structures and pathways could be proposed to facilitate the interpretation of carbohydrate ETD spectra, and the main mechanisms were investigated. ETD should contribute substantially to confident structural analysis of a wide variety of oligosaccharides.

  11. Quantum coherent contributions in biological electron transfer

    Dorner, Ross; Heaney, Libby; Farrow, Tristan; Roberts, Philippa G; Hirst, Judy; Vedral, Vlatko

    2011-01-01

    Many biological electron transfer (ET) reactions are mediated by metal centres in proteins. NADH:ubiquinone oxidoreductase (complex I) contains an intramolecular chain of seven iron-sulphur (FeS) clusters, one of the longest chains of metal centres in biology and a test case for physical models of intramolecular ET. In biology, intramolecular ET is commonly described as a diffusive hopping process, according to the semi-classical theories of Marcus and Hopfield. However, recent studies have raised the possibility that non-trivial quantum mechanical effects play a functioning role in certain biomolecular processes. Here, we extend the semi-classical model for biological ET to incorporate both semi-classical and coherent quantum phenomena using a quantum master equation based on the Holstein Hamiltonian. We test our model on the structurally-defined chain of FeS clusters in complex I. By exploring a wide range of realistic parameters we and that, when the energy profile for ET along the chain is relatively at, ...

  12. Activation entropy of electron transfer reactions

    Milischuk, Anatoli A.; Matyushov, Dmitry V.; Newton, Marshall D.

    2006-05-01

    We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by continuum models is not supported by the microscopic theory. Also, the reorganization and overall solvation entropies are substantially larger in the microscopic theory compared to continuum models.

  13. Activation entropy of electron transfer reactions

    We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by continuum models is not supported by the microscopic theory. Also, the reorganization and overall solvation entropies are substantially larger in the microscopic theory compared to continuum models

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

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

  15. Photoinduced electron transfer reaction in diaminostilbene-tethered DNA duplexes.

    Ito, Takeo; Hayashi, Aiko; Uchida, Tsukasa; Tanabe, Kazuhito; Yamada, Hisatsugu; Nishimoto, Sei-Ichi

    2009-01-01

    DNA duplexes containing diaminostilbene (DAS) as a photoinduced electron donor were synthesized to investigate mechanisms of electron injection into DNA and the succeeding electron transfer in the duplexes. DAS-Capped hairpin DNA showed a high structural stability thereby attains large interaction between DAS and the terminal base pair. DAS-Tethered DNA by a single linker at the end of the duplex was also synthesized and the yields of photoinduced electron transfer through mismatched base pairs were quantified. Both duplexes showed similar electron transfer efficiencies depending on the base pairs, which suggests DAS stacks well on the "pi-way" of the duplex DNA. PMID:19749330

  16. A study of interfacial heat transfer and process parameters in squeeze casting and low pressure permanent mold casting

    Krishna, Prasad

    2001-08-01

    With the emerging demand for energy efficient and environment-friendly automobiles, cast aluminum alloys are increasingly being used in their manufacture. In this context, two permanent mold casting processes, namely, Squeeze Cast Permanent Mold and Low Pressure Permanent Mold (LPPM) have become very popular in the production of high integrity shape-cast aluminum components. However, many industries are yet to benefit from the full potential of these processes due to limited understanding of the effect of process parameters on casting quality and the necessary boundary conditions for computer modeling and simulation so as to minimize costly field trials. This dissertation attempts to address some of these concerns facing today's foundry industry. An experimental investigation of the Indirect Squeeze Casting Process was conducted by pouring molten Al-7Si-0.3Mg (A356) alloy into a specially designed and instrumented mold, mounted on a horizontal clamped-vertical shot squeeze caster (HVSC). Temperature measurements close to the metal/mold interface were made and compared with the results of the numerical simulation of heat flow during solidification and cooling of castings. The Heat Transfer Coefficient (HTC), a critical parameter essential for any solidification simulation, was estimated based on the simulation that gave the best fit to the experimental temperature data. During the solidification process, the HTC is relatively uniform over the entire casting and on reaching a critical solidification pressure, the HTC is close to 4500 W/m2 K. The work has also provided a correlation of Secondary Dendrite Arm Spacing (SDAS) with cooling rate for a modified A356 alloy. Low Pressure Permanent Mold Casting experiments were conducted by pouring a nearly identical aluminum alloy into an instrumented, coated mold mounted on a low pressure casting machine. The pressure levels, along with the time required to achieve complete filling, were microprocessor controlled in the casting machine. The HTC evaluation and SDAS-Cooling Rate Correlation were made in a similar manner to the Squeeze Casting study. A novel approach to estimating the HTC, accounting for the temporal and spatial temperature and thermal property variations, is presented. The maximum and minimum values of the HTC in this case were close to 2000 W/m2 K with no air gap and 400 W/m2 K with an air gap formation. The influences of air gap formation and mold coatings in controlling interfacial heat transfer were also modeled. It is expected that the HTCs and SDAS-Cooling Rate Correlations for the two casting processes will assist foundry engineers in deriving maximum benefits from each process.

  17. Probing the Mechanism of Electron Capture and Electron Transfer Dissociation Using Tags with Variable Electron Affinity

    Sohn, Chang Ho; Chung, Cheol K.; Yin, Sheng; Ramachandran, Prasanna; Loo, Joseph A; Beauchamp, J. L.

    2009-01-01

    Electron capture dissociation (ECD) and electron transfer dissociation (ETD) of doubly protonated electron affinity (EA)-tuned peptides were studied to further illuminate the mechanism of these processes. The model peptide FQpSEEQQQTEDELQDK, containing a phosphoserine residue, was converted to EA-tuned peptides via β-elimination and Michael addition of various thiol compounds. These include propanyl, benzyl, 4-cyanobenzyl, perfluorobenzyl, 3,5-dicyanobenzyl, 3-nitrobenzyl, and 3,5-dinitrobenz...

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

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

    2013-01-01

    An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2′,7′-dichlorofluorescein (DCF) anchored to the surface of iron(iii) oxide nanoparticles to create iron(ii) surface atoms via...... photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported....... We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115...

  19. Ultrafast Electron Transfer at Organic Semiconductor Interfaces: Importance of Molecular Orientation

    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.

  20. Comparison of hydrolytic and non-hydrolytic atomic layer deposition chemistries: Interfacial electronic properties at alumina-silicon interfaces

    We report the differences in the passivation and electronic properties of aluminum oxide (Al2O3) deposited on silicon via traditional hydrolytic atomic layer deposition (ALD) and non-hydrolytic (NH) ALD chemistries. Traditional films were grown using trimethylaluminum (TMA) and water and NHALD films grown using TMA and isopropanol at 300 °C. Hydrolytically grown ALD films contain a smaller amount of fixed charge than NHALD films (oxide fixed charge Qf Traditional = −8.1 × 1011 cm−2 and Qf NHALD = −3.6 × 1012 cm−2), and a larger degree of chemical passivation than NHALD films (density of interface trap states, Dit Traditional = 5.4 × 1011 eV−1 cm−2 and Dit NHALD = 2.9 × 1012 eV−1 cm−2). Oxides grown with both chemistries were found to have a band gap of 7.1 eV. The conduction band offset was 3.21 eV for traditionally grown films and 3.38 eV for NHALD. The increased Dit for NHALD films may stem from carbon impurities in the oxide layer that are at and near the silicon surface, as evidenced by both the larger trap state time constant (τTraditional = 2.2 × 10−9 s and τNHALD = 1.7 × 10−7 s) and the larger carbon concentration. We have shown that the use of alcohol-based oxygen sources in NHALD chemistry can significantly affect the resulting interfacial electronic behavior presenting an additional parameter for understanding and controlling interfacial electronic properties at semiconductor-dielectric interfaces

  1. Probing active electron transfer branch in photosystem I reaction center.

    Savikhin, Sergei; Dashdorj, Naranbaatar; Xu, Wu; Martinsson, Peter; Chitnis, Parag

    2003-03-01

    Complimentary point mutations were introduced at the primary electron acceptor sites in A and B branches of the photosystem I (PS I) reaction center (RC) from Synechocystis sp. PCC 6803 and their effect on the kinetics of the electron transfer process was studied by means of ultrafast pump-probe spectroscopy. The results indicate that in these species the electron transfer occurs primarily along the A-branch. Previous optical experiments on PS I complexes from Chlorella sorokiniana demonstrated that both branches of RC are equally active. That suggests that the directionality of electron transfer in PS I is species dependent.

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

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

  3. 76 FR 29901 - Electronic Fund Transfers

    2011-05-23

    ... Board anticipates that final rules on remittance transfers will be issued by the Bureau. \\26\\ 75 FR.... Thus, consumers could benefit from consistent, accessible disclosures regarding remittance transfers... approximate fees and exchange rates. When asked about the usefulness of a storefront sign showing how much...

  4. Electronic Publishing and the Information Transfer Process.

    Aveney, Brian

    1983-01-01

    Discusses new information forms that promise to force changes in the information transfer process which is based on the organization, storage, and distribution of edition printed products. Roles of authors, publishers, jobbers, librarians, and users in the information transfer process are highlighted. (EJS)

  5. Vectorial electron transfer in spatially ordered arrays. Progress report, August 1994--January 1997

    Fox, M.A.

    1997-01-01

    With DOE support from August 1994 to August 1997, this project sought to identify methods for controlled placement of light absorbers, relays, and multielectron catalysts at defined sites from a fixed semiconductor or metal surface and, thus, to develop methods for preparing chemically modified photoactive surfaces as artificial photosynthetic units. These designed materials have been evaluated as efficient light collection devices and as substrates for defining the key features that govern the efficiency of long distance electron transfer and energy migration. The authors have synthesized several different families of integrated chemical systems as soluble arrays, as solid thin films, and as adsorbates on solid electrodes, seeking to establish how spatial definition deriving from covalent attachment to a helical polymer backbone, from self assembly of functionalized tethers on gold or metal oxide surfaces, and from rigid or layered block polymers can lead to controlled electron and energy transfer. The authors have also conducted physical characterization of semiconductor-containing composites active in controlled interfacial electron transfer, with charge transport in these materials having been evaluated by photophysical and electrochemical methods.

  6. Particle size and interfacial effects on thermo-physical and heat transfer characteristics of water-based α-SiC nanofluids

    The effect of average particle sizes on basic macroscopic properties and heat transfer performance of α-SiC/water nanofluids was investigated. The average particle sizes, calculated from the specific surface area of nanoparticles, were varied from 16 to 90 nm. Nanofluids with larger particles of the same material and volume concentration provide higher thermal conductivity and lower viscosity increases than those with smaller particles because of the smaller solid/liquid interfacial area of larger particles. It was also demonstrated that the viscosity of water-based nanofluids can be significantly decreased by pH of the suspension independently from the thermal conductivity. Heat transfer coefficients were measured and compared to the performance of base fluids as well as to nanofluids reported in the literature. Criteria for evaluation of the heat transfer performance of nanofluids are discussed and optimum directions in nanofluid development are suggested.

  7. Electron Transfer Rate Maxima at Large Donor-Acceptor Distances.

    Kuss-Petermann, Martin; Wenger, Oliver S

    2016-02-01

    Because of their low mass, electrons can transfer rapidly over long (>15 Å) distances, but usually reaction rates decrease with increasing donor-acceptor distance. We report here on electron transfer rate maxima at donor-acceptor separations of 30.6 Å, observed for thermal electron transfer between an anthraquinone radical anion and a triarylamine radical cation in three homologous series of rigid-rod-like donor-photosensitizer-acceptor triads with p-xylene bridges. Our experimental observations can be explained by a weak distance dependence of electronic donor-acceptor coupling combined with a strong increase of the (outer-sphere) reorganization energy with increasing distance, as predicted by electron transfer theory more than 30 years ago. The observed effect has important consequences for light-to-chemical energy conversion. PMID:26800279

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

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

  9. Sustaining reactivity of Fe(0) for nitrate reduction via electron transfer between dissolved Fe(2+) and surface iron oxides.

    Han, Luchao; Yang, Li; Wang, Haibo; Hu, Xuexiang; Chen, Zhan; Hu, Chun

    2016-05-01

    The mechanism of the effects of Fe(2+)aq on the reduction of NO3(-) by Fe(0) was investigated. The effects of initial pH on the rate of NO3(-) reduction and the Fe(0) surface characteristics revealed Fe(2+)aq and the characteristics of minerals on the surface of Fe(0) played an important role in NO3(-) reduction. Both NO3(-) reduction and the decrease of Fe(2+)aq exhibited similar kinetics and were promoted by each other. This promotion was associated with the types of the surface iron oxides of Fe(0). Additionally, further reduction of NO3(-) produced more surface iron oxides, supplying more active sites for Fe(2+)aq, resulting in more electron transfer between Fe(2+) and surface iron oxides and a higher reaction rate. Using the isotope specificity of (57)Fe Mossbauer spectroscopy, it was verified that the Fe(2+)aq was continuously converted into Fe(3+) oxides on the surface of Fe(0) and then converted into Fe3O4 via electron transfer between Fe(2+) and the pre-existing surface Fe(3+) oxides. Electrochemistry measurements confirmed that the spontaneous electron transfer between the Fe(2+) and structural Fe(3+) species accelerated the interfacial electron transfer between the Fe species and NO3(-). This study provides a new insight into the interaction between Fe species and contaminants and interface electron transfer. PMID:26835898

  10. Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy

    Vlček Jr., Antonín; Kvapilová, Hana; Towrie, M.; Záliš, Stanislav

    2015-01-01

    Roč. 48, č. 3 (2015), s. 868-876. ISSN 0001-4842 Institutional support: RVO:61388955 Keywords : electron transfer * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 22.323, year: 2014

  11. A tubular view of electron transfer in azurin

    A new theoretical approach emphasizes tubes (tightly grouped families of pathways) for electron transfer and looks for interaction between these families rather than focussing on individual paths. in some cases, for a given donor D and acceptor A, the electron transfer can be thought of as pathway-like wherein the protein bridge can be physically reduced to a tube without changing the overall coupling. In other cases, the transfer is characterized by multiple tubes which can interfere with one another, and a single path assumption will fail to identify all of the structural elements which control the coupling. Reducing the protein to only the relevant parts (tubes) that mediate the tunneling matrix element is a useful tool for understanding electron transfer in biological medium. An example is carried out on blue copper protein azurin that plays an important role as an electron carrier in biological systems. (N.T.)

  12. Theoretical aspects of electron transfer reactions of complex molecules

    Kuznetsov, A. M.; Ulstrup, Jens

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

  13. Hierarchical assembly of ultrathin hexagonal SnS2 nanosheets onto electrospun TiO2 nanofibers: enhanced photocatalytic activity based on photoinduced interfacial charge transfer

    Zhang, Zhenyi; Shao, Changlu; Li, Xinghua; Sun, Yangyang; Zhang, Mingyi; Mu, Jingbo; Zhang, Peng; Guo, Zengcai; Liu, Yichun

    2012-12-01

    Well-designed hierarchical nanostructures with one dimensional (1D) TiO2 nanofibers (120-350 nm in diameter and several micrometers in length) and ultrathin hexagonal SnS2 nanosheets (40-70 nm in lateral size and 4-8 nm in thickness) were successfully synthesized by combining the electrospinning technique (for TiO2 nanofibers) and a hydrothermal growth method (for SnS2 nanosheets). The single-crystalline SnS2 nanosheets with a 2D layered structure were uniformly grown onto the electrospun TiO2 nanofibers consisted of either anatase (A) phase or anatase-rutile (AR) mixed phase TiO2 nanoparticles. The definite heterojunction interface between SnS2 nanosheets and TiO2 (A or R) nanoparticles were investigated by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Moreover, the as-prepared SnS2/TiO2 hierarchical nanostructures as nanoheterojunction photocatalysts exhibited excellent UV and visible light photocatalytic activities for the degradation of organic dyes (rhodamine B and methyl orange) and phenols (4-nitrophenol), remarkably superior to the TiO2 nanofibers and the SnS2 nanosheets, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the SnS2/TiO2 heterojunction. Significantly, the SnS2/TiO2 (AR) hierarchical nanostructures as the tricomponent heterojunction system possessed stronger photocatalytic activity than the bicomponent heterojunction system of SnS2/TiO2 (A) hierarchical nanostructures or TiO2 (AR) nanofibers, which was discussed in terms of the three-way photosynergistic effect between SnS2, TiO2 (A) and TiO2 (R) component in the SnS2/TiO2 (AR) heterojunction resulting in the high separation efficiency of photoinduced electron-hole pairs, as evidenced by photoluminescence (PL) and surface photovoltage spectra (SPS).Well-designed hierarchical nanostructures with one dimensional (1D) TiO2 nanofibers (120-350 nm in diameter and several micrometers in length) and ultrathin hexagonal SnS2 nanosheets (40-70 nm in lateral size and 4-8 nm in thickness) were successfully synthesized by combining the electrospinning technique (for TiO2 nanofibers) and a hydrothermal growth method (for SnS2 nanosheets). The single-crystalline SnS2 nanosheets with a 2D layered structure were uniformly grown onto the electrospun TiO2 nanofibers consisted of either anatase (A) phase or anatase-rutile (AR) mixed phase TiO2 nanoparticles. The definite heterojunction interface between SnS2 nanosheets and TiO2 (A or R) nanoparticles were investigated by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Moreover, the as-prepared SnS2/TiO2 hierarchical nanostructures as nanoheterojunction photocatalysts exhibited excellent UV and visible light photocatalytic activities for the degradation of organic dyes (rhodamine B and methyl orange) and phenols (4-nitrophenol), remarkably superior to the TiO2 nanofibers and the SnS2 nanosheets, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the SnS2/TiO2 heterojunction. Significantly, the SnS2/TiO2 (AR) hierarchical nanostructures as the tricomponent heterojunction system possessed stronger photocatalytic activity than the bicomponent heterojunction system of SnS2/TiO2 (A) hierarchical nanostructures or TiO2 (AR) nanofibers, which was discussed in terms of the three-way photosynergistic effect between SnS2, TiO2 (A) and TiO2 (R) component in the SnS2/TiO2 (AR) heterojunction resulting in the high separation efficiency of photoinduced electron-hole pairs, as evidenced by photoluminescence (PL) and surface photovoltage spectra (SPS). Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32301j

  14. Structural and interfacial characteristics of thin (2 films grown by electron cyclotron resonance plasma oxidation on [100] Si substrates

    The feasibility of fabricating ultra-thin SiO2 films on the order of a few nanometer thickness has been demonstrated. SiO2 thin films of approximately 7 nm thickness have been produced by ion flux-controlled Electron Cyclotron Resonance plasma oxidation at low temperature on [100] Si substrates, in reproducible fashion. Electrical measurements of these films indicate that they have characteristics comparable to those of thermally grown oxides. The thickness of the films was determined by ellipsometry, and further confirmed by cross-sectional High-Resolution Transmission Electron Microscopy. Comparison between the ECR and the thermal oxide films shows that the ECR films are uniform and continuous over at least a few microns in lateral direction, similar to the thermal oxide films grown at comparable thickness. In addition, HRTEM images reveal a thin (1--1.5 nm) crystalline interfacial layer between the ECR film and the [100] substrate. Thinner oxide films of approximately 5 nm thickness have also been attempted, but so far have resulted in nonuniform coverage. Reproducibility at this thickness is difficult to achieve

  15. A study of the dispersed flow interfacial heat transfer model of RELAP5/MOD2.5 and RELAP5/MOD3

    Andreani, M. [Swiss Federal Institute of Technology, Zurich (Switzerland); Analytis, G.T.; Aksan, S.N. [Paul Scherrer Institute, Villigen (Switzerland)

    1995-09-01

    The model of interfacial heat transfer for the dispersed flow regime used in the RELAP5 computer codes is investigated in the present paper. Short-transient calculations of two low flooding rate tube reflooding experiments have been performed, where the hydraulic conditions and the heat input to the vapour in the post-dryout region were controlled for the predetermined position of the quench front. Both RELAP5/MOD2.5 and RELAP5/MOD3 substantially underpredicted the exit vapour temperature. The mass flow rate and quality, however, were correct and the heat input to the vapour was larger than the actual one. As the vapour superheat at the tube exit depends on the balance between the heat input from the wall and the heat exchange with the droplets, the discrepancy between the calculated and the measured exit vapour temperature suggested that the inability of both codes to predict the vapour superheat in the dispersed flow region is due to the overprediction of the interfacial heat transfer rate.

  16. Ordered Assembly and Controlled Electron Transfer of the Blue Copper Protein Azurin at Gold (111) Single-Crystal Substrates

    Chi, Qijin; Zhang, Jingdong; Andersen, Jens Enevold Thaulov; Ulstrup, Jens

    2001-01-01

    molecular resolution reveals that both well-ordered alkanethiol and protein adlayers are present. Adsorbed azurin molecules exhibit high stability and retain electron transfer (ET) function. Long-range interfacial ET between azurin and Au(111) across variable-length alkanethiol bridges was systematically...... (beta) of 1.03 +/- 0.02 per CH2 unit at longer chain lengths. Overvoltage-dependent ET was also examined. The results provide a strategy to ordered molecular assemblies, and controlled orientation and ET of azurin at atomically planar metallic surfaces. This approach can in principle be extended to...

  17. Nuclear interlevel transfer driven by electronic transitions

    We show how a gamma-ray laser might be made by optically exciting a transfer of population from a long-lived isomer to an energetically adjacent short-lived state of the same nucleus. We compare the advantages of using transitions of high multipolarity versus transitions of low multi-polarity. Preliminary numerical investigations of the mechanism show it to be somewhat favorable. 35 refs., 4 figs

  18. Laser pulse control of bridge mediated heterogeneous electron transfer

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

  19. Freezing hot electrons. Electron transfer and solvation dynamics at D{sub 2}O and NH{sub 3}-metal interfaces

    Staehler, A.J.

    2007-05-15

    The present work investigates the electron transfer and solvation dynamics at the D{sub 2}O/Cu(111), D{sub 2}O/Ru(001), and NH{sub 3}/Cu(111) interfaces using femtosecond time-resolved two-photon photoelectron spectroscopy. Within this framework, the influence of the substrate, adsorbate structure and morphology, solvation site, coverage, temperature, and solvent on the electron dynamics are studied, yielding microscopic insight into the underlying fundamental processes. Transitions between different regimes of ET, substrate-dominated, barrier-determined, strong, and weak coupling are observed by systematic variation of the interfacial properties and development of empirical model descriptions. It is shown that the fundamental steps of the interfacial electron dynamics are similar for all investigated systems: Metal electrons are photoexcited to unoccupied metal states and transferred into the adlayer via the adsorbate's conduction band. The electrons localize at favorable sites and are stabilized by reorientations of the surrounding polar solvent molecules. Concurrently, they decay back two the metal substrate, as it offers a continuum of unoccupied states. However, the detailed characteristics vary for the different investigated interfaces: For amorphous ice-metal interfaces, the electron transfer is initially, right after photoinjection, dominated by the substrate's electronic surface band structure. With increasing solvation, a transient barrier evolves at the interface that increasingly screens the electrons from the substrate. Tunneling through this barrier becomes the rate-limiting step for ET. The competition of electron decay and solvation leads to lifetimes of the solvated electrons in the order of 100 fs. Furthermore, it is shown that the electrons bind in the bulk of the ice layers, but on the edges of adsorbed D{sub 2}O clusters and that the ice morphology strongly influences the electron dynamics. For the amorphous NH{sub 3}/Cu(111) interface, two isomers of solvated electrons are found. One exhibits electron dynamics on femtosecond, the other one on picosecond timescales. A similar transition between ET regimes is observed as for ice, but, furthermore, it is shown that - depending on layer thickness - the weak coupling limit is reached, where ET is mediated by thermally activated rearrangement of the solvent. Upon crystallization, the electron dynamics change significantly. Instead of femto- or picoseconds, the electrons reside for minutes in the adlayer. The observation of their formation dynamics allows analysis of their energetic stabilization over 17 orders of magnitude in time. It is shown that their high degree of screening is achieved by localization at orientational defects at the adsorbate-vacuum interface. (orig.)

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

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 1011 s−1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  1. Electron transfer reactions in microporous solids

    Mallouk, T.E.

    1993-01-01

    Basic thrust the research program involves use of microporous solids (zeolites, clays, layered and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. Purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H[sub 2] and I[sub 3][sup [minus

  2. Electron and proton transfer in chemistry and biology

    This book constitutes the proceedings of an international meeting held in September 19-21, 1990, at Zentrum fuer Interdisziplinaere Forschung, Universitaet Bielefeld, Germany. It describes various aspects of electron and proton transfer in chemistry and biology. The book starts with a survey of physiochemical principles of electron transfer in the gas and the solid phase, with thermodynamic and photochemical driving force. Inner and outer sphere mechanisms and the coupling of electron transfer to nuclear rearrangements are reviewed. These principles are applied to construct artificial photosynthesis. This leads to biological electron transfer involving proteins with transition metal and/or organic redox centres. The tuning of the free energy profile on the reaction trajectory through the protein by single amino acids or by the larger ensemble that determines the electrostatic properties of the reaction path is one major issue. Another one is the transformation of one-electron to paired-electron steps with protection against hazardous radical intermediates. The diversity of electron transport systems is represented in some chapters with emphasis on photosynthesis, respiration and nitrogenases. In photosynthesis of green plants light driven vectorial electron transfer is coupled to protolytic reactions, with about one quarter of the useful work derived from light quanta utilized for proton pumping across a coupling membrane. That is where the interchange of electrochemical (Dm) and chemical (ATP) forms of free energy storage and transfer in cellular energetics starts. The proton is distinguished from other reactants by an extremely small diameter and the ability of tunneling at reasonable rates. This is the basis for particular polarization, solvent and isotope effects as well as for hydrogen-bonded networks that are suited to long-range proton-transfer. (author). refs.; figs.; tabs

  3. Probing Interfacial Electronic States in CdSe Quantum Dots using Second Harmonic Generation Spectroscopy

    Doughty, Benjamin L [ORNL; Ma, Yingzhong [ORNL; Shaw, Robert W [ORNL

    2015-01-01

    Understanding and rationally controlling the properties of nanomaterial surfaces is a rapidly expanding field of research due to the dramatic role they play on the optical and electronic properties vital to light harvesting, emitting and detection technologies. This information is essential to the continued development of synthetic approaches designed to tailor interfaces for optimal nanomaterial based device performance. In this work, closely spaced electronic excited states in model CdSe quantum dots (QDs) are resolved using second harmonic generation (SHG) spectroscopy, and the corresponding contributions from surface species to these states are assessed. Two distinct spectral features are observed in the SHG spectra, which are not readily identified in linear absorption and photoluminescence excitation spectra. These features include a weak band at 395 6 nm, which coincides with transitions to the 2S1/2 1Se state, and a much more pronounced band at 423 4 nm arising from electronic transitions to the 1P3/2 1Pe state. Chemical modification of the QD surfaces through oxidation resulted in disappearance of the SHG band corresponding to the 1P3/2 1Pe state, indicating prominent surface contributions. Signatures of deep trap states localized on the surfaces of the QDs are also observed. We further find that the SHG signal intensities depend strongly on the electronic states being probed and their relative surface contributions, thereby offering additional insight into the surface specificity of SHG signals from QDs.

  4. Effect of Electron Beam Irradiation of the Characteristics of Jute Fibers and the Interfacial Properties of Jute/PLA Green Composites

    Cellulose-based natural fibers such as jute, knife and hemp have promising potential as a replacement for glass fibers in a polymer composite system because of their many advantages like natural abundance, low cost, light weight, biodegradability, carbon dioxide reduction in nature and acceptable mechanical properties. However, natural fibers need an appropriate surface treatment modifying their surface characteristics in order to effectively improve the interfacial properties as well as the mechanical and thermal properties. Electron beam irradiation technique is particularly interesting as it may offer the possibility to modify the surfaces and to enhance the properties of polymer materials such as fibers, films and composites. In addition, electron beam processing has a merit because it is a dry, solvent free and eco-friendly method with a fast throughput rate. In the present study, Jute fibers were irradiated at different dosages of electron beam from 10 to 100 kGy. The result was compared with raw jute fibers un-irradiated, showing the effect on the interfacial shear strength between jute fibers and PLA in terms of single fiber tensile property, fiber surface topology, and chemical composition occurring in jute fibers upon irradiation. It has been found that the surface topology and chemical characteristics of jute fibers significantly depended on the electron beam dosage irradiated, directly influencing the interfacial shear strength and interlaminar shear strength of jute-PLA green composites. It was concluded that electron beam irradiation played a contributing role not only in physically modifying the jute fiber surfaces but also in improving the interfacial properties between jute fibers and poly in the green composite, exhibiting the most effectiveness at a low electron beam energy of 10 kGy

  5. Effect of Electron Beam Irradiation of the Characteristics of Jute Fibers and the Interfacial Properties of Jute/PLA Green Composites

    Ji, Sang Gyu; Cho, Dong Hwan [Kumoh National Institute of Technology, Gumi (Korea, Republic of); Lee, Byung Cheol [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-07-01

    Cellulose-based natural fibers such as jute, knife and hemp have promising potential as a replacement for glass fibers in a polymer composite system because of their many advantages like natural abundance, low cost, light weight, biodegradability, carbon dioxide reduction in nature and acceptable mechanical properties. However, natural fibers need an appropriate surface treatment modifying their surface characteristics in order to effectively improve the interfacial properties as well as the mechanical and thermal properties. Electron beam irradiation technique is particularly interesting as it may offer the possibility to modify the surfaces and to enhance the properties of polymer materials such as fibers, films and composites. In addition, electron beam processing has a merit because it is a dry, solvent free and eco-friendly method with a fast throughput rate. In the present study, Jute fibers were irradiated at different dosages of electron beam from 10 to 100 kGy. The result was compared with raw jute fibers un-irradiated, showing the effect on the interfacial shear strength between jute fibers and PLA in terms of single fiber tensile property, fiber surface topology, and chemical composition occurring in jute fibers upon irradiation. It has been found that the surface topology and chemical characteristics of jute fibers significantly depended on the electron beam dosage irradiated, directly influencing the interfacial shear strength and interlaminar shear strength of jute-PLA green composites. It was concluded that electron beam irradiation played a contributing role not only in physically modifying the jute fiber surfaces but also in improving the interfacial properties between jute fibers and poly in the green composite, exhibiting the most effectiveness at a low electron beam energy of 10 kGy.

  6. Determining the effect of solid and liquid vectors on the gaseous interfacial area and oxygen transfer rates in two-phase partitioning bioreactors

    The effect of liquid and solid transfer vectors (silicone oil and Desmopan, respectively) on the gaseous interfacial area (ag) was evaluated in a two-phase partitioning bioreactor (TPPB) using fresh mineral salt medium and the cultivation broth of a toluene degradation culture (Pseudomonas putida DOT-T1E cultures continuously cultivated with and without silicone oil at low toluene loading rates). Higher values of ag were recorded in the presence of both silicone oil and Desmopan compared to the values obtained in the absence of a vector, regardless of the aqueous medium tested (1.6 and 3 times higher, respectively, using fresh mineral salt medium). These improvements in ag were well correlated to the oxygen mass transfer enhancements supported by the vectors (1.3 and 2.5 for liquid and solid vectors, respectively, using fresh medium). In this context, oxygen transfer rates of 2.5 g O2 L-1 h-1 and 1.3 g O2 L-1 h-1 were recorded in the presence of Desmopan and silicone oil, respectively, which are in agreement with previously reported values in literature. These results suggest that mass transfer enhancements in TPPBs might correspond to an increase in ag rather than to the establishment of a high-performance gas/vector/water transfer pathway.

  7. Determining the effect of solid and liquid vectors on the gaseous interfacial area and oxygen transfer rates in two-phase partitioning bioreactors

    Quijano, Guillermo [Departmento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Paseo del Prado de la Magdalena, s/n, 47005 Valladolid (Spain); Departamento de Biotecnologia y Bioingenieria, Centro de Investigacion y de Estudios, Avanzados del IPN (Cinvestav), Apdo. Postal 14-740, 07360 Mexico, D.F. (Mexico); Rocha-Rios, Jose [Departmento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Paseo del Prado de la Magdalena, s/n, 47005 Valladolid (Spain); Departamento de Ingenieria de Procesos e Hidraulica (IPH), Universidad Autonoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco No. 186, 09340 Mexico, D.F. (Mexico); Hernandez, Maria; Villaverde, Santiago [Departmento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Paseo del Prado de la Magdalena, s/n, 47005 Valladolid (Spain); Revah, Sergio [Departamento de Procesos y Tecnologia, Universidad Autonoma Metropolitana-Cuajimalpa, c/o IPH, UAM-Iztapalapa, Av. San Rafael Atlixco No. 186, 09340 Mexico, D.F. (Mexico); Munoz, Raul, E-mail: mutora@iq.uva.es [Departmento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Paseo del Prado de la Magdalena, s/n, 47005 Valladolid (Spain); Thalasso, Frederic [Departamento de Biotecnologia y Bioingenieria, Centro de Investigacion y de Estudios, Avanzados del IPN (Cinvestav), Apdo. Postal 14-740, 07360 Mexico, D.F. (Mexico)

    2010-03-15

    The effect of liquid and solid transfer vectors (silicone oil and Desmopan, respectively) on the gaseous interfacial area (a{sub g}) was evaluated in a two-phase partitioning bioreactor (TPPB) using fresh mineral salt medium and the cultivation broth of a toluene degradation culture (Pseudomonas putida DOT-T1E cultures continuously cultivated with and without silicone oil at low toluene loading rates). Higher values of a{sub g} were recorded in the presence of both silicone oil and Desmopan compared to the values obtained in the absence of a vector, regardless of the aqueous medium tested (1.6 and 3 times higher, respectively, using fresh mineral salt medium). These improvements in a{sub g} were well correlated to the oxygen mass transfer enhancements supported by the vectors (1.3 and 2.5 for liquid and solid vectors, respectively, using fresh medium). In this context, oxygen transfer rates of 2.5 g O{sub 2} L{sup -1} h{sup -1} and 1.3 g O{sub 2} L{sup -1} h{sup -1} were recorded in the presence of Desmopan and silicone oil, respectively, which are in agreement with previously reported values in literature. These results suggest that mass transfer enhancements in TPPBs might correspond to an increase in a{sub g} rather than to the establishment of a high-performance gas/vector/water transfer pathway.

  8. Mathematics and electronics - the conceptual transfer problem

    Waks, S.

    1988-07-01

    The article deals with the gap between the technological-school student's mastery of pure mathematical principles and his/her competence in their implementation in electronics and suggests a means for narrowing this, using a case study. A cooperative effort by mathematics and electronics teachers, involving coordination of content, teaching strategies and timing, was implemented on two groups (treatment and control). The treatment group achieved significantly higher average scores in tests in those questions where the mathematical reinforcement provided in the treatment process could be used - and this in spite of the group's weaker standing in the electronics course. Moreover, it was establised that treatment students adopted a more analytical approach in their solution strategies, while control students tended to rely more on recall and 'ready-made' formulae. The main conclusion of our case study is that mastery of mathematical theory and principles is a prerequisite to efficient tackling of technological problems, but is not always enough. Cooperation between the maths and electronics teachers contributes to improvement of the teaching-learning process in a technological discipline.

  9. Atomic scale interfacial structure of hydroxyapatite observed with high-resolution transmission electron microscopy

    Sato, K.; Kumagai, Y. [Japan Science and Technology, Kawaguchi, Saitama (Japan). CREST; Kogure, T. [Japan Science and Technology, Kawaguchi, Saitama (Japan). CREST; Tokyo Univ. (Japan). Dept. of Earth and Planetary Science; Ikoma, T.; Tanaka, J. [Japan Science and Technology, Kawaguchi, Saitama (Japan). CREST; National Inst. for Research in Inorganic Materials, Tsukuba (Japan)

    2001-07-01

    The structure of {l_brace}100{r_brace} interfaces of sintered hydroxyapatite (HAp) was characterized with high-resolution transmission electron microscopy. The grain boundaries parallel to {l_brace}100{r_brace} planes were terminated with a plane crossing the hydroxyl columns, where existed PO{sub 4} tetrahedra and Ca(2) ions. When subjected to continuous electron beam irradiation parallel to the [001] zone axis, irradiation-induced damage of HAp occurred, resulting in the vitrification of hexagonal areas surrounded with {l_brace}100{r_brace} planes. The interfaces between the vitrified and crystalline regions are expected to posses the atomic arrangement identical to that observed in the grain boundaries. We propose the atomic arrangement as the most stable structure of the {l_brace}100{r_brace} facet. (orig.)

  10. Hydrogen diffusion and radiationless electron transfer in metal hydrides

    The activation energies of the radiationless electron transfer are calculated from the optical spectra of some Sc, Y, La, Lu, Nb, Pd, and Mg2Ni hydrides. These are practically the same with the values of the activation energies for hydrogen diffusion, pointing out to the importance of electron transfer from localized states to the conduction band in the mechanism of hydrogen diffusion. The exponential temperature dependence of the radiationless electron transfer probability together with vibrational tunneling at low temperatures can account for the temperature dependence of H diffusion in the entire temperature range. A comparison between the electronic structures of NiH and PdH qualitatively explains the higher activation energy of H diffusion in Ni. Isotopic effects in Pd hydrides and a treatment based on Frenkel defects also support the proposed model. (author)

  11. Numerical modeling of fast electron energy transfer

    In this paper methods of calculating energy transport by fast electrons that are currently used in the ''Diana'' program are described; this program is intended to address issues in laser thermonuclear fusion. A method is proposed for solving a kinetic equation which has the following properties: conservativeness, the absence of constraints on the grid spacing relation, monitonicity, and second order approximation. The applicability of a ''front-back'' approximation is analyzed

  12. Theory of electron transfer in ion-atom collisions

    Current development of the theory of electron transfer in ion-atom collisions is summarized. Preliminary results indicate that K-K capture cross sections at lower energies are sensitive to the proper treatment of the atomic model. It was shown that electron capture from outer shells of multielectron atoms can be calculated using the present method, in conjunction with the simple independent electron model. Some recent research is summarized. 8 references

  13. CRADA Final Report for CRADA No. ORNL99-0544, Interfacial Properties of Electron Beam Cured Composites

    Janke, C.J.

    2005-10-17

    Electron beam (EB) curing is a technology that promises, in certain applications, to deliver lower cost and higher performance polymer matrix composite (PMC) structures compared to conventional thermal curing processes. PMCs enhance performance by making products lighter, stronger, more durable, and less energy demanding. They are essential in weight- and performance-dominated applications. Affordable PMCs can enhance US economic prosperity and national security. US industry expects rapid implementation of electron beam cured composites in aircraft and aerospace applications as satisfactory properties are demonstrated, and implementation in lower performance applications will likely follow thereafter. In fact, at this time and partly because of discoveries made in this project, field demonstrations are underway that may result in the first fielded applications of electron beam cured composites. Serious obstacles preventing the widespread use of electron beam cured PMCs in many applications are their relatively poor interfacial properties and resin toughness. The composite shear strength and resin toughness of electron beam cured carbon fiber reinforced epoxy composites were about 25% and 50% lower, respectively, than those of thermally cured composites of similar formulations. The essential purpose of this project was to improve the mechanical properties of electron beam cured, carbon fiber reinforced epoxy composites, with a specific focus on composite shear properties for high performance aerospace applications. Many partners, sponsors, and subcontractors participated in this project. There were four government sponsors from three federal agencies, with the US Department of Energy (DOE) being the principal sponsor. The project was executed by Oak Ridge National Laboratory (ORNL), NASA and Department of Defense (DOD) participants, eleven private CRADA partners, and two subcontractors. A list of key project contacts is provided in Appendix A. In order to properly manage the large project team and properly address the various technical tasks, the CRADA team was organized into integrated project teams (IPT's) with each team focused on specific research areas. Early in the project, the end user partners developed ''exit criteria'', recorded in Appendix B, against which the project's success was to be judged. The project team made several important discoveries. A number of fiber coatings or treatments were developed that improved fiber-matrix adhesion by 40% or more, according to microdebond testing. The effects of dose-time and temperature-time profiles during the cure were investigated, and it was determined that fiber-matrix adhesion is relatively insensitive to the irradiation procedure, but can be elevated appreciably by thermal postcuring. Electron beam curable resin properties were improved substantially, with 80% increase in electron beam 798 resin toughness, and {approx}25% and 50% improvement, respectively, in ultimate tensile strength and ultimate tensile strain vs. earlier generation electron beam curable resins. Additionally, a new resin electron beam 800E was developed with generally good properties, and a very notable 120% improvement in transverse composite tensile strength vs. earlier generation electron beam cured carbon fiber reinforced epoxies. Chemical kinetics studies showed that reaction pathways can be affected by the irradiation parameters, although no consequential effects on material properties have been noted to date. Preliminary thermal kinetics models were developed to predict degree of cure vs. irradiation and thermal parameters. These models are continually being refined and validated. Despite the aforementioned impressive accomplishments, the project team did not fully realize the project objectives. The best methods for improving adhesion were combined with the improved electron beam 3K resin to make prepreg and uni-directional test laminates from which composite properties could be determined. Nevertheless, only minor improvements in the composite shear strength, and moderate improvements in the transverse tensile strength, were achieved. The project team was not satisfied with the laminate quality achieved, and low quality (specifically, high void fraction) laminates will compromise the composite properties. There were several problems with the prepregging and fabrication, many of them related to the use of new fiber treatments.

  14. Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin-Gold Nanoparticle Hybrid Systems

    Jensen, Palle Skovhus; Chi, Qijin; Zhang, Jingdong; Ulstrup, Jens

    2009-01-01

    We have prepared a "hybrid" of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au-S chemisorption of a 4...

  15. Adsorption and interfacial electron transfer of Saccharomyces cerevisiae yeast cytochrome c monolayers on Au(111) electrodes

    Hansen, Allan Glargaard; Boisen, Anja; Nielsen, Jens Ulrik; Wackerbarth, Hainer; Chorkendorff, Ib; Andersen, Jens Enevold Thaulov; Zhang, Jingdong; Ulstrup, Jens

    2003-01-01

    gold without drastic protein unfolding. A comprehensive approach, based on linear sweep and differential pulse voltammetry, capacitance measurements, X-ray photoelectron spectroscopy (XPS), in situ scanning tunneling microscopy (STM), and microcantilever sensor (MCS) techniques has been used. The...... voltammetric data display a thiol reductive desorption signal corresponding to close to monolayer coverage. Reductive desorption is also reflected in a capacitance peak. Voltammetric signals from the heme group in both native and partially denatured states could also be detected. XPS shows clear Au-S bond...... negative of the 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-coated MCS, with distinguishable adsorption phases in the time range from...

  16. Electronic and Interfacial Properties of PD/6H-SiC Schottky Diode Gas Sensors

    Chen, Liang-Yu; Hunter, Gary W.; Neudeck, Philip G.; Bansal, Gaurav; Petit, Jeremy B.; Knight, Dak; Liu, Chung-Chiun; Wu, Qinghai

    1996-01-01

    Pd/SiC Schottky diodes detect hydrogen and hydrocarbons with high sensitivity. Variation of the diode temperature from 100 C to 200 C shows that the diode sensitivity to propylene is temperature dependent. Long-term heat treating at 425 C up to 140 hours is carried out to determine the effect of extended heat treating on the diode properties and gas sensitivity. The heat treating significantly affects the diode's capacitive characteristics, but the diode's current carrying characteristics are much more stable with a large response to hydrogen. Scanning Electron Microscopy and X-ray Spectrometry studies of the Pd surface after the heating show cluster formation and background regions with grain structure observed in both regions. The Pd and Si concentrations vary between grains. Auger Electron Spectroscopy depth profiles revealed that the heat treating promoted interdiffusion and reaction between the Pd and SiC dw broadened the interface region. This work shows that Pd/SiC Schottky diodes have significant potential as high temperature gas sensors, but stabilization of the structure is necessary to insure their repeatability in long-term, high temperature applications.

  17. Electron transfer from nucleobase electron adducts to 5-bromouracil: a radiation chemical study

    Electron transfer to 5-bromouracil from their nucleobase electron adducts and their protonated forms has been studied by product analysis. When an electron is transferred to 5-bromouracil, the ensuing 5-bromouracil radical anion rapidly loses a bromide ion. The uracilyl radical thus formed reacts with added t-butanol, yielding uracil. From the uracil yields measured as a function of (N)/(5-BrU) after γ-radiolysis of Ar-saturated solutions it is concluded that the hetero atom protonated forms transfer electron quantitatively to 5-bromouracil. (author). 3 refs., 1 fig

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

    PravinMallaShrestha

    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. Optical and interfacial electronic properties of diamond-like carbon films

    Woollam, J. A.; Natarajan, V.; Lamb, J.; Khan, A. A.; Bu-Abbud, G.; Banks, B.; Pouch, J.; Gulino, D. A.; Domitz, S.; Liu, D. C.

    1984-01-01

    Hard, semitransparent carbon films were prepared on oriented polished crystal wafers of silicon, indium phosphide and gallium arsenide, as well as on KBr and quartz. Properties of the films were determined using IR and visible absorption spectrocopy, ellipsometry, conductance-capacitance spectroscopy and alpha particle-proton recoil spectroscopy. Preparation techniques include RF plasma decomposition of methane (and other hydrocarbons), ion beam sputtering, and dual-ion-beam sputter deposition. Optical energy band gaps as large as 2.7 eV and extinction coefficients lower than 0.1 at long wavelengths are found. Electronic state densities at the interface with silicon as low as 10 to the 10th states/eV sq cm per were found.

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

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

  1. Interfacial electronic structure at the CH{sub 3}NH{sub 3}PbI{sub 3}/MoO{sub x} interface

    Liu, Peng; Liu, Xiaoliang, E-mail: xl-liu@csu.edu.cn, E-mail: ygao@pas.rochester.edu; Lyu, Lu; Xie, Haipeng; Zhang, Hong; Niu, Dongmei; Huang, Han [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, College of Physics and Electronics, Central South University, Changsha 410083 (China); Bi, Cheng; Xiao, Zhengguo; Huang, Jinsong [Department of Mechanical and Materials Engineering and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Lincoln, Nebraska 68588-0656 (United States); Gao, Yongli, E-mail: xl-liu@csu.edu.cn, E-mail: ygao@pas.rochester.edu [Department of Physics and Astronomy, University of Rochester, Rochester, New York 14627 (United States)

    2015-05-11

    Interfacial electronic properties of the CH{sub 3}NH{sub 3}PbI{sub 3} (MAPbI{sub 3})/MoO{sub x} interface are investigated using ultraviolet photoemission spectroscopy and X-ray photoemission spectroscopy. It is found that the pristine MAPbI{sub 3} film coated onto the substrate of poly (3,4-ethylenedioxythiophene) poly(styrenesulfonate)/indium tin oxide by two-step method behaves as an n-type semiconductor, with a band gap of ?1.7?eV and a valence band edge of 1.40?eV below the Fermi energy (E{sub F}). With the MoO{sub x} deposition of 64? upon MAPbI{sub 3}, the energy levels of MAPbI{sub 3} shift toward higher binding energy by 0.25?eV due to electron transfer from MAPbI{sub 3} to MoO{sub x}. Its conduction band edge is observed to almost pin to the E{sub F}, indicating a significant enhancement of conductivity. Meanwhile, the energy levels of MoO{sub x} shift toward lower binding energy by ?0.30?eV, and an interface dipole of 2.13?eV is observed at the interface of MAPbI{sub 3}/MoO{sub x}. Most importantly, the chemical reaction taking place at this interface results in unfavorable interface energy level alignment for hole extraction. A potential barrier of ?1.36?eV observed for hole transport will impede the hole extraction from MAPbI{sub 3} to MoO{sub x}. On the other hand, a potential barrier of ?0.14?eV for electron extraction is too small to efficiently suppress electrons extracted from MAPbI{sub 3} to MoO{sub x}. Therefore, such an interface is not an ideal choice for hole extraction in organic photovoltaic devices.

  2. Electron microscopic study on interfacial characterization of electroless Ni-W-P plating on aluminium alloy

    The interface between electroless plating Ni-W-P deposit and aluminium alloy (Al) matrix at different temperature heated for 1 h was studied using transmission electron microscope. The results show that the interface between as-deposited Ni-W-P deposit and Al matrix is clear. There are no crack and cavity. The bonding of Ni-W-P deposit and Al matrix is in good condition. The Ni-W-P plating is nanocrystalline phase (5-6 nm) in diameter. After being heated at 200 deg. C for 1 h, the interface of Ni-W-P deposit and Al matrix is clear, without the appearance of the diffusion layer. There exist a diffusion layer and educts of intermetallic compounds of nickle and aluminium such as Al3Ni, Al3Ni2, NiAl, Ni5Al3 and so on between Ni-W-P deposit and Al matrix after being heated at 400 deg. C for 1 h

  3. Electron microscopic study on interfacial characterization of electroless Ni W P plating on aluminium alloy

    Hu, Yong-jun; Xiong, Ling; Meng, Ji-long

    2007-03-01

    The interface between electroless plating Ni-W-P deposit and aluminium alloy (Al) matrix at different temperature heated for 1 h was studied using transmission electron microscope. The results show that the interface between as-deposited Ni-W-P deposit and Al matrix is clear. There are no crack and cavity. The bonding of Ni-W-P deposit and Al matrix is in good condition. The Ni-W-P plating is nanocrystalline phase (5-6 nm) in diameter. After being heated at 200 °C for 1 h, the interface of Ni-W-P deposit and Al matrix is clear, without the appearance of the diffusion layer. There exist a diffusion layer and educts of intermetallic compounds of nickle and aluminium such as Al 3Ni, Al 3Ni 2, NiAl, Ni 5Al 3 and so on between Ni-W-P deposit and Al matrix after being heated at 400 °C for 1 h.

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

    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 digest by themselves. Here, we review the transfer of hydrogen and formate between bacteria and archaea that helps to sustain growth in syntrophic methanogenic communities. We also describe the proces...

  5. Electron transfer statistics and thermal fluctuations in molecular junctions

    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

  6. Coherent single-electron transfer in coupled quantum dots

    Fountoulakis, Antonios; Terzis, Andreas F.; Paspalakis, Emmanuel

    2009-10-01

    We theoretically investigate the coherent transfer of one electron between the ground states of a double coupled quantum dot structure. The coherent transfer of the electron is externally controlled by applied electromagnetic fields with on- or close-resonance driving frequencies and various shapes and duration. We derive the analytical expressions for the parameters of the external fields by approximating the quantum dot system as a three-level ?-type system. The analytical solutions are compared with numerical results and good agreement is found. The control methods developed here are applicable in symmetric and asymmetric quantum dot nanostructures.

  7. High-pressure effects on intramolecular electron transfer compounds

    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.

  8. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  9. Coupling of narrow and wide band-gap semiconductors on uniform films active in bacterial disinfection under low intensity visible light: Implications of the interfacial charge transfer (IFCT)

    Rtimi, S., E-mail: sami.rtimi@epfl.ch [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-GPAO, Station 6, CH-1015 Lausanne (Switzerland); UR Catalyse/Matériaux pour l‘Environnement et les Procédés (URCMEP), Faculté des Sciences de Gabès, Université de Gabès, 6072 Gabès (Tunisia); Sanjines, R. [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-IPMC-LNNME, Bat PH, Station 3, CH1015 Lausanne (Switzerland); Pulgarin, C., E-mail: cesar.pulgarin@epfl.ch [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-GPAO, Station 6, CH-1015 Lausanne (Switzerland); Houas, A. [UR Catalyse/Matériaux pour l‘Environnement et les Procédés (URCMEP), Faculté des Sciences de Gabès, Université de Gabès, 6072 Gabès (Tunisia); Lavanchy, J.-C. [Université de Lausanne, IMG, Centre d’Analyse Minérale, Bat Anthropole, CH-1015 Lausanne (Switzerland); Kiwi, J. [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LPI, Bat Chimie, Station 6, CH1015 Lausanne (Switzerland)

    2013-09-15

    Highlights: • Design, preparation, testing and characterization of uniform sputtered films. • Interfacial charge transfer from the Ag{sub 2}O (cb) to the lower laying Ta{sub 2}O{sub 5} (cb). • The optical absorption of TaON and TaON/Ag was proportional to E. coli inactivation. • Self-cleaning of the TaON/Ag polyester enables repetitive E. coli inactivation. -- Abstract: This study reports the design, preparation, testing and surface characterization of uniform films deposited by sputtering Ag and Ta on non-heat resistant polyester to evaluate the Escherichia coli inactivation by TaON, TaN/Ag, Ag and TaON/Ag polyester. Co-sputtering for 120 s Ta and Ag in the presence of N{sub 2} and O{sub 2} led to the faster E. coli inactivation by a TaON/Ag sample within ∼40 min under visible light irradiation. The deconvolution of TaON/Ag peaks obtained by X-ray photoelectron spectroscopy (XPS) allowed the assignment of the Ta{sub 2}O{sub 5} and Ag-species. The shifts observed for the XPS peaks have been assigned to AgO to Ag{sub 2}O and Ag{sup 0}, and are a function of the applied sputtering times. The mechanism of interfacial charge transfer (IFCT) from the Ag{sub 2}O conduction band (cb) to the lower laying Ta{sub 2}O{sub 5} (cb) is discussed suggesting a reaction mechanism. The optical absorption of the TaON and TaON/Ag samples found by diffuse reflectance spectroscopy (DRS) correlated well with the kinetics of E. coli inactivation. The TaON/Ag sample microstructure was characterized by contact angle (CA) and by atomic force microscopy (AFM). Self-cleaning of the TaON/Ag polyester after each disinfection cycle enabled repetitive E. coli inactivation.

  10. Magneto-controlled Quantized Electron Transfer to Surface-confined Redox Units and Metal Nanoparticles

    Itamar Willner

    2006-04-01

    Full Text Available Hydrophobic magnetic nanoparticles (NPs consisting of undecanoate-cappedmagnetite (Fe3O4, average diameter ca. 5 nm are used to control quantized electron transferto surface-confined redox units and metal NPs. A two-phase system consisting of anaqueous electrolyte solution and a toluene phase that includes the suspended undecanoate-capped magnetic NPs is used to control the interfacial properties of the electrode surface.The attracted magnetic NPs form a hydrophobic layer on the electrode surface resulting inthe change of the mechanisms of the surface-confined electrochemical processes. Aquinone-monolayer modified Au electrode demonstrates an aqueous-type of theelectrochemical process (2e- 2H+ redox mechanism for the quinone units in the absence ofthe hydrophobic magnetic NPs, while the attraction of the magnetic NPs to the surfaceresults in the stepwise single-electron transfer mechanism characteristic of a dry non-aqueous medium. Also, the attraction of the hydrophobic magnetic NPs to the Au electrodesurface modified with Au NPs (ca. 1.4 nm yields a microenvironment with a low dielectricconstant that results in the single-electron quantum charging of the Au NPs.

  11. Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles

    Chi, C.-C.; Hsiao, C.-H.; Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw [Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Skoropata, E.; Lierop, J. van [Department of Physics and Astronomy, University of Manitoba, Winnipeg, Manitoba R3T 2N2 (Canada)

    2015-05-07

    Significant efforts towards understanding bi-magnetic core-shell nanoparticles are underway currently as they provide a pathway towards properties unavailable with single-phased systems. Recently, we have demonstrated that the magnetism of ?-Fe2O3/CoO core-shell nanoparticles, in particular, at high temperatures, originates essentially from an interfacial doped iron-oxide layer that is formed by the migration of Co{sup 2+} from the CoO shell into the surface layers of the ?-Fe2O3 core [Skoropata et al., Phys. Rev. B 89, 024410 (2014)]. To examine directly the nature of the intermixed layer, we have used high-resolution transmission electron microscopy (HRTEM) and first-principles calculations to examine the impact of the core-shell intermixing at the atomic level. By analyzing the HRTEM images and energy dispersive spectra, the level and nature of intermixing was confirmed, mainly as doping of Co into the octahedral site vacancies of ?-Fe2O3. The average Co doping depths for different processing temperatures (150?C and 235?C) were 0.56?nm and 0.78?nm (determined to within 5% through simulation), respectively, establishing that the amount of core-shell intermixing can be altered purposefully with an appropriate change in synthesis conditions. Through first-principles calculations, we find that the intermixing phase of ?-Fe2O3 with Co doping is ferromagnetic, with even higher magnetization as compared to that of pure ?-Fe2O3. In addition, we show that Co doping into different octahedral sites can cause different magnetizations. This was reflected in a change in overall nanoparticle magnetization, where we observed a 25% reduction in magnetization for the 235?C versus the 150?C sample, despite a thicker intermixed layer.

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

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

  13. Hierarchical Sheet-on-Sheet ZnIn2S4/g-C3N4 Heterostructure with Highly Efficient Photocatalytic H2 production Based on Photoinduced Interfacial Charge Transfer

    Zhang, Zhenyi; Liu, Kuichao; Feng, Zhiqing; Bao, Yanan; Dong, Bin

    2016-01-01

    We have realized in-situ growth of ultrathin ZnIn2S4 nanosheets on the sheet-like g-C3N4 surfaces to construct a sheet-on-sheet hierarchical heterostructure. The as-synthesized ZnIn2S4/g-C3N4 heterojunction nanosheets exhibit remarkably enhancement on the photocatalytic activity for H2 production. This enhanced photoactivity is mainly attributed to the efficient interfacial transfer of photoinduced electrons and holes from g-C3N4 to ZnIn2S4 nanosheets, resulting in the decreased charge recombination on g-C3N4 nanosheets and the increased amount of photoinduced charge carriers in ZnIn2S4 nanosheets. Meanwhile, the increased surface-active-sites and extended light absorption of g-C3N4 nanosheets after the decoration of ZnIn2S4 nanosheets may also play a certain role for the enhancement of photocatalytic activity. Further investigations by the surface photovoltage spectroscopy and transient photoluminescence spectroscopy demonstrate that ZnIn2S4/g-C3N4 heterojunction nanosheets considerable boost the charge transfer efficiency, therefore improve the probability of photoinduced charge carriers to reach the photocatalysts surfaces for highly efficient H2 production. PMID:26753795

  14. Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis*

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

    2010-01-01

    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-resolu...

  15. Extremely efficient clocked electron transfer on superfluid helium

    Bradbury, F. R.; Takita, Maika; Gurrieri, T. M.; Wilkel, K. J.; Eng, Kevin; Carroll, M. S.; Lyon, S. A.

    2011-01-01

    Unprecedented transport efficiency is demonstrated for electrons on the surface of micron-scale superfluid helium filled channels by co-opting silicon processing technology to construct the equivalent of a charge-coupled device (CCD). Strong fringing fields lead to undetectably rare transfer failures after over a billion cycles in two dimensions. This extremely efficient transport is measured in 120 channels simultaneously with packets of up to 20 electrons, and down to singly occupied pixels...

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

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

    2015-01-01

    Roč. 50, č. 3 (2015), s. 470-475. ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : electron transfer dissociation * laser photodissociation * peptide ions * cation radical * chromophores * isomer distinction Subject RIV: CE - Biochemistry Impact factor: 2.379, year: 2014

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

    Farver, O; Skov, L K; Pascher, T; Karlsson, B G; Nordling, M; Lundberg, L G; Vänngård, T; Pecht, I

    1993-01-01

    apparently only marginally involved in electron transfer in wild-type azurin. Pathway calculations also suggest that a longer, through-backbone path is more efficient than the shorter one involving Trp48. The former pathway yields an exponential decay factor, beta, of 6.6 nm-1. Another mutation, raising the...

  18. Electron transfer reactions involving porphyrins and chlorophyll a

    Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H2TPP), its tetracarboxy derivative (H2TCPP), the sodium and zinc compounds (Na2TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH3)2CO-. Reduction by (CH3)2COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H2TCPP-., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H2TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 107-109 M-1 s-1 which depend on the pH and the quinone reduction potential. Reactions of Na2TPP-., ZnTPP-., and Chl a-. with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 109 M-1 s-1. The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q-.]. 8 figures, 2 tables

  19. 76 FR 81019 - Electronic Fund Transfers (Regulation E)

    2011-12-27

    ... this rule. See 76 FR 43569 (July 21, 2011). \\4\\ Public Law 111-203, section 1002(14) (defining... response to a notice published at 76 FR 75825 (Dec. 5, 2011) concerning its efforts to identify priorities... an employer and to which electronic fund transfers of the consumer's wages, salary, or other...

  20. A molecularly based theory for electron transfer reorganization energy

    Zhuang, Bilin; Wang, Zhen-Gang

    2015-12-01

    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.

  1. Photoinduced Reductive Electron Transfer in LNA:DNA Hybrids

    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...

  2. 77 FR 30923 - Electronic Fund Transfers (Regulation E)

    2012-05-24

    ... to gift cards, however, the Board was careful to note that a general-use prepaid card did not include... cards, payroll cards, electronic benefit transfers (EBTs), or gift cards. \\1\\ Mercator Advisory Group... fees, service fees, or expiration dates on gift cards, which might take the form of a gift...

  3. A molecularly based theory for electron transfer reorganization energy

    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

  4. Electronic excitation energy transfer between quasi-zero-dimensional systems

    Král, Karel; Menšík, Miroslav

    Ostrava : Tanger, 2013. ISBN 978-80-87294-44-4. [International Conference NANOCON 2013 /5./. Brno (CZ), 16.10.2013-18.10.2013] R&D Projects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron-phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism

  5. 31 CFR 208.3 - Payment by electronic funds transfer.

    2010-07-01

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

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

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

    2012-01-01

    deuteration and explain, thereby, recent experiments performed on Drosophila melanogaster. Our demonstration is based on known physical properties of biological electron transfer and on ab initio calculations on odorants carried out for the purpose of the present study. We identify a range of physical...

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

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

    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 is in...

  8. CORRELATING ELECTRONIC AND VIBRATIONAL MOTIONS IN CHARGE TRANSFER SYSTEMS

    Khalil, Munira

    2014-06-27

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

  9. Reduced density matrix hybrid approach: Application to electronic energy transfer

    Berkelbach, Timothy C; Reichman, David R

    2011-01-01

    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 t...

  10. Modulating indium doped tin oxide electrode properties for laccase electron transfer enhancement

    Indium doped tin oxide (ITO) electrodes were functionalized with gold nanoparticles (GNPs) and cysteamine monolayer to enhance the heterogeneous electron transfer process of laccase from Trametes versicolor. The assembly of GNP on ITO support was performed through generation of H+ species at the electrode surface by hydroquinone electrooxidation at 0.9 V vs Ag/AgCl. Uniform distribution of gold nanoparticle aggregates on electrode surfaces was confirmed by atomic force microscopy. The size of GNP aggregates was in the range of 200–500 nm. The enhanced charge transfer at the GNP functionalized ITO electrodes was observed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy. Electrocatalytic behavior of laccase immobilized on ITO modified electrode toward oxygen reduction reaction was evaluated using CV in the presence of 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulfuric acid (ABTS). The obtained sigmoidal-shaped voltammograms for ABTS reduction in oxygen saturated buffer solution are characteristic for a catalytic process. The intensity of catalytic current increased linearly with mediator concentration up to 6.2 × 10−4 M. The registered voltammogram in the absence of ABTS mediator clearly showed a significant faradaic current which is the evidence of the interfacial oxygen reduction. - Highlights: • Assembly of gold nanoparticles on indium tin oxide support at positive potentials • Electrochemical and morphological evaluation of the gold nanoparticle layer assembly • Bioelectrocatalytic oxygen reduction on laccase modified electrode

  11. Modulating indium doped tin oxide electrode properties for laccase electron transfer enhancement

    Diaconu, Mirela [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Chira, Ana [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania); Radu, Lucian, E-mail: gl_radu@chim.upb.ro [Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania)

    2014-08-28

    Indium doped tin oxide (ITO) electrodes were functionalized with gold nanoparticles (GNPs) and cysteamine monolayer to enhance the heterogeneous electron transfer process of laccase from Trametes versicolor. The assembly of GNP on ITO support was performed through generation of H{sup +} species at the electrode surface by hydroquinone electrooxidation at 0.9 V vs Ag/AgCl. Uniform distribution of gold nanoparticle aggregates on electrode surfaces was confirmed by atomic force microscopy. The size of GNP aggregates was in the range of 200–500 nm. The enhanced charge transfer at the GNP functionalized ITO electrodes was observed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy. Electrocatalytic behavior of laccase immobilized on ITO modified electrode toward oxygen reduction reaction was evaluated using CV in the presence of 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulfuric acid (ABTS). The obtained sigmoidal-shaped voltammograms for ABTS reduction in oxygen saturated buffer solution are characteristic for a catalytic process. The intensity of catalytic current increased linearly with mediator concentration up to 6.2 × 10{sup −4} M. The registered voltammogram in the absence of ABTS mediator clearly showed a significant faradaic current which is the evidence of the interfacial oxygen reduction. - Highlights: • Assembly of gold nanoparticles on indium tin oxide support at positive potentials • Electrochemical and morphological evaluation of the gold nanoparticle layer assembly • Bioelectrocatalytic oxygen reduction on laccase modified electrode.

  12. Photoinduced electron transfer of chlorophyll in lipid bilayer system

    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.

  13. Charge-transfer properties in the gas electron multiplier

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

  14. Synergistic Effect of Dual Electron-Cocatalysts for Enhanced Photocatalytic Activity: rGO as Electron-Transfer Mediator and Fe(III) as Oxygen-Reduction Active Site

    Yu, Huogen; Tian, Jing; Chen, Feng; Wang, Ping; Wang, Xuefei

    2015-01-01

    For a high-performance cocatalyst-modified photocatalyst, an effective interfacial separation of photogenerated electron from its corresponding holes and its following reduction reaction at the active sites are highly required. However, it is difficult for a single-component cocatalyst to simultaneously realize the crucial functions. In this study, an effective interfacial transfer of photogenerated electrons and its following rapid oxygen-reduction can be easily realized in a dual electron-cocatalyst modified Fe(III)/rGO-TiO2 photocatalyst, where the rGO nanosheets function as an electron-transfer mediator for the effective transfer of photogenerated electrons from the TiO2 surface while the Fe(III) cocatalyst serves as an electron-reduction active site to promote the following interfacial oxygen reduction. In this case, the rGO nanosheets were firstly loaded on the TiO2 nanoparticle surface by a hydrothermal method and then the Fe(III) cocatalyst was further modified on the rGO nanosheets by an impregnation method to prepare the Fe(III)/rGO-TiO2 photocatalyst. It was found that the dual electron-cocatalyst modified Fe(III)/rGO-TiO2 photocatalyst showed an obviously higher photocatalytic performance than the naked TiO2 and single-cocatalyst modified photocatalysts (such as Fe(III)/TiO2 and rGO-TiO2) owing to the synergistic effect of rGO and Fe(III) bi-cocatalysts. The present work can provide some new insights for the smart design of high-efficiency photocatalytic materials. PMID:26272870

  15. Synergistic Effect of Dual Electron-Cocatalysts for Enhanced Photocatalytic Activity: rGO as Electron-Transfer Mediator and Fe(III) as Oxygen-Reduction Active Site

    Yu, Huogen; Tian, Jing; Chen, Feng; Wang, Ping; Wang, Xuefei

    2015-08-01

    For a high-performance cocatalyst-modified photocatalyst, an effective interfacial separation of photogenerated electron from its corresponding holes and its following reduction reaction at the active sites are highly required. However, it is difficult for a single-component cocatalyst to simultaneously realize the crucial functions. In this study, an effective interfacial transfer of photogenerated electrons and its following rapid oxygen-reduction can be easily realized in a dual electron-cocatalyst modified Fe(III)/rGO-TiO2 photocatalyst, where the rGO nanosheets function as an electron-transfer mediator for the effective transfer of photogenerated electrons from the TiO2 surface while the Fe(III) cocatalyst serves as an electron-reduction active site to promote the following interfacial oxygen reduction. In this case, the rGO nanosheets were firstly loaded on the TiO2 nanoparticle surface by a hydrothermal method and then the Fe(III) cocatalyst was further modified on the rGO nanosheets by an impregnation method to prepare the Fe(III)/rGO-TiO2 photocatalyst. It was found that the dual electron-cocatalyst modified Fe(III)/rGO-TiO2 photocatalyst showed an obviously higher photocatalytic performance than the naked TiO2 and single-cocatalyst modified photocatalysts (such as Fe(III)/TiO2 and rGO-TiO2) owing to the synergistic effect of rGO and Fe(III) bi-cocatalysts. The present work can provide some new insights for the smart design of high-efficiency photocatalytic materials.

  16. 76 FR 35219 - Federal Acquisition Regulation; Information Collection; Payment by Electronic Fund Transfer

    2011-06-16

    ... Regulation; Information Collection; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD... extension of a previously approved information collection requirement concerning payment by electronic fund... contract by electronic fund transfer (EFT). The information necessary to make the EFT transaction...

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

    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.

  18. Interfacial heat transfer in squeeze casting of magnesium alloy AM60 with variation of applied pressures and casting wall-thicknesses

    Zhang, Xuezhi; Fang, Li; Sun, Zhizhong; Hu, Henry; Nie, Xueyuan; Tjong, Jimi

    2015-12-01

    The heat transfer coefficient at the casting-die interface is the most important factor on the solidification process. With the 75-ton hydraulic press machine and P20 steel die mold, 5-step castings of magnesium alloy AM60 with different wall-thicknesses (3, 5, 8, 12, 20 mm) were poured under various hydraulic pressures (30, 60, and 90 MPa) using an indirect squeeze casting process. Thermal histories throughout the die wall and the casting surface have been recorded by fine type-K thermocouples. The in-cavity local pressures measured by pressure transducers were explored at the casting-die interfaces of 5 steps. The casting-die interfacial heat transfer coefficients (IHTC) initially reached a maximum peak value followed by a gradually decline to the lower level. Similar characteristics of IHTC peak values can be observed at the applied pressures of 30, 60 and 90 MPa. With the applied pressure of 90 MPa, the peak IHTC values from steps 1 to 5 varied from 5623 to 10,649 W/m2 K. As the applied hydraulic pressure increased, the IHTC peak value of each step was increased accordingly. The wall thickness also affected IHTC peak values significantly. The peak IHTC value and heat flux increased as the step became thicker. The empirical equations relating the IHTCs to the local pressures and the solidification temperature at the casting surface were developed based on the multivariate linear and polynomial regression.

  19. Scanning Electron Microscopic Evaluation of Composite Resin-Dentin, Calcium Hydroxide-Dentin and Resin- Calcium Hydroxide Interfacial Gap with Composite Resin Restorations- An in vitro Study

    Manoranjan Reddy,

    2011-07-01

    Full Text Available The dental pulp has been shown to have its own reparative capacity and is capable not only of healing but alsoof providing a dentinal bridge in the absence of calcium hydroxide. The present study was performed to evaluateinterfacial gaps formed due to polymerization shrinkage of composite resin. 20 Maxillary or Mandibular, freshly extractedhuman third molars were prepared and filled using composite with a calcium hydroxide base. The samples were dividedinto two groups based on primer/bonding agent used i.e. Scotchbond multipurpose (Group I and Single bond (GroupII.Sectioned samples were gold sputtered and analyzed using Scanning Electron Microscope (SEM. The interfacial gap inspecimens belonging to group I and II was observed at the 3 interfaces viz; Calcium hydroxide-dentin interface (A,Composite resin - calcium hydroxide interface (B and Composite resin - dentin interface (C. The interfacial gap formedbetween calcium hydroxide and dentin (A was highly significant (p <0.01 in both groups i.e. Group I and Group II, whenit was compared with ‘B’ and ‘C’ of the same group. There was no statistical significant difference between group ‘B’ and‘C’. Thus in both the groups an interfacial gap was found between the calcium hydroxide and dentin. Interposition ofcalcium hydroxide between tooth and resin possesses some clinical disadvantages and is recommended in selectiveclinical situations.

  20. Electron Transfer Mechanisms of DNA Repair by Photolyase

    Zhong, Dongping

    2015-04-01

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

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

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-01

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the 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. PMID:22988080

  2. Electron transfer, decoherence, and protein dynamics: insights from atomistic simulations.

    Narth, Christophe; Gillet, Natacha; Cailliez, Fabien; Lévy, Bernard; de la Lande, Aurélien

    2015-04-21

    Electron transfer in biological systems drives the processes of life. From cellular respiration to photosynthesis and enzymatic catalysis, electron transfers (ET) are chemical processes on which essential biological functions rely. Over the last 40 years, scientists have sought understanding of how these essential processes function in biology. One important breakthrough was the discovery that Marcus theory (MT) of electron transfer is applicable to biological systems. Chemists have experimentally collected both the reorganization energies (λ) and the driving forces (ΔG°), two parameters of Marcus theory, for a large variety of ET processes in proteins. At the same time, theoretical chemists have developed computational approaches that rely on molecular dynamics and quantum chemistry calculations to access numerical estimates of λ and ΔG°. Yet another crucial piece in determining the rate of an electron transfer is the electronic coupling between the initial and final electronic wave functions. This is an important prefactor in the nonadiabatic rate expression, since it reflects the probability that an electron tunnels from the electron donor to the acceptor through the intervening medium. The fact that a protein matrix supports electron tunneling much more efficiently than vacuum is now well documented, both experimentally and theoretically. Meanwhile, many chemists have provided examples of the rich physical chemistry that can be induced by protein dynamics. This Account describes our studies of the dynamical effects on electron tunneling. We present our analysis of two examples of natural biological systems through MD simulations and tunneling pathway analyses. Through these examples, we show that protein dynamics sustain efficient tunneling. Second, we introduce two time scales: τcoh and τFC. The former characterizes how fast the electronic coupling varies with nuclear vibrations (which cause dephasing). The latter reflects the time taken by the system to leave the crossing region. In the framework of open quantum systems, τFC is a short time approximation of the characteristic decoherence time of the electronic subsystem in interaction with its nuclear environment. The comparison of the respective values of τcoh and τFC allows us to probe the occurrence of non-Condon effects. We use ab initio MD simulations to analyze how decoherence appears in several biological cofactors. We conclude that we cannot account for its order of magnitude by considering only the atoms or bonds directly concerned with the transfer. Decoherence results from contributions from all atoms of the system appearing with a time delay that increases with the distance from the primarily concerned atoms or bonds. The delay and magnitude of the contributions depend on the chemical nature of the system. Finally, we present recent developments based on constrained DFT for efficient and accurate evaluations of the electronic coupling in ab initio MD simulations. These are promising methods to study the subtle fluctuations of the electronic coupling and the mechanisms of electronic decoherence in biological systems. PMID:25730126

  3. Direct-contact condensation heat transfer with noncondensable gases and interfacial shear for co-current stratified wavy flow in nearly-horizontal channels

    The calibrating method for an electrochemical probe, neglecting the effect of the normal velocity on the mass transport, can cause large errors when applied to the measurement of wall shear rates in thin wavy flow with large amplitude waves. An extended calibrating method is developed to consider the contributions of the normal velocity. The turbulence-induced normal velocity component is included into the 2-D mass transport equation by means of its root mean square value multiplied by a random function. The wave-induced normal velocity component is postulated to be proportional to the normal interfacial velocity in thin wavy flow. The inclusion of the turbulence-induced normal velocity term is found to have a negligible effect on the mass transfer coefficient. The contribution of the wave-induced normal velocity can be classified on the dimensionless parameter, V. If V is above a critical value of V, Vcrit, the effects of the wave-induced normal velocity become larger with an increase in V. While its effects negligible for V < Vcrit. The unknown shear rate is numerically determined by solving the 2-D mass transport equation inversely. The present inverse method can predict the unknown shear rate more accurately in thin wavy flow with large amplitude waves than the previous method. If the normal velocity is neglected, the error that the predicted shear rate is lower than the real value is obtained. The interfacial shear stress is experimentally investigated for co-current air-water stratified flow inclined rectangular channels having a length of 1854mm, width of 120mm and height of 40mm at almost atmospheric pressure. Experiments are carried out in several inclinations from 0 .deg. up to 10 .deg. .The local film thickness and the wave height are measured at three locations, i.e., L/H = 8, 23, and 40. According to the inclination angle, the experimental data are categorized into two groups: nearly horizontal data group (0 .deg. ≤ θ ≤ 0.7 .deg. ), and inclined channel data group (0.7 .deg. ≤ θ ≤10 .deg. ). Experimental observations show that the super-critical flow only exists in the channel for the inclined channel data group while the water level gradient and hydraulic jump do for the nearly horizontal data group. For the inclined channel data group, a dimensionless wave height, Δh/h, is empirically correlated in terms of ReG and h/H. A modified root-mean-square wave height is proposed to consider the effects of the interfacial and wave propagation velocities. It is found that an equivalent roughness has a linear relationship with the modified root-mean-square wave height. Direct-contact condensation experiments of atmospheric steam and steam/air mixture on subcooled water flowing co-currently in nearly horizontal channels are carried out and the logarithmic and local heat transfer coefficients are obtained. In the case of pure steam, the heat transfer coefficient increases as an increase in the inlet steam flow rate and inclination. The heat transfer coefficient due to the increased inlet water flow rate is slightly increased. In the presence of noncondensable gas, the heat transfer coefficient is much reduced as an increase in the inlet air mass fraction. The heat transfer coefficient increases as an increase in the inlet mixture flow rate. However, it decreases as an increase in the inlet water flow rate due to the change of the heat transfer mechanism from water layer to the mixture layer. The local heat transfer coefficient is enhanced in the large amplitude region even though the noncondensable gas exists. The heat transfer resistance also depends on the water side for the large amplitude region. For all cases it is found that the heat transfer coefficient increases as an increase in inclination. Direct-contact condensation database is constructed. Assessment and improvement of the direct-condensation model in RELAP5/MOD3.2 are performed. The horizontally stratified condensation model of RELAP5/MOD3.2 overpredicts both co-current and counter-current experimental data. The correlation proposed by Kim. predicts the database relatively well compared with that of RELAP5/MOD3.2. In the presence of noncondensable gases, RELAP5/MOD3.2 overpredicts the database with a percentage error of 103.0% and 65.0% for θ = 2.1 .deg. and θ = 5.0 .deg. , respectively. However, when Kim's correlation is substituted with the Dittus-Boelter type correlation in RELAP5/MOD3.2, the prediction errors are much reduced to 25.9% and 30.0% for θ = 2.1 .deg. and θ =5.0 .deg. , respectively. Therefore, it is concluded that Kim's correlation is superior to the correlation used in RELAP5/MOD3.2 both with and without noncondensable gases

  4. Electron Transfer in DNA through magnetic bound states

    Cox, D L; Pati, S K

    2000-01-01

    Electron transfer (ET) via quantum mechanical tunneling between well separated donor (D) and acceptor (A) complexes is part of such biological processes as respiration, photosynthesis, and possibly DNA repair or damage. Data and theory for ET in proteins give a typical tunneling length of 0.1 nm. In contrast, fluorescence quenching in DNA at D/A distances of 4 nm or more suggests ET with tunneling lengths of order 1 nm. We show how such long ranged ET can be mediated by rapidly forming magnetic Kondo bound states (KS) arising from: (1) strong electron interactions and magnetic moments on D and/or A complexes satisfying suitable energy requirements, and (2) "quantum deconfinement" of electrons through extended bridge molecular orbitals. Realistic long range Coulomb interaction strengths between bridge electrons and localized D/A charges modestly enhance these ET rates.

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

    2015-01-01

    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. PMID:26439818

  6. Transfer of angular momentum in electron collisions with alkali atoms

    Measurements of the transfer of angular momentum to rubidium and sodium atoms in collisions with electrons are reported. For excitation of the rubidium 52S1/2-52P3/2 transition, it is found that existing first order distorted wave Born approximation calculations show poor agreement with the data and that a model which includes the relativistic interaction between the electrons and the atoms in the potential is needed. For the de-excitation of the sodium 42S1/2-32P3/2 transition, a long standing proposal relating to the sign of the transferred angular momentum is not supported except at small scattering angles. A convergent close coupling calculation displays excellent agreement with the measured data. Copyright (1999) CSIRO Australia

  7. Nile blue can photosensitize DNA damage through electron transfer.

    Hirakawa, Kazutaka; Ota, Kazuhiro; Hirayama, Junya; Oikawa, Shinji; Kawanishi, Shosuke

    2014-04-21

    The mechanism of DNA damage photosensitized by Nile blue (NB) was studied using (32)P-5'-end-labeled DNA fragments. NB bound to the DNA strand was possibly intercalated through an electrostatic interaction. Photoirradiated NB caused DNA cleavage at guanine residues when the DNA fragments were treated with piperidine. Consecutive guanines, the underlined G in 5'-GG and 5'-GGG, were selectively damaged through photoinduced electron transfer. The fluorescence lifetime of NB was decreased by guanine-containing DNA sequence, supporting this mechanism. Single guanines were also slightly damaged by photoexcited NB, and DNA photodamage by NB was slightly enhanced in D2O. These results suggest that the singlet oxygen mechanism also partly contributes to DNA photodamage by NB. DNA damage photosensitized by NB via electron transfer may be an important mechanism in medicinal applications of photosensitizers, such as photodynamic therapy in low oxygen. PMID:24576317

  8. Large scale oil lease automation and electronic custody transfer

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

  9. Electron transfer between quasi-zero-dimensional nanostructures

    Král, Karel; Menšík, Miroslav

    Munich : IEEE, 2010, s. 1-5. ISBN 978-1-4244-7799-9. [International Conference on Transparent Optical Networks /12./. Mnichov (DE), 27.06.2010-01.07.2010] R&D Projects: GA MŠk(CZ) OC10007; GA MŠk ME 866 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40500505 Keywords : electron transfer * quantum dots * electron -phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism http://dx.doi.org/10.1109/ICTON.2010.5548991

  10. Insights into Proton-Coupled Electron Transfer from Computation

    Provorse, Makenzie R.

    Proton-coupled electron transfer (PCET) is utilized throughout Nature to facilitate essential biological processes, such as photosynthesis, cellular respiration, and DNA replication and repair. The general approach to studying PCET processes is based on a two-dimensional More O'Ferrall-Jencks diagram in which electron transfer (ET) and proton transfer (PT) occur in a sequential or concerted fashion. Experimentally, it is difficult to discern the contributing factors of concerted PCET mechanisms. Several theoretical approaches have arisen to qualitatively and quantitatively investigate these reactions. Here, we present a multistate density functional theory (MSDFT) method to efficiently and accurately model PCET mechanisms. The MSDFT method is validated against experimental and computational data previously reported on an isoelectronic series of small molecule self-exchange hydrogen atom transfer reactions and a model complex specifically designed to study long-range ET through a hydrogen-bonded salt-bridge interface. Further application of this method to the hydrogen atom abstraction of ascorbate by a nitroxyl radical demonstrates the sensitivity of the thermodynamic and kinetic properties to solvent effects. In particular, the origin of the unusual kinetic isotope effect is investigated. Lastly, the MSDFT is employed in a combined quantum mechanical/molecular mechanical (QM/MM) approach to explicitly model PCET in condensed phases.

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

    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.

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

    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

  13. Crossed Andreev reflection versus electron transfer in graphene nanoribbons

    Haugen, Håvard; Huertas-Hernando, Daniel; Brataas, Arne; Waintal, Xavier

    2009-01-01

    We investigate the transport properties of three-terminal graphene devices, where one terminal is superconducting and two are normal metals. The terminals are connected by nanoribbons. Electron transfer (ET) and crossed Andreev reflection (CAR) are identified via the non-local signal between the two normal terminals. Analytical expressions for ET and CAR in symmetric devices are found. We compute ET and CAR numerically for asymmetric devices. ET dominates CAR in symmetric devices, but CAR can...

  14. Heterogeneous electron transfer of pesticides. Current trends and applications

    Sokolová, Romana; Hromadová, Magdaléna; Pospíšil, Lubomír

    Kerala : Transworld Research Network, 2008 - (Colombini, M.; Tassi, L.), s. 43-76 ISBN 978-81-7895-343-4 R&D Projects: GA AV ČR IAA400400505; GA MŠk LC510; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous electron transfer * pesticides * redox reactions Subject RIV: CF - Physical ; Theoretical Chemistry

  15. The Electron Transfer System of Syntrophically Grown Desulfovibrio vulgaris

    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.

  16. The electron transfer system of syntrophically grown Desulfovibrio vulgaris

    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.

  17. Electron transfer processs with excited molecules at semiconductor electrodes

    Memming, R.

    In the first part of the paper, energy levels used in solid-state physics, in electrochemistry and in photochemistry are introduced and combined in a l- electron energy concept. This is also applied to excited molecules being adsorbed at semiconductor electrodes. On the basis of this concept, theoretical models concerning electron-transfer processes between molecules in their ground and excited state and semiconductor electrodes are then developed. In the last part of the paper, a number of typical results are presented and discussed. It is shown that the primary step is an electron-transfer reaction between an excited molecule and the semiconductor, whereas energy transfer plays only a minor role, which leads mostly to quenching. Most processes can be interpreted on the basis of the theoretical model mentioned above. Various phenomena, such as quantum yield, supersensitization, quenching, and influence of pH and doping of the semiconductor are discussed in detail. Finally, a brief outlook at the applications in solar-energy conversion systems is given.

  18. Electron transfer and projectile excitation in single collisions

    Studies of electron transfer (capture) and projectile excitation together in a single encounter are reviewed. This combined capture and excitation can result from either a correlated or an uncorrelated interaction. The correlated process is referred to as resonant transfer and excitation (RTE), while the uncorrelated process is called nonresonant transfer and excitation (NTE). RTE is analogous to dielectronic recombination (DR) which occurs in the interaction between an ion and a free electron. Experimental and theoretical works leading to establishing the existence of RTE are reviewed as well as considerations relevant to distinguishing RTE from NTE. The dependences of RTE on projectile atomic number (14 ≤ Z ≤ 23) for Li-like ions, and on projectile charge state for H-like to Ne-like ions have been measured and compared with theory. The effect of the target electron momentum distribution on RTE has been demonstrated by comparing measurements for H2 and He targets. Measurements of RTE involving L-shell excitation have been conducted and compared with K-shell results. All of the measured RTE cross sections to date for H2 and He targets are in reasonable agreement with calculations based on theoretical DR cross sections averaged over the target electron momentum distribution; however, systematic discrepancies between experiment and theory exist. Additionally, is has been found that RTE can contribute considerably to total single-electron capture cross sections in the region where RTE is important, accounting for nearly half of the total capture events for calcium ions colliding with H2. (orig.)

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

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

    2015-06-01

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

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

    Hansen, Allan Glargaard; Zhang, Jingdong; Christensen, Hans Erik Mølager; Welinder, A.C.; Wackerbarth, Hainer; Ulstrup, Jens

    Voltammetry based on single-crystal, atomically-planar metal electrodes is novel in bioelectrochemistry. Together with in situ scanning tunneling microscopy (STM) directly in aqueous buffer, single-crystal voltammetry has disclosed new detail in molecular adsorption and interfacial electron trans...

  1. Coupling of narrow and wide band-gap semiconductors on uniform films active in bacterial disinfection under low intensity visible light: implications of the interfacial charge transfer (IFCT).

    Rtimi, S; Sanjines, R; Pulgarin, C; Houas, A; Lavanchy, J-C; Kiwi, J

    2013-09-15

    This study reports the design, preparation, testing and surface characterization of uniform films deposited by sputtering Ag and Ta on non-heat resistant polyester to evaluate the Escherichia coli inactivation by TaON, TaN/Ag, Ag and TaON/Ag polyester. Co-sputtering for 120 s Ta and Ag in the presence of N₂ and O₂ led to the faster E. coli inactivation by a TaON/Ag sample within ∼40 min under visible light irradiation. The deconvolution of TaON/Ag peaks obtained by X-ray photoelectron spectroscopy (XPS) allowed the assignment of the Ta₂O₅ and Ag-species. The shifts observed for the XPS peaks have been assigned to AgO to Ag₂O and Ag(0), and are a function of the applied sputtering times. The mechanism of interfacial charge transfer (IFCT) from the Ag₂O conduction band (cb) to the lower laying Ta₂O₅ (cb) is discussed suggesting a reaction mechanism. The optical absorption of the TaON and TaON/Ag samples found by diffuse reflectance spectroscopy (DRS) correlated well with the kinetics of E. coli inactivation. The TaON/Ag sample microstructure was characterized by contact angle (CA) and by atomic force microscopy (AFM). Self-cleaning of the TaON/Ag polyester after each disinfection cycle enabled repetitive E. coli inactivation. PMID:23867967

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

    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

  3. Electron transfer rates and equilibrium within cytochrome c oxidase

    Farver, O; Einarsdóttir, O; Pecht, I

    2000-01-01

    identical within experimental error and independent of the enzyme concentration. This demonstrates that a fast intramolecular electron equilibration is taking place between CuA and heme a. The rate constants for CuA --> heme a ET and the reverse (heme a --> CuA) process were found to be 13 000 s-1 and 3700......Intramolecular electron transfer (ET) between the CuA center and heme a in bovine cytochrome c oxidase was investigated by pulse radiolysis. CuA, the initial electron acceptor, was reduced by 1-methyl nicotinamide radicals in a diffusion-controlled reaction, as monitored by absorption changes at...... 830 nm. After the initial reduction phase, the 830 nm absorption was partially restored, corresponding to reoxidation of the CuA center. Concomitantly, the absorption at 445 nm and 605 nm increased, indicating reduction of heme a. The rate constants for heme a reduction and CuA reoxidation were...

  4. Noise-assisted quantum electron transfer in photosynthetic complexes

    Nesterov, Alexander I; Martnez, Jos Manuel Snchez; 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...

  5. 77 FR 34127 - Financial Management Service; Proposed Collection of Information: Electronic Transfer Account...

    2012-06-08

    ... Account (ETA) Financial Agency Agreement AGENCY: Financial Management Service, Fiscal Service, Treasury... Financial Management Service solicits comments concerning form FMS-111, ``Electronic Transfer Account (ETA...: Electronic Transfer Account (ETA) Financial Agency Agreement. OMB Number: 1510-0073. Form Number: FMS...

  6. 77 FR 24667 - TANF Assistance and Electronic Benefit Transfer Transactions; Request for Public Comment

    2012-04-25

    ... Electronic Benefit Transfer Transactions; Request for Public Comment AGENCY: Department of Health and Human... States have implemented policies and practices to prevent electronic benefit transfer transactions involving TANF assistance in liquor stores, casinos, gambling casinos, or other gaming establishments,...

  7. Low activation barriers characterize intramolecular electron transfer in ascorbate oxidase

    Farver, O; Pecht, I

    1992-01-01

    Anaerobic reduction kinetics of the zucchini squash ascorbate oxidase (AO; L-ascorbate:oxygen oxidoreductase, EC 1.10.3.3) by pulse radiolytically produced CO2- radical ions were investigated. Changes in the absorption bands of type 1 [Cu(II)] (610 nm) and type 3 [Cu(II)] (330 nm) were monitored...... transfer to type 3 [Cu(II)]. The observed specific rates are similar to values reported for the limiting-rate constants of AO reduction by excess substrate, suggesting that internal electron transfer is the rate-determining step of AO activity. The temperature dependence of the intramolecular electron...... transfer rate constants was measured from 275 to 308 K at pH 5.5 and, from the Eyring plots, low activation enthalpies were calculated--namely, 9.1 +/- 1.1 and 6.8 +/- 1.0 kJ.mol-1 for the fastest and slowest phases, respectively. The activation entropies observed for these respective phases were -170...

  8. Electron-transfer reactions of tryptophan and tyrosine derivatives

    Oxidation of tryptophan, tyrosine, and derivatives by oxidizing radicals was studied by pulse radiolysis in aqueous solutions at 20 0C. Rate constants for the oxidation of tryptophan derivatives with .N3 and Br2-. radicals vary from 8 x 108 to 4.8 and 109 M-1 s-1 and oxidation goes to completion; no pH dependence was observed. Oxidation rate constants for tyrosine derivatives increase upon deprotonation of the phenolic residue at higher pH. Redox potentials for the indolyl and phenoxyl radicals were derived from the measured equilibrium constants by using p-methoxyphenol (E/sub 7.5/ = 0.6 and E13 = 0.4 V), bisulfite (E3 = 0.84 V), and guanosine (E7 = 0.91 V) redox couples as reference systems. Redox potentials of tryptophan derivatives were found to be in dependent on the nature of the side chain and higher than the redox potentials of tryptophan derivatives. Electron transfer from tyrosine to tryptophyl radical was found to be slow in neutral media and is suggested to proceed via multiple steps, one of which is proton transfer from tyrosine to tryptophyl radical followed by electron transfer. 26 references, 2 figures, 4 tables

  9. Electron transfer behaviour of biological macromolecules towards the single-molecule level

    Redox metalloproteins immobilized on metallic surfaces in contact with aqueous biological media are important in many areas of pure and applied sciences. Redox metalloprotein films are currently being addressed by new approaches where biotechnology including modified and synthetic proteins is combined with state-of-the-art physical electrochemistry with emphasis on single-crystal, atomically planar electrode surfaces, in situ scanning tunnelling microscopy (STM) and other surface techniques. These approaches have brought bioelectrochemistry important steps forward towards the nanoscale and single-molecule levels. We discuss here these advances with reference to two specific redox metalloproteins, the blue single-copper protein Pseudomonas aeruginosa azurin and the single-haem protein Saccharomyces cerevisiae yeast cytochrome c, and a short oligonucleotide. Both proteins can be immobilized on Au(111) by chemisorption via exposed sulfur-containing residues. Voltammetric, interfacial capacitance, x-ray photoelectron spectroscopy and microcantilever sensor data, together with in situ STM with single-molecule resolution, all point to a coherent view of monolayer organization with protein electron transfer (ET) function retained. In situ STM can also address the microscopic mechanisms for electron tunnelling through the biomolecules and offers novel notions such as coherent multi-ET between the substrate and tip via the molecular redox levels. This differs in important respects from electrochemical ET at a single metal/electrolyte interface. Similar data for a short oligonucleotide immobilized on Au(111) show that oligonucleotides can be characterized with comparable detail, with novel perspectives for addressing DNA electronic conduction mechanisms and for biological screening towards the single-molecule level

  10. Electronic Energy transfer in light-harvesting antenna complexes

    Hossein-Nejad, Hoda

    The studies presented in this thesis explore electronic energy transfer (EET) in light-harvesting antenna complexes and investigate the role of quantum coherence in EET. The dynamics of energy transfer are investigated in three distinct length scales and a different formulation of the exciton transport problem is applied at each scale. These scales include: the scale of a molecular dimer, the scale of a single protein and the scale of a molecular aggregate. The antenna protein phycoerythrin 545 (PE545) isolated from the photosynthetic cryptophyte algae Rhodomonas CS4 is specifically studied in two chapters of this thesis. It is found that formation of small aggregates delocalizes the excitation across chromophores of adjacent proteins, and that this delocalization has a dramatic effect in enhancing the rate of energy transfer between pigments. Furthermore, we investigate EET from a donor to an acceptor via an intermediate site and observe that interference of coherent pathways gives a finite correction to the transfer rate that is sensitively dependent on the nature of the vibrational interactions in the system. The statistical fluctuations of a system exhibiting EET are investigated in the final chapter. The techniques of non-equilibrium statistical mechanics are applied to investigate the steady-state of a typical system exhibiting EET that is perturbed out of equilibrium due to its interaction with a fluctuating bath.

  11. Interfacial Energy Transfer during Gamma Radiolysis of Water on the Surface of ZrO2 and Some Other Oxides

    Petrik, Nikolay G.(BATTELLE (PACIFIC NW LAB)); Alexandrov, Alexandr B.(ASSOC WESTERN UNIVERSITY); Vall, Andrey I.(Institute of Technology)

    2000-12-01

    Effect of oxide interface on 60Co gamma radiolysis of water molecules was studied. Based on the molecular hydrogen yield when compared with that from the radiolysis of pure gas-phase water, all tested oxides can be classified into three groups: (i) inhibitors - MnO2, Co3O4, CuO and Fe2O3; (ii) oxides with H2 yields, which are similar to or slightly greater than radiolysis of pure gas-phase water - MgO, CaO, SrO, BaO, ZnO, CdO, Cu2O, NiO, Cr2O3, Al2O3, CeO2, SiO2, TiO2, Nb2O5 and WO3; (iii) promoters - Ga2O3, Y2O3, La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Yb2O3, Er2O3, HfO2, and ZrO2. H2O radiolysis enhancement for ZrO2 and other promoters is result of effective energy transfer at the oxide/water interface, presumably due to migration of excitons to the surface and their resonant coupling with the H2O adsorption complex. Plot''effective H2 yield vs. band-gap (Eg) energy'' shows a maximum near 5 eV.

  12. Interfacial Symmetry Control of Emergent Ferromagnetism

    Grutter, Alexander; Borchers, Julie; Kirby, Brian; He, Chunyong; Arenholz, Elke; Vailionis, Arturas; Flint, Charles; Suzuki, Yuri

    Atomically precise complex oxide heterostructures provide model systems for the discovery of new emergent phenomena since their magnetism, structure and electronic properties are strongly coupled. Octahedral tilts and rotations have been shown to alter the magnetic properties of complex oxide heterostructures, but typically induce small, gradual magnetic changes. Here, we demonstrate sharp switching between ferromagnetic and antiferromagnetic order at the emergent ferromagnetic interfaces of CaRuO3/CaMnO3 superlattices. Through synchrotron X-ray diffraction and neutron reflectometry, we show that octahedral distortions in superlattices with an odd number of CaMnO3 unit cells in each layer are symmetry mismatched across the interface. In this case, the rotation symmetry switches across the interface, reducing orbital overlap, suppressing charge transfer from Ru to Mn, and disrupting the interfacial double exchange. This disruption switches half of the interfaces from ferromagnetic to antiferromagnetic and lowers the saturation magnetic of the superlattice from 1.0 to 0.5 μB/interfacial Mn. By targeting a purely interfacial emergent magnetic system, we achieve drastic alterations to the magnetic ground state with extremely small changes in layer thickness.

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

    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. PMID:26863985

  14. Controlling time scales for electron transfer through proteins

    Scot Wherland

    2015-12-01

    Full Text Available Electron transfer processes within proteins constitute key elements in biological energy conversion processes as well as in a wide variety of biochemical transformations. Pursuit of the parameters that control the rates of these processes is driven by the great interest in the latter reactions. Here, we review a considerable body of results emerging from investigation of intramolecular electron transfer (ET reactions in two types of proteins, all done by the use of the pulse-radiolysis method: first are described results of extensive studies of a model system, the bacterial electron mediating protein azurin, where an internal ET between the disulfide radical ion and the Cu(II is induced. Impact of specific structural changes introduced into azurin on the reaction rates and the parameters controlling it are discussed. Then, the presentation is extended to results of investigations of intra-protein ET reactions that are part of catalytic cycles of multi-copper containing enzymes. Again, the rates and the parameters controlling them are presented and discussed in the context of their efficacy and possible constraints set on their evolution.

  15. Electronic Energy Transfer: Localized Operator Partitioning of Electronic Energy in Composite Quantum Systems

    Khan, Yaser R.; Brumer, Paul

    2012-01-01

    A Hamiltonian based approach using spatially localized projection operators is introduced to give precise meaning to the chemically intuitive idea of the electronic energy on a quantum subsystem. This definition facilitates the study of electronic energy transfer in arbitrarily coupled quantum systems. In particular, the decomposition scheme can be applied to molecular components that are strongly interacting (with significant orbital overlap) as well as to isolated fragments. The result lead...

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

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

    2015-04-28

    In this work, we demonstrate that chronoabsorptometry and more specifically cyclic voltabsorptometry are particularly well suited techniques for acquiring a comprehensive understanding of the dynamics of electron transfer/charge transport within a transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye. This is illustrated with the quantitative analysis of the spectroelectrochemical responses of two distinct heme-based redox probes adsorbed in highly-ordered mesoporous TiO2 thin films (prepared from evaporation-induced self-assembly, EISA). On the basis of a finite linear diffusion-reaction model as well as the establishment of the analytical expressions governing the limiting cases, it was possible to quantitatively analyse, predict and interpret the unusual voltabsorptometric responses of the adsorbed redox species as a function of the potential applied to the semiconductive film (i.e., as a function of the transition from an insulating to a conductive state or vice versa). In particular, we were able to accurately determine the interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor. Another important and unexpected finding, inferred from the voltabsorptograms, is an interfacial electron transfer process predominantly governed by the extended conduction band states of the EISA TiO2 film and not by the localized traps in the bandgap. This is a significant result that contrasts those previously observed for dye-sensitized solar cells formed of randomly sintered TiO2 nanoparticles, a behaviour that was ascribed to a particularly low density of localized surface states in EISA TiO2. The present methodology also provides a unique and straightforward access to an activation-driving force relationship according to the Marcus theory, thus opening new opportunities not only to investigate the driving-force effects on electron recombination dynamics in dye-sensitized solar cells but also to study the electron transfer/transport mechanisms in heterogeneous photoelectrocatalytic systems combining nanostructured semiconductor electrodes and heterogeneous redox-active catalysts. PMID:25804293

  17. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    Gupta, Sanju; Irihamye, Aline

    2015-03-01

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py-1SO3), 1-pyrenemethylamine salt (Py - Me-NH2) and Pluronic® P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr_LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr_LPE (the one prepared with Pluronic® P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (kET) using two different analytical approaches namely, linear sweep voltammetry and Laviron's theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical wiring of the redox centers (with an increase in catalytic efficiency of Cyt c and Mb in the presence of GFNs attributed partially to the surface functional (carboxyl, epoxide and hydroxyl) groups on GO and rGO facilitating rapid charge transfer.

  18. Immobilization, hybridization, and oxidation of synthetic DNA on gold surface: Electron transfer investigated by electrochemistry and scanning tunneling microscopy

    McEwen, Gerald D.; Chen Fan [Biological Engineering Program, Department of Biological and Irrigation Engineering, Utah State University, 4105 Old Main Hill, Logan, UT 84322-4105 (United States); Zhou Anhong, E-mail: Anhong.Zhou@usu.edu [Biological Engineering Program, Department of Biological and Irrigation Engineering, Utah State University, 4105 Old Main Hill, Logan, UT 84322-4105 (United States)

    2009-06-08

    Fundamental understanding of interfacial electron transfer (ET) among electrolyte/DNA/solid-surface will facilitate the design for electrical detection of DNA molecules. In this report, the electron transfer characteristics of synthetic DNA (sequence from pathogenic Cryptosporidium parvum) self-assembled on a gold surface was electrochemically studied. The effects of immobilization order on the interface ET related parameters such as diffusion coefficient (D{sub 0}), surface coverage ({theta}{sub R}), and monolayer thickness (d{sub i}) were determined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). DNA surface density ({Gamma}{sub DNA}) was determined by the integration of the charge of the electro-oxidation current peaks during the initial cyclic voltammetry scans. It was found that the DNA surface densities at different modifications followed the order: {Gamma}{sub DNA} (dsS-DNA/Au) > {Gamma}{sub DNA} (MCH/dsS-DNA/Au) > {Gamma}{sub DNA} (dsS-DNA/MCH/Au). It was also revealed that the electro-oxidation of the DNA modified gold surface would involve the oxidation of nucleotides (guanine and adenine) with a 5.51 electron transfer mechanism and the oxidative desorption of DNA and MCH molecules by a 3 electron transfer mechanism. STM topography and current image analysis indicated that the surface conductivity after each surface modification followed the order: dsS-DNA/Au < MCH/dsS-DNA/Au < oxidized MCH/dsS-DNA/Au < Hoechst/oxidized MCH/dsS-DNA/Au. The results from this study suggested a combination of variations in immobilization order may provide an alternative approach for the optimization of DNA hybridization and the further development for electrical detection of DNA.

  19. Immobilization, hybridization, and oxidation of synthetic DNA on gold surface: Electron transfer investigated by electrochemistry and scanning tunneling microscopy

    Fundamental understanding of interfacial electron transfer (ET) among electrolyte/DNA/solid-surface will facilitate the design for electrical detection of DNA molecules. In this report, the electron transfer characteristics of synthetic DNA (sequence from pathogenic Cryptosporidium parvum) self-assembled on a gold surface was electrochemically studied. The effects of immobilization order on the interface ET related parameters such as diffusion coefficient (D0), surface coverage (?R), and monolayer thickness (di) were determined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). DNA surface density (?DNA) was determined by the integration of the charge of the electro-oxidation current peaks during the initial cyclic voltammetry scans. It was found that the DNA surface densities at different modifications followed the order: ?DNA (dsS-DNA/Au) > ?DNA (MCH/dsS-DNA/Au) > ?DNA (dsS-DNA/MCH/Au). It was also revealed that the electro-oxidation of the DNA modified gold surface would involve the oxidation of nucleotides (guanine and adenine) with a 5.51 electron transfer mechanism and the oxidative desorption of DNA and MCH molecules by a 3 electron transfer mechanism. STM topography and current image analysis indicated that the surface conductivity after each surface modification followed the order: dsS-DNA/Au < MCH/dsS-DNA/Au < oxidized MCH/dsS-DNA/Au < Hoechst/oxidized MCH/dsS-DNA/Au. The results from this study suggested a combination of variations in immobilization order may provide an alternative approach for the optimization of DNA hybridization and the further development for electrical detection of DNA.

  20. Extracellular electron transfer from cathode to microbes: application for biofuel production

    Choi, Okkyoung; Sang, Byoung-In

    2016-01-01

    Extracellular electron transfer in microorganisms has been applied for bioelectrochemical synthesis utilizing microbes to catalyze anodic and/or cathodic biochemical reactions. Anodic reactions (electron transfer from microbe to anode) are used for current production and cathodic reactions (electron transfer from cathode to microbe) have recently been applied for current consumption for valuable biochemical production. The extensively studied exoelectrogenic bacteria Shewanella and Geobacter ...

  1. Suppression of Electron Transfer to Dioxygen by Charge Transfer and Electron Transfer Complexes in the FAD-dependent Reductase Component of Toluene Dioxygenase*

    Lin, Tzong-Yuan; Werther, Tobias; Jeoung, Jae-Hun; Dobbek, Holger

    2012-01-01

    The three-component toluene dioxygenase system consists of an FAD-containing reductase, a Rieske-type [2Fe-2S] ferredoxin, and a Rieske-type dioxygenase. The task of the FAD-containing reductase is to shuttle electrons from NADH to the ferredoxin, a reaction the enzyme has to catalyze in the presence of dioxygen. We investigated the kinetics of the reductase in the reductive and oxidative half-reaction and detected a stable charge transfer complex between the reduced reductase and NAD+ at the end of the reductive half-reaction, which is substantially less reactive toward dioxygen than the reduced reductase in the absence of NAD+. A plausible reason for the low reactivity toward dioxygen is revealed by the crystal structure of the complex between NAD+ and reduced reductase, which shows that the nicotinamide ring and the protein matrix shield the reactive C4a position of the isoalloxazine ring and force the tricycle into an atypical planar conformation, both factors disfavoring the reaction of the reduced flavin with dioxygen. A rapid electron transfer from the charge transfer complex to electron acceptors further reduces the risk of unwanted side reactions, and the crystal structure of a complex between the reductase and its cognate ferredoxin shows a short distance between the electron-donating and -accepting cofactors. Attraction between the two proteins is likely mediated by opposite charges at one large patch of the complex interface. The stability, specificity, and reactivity of the observed charge transfer and electron transfer complexes are thought to prevent the reaction of reductaseTOL with dioxygen and thus present a solution toward conflicting requirements. PMID:22992736

  2. Suppression of electron transfer to dioxygen by charge transfer and electron transfer complexes in the FAD-dependent reductase component of toluene dioxygenase.

    Lin, Tzong-Yuan; Werther, Tobias; Jeoung, Jae-Hun; Dobbek, Holger

    2012-11-01

    The three-component toluene dioxygenase system consists of an FAD-containing reductase, a Rieske-type [2Fe-2S] ferredoxin, and a Rieske-type dioxygenase. The task of the FAD-containing reductase is to shuttle electrons from NADH to the ferredoxin, a reaction the enzyme has to catalyze in the presence of dioxygen. We investigated the kinetics of the reductase in the reductive and oxidative half-reaction and detected a stable charge transfer complex between the reduced reductase and NAD(+) at the end of the reductive half-reaction, which is substantially less reactive toward dioxygen than the reduced reductase in the absence of NAD(+). A plausible reason for the low reactivity toward dioxygen is revealed by the crystal structure of the complex between NAD(+) and reduced reductase, which shows that the nicotinamide ring and the protein matrix shield the reactive C4a position of the isoalloxazine ring and force the tricycle into an atypical planar conformation, both factors disfavoring the reaction of the reduced flavin with dioxygen. A rapid electron transfer from the charge transfer complex to electron acceptors further reduces the risk of unwanted side reactions, and the crystal structure of a complex between the reductase and its cognate ferredoxin shows a short distance between the electron-donating and -accepting cofactors. Attraction between the two proteins is likely mediated by opposite charges at one large patch of the complex interface. The stability, specificity, and reactivity of the observed charge transfer and electron transfer complexes are thought to prevent the reaction of reductase(TOL) with dioxygen and thus present a solution toward conflicting requirements. PMID:22992736

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

    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.

  4. Charge-sharing and electron-transfer characteristics of a gas electron multiplier (GEM)

    The charge sharing and electron-transfer process of a gas electron multiplier (GEM) with a high density of holes (60 μm in diameter at 100 μm of pitch) were examined. The GEM operated at a lower applied voltage due to the smaller size of the GEM holes; thus, a higher electric field is seen in the multiplication channels. The electron collection efficiency and the charge sharing were found to depend on the external field, as well as on the GEM voltage. The electron collection efficiency approached 90 % with a full collection of primary electrons under optimized GEM field conditions, and the range of the drift field for efficient electron collection to reach a plateau increased with the GEM voltage. The positive-ion feedback is also estimated

  5. Charge-sharing and electron-transfer characteristics of a gas electron multiplier (GEM)

    Han, Sang Hyo; Kang, Hee Dong [Kyungpook National Univ., Daegu (Korea, Republic of); Kim, Yong Kyun; Moon, Byung Soo; Chung, Chong Eun [KAERI, Daejon (Korea, Republic of); Cho, Hyo Sung; Kang, Sang Mook [Yonsei Univ., Wonju (Korea, Republic of)

    2002-05-01

    The charge sharing and electron-transfer process of a gas electron multiplier (GEM) with a high density of holes (60 {mu}m in diameter at 100 {mu}m of pitch) were examined. The GEM operated at a lower applied voltage due to the smaller size of the GEM holes; thus, a higher electric field is seen in the multiplication channels. The electron collection efficiency and the charge sharing were found to depend on the external field, as well as on the GEM voltage. The electron collection efficiency approached 90 % with a full collection of primary electrons under optimized GEM field conditions, and the range of the drift field for efficient electron collection to reach a plateau increased with the GEM voltage. The positive-ion feedback is also estimated.

  6. Electronic excitation energy transfer between quasi-zero-dimensional systems

    Král, Karel; Menšík, Miroslav; Mao, H.

    Tokyo : The Surface Science Society of Japan, 2014, s. 11-17. ISSN 1348-0391. [International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures /12/ - International Colloquium on Scanning Probe Microscopy /21./. Tsukuba (JP), 04.11.2013-08.11.2013] R&D Projects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron -phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism https://www.jstage.jst.go.jp/result?item1=4&word1=Atomically+Controlled+Surfaces+ AND +kral

  7. Light induced electron transfer reactions of metal complexes

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  8. Photoinduced electron transfer from phycoerythrin to colloidal metal semiconductor nanoparticles

    Kathiravan, A.; Chandramohan, M.; Renganathan, R.; Sekar, S.

    2009-04-01

    Phycoerythrin is a water soluble pigment which absorbs in the visible region at 563 nm. The interaction of phycoerythrin with colloidal metal semiconductors was studied by absorption, FT-IR and fluorescence spectroscopy. Phycoerythrin adsorbed strongly on the surface of TiO 2 nanoparticles, the apparent association constant for the association between colloidal metal-TiO 2 nanoparticles and phycoerythrin was determined from fluorescence quenching data. The free energy change (Δ Get) for electron transfer process has been calculated by applying Rehm-Weller equation.

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

    A review is given of the experimental results from a series of measurements at SLAC of large momentum transfer (Q2 > 20 fm-2) electron scattering at forward angles from nuclei with A less than or equal to 4. Theoretical interpretations of these data in terms of traditional nuclear physics models and in terms of quark constituent models are described. Some physics questions for future experiments are explored, and a preview of possible future measurements of magnetic structure functions of light nuclei at large Q2 is given

  10. Parton models of high momentum transfer electron-nuclear scattering

    High-energy electron-nuclear scattering processes are discussed from the point of view of a parton model description. The light-cone formalism is introduced in a schematic presentation emphasizing: (i) the connection to relativistic dynamics, (ii) the phenomenological construction of the far off-shell components of wave functions, and (iii) asymptotic scaling laws. A survey is made of some of the recent calculations based on a nucleon constituent parton model and their comparison with data for momentum transfers Q22. A prospective discussion is also made on multiquark nuclear components and the quark parton model in QCD

  11. Promoting direct interspecies electron transfer with activated carbon

    Liu, Fanghua; Rotaru, Amelia-Elena; Shrestha, Pravin M.; Malvankar, Nikhil S.; Nevin, Kelly P.; Lovley, Derek R.

    2012-01-01

    Granular activated carbon (GAC) is added to methanogenic digesters to enhance conversion of wastes to methane, but the mechanism(s) for GAC’s stimulatory effect are poorly understood. GAC has high electrical conductivity and thus it was hypothesized that one mechanism for GAC stimulation of...... were attached to GAC, but did not aggregate as they do when making biological electrical connections between cells. Studies with a series of gene deletion mutants eliminated the possibility that GAC promoted electron exchange via interspecies hydrogen or formate transfer and demonstrated that DIET in...

  12. Human ceruloplasmin. Intramolecular electron transfer kinetics and equilibration

    Farver, O; Bendahl, L; Skov, L K; Pecht, I

    1999-01-01

    Pulse radiolytic reduction of disulfide bridges in ceruloplasmin yielding RSSR(-) radicals induces a cascade of intramolecular electron transfer (ET) processes. Based on the three-dimensional structure of ceruloplasmin identification of individual kinetically active disulfide groups and type 1 (T1...... with a rate constant of 3.9 +/- 0.8. No reoxidation of T1B Cu(I) could be resolved. It appears that the third T1 center (T1C of domain 2) is not participating in intramolecular ET, as it seems to be in a reduced state in the resting enzyme....

  13. Electronic state selectivity in dication-molecule single electron transfer reactions: NO+ + NO

    Parkes, M. A.; Lockyear, J. F.; Schröder, Detlef; Roithová, J.; Price, S. D.

    2011-01-01

    Roč. 13, č. 41 (2011), s. 18386-18392. ISSN 1463-9076 R&D Projects: GA ČR GA203/09/1223 Institutional research plan: CEZ:AV0Z40550506 Keywords : coincidence experiments * dications * electron transfer * energy partitioning * state selectivity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

  14. Direct probing of the structure and electron transfer of fullerene/ferrocene hybrid on Au(111) electrodes by in situ electrochemical STM.

    Chen, Ting; Wang, Dong; Gan, Li-Hua; Matsuo, Yutaka; Gu, Jing-Ying; Yan, Hui-Juan; Nakamura, Eiichi; Wan, Li-Jun

    2014-02-26

    The electron donor-acceptor dyads are an emerging class of materials showing important applications in nonlinear optics, dye-sensitized solar cells, and molecular electronics. Investigation of their structure and electron transfer at the molecular level provides insights into the structure-property relationship and can benefit the design and preparation of electron donor-acceptor dyad materials. Herein, the interface adstructure and electron transfer of buckyferrocene Fe(C60Me5)Cp, a typical electron donor-acceptor dyad, is directly probed using in situ electrochemical scanning tunneling microscopy (STM) combined with theoretical simulations. It is found that the adsorption geometry and assembled structure of Fe(C60Me5)Cp is significantly affected by the electrochemical environments. In 0.1 M HClO4 solution, Fe(C60Me5)Cp forms well-ordered monolayers and multilayers on Au(111) surfaces with molecular dimer as the building block. In 0.1 M NaClO4 solution, typical six-fold symmetric close-packed monolayer with vertically adsorbed Fe(C60Me5)Cp is formed. Upon electrochemical oxidation, the oxidized Fe(C60Me5)Cp shows higher brightness in an STM image, which facilitates the direct visualization of the interfacial electrochemical electron transfer process. Theoretical simulation indicates that the electrode potential-activated, one-electron transfer from Fe(C60Me5)Cp to the electrode leads to the change of the delocalization character of the frontier orbital in the molecule, which is responsible for the STM image contrast change. This result is beneficial for understanding the structure and property of single electron donor-acceptor dyads. It also provides a direct approach to study the electron transfer of electron donor-acceptor compounds at the molecular level. PMID:24483295

  15. Generalized Holstein model for spin-dependent electron transfer reaction

    Yang, Li-Ping; Sun, C P

    2011-01-01

    Some chemical reactions are described by electron transfer (ET) processes. The underlying mechanism could be modeled as a polaron motion in the molecular crystal-the Holstein model. By taking spin degrees of freedom into consideration, we generalize the Holstein model (molecular crystal model) to microscopically describe an ET chemical reaction. In our model, the electron spins in the radical pair simultaneously interact with a magnetic field and their nuclear-spin environments. By virtue of the perturbation approach, we obtain the chemical reaction rates for different initial states. It is discovered that the chemical reaction rate of the triplet state demonstrates its dependence on the direction of the magnetic field while the counterpart of the singlet state does not. This difference is attributed to the explicit dependence of the triplet state on the direction when the axis is rotated. Our model may provide a possible candidate for the microscopic origin of avian compass.

  16. Intramolecular electron transfer in Pseudomonas aeruginosa cd(1) nitrite reductase

    Farver, Ole; Brunori, Maurizio; Cutruzzolà, Francesca; Rinaldo, Serena; Wherland, Scot; Pecht, Israel

    2009-01-01

    The cd(1) nitrite reductases, which catalyze the reduction of nitrite to nitric oxide, are homodimers of 60 kDa subunits, each containing one heme-c and one heme-d(1). Heme-c is the electron entry site, whereas heme-d(1) constitutes the catalytic center. The 3D structure of Pseudomonas aeruginosa...... nitrite reductase has been determined in both fully oxidized and reduced states. Intramolecular electron transfer (ET), between c and d(1) hemes is an essential step in the catalytic cycle. In earlier studies of the Pseudomonas stutzeri enzyme, we observed that a marked negative cooperativity is...... controlling this internal ET step. In this study we have investigated the internal ET in the wild-type and His369Ala mutant of P. aeruginosa nitrite reductases and have observed similar cooperativity to that of the Pseudomonas stutzeri enzyme. Heme-c was initially reduced, in an essentially diffusion...

  17. The electronic transfer of information and aerospace knowledge diffusion

    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.

  18. Electron transfer pathway analysis in bacterial photosynthetic reaction center

    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.

  19. Theoretical studies of excess electrons in fluids: structure and electron transfer. Progress report, August 1981-August 1982

    Research reported involved studies of electron transfer reactions, negative water clusters, spin pairing in metal ammonia solutions, water-water interactions, interaction of Hexa aquo iron complexes, and proton transfer

  20. Numerical study of interfacial convective heat transfer coefficient in two-energy equation model of porous media; Takoshitsutai ni energy hoteishiki model ni okeru kaimken netsu dentatsuritsu ni kansuru suchi jikkenteki kenkyu

    Kuwahara, F.; Nakayama, A. [Shizuoka University, Shizuoka (Japan). Faculty of Engineeering; Shirota, M. [Shizuoka University, Shizuoka (Japan)

    2000-05-25

    A numerical experiment has been conducted to determine the interfacial convective heat transfer coefficient in the two-energy equation model of porous media, which is needed when the assumption of the local thermal equilibrium between the fluid and solid phases is not valid. The similarity of the fully developed temperature profile allows one to perform a numerical experiment using only a single structural unit, for determining the fully-developed heat transfer coefficient without any empiricism. A universal correlation for the Nusselt number, which agrees very well with the experimental data, has been established using the results obtained for a wide range of porosity, Prandtl and Reynolds numbers. (author)

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

    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...

  2. Effect of swift heavy ion irradiation on magnetic, surface morphology and electronic transport across CoFe/n-Si interfacial structures

    Kumar, Arvind; Srivastava, P. C.

    2016-04-01

    In this study, swift heavy ion induced modifications on magnetic, morphological and electronic transport properties of CoFe/n-Si bilayers was investigated. Structural investigations have revealed the interfacial intermixing across the interface upon irradiation to result in the formation of magnetic silicide phases with enhanced crystallite size as compared to unirradiated structure. On irradiation, surface topography (from atomic force microscopy) has revealed the columnar arrangement of grains with increased value of rms surface roughness which in turn also affects the magnetic behaviour. Magnetization measurements have shown the enhancement in saturation magnetization and coercivity value with increased magnetic signal strength after irradiation. Current-voltage measurement across the irradiated CoFe/n-Si interface has shown the enhancement in current data by two orders of magnitude as compared to unirradiated interface. The observed significant changes in magnetic and transport properties for the irradiated interface has been explained on the basis of disorder/defect creation and interfacial chemistry modifications in the structure due to swift heavy ions.

  3. Synchronized energy and electron transfer processes in covalently linked CdSe-squaraine dye-TiO2 light harvesting assembly.

    Choi, Hyunbong; Santra, Pralay K; Kamat, Prashant V

    2012-06-26

    Manipulation of energy and electron transfer processes in a light harvesting assembly is an important criterion to mimic natural photosynthesis. We have now succeeded in sequentially assembling CdSe quantum dot (QD) and squaraine dye (SQSH) on TiO(2) film and couple energy and electron transfer processes to generate photocurrent in a hybrid solar cell. When attached separately, both CdSe QDs and SQSH inject electrons into TiO(2) under visible-near-IR irradiation. However, CdSe QD if linked to TiO(2) with SQSH linker participates in an energy transfer process. The hybrid solar cells prepared with squaraine dye as a linker between CdSe QD and TiO(2) exhibited power conversion efficiency of 3.65% and good stability during illumination with global AM 1.5 solar condition. Transient absorption spectroscopy measurements provided further insight into the energy transfer between excited CdSe QD and SQSH (rate constant of 6.7 × 10(10) s(-1)) and interfacial electron transfer between excited SQSH and TiO(2) (rate constant of 1.2 × 10(11) s(-1)). The synergy of covalently linked semiconductor quantum dots and near-IR absorbing squaraine dye provides new opportunities to harvest photons from selective regions of the solar spectrum in an efficient manner. PMID:22658983

  4. Interfacial electronic structure and full spectral Hamaker constants of Si3N4 intergranular films from VUV and SR-VEEL spectroscopy

    The interfacial electronic structure, presented as the interband transition strength Jcv(ω) of the interatomic bonds, can be determined by Kramers Kronig (KK) analysis of vacuum ultraviolet (VUV) reflectance or spatially resolved valence electron energy loss (SR-VEEL) spectra. For the wetted interfaces in Si3N4, equilibrium thin glass films are formed whose thickness is determined by a force balance between attractive and repulsive force terms KK analysis of Jcv(ω) to yield var-epsilon 2(ξ) for the phases present, permits the direct calculation of the configuration-dependent Hamaker constants for the attractive vdW forces from the interfacial electronic structure. Interband transition strengths and full spectral Hamaker constants for Si3N4samples containing a SiYAlON glass have been determined using SR-VEELS from grains and grain boundaries and compared with results from bulk VUV spectroscopy on separate samples of glass and nitride. The A121Hamaker constant for Si3N4 with glass of the bulk composition is 8 zJ (zJ = 10-21J) from the more established optical method. The EELS method permits the determination of vdW forces based upon actual local compositions and structure, which may differ noticeably from bulk standards. Current results show that full spectral Hamaker constants determined from VUV and SR-VEEL measurements of uniform bulk samples agree, but care must be take in the single scattering and zero loss subtraction corrections, and more work is ongoing in this area. Still the results show that for the grain boundary films present in these polycrystalline Si3N4 samples the glass composition is of lower index of refraction. This can arise from increased oxygen content in determined in situ from the SR-VEELS of a particular grain boundary film. 45 refs

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

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

    2015-01-01

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

  6. Interfacial electronic structure and density of states of intrinsic a-Si:H deposited on clean and oxidized stainless steel

    Photoemission and Auger measurements on thin a-Si:H films prepared in situ have revealed the presence of an interfacial potential step of 0.3 eV between clean stainless steel and a-Si:H, and 0.5 eV between oxidized stainless steel and a-Si:H. A small shift in the valence-band maximum (VBM) as the thickness of the a-Si:H is increased, if interpreted as band bending, gives an upper limit for the bulk density of states of about 7 x 1018 states cm-3 eV-1. Direct measurement of the optical density of states reveals less than 1019 states cm-3 eV-1 at energies more than 0.30 eV above the VBM

  7. Cluster PEACE observations of electrons during magnetospheric flux transfer events

    C. J. Owen

    Full Text Available During the first quarter of 2001 the apogees of the Cluster spacecraft quartet precessed through midday local times. This provides the first opportunity for 4 spacecraft studies of the bow shock, magnetosheath and the dayside magnetopause current layer and boundary layers. In this paper, we present observations of electrons in the energy range ~ 10 eV–26 keV made by the Plasma Electron And Current Experiment (PEACE located just inside the magnetopause boundary, together with supporting observations by the Flux Gate Magnetometer (FGM. During these observations, the spacecraft have separations of ~ 600 km. This scale size is of the order or less than the typical size of flux transfer events (FTEs, which are expected to be observed following bursts of reconnection on the dayside magnetopause. We study, in detail, the 3-D configuration of electron populations observed around a series of enhancements of magnetosheath-like electrons which were observed within the magnetosphere on 2 February 2001. We find that individual spacecraft observe magnetic field and electron signatures that are consistent with previous observations of magnetospheric FTEs. However, the differences in the signatures between spacecraft indicate that these FTEs have substructure on the scale of the spacecraft separation. We use these differences and the timings of the 4 spacecraft observations to infer the motions of the electron populations and thus the configuration of these substructures. We find that these FTEs are moving from noon towards dusk. The inferred size and speed of motion across the magnetopause, in one example, is ~ 0.8 RE and ~ 70 km s-1 respectively. In addition, we observe a delay in and an extended duration of the signature at the spacecraft furthest from the magnetopause. We discuss the implications of these 4 spacecraft observations for the structure of these FTEs. We suggest that these may include a compression of the closed flux tubes ahead of the FTE, which causes density and field strength enhancements; a circulation of open flux tubes within the FTE itself, which accounts for the delay in the arrival of the magnetosheath electron populations at locations deepest within the magnetosphere; and a possible trapping of magnetospheric electrons on the most recently opened flux tubes within the FTE.

    Key words. Magnetospheric physics (magnetopause, cusp and boundary layers; solar wind - magnetosphere interactions

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

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Aklujkar, Muktak; Liu, Fanghua; Shrestha, Minita; Summers, Zarath M; Malvankar, Nikhil; Flores, Dan Carlo; Lovley, Derek R

    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 to supp...... 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.......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 to...

  9. Nb and Ta layer doping effects on the interfacial energetics and electronic properties of LaAlO3/SrTiO3 heterostructure: first-principles analysis.

    Nazir, Safdar; Behtash, Maziar; Cheng, Jianli; Luo, Jian; Yang, Kesong

    2016-01-20

    The two-dimensional electron gas (2DEG) formed at the n-type (LaO)(+1)/(TiO2)(0) interface in the polar/nonpolar LaAlO3/SrTiO3 (LAO/STO) heterostructure (HS) has emerged as a prominent research area because of its great potential for nanoelectronic applications. Due to its practical implementation in devices, desired physical properties such as high charge carrier density and mobility are vital. In this respect, 4d and 5d transition metal doping near the interfacial region is expected to tailor electronic properties of the LAO/STO HS system effectively. Herein, we studied Nb and Ta-doping effects on the energetics, electronic structure, interfacial charge carrier density, magnetic moment, and the charge confinements of the 2DEG at the n-type (LaO)(+1)/(TiO2)(0) interface of LAO/STO HS using first-principles density functional theory calculations. We found that the substitutional doping of Nb(Ta) at Ti [Nb(Ta)@Ti] and Al [Nb(Ta)@Al] sites is energetically more favorable than that at La [Nb(Ta)@La] and Sr [Nb(Ta)@Sr] sites, and under appropriate thermodynamic conditions, the changes in the interfacial energy of HS systems upon Nb(Ta)@Ti and Nb(Ta)@Al doping are negative, implying that the formation of these structures is energetically favored. Our calculations also showed that Nb(Ta)@Ti and Nb(Ta)@Al doping significantly improve the interfacial charge carrier density with respect to that of the undoped system, which is because the Nb(Ta) dopant introduces excess free electrons into the system, and these free electrons reside mainly on the Nb(Ta) ions and interfacial Ti ions. Hence, along with the Ti 3d orbitals, the Nb 4d and Ta 5d orbitals also contribute to the interfacial metallic states; accordingly, the magnetic moments on the interfacial Ti ions increase significantly. As expected, the Nb@Al and Ta@Al doped LAO/STO HS systems show higher interfacial charge carrier density than the undoped and other doped systems. In contrast, Nb@Ti and Ta@Ti doped systems may show higher charge carrier mobility because of the lower electron effective mass. PMID:26562134

  10. An excellent candidate for largely reducing interfacial thermal resistance: a nano-confined mass graded interface

    Zhou, Yanguang; Zhang, Xiaoliang; Hu, Ming

    2016-01-01

    Pursuing extremely low interfacial thermal resistance has long been the task of many researchers in the area of nano-scale heat transfer, in particular pertaining to improve heat dissipation performance in electronic cooling. While it is well known and documented that confining a macroscopic third layer between two dissimilar materials usually increases the overall interfacial thermal resistance, no research has realized the fundamental decrease in resistance so far. By performing nonequilibrium molecular dynamics simulations, we report that the overall interfacial thermal resistance can be reduced by 6 fold by confining mass graded materials with thickness of the order of nanometers. As comparison we also studied the thermal transport across the perfectly abrupt interface and the widely used alloyed (rough) interface, which shows an opposing and significantly large increase in the overall thermal resistance. With the help of frequency dependent interfacial thermal conductance and wave packet dynamics simulation, different mechanisms governing the heat transfer across these three types of interfaces are identified. It is found that for the rough interface there are two different regimes of interfacial heat transfer, which originates from the competition between phonon scattering and the thickness of the interface. The mechanism of dramatically improved interfacial heat transfer across the nano-confined mass graded interface resides in the minor phonon reflection when the phonons first reach the mass graded area and the rare occurrence of phonon scattering in the subsequent interior region. The phonons are found to be gradually truncated by the geometric interfaces and can travel through the mass graded layer with a high transmission coefficient, benefited from the small mass mismatch between two neighboring layers in the interfacial region. Our findings provide deep insight into the phonon transport across nano-confined mass graded layers and also offer significant guidance for designing advanced thermal interface materials.

  11. An excellent candidate for largely reducing interfacial thermal resistance: a nano-confined mass graded interface.

    Zhou, Yanguang; Zhang, Xiaoliang; Hu, Ming

    2016-01-21

    Pursuing extremely low interfacial thermal resistance has long been the task of many researchers in the area of nano-scale heat transfer, in particular pertaining to improve heat dissipation performance in electronic cooling. While it is well known and documented that confining a macroscopic third layer between two dissimilar materials usually increases the overall interfacial thermal resistance, no research has realized the fundamental decrease in resistance so far. By performing nonequilibrium molecular dynamics simulations, we report that the overall interfacial thermal resistance can be reduced by 6 fold by confining mass graded materials with thickness of the order of nanometers. As comparison we also studied the thermal transport across the perfectly abrupt interface and the widely used alloyed (rough) interface, which shows an opposing and significantly large increase in the overall thermal resistance. With the help of frequency dependent interfacial thermal conductance and wave packet dynamics simulation, different mechanisms governing the heat transfer across these three types of interfaces are identified. It is found that for the rough interface there are two different regimes of interfacial heat transfer, which originates from the competition between phonon scattering and the thickness of the interface. The mechanism of dramatically improved interfacial heat transfer across the nano-confined mass graded interface resides in the minor phonon reflection when the phonons first reach the mass graded area and the rare occurrence of phonon scattering in the subsequent interior region. The phonons are found to be gradually truncated by the geometric interfaces and can travel through the mass graded layer with a high transmission coefficient, benefited from the small mass mismatch between two neighboring layers in the interfacial region. Our findings provide deep insight into the phonon transport across nano-confined mass graded layers and also offer significant guidance for designing advanced thermal interface materials. PMID:26700890

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

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

    Jo, Mingyu; Uchida, Takafumi; Tsurumaki-Fukuchi, Atsushi; Arita, Masashi; Fujiwara, Akira; Ono, Yukinori; Nishiguchi, Katsuhiko; Inokawa, Hiroshi; Takahashi, Yasuo

    2015-12-01

    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.

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

    Sofer, Zden?k; Sedmidubsk, David; Huber, t?pn; Luxa, Jan; Boua, Daniel; Boothroyd, Chris; Pumera, Martin

    2016-03-01

    Layered elemental materials, such as black phosphorus, exhibit unique properties originating from their highly anisotropic layered structure. The results presented herein demonstrate an anomalous anisotropy for the electrical, magnetic, and electrochemical properties of black phosphorus. It is shown that heterogeneous electron transfer from black phosphorus to outer- and inner-sphere molecular probes is highly anisotropic. The electron-transfer rates differ at the basal and edge planes. These unusual properties were interpreted by means of calculations, manifesting the metallic character of the edge planes as compared to the semiconducting properties of the basal plane. This indicates that black phosphorus belongs to a group of materials known as topological insulators. Consequently, these effects render the magnetic properties highly anisotropic, as both diamagnetic and paramagnetic behavior can be observed depending on the orientation in the magnetic field. PMID:26822395

  15. Facile direct electron transfer in glucose oxidase modified electrodes

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

  16. A stochastic reorganizational bath model for electronic energy transfer

    Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts the reorganization shift to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This simple relationship allows one to understand the physical origin of the Stokes shifts in molecular aggregates

  17. Light-induced electron transfer vs. energy transfer in molecular thin-film systems

    Renschler, C. L.; Faulkner, L. R.

    1980-01-01

    Quenching of fluoranthene (FA) singlets by tetrabromo-o-benzoquinone (TBBQ) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) was studied both in xylene solutions and in spin-cast polystyrene (PS) films. Emphasis was placed on time-resolved fluorescence transients resulting from pulsed excitation. Linear Stern-Volmer plots were obtained for quenching in solution and gave diffusion-controlled rate constants, of 1.45 x 10/sup 10/ M/sup -1/ sec/sup -1/ and 1.53 x 10/sup 10/ M/sup -1/ sec/sup -1/ for TBBQ and TMPD, respectively. TBBQ was found to quench FA singlets in PS over the studied concentration range 12 mM < (TBBQ) < 48 mM, but in its presence FA singlets decayed nonexponentially. The results were interpreted quantitatively in terms of pure Foerster's transfer from FA to TBBQ without diffusion of excitons. The critical transfer radius R/sub 0/ was experimentally determined to be 24.3 A, which is in good agreement with the theoretical value of 23 A calculated from spectral data. Quenching of FA singlets in PS films was found to be independent of FA concentration over a 300 mM to 1200 mM FA concentration range for a constant TBBQ concentration of 24.0 mM. TMPD was only slightly effective as a quencher of FA singlets in PS because it apparently behaves strictly as a contact quencher based on reversible charge transfer. The implications of these results for the design of systems intended to exploit light-induced electron transfer are discussed.

  18. Electron transfer from flavin to iron in the Pseudomonas oleovorans rubredoxin reductase-rubredoxin electron transfer complex.

    Lee, H J; Basran, J; Scrutton, N S

    1998-11-01

    Rubredoxin reductase (RR) and rubredoxin form a soluble and physiological eT complex. The complex provides reducing equivalents for a membrane-bound omega-hydroxylase, required for the hydroxylation of alkanes and related compounds. The gene (alkT) encoding RR has been overexpressed and the enzyme purified in amounts suitable for studies of eT by stopped-flow spectroscopy. The eT reactions from NADH to the flavin of RR and from reduced RR to the 1Fe and 2Fe forms of rubredoxin have been characterized by transient kinetic and thermodynamic analysis. The reductive half-reaction proceeds in a one-step reaction involving oxidized enzyme and a two-electron-reduced enzyme-NAD+ charge-transfer complex. Flavin reduction is observed at 450 nm and charge-transfer formation at 750 nm; both steps are hyperbolically dependent on NADH concentration. The limiting flavin reduction rate (180 +/- 4 s-1) is comparable to the limiting rate for charge-transfer formation (189 +/- 7 s-1) and analysis at 450 and 750 nm yielded enzyme-NADH dissociation constants of 36 +/- 2 and 43 +/- 5 microM, respectively. Thermodynamic analysis of the reductive half-reaction yielded values for changes in entropy (DeltaS = -65.8 +/- 2.2 J mol-1 K-1), enthalpy (DeltaH = 37.8 +/- 0.6 kJ mol-1) and Gibbs free energy (DeltaG = 57.5 +/- 0.7 kJ mol-1 at 298 K) during hydride ion transfer to the flavin N5 atom. Spectral analysis of mixtures of 1Fe or 2Fe rubredoxin and RR suggest that conformational changes accompany eT complex assembly. Both the 1Fe (nonphysiological) and 2Fe (physiological) forms of rubredoxin were found to oxidize two electron-reduced rubredoxin reductase with approximately equal facility. Rates for the reduction of rubredoxin are hyperbolically dependent on rubredoxin concentration and the limiting rates are 72. 7 +/- 0.6 and 55.2 +/- 0.3 s-1 for the 1Fe and 2Fe forms, respectively. Analysis of the temperature dependence of eT to rubredoxin using eT theory revealed that the reaction is not adequately described as a nonadiabatic eT reaction (HAB > 80 cm-1). eT to both the 1Fe and 2Fe forms of rubredoxin is therefore gated by an adiabatic process that precedes the eT reaction from flavin to iron. Possible origins of this adiabatic event are discussed. PMID:9799514

  19. Distance dependent electron transfer at TiO2 interfaces sensitized with phenylene ethynylene bridged Ru(II)-isothiocyanate compounds.

    Johansson, Patrik G; Kopecky, Andrew; Galoppini, Elena; Meyer, Gerald J

    2013-06-01

    Excess electrons present in semiconductor nanocrystallites generate a significant electric field, yet the role this field plays in molecular charge transfer processes remains poorly understood. Three ruthenium bipyridyl cis-Ru(bpy)(LL)(NCS)2 compounds, where LL is a 4-substituted bpy, with zero, one, or two phenylene ethynylene bridge units, were anchored to mesoporous nanocrystalline TiO2 thin films to specifically quantify interfacial charge transfer with chromophores designed to be set at variable distances from the surface. Injection of electrons into TiO2 resulted in a blue shift of the metal-to-ligand charge transfer absorption consistent with an underlying Stark effect. The electroabsorption data were used to quantify the electric field experienced by the compounds that decreased from 0.85 to 0.22 MV/cm as the number of OPE spacers increased from 0 to 2. Charge recombination on the 10(-8)-10(-5) s time scale correlated with the magnitude of the electric field with an apparent attenuation factor β = 0.12 Å(-1). Slow components to charge recombination observed on the 10(-4)-10(-1) s time scale that were unaffected by temperature, irradiance, or the bridge units present on the molecular sensitizer were attributed to electron tunneling between TiO2 acceptor states. The photocurrent efficiencies of solar cells based on these compounds decreased markedly when the bridge units were present on the sensitizer. Iodine was found to form adducts with all three compounds, K = 1.8 ± 0.2 × 10(4) M(-1), but only significantly lowered the excited state injection yield for those that possessed the bridge units. PMID:23692179

  20. Electron-transfer reactions induced by ionizing radiation and photoirradiation

    Photoirradiation of a methanol solution of ?-methylstyrene and EuCl3.6H2O with Pyrex filter resulted in the formation of 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylpentanol in high yields. This reaction was initiated by the excitation of Eu(III)CH3OH CT-bands and followed by a successive photochemical reaction of Eu(II) ions formed. When 1,3-dimethyluracil was used as a substrate a regioselective hydroxymethylation took place in high efficiency, probably via an electron-transfer mechanism. ?-Radiolysis of 1,3-dimethyluracil and its derivatives in methanol also resulted in the regioselective hydroxymethylation at C-5 position of the pyrimidine ring. Analogous additions of ethanol, 2-propanol and tetrahydrofuran to 1,3-dimethyluracil occured in high efficiency. A mechanism via the one-electron reduction of 1,3-dimethyluracil is presented and compared with that of the photochemical reactions. (author)

  1. Time-optimal polarization transfer from an electron spin to a nuclear spin

    Yuan, Haidong; Zeier, Robert; Pomplun, Nikolas; Glaser, Steffen J.; Khaneja, Navin

    2015-01-01

    Polarization transfers from an electron spin to a nuclear spin are essential for various physical tasks, such as dynamic nuclear polarization in nuclear magnetic resonance and quantum state transformations on hybrid electron-nuclear spin systems. We present time-optimal schemes for electron-nuclear polarization transfers which improve on conventional approaches and will have wide applications.

  2. Identification of an electron transfer locus in plastocyanin by chromium(II) affinity labeling

    Farver, O; Pecht, I

    1981-01-01

    aromatic residues. These are proposed to be involved in the electron transfer process. A mechanism for that process is presented that involves interaction between the d electrons of the metal ions with d pi-pi* delocalization through a weakly coupled pi* system. The rationale of this electron transfer...

  3. Theory of Electron-Transfer Reactions and of Related Phenomena

    Data on electronexchange reactions have provided insight into factors influencing rates of electron-transfer reactions in solution. The present paper has the twofold purpose of discussing some of these factors and of describing applications of these exchange data and theory to other phenomena. The reaction rate depends upon the extent of reorganization of bond lengths (angles) in the reactants and of solvent reorientation outside them. The reorganization is facilitated or hindered in a comparatively simple way by a favorable or unfavorable standard free energy of reaction. The rate depends, too, on coulombic and other interactions, as evidenced perhaps by certain salt effects, though probably only by a few orders of magni - tude typically. The observed variation of rates of some 15 orders of magnitude is best attributed primarily to differences in the vibrational reorganization term, a factor calculable from bond lengths and force constants when known. A remaining factor, non-adiabaticity, is at present of uncertain importance. Arrhenius frequency factors in chemical and electrochemical exchange rate constants would provide the most direct information, but can be complicated or even dwarfed by solvent reordering effects in the coulombic interaction. Available data are few. They provide examples where a non-adiabatic effect is minor. There appear to be no known examples where it is major (Fe2+ - Fe3+, could be a candidate but its mechanism is apparently uncertain). Reorganization in reactants and in solvent occurs in a variety of related phenomena, and related concepts will be applied to treat them. In turn, chemical exchange data have useful applications to the latter. These areas include electrochemical exchange reactions, chemiluminescent electron-transfer reactions (between positive and negative aromatic ions, for example), and redox reactions of the solvated electron. An explanation for the chemiluminescent reactions will be based on the possible ''inverse ΔF°'' effect, discussed several years ago by the author. A related phenomenon involving solvent 'orientation strain' occurs in light absorption or emission by polar solutes in polar solvents, and the theoretical approach used by the author for treating it is closely related to that used for the exchange reactions. (author)

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

    In this article, ab initio calculation has been performed to evaluate the transition energy of electronic excitation in tryptophan and tyrosine by using semiempirical molecular orbital method AM1 and complete active space self-consistent field method. The solvent effect has been considered by means of the conductor-like screening model. After geometric optimizations of isolated tryptophan and tyrosine, and their corresponding radicals and cations, reaction heat of these electron transfer reactions have been obtained by the means of complete active space self-consistent field method. The transition energies from the ground state, respectively, to the lowest excited state and to the lowest triplet state of these two amino acids are also calculated and compared with the experimentally observed values. The ionization potential and electron affinity are also calculated for tryptophan and tyrosine employing Koopmans' theorem and ab initio calculation. Compared with the experimental measurements, the theoretical results are found satisfactory. Theoretical results give good explanations on the experimental phenomena that N3· can preferably oxide the side chain of tryptophan residue and then the electron transfer from tyrosine residue to tryptophan residue follows in peptides involving tryptophan and tyrosine

  5. Correlation properties of surface and percolation transfer of electrons

    In this work was received equation, connecting correlatively properties of surface with electrons distribution function. Usually for equilibrium is necessary a large number of collisions. Collisions are 'destroying' correlations. In case rare collisions large importance have correlations and 'memory' effects. Non-Markov's character of emitting particles by surface lead to strongly nonequilibrium condition of 'gas'. Here kinetic equation of diffusive form does not apply. Classical kinetic equation are described only conditions near to equilibrium. This work offers to use ideas anomal diffusion in phase-space. The correlation properties of surface describe by correlations of velocities of emitting electrons: B(t). We offer to use functional equation for probability collision instead of kinetic equation: ∫0ν0WnoncollF(ν) dv = 1 - B(t). This functional allow to consider 'memory' effects. It is important for consideration of electrons and clusters near surfaces. Distribution function become direct connected with correlations. In classical Kubo-Mory theory of transfer is necessary to get nondivergences integral: D ∝ ∫0∞B(t). In considering case we can use even 'power function'. It was used 'slow' correlation function as Kohlraush in calculations. The information about kinetics and correlations properties are containing in one functional equation. It was received solution of this equation in form Levy function: F(ν) ∝ 1/να exp(-1/ν). The solution of this form can not be get with help asymptotic methods of kinetic theory. Asymptotics of solution have scale-invariant character F(V) ∝ 1/Vα. This indicate on fractal properties phase-space. (author)

  6. A comparative study of organic electron transfer redox mediators: electron transfer kinetics for triarylimidazole and triarylamine mediators in the oxidation of 4-methoxybenzyl alcohol

    The triarylimidazoles (TAIs) constitute a promising class of organic electron transfer redox mediators that have been used to achieve indirect electrochemical C-H bonds activation and functionalization. Herein we report the diffusion and electron transfer rates for the oxidation of 4-methoxybenzyl alcohol using TAI and compare its electrochemical behavior with that of tris(4-bromophenyl)amine (TBPA). The results contribute to our understanding of the electron transfer process of electrocatalytic oxidation using TAIs, and offer useful guidelines for their further development and use

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

    Hoffman, David P.

    2013-04-11

    Interfacial electron transfer between sensitizers and semiconducting nanoparticles is a crucial yet poorly understood process. To address this problem, we have used transient absorption (TA) and femtosecond stimulated Raman spectroscopy (FSRS) to investigate the photoexcited dynamics of a series of triphenylamine-coumarin dye/TiO2 conjugates. The TA decay is multiexponential, spanning time scales from 100 fs to 100 ps, while the characteristic transient Raman spectrum of the radical cation decays biexponentially with a dominant ∼3 ps component. To explain these observations, we propose a model in which the decay of the TA is due to hot electrons migrating from surface trap states to the conduction band of TiO 2 while the decay of the Raman signature is due to internal conversion of the dye molecule. Furthermore, the S1 Raman spectrum of TPAC3, a dye wherein a vinyl group separates the triphenylamine and coumarin moieties, is similar to the S1 Raman spectrum of trans-stilbene; we conclude that their S1 potential energy surfaces and reactivity are also similar. This correlation suggests that dyes containing vinyl linkers undergo photoisomerization that competes with electron injection. © 2013 American Chemical Society.

  8. Light-induced electron transfer vs. energy transfer in molecular thin-film systems

    Quenching of fluoranthene (FA) singlets by tetrabromo-o-benzoquinone (TBBQ) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) was studied both in xylene solutions and in spin-cast polystyrene (PS) films. Emphasis was placed on time-resolved fluorescence transients resulting from pulsed excitation. Linear Stern-Volmer plots were obtained for quenching in solution and gave diffusion-controlled rate constants, of 1.45 x 1010 M-1 sec-1 and 1.53 x 1010 M-1 sec-1 for TBBQ and TMPD, respectively. TBBQ was found to quench FA singlets in PS over the studied concentration range 12 mM 0 was experimentally determined to be 24.3 A, which is in good agreement with the theoretical value of 23 A calculated from spectral data. Quenching of FA singlets in PS films was found to be independent of FA concentration over a 300 mM to 1200 mM FA concentration range for a constant TBBQ concentration of 24.0 mM. TMPD was only slightly effective as a quencher of FA singlets in PS because it apparently behaves strictly as a contact quencher based on reversible charge transfer. The implications of these results for the design of systems intended to exploit light-induced electron transfer are discussed

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

    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.

  10. Competitive-channel of double electron transfer in ion-atom collision

    Full text: Recent development in the theoretical and experimental studies on electron transfer is highlighted. Validity of single collision condition and isolated atom concept were achieved by gas target measurement. Studies on subshell resolved electron transfer for solid targets were also extrapolated to vanishing thicknesses. Predictions of the recently developed theory of a Close Coupling Calculations (CCC) based on Two State Atomic Expansion (TSAE) and Continuum Distorted Wave eikonal initial state (CDW-EIS) were compared with the experimental results. The cross-section for the simultaneous transfer of two electrons is comparable to the singe electron transfer cross-sections as the symmetry of the collision system is approached

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

    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.

  12. ELECTRONIC FUNDS TRANSFER: EXPLORING THE DIFFICULTIES OF SECURITY

    MPAKWANA ANNASTACIA MTHEMBU

    2010-09-01

    Full Text Available 800x600 Normal 0 false false false EN-GB X-NONE X-NONE MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-parent:""; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:"Calibri","sans-serif"; mso-bidi-font-family:"Times New Roman";} Generally the banking laws, regulations and supervision were designed primarily to address the fundamental principle relating to safe and sound business practices by financial institutions. In order to maintain safe and sound business practice it is of outmost importance that customers are protected against losses resulting from inadequate remedies available to them. Banking by its very nature is a high risk business. However, the major risks associated with banking are legal risks, credit interest rates and liquidity. Internet banking has increased some of these risks by creating new ones. Electronic funds transfers are based on technology which by its nature is designed to extend the geographical reach of banks and customers. This kind of a market expansion extend beyond borders, therefore there will be problems which banks will try to avoid like regulation and supervision. Other regulatory and legal risks include, the uncertainty about legal requirements in some countries and jurisdiction ambiguities regarding the responsibilities of different national authorities. Customers and banks may be exposed to legal risks associated with non-compliance with different national laws and regulations including consumer protection laws, record keeping and report requirements. Due to insecurity created by electronic funds transfer, it of importance to analyse measures under South African Law and whether these measures can effectively prevent insecurity and what lessons can be learned from abroad.

  13. Electron transfer reactions of macrocyclic compounds of cobalt

    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.

  14. Faradaic impedance titration and control of electron transfer of 1-(12-mercaptododecyl)imidazole monolayer on a gold electrode

    In this work, we studied interfacial proton transfer of the self-assembled monolayer (SAM) of 1-(12-mercaptododecyl)imidazole on a gold electrode by faradaic impedance titration method with Fe(CN)63- as an anionic redox probe molecule. The surface pK1/2 was found to be 7.3, which was nearly the same as that of 1-alkylimidazole in solution. We also investigated the electrochemical properties of the SAM-modified electrode by cyclic voltammetry. Cyclic voltammetry was performed (1) in the solution containing Fe(CN)63- with repeated alternation of pH values to investigate the electrostatic interaction of the protonated or deprotonated imidazole with Fe(CN)63- and (2) in the acidic or basic electrolyte containing Ru(NH3)63+ as a cationic redox probe to verify the effect of the polarity of a redox probe. We observed the reversible adsorption/desorption of Fe(CN)63- and concluded that the adsorbed Fe(CN)63- catalyzed the electron transfer of both Fe(CN)63- itself and cationic Ru(NH3)63+

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

    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, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

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

    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.

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

    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 0.25mA·cm(-2) for the ORR at T1Cu of the adsorbed laccase on carbon is 0.8V 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. PMID:26883057

  18. Single cell activity reveals direct electron transfer in methanotrophic consortia

    McGlynn, Shawn E.; Chadwick, Grayson L.; Kempes, Christopher P.; Orphan, Victoria J.

    2015-10-01

    Multicellular assemblages of microorganisms are ubiquitous in nature, and the proximity afforded by aggregation is thought to permit intercellular metabolic coupling that can accommodate otherwise unfavourable reactions. Consortia of methane-oxidizing archaea and sulphate-reducing bacteria are a well-known environmental example of microbial co-aggregation; however, the coupling mechanisms between these paired organisms is not well understood, despite the attention given them because of the global significance of anaerobic methane oxidation. Here we examined the influence of interspecies spatial positioning as it relates to biosynthetic activity within structurally diverse uncultured methane-oxidizing consortia by measuring stable isotope incorporation for individual archaeal and bacterial cells to constrain their potential metabolic interactions. In contrast to conventional models of syntrophy based on the passage of molecular intermediates, cellular activities were found to be independent of both species intermixing and distance between syntrophic partners within consortia. A generalized model of electric conductivity between co-associated archaea and bacteria best fit the empirical data. Combined with the detection of large multi-haem cytochromes in the genomes of methanotrophic archaea and the demonstration of redox-dependent staining of the matrix between cells in consortia, these results provide evidence for syntrophic coupling through direct electron transfer.

  19. Synthesis, Characterization, Photophysics and Photochemistry of Pyrylogen Electron Transfer Sensitizers

    Clennan, Edward L. [University of Wyoming, Laramie; Liao, Chen [ORNL

    2014-01-01

    A series of new dicationic sensitizers that are hybrids of pyrylium salts and viologens has been synthesized. The electrochemical and photophysical properties of these "pyrylogen" sensitizers are reported in sufficient detail to allow rationale design of new photoinduced electron transfer reactions. The range of their reduction potentials (+0.37-+0.05V vs SCE) coupled with their range of singlet (48-63 kcal mol(-1)) and triplet (48-57kcalmol(-1)) energies demonstrate that they are potent oxidizing agents in both their singlet and triplet excited states, thermodynamically capable of oxidizing substrates with oxidation potentials as high as 3.1eV. The pyrylogens are synthesized in three steps from readily available starting materials in modest overall 11.4-22.3% yields. These sensitizers have the added advantages that: (1) their radical cations do not react on the CV timescale with oxygen bypassing the need to run reactions under nitrogen or argon and (2) have long wavelength absorptions between 413 and 523nm well out of the range where competitive absorbance by most substrates would cause a problem. These new sensitizers do react with water requiring special precautions to operate in a dry reaction environment.

  20. Electron transfer precedes ATP hydrolysis during nitrogenase catalysis.

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

    2013-10-01

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

  1. Electron transfer of peroxidase assemblies at tailored nanocarbon electrodes

    In bioelectrochemistry, the catalytic function of redox enzymes depends largely upon the nature of the working electrode material. One major example of this phenomenon is the improvement of biogenic analyte detection at graphitic carbon with increased edge plane character in the graphene lattice. In our laboratories, we have found that the edge plane character of carbon nanotubes (CNTs) prepared using chemical vapor deposition (CVD) can be tuned via selective doping with nitrogen, termed N-CNTs. In this report, we extend these studies to investigate the influence of N-doping of nanocarbons on the electron transfer of horseradish peroxidase (HRP) using spectrophotometric enzyme activity assays and electrochemical measurements. Our findings demonstrate that HRP adsorption at N-CNTs increases by a factor of two relative to that of nondoped CNTs, with surface coverages, ?m, of 75 4 and 33 5 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) U/mg, respectively. Surprisingly, however, only ?40% of the HRP adsorbed at N-CNTs is electroactive, as assessed by voltammetry of the HRP Fe2+/3+ redox response. By contrast, HRP adsorbed at nondoped CNTs is nearly 100% electroactive, suggesting that the nature of the HRP adsorption (e.g., electrostatic, van der Waals) and geometric factors of heme orientation affect the biocatalytic performance. We also describe studies that utilize the properties of both nondoped CNTs and N-CNTs with adsorbed HRP for unmediated, quantitative H2O2 sensing

  2. 77 FR 77187 - Electronic Fund Transfers (Regulation E)

    2012-12-31

    ... fees may be disclosed. If a remittance transfer provider does not have specific knowledge regarding... remittance transfer provider does not have specific knowledge regarding variables that affect the amount of... intermediary institutions in connection with an international wire transfer, and taxes imposed on a...

  3. Protein dynamics and electron transfer: Electronic decoherence and non-Condon effects

    Skourtis, Spiros S.; Balabin, Ilya A.; Kawatsu, Tsutomu; Beratan, David N.

    2005-01-01

    We compute the autocorrelation function of the donor-acceptor tunneling matrix element 〈TDA(t)TDA(0)〉 for six Ru-azurin derivatives. Comparison of this decay time to the decay time of the time-dependent Franck-Condon factor {computed by Rossky and coworkers [Lockwood, D. M., Cheng, Y.-K. & Rossky, P. J. (2001) Chem. Phys. Lett. 345, 159-165]} reveals the extent to which non-Condon effects influence the electron-transfer rate. 〈TDA(t)TDA(0)〉 is studied as a function of donor-acceptor distance,...

  4. Modeling of ultrafast electron-transfer processes: Validity of multilevel Redfield theory

    The capability of multilevel Redfield theory to describe ultrafast photoinduced electron-transfer reactions is investigated. Adopting a standard model of photoinduced electron transfer in a condensed-phase environment, we consider electron-transfer reactions in the normal and inverted regimes, as well as for different values of the electron-transfer parameters, such as reorganization energy, electronic coupling, and temperature. Based on the comparison with numerically exact reference results, obtained using the self-consistent hybrid method, we discuss in some detail the advantages and shortcomings of two different versions of Redfield theory, which employ the time-dependent and stationary Redfield tensor, respectively. The results of the study demonstrate that multilevel Redfield theory, if applied in the appropriate parameter regime, is well suited to describe the ultrafast coherent dynamics of photoinduced electron-transfer reactions

  5. Effects of the electron irradiation energy on synthesis of gold nanoparticles using gas-liquid interfacial plasma

    Structure controlled gold nanoparticles (AuNPs) are synthesized at the surface of the ionic liquid by the plasma irradiation under the strong magnetic field. The AuNPs are easily synthesized in the region where the edge of the plasma is irradiated, while hardly synthesized in the region where the core plasma is irradiated. In the plasma edge region, high energy electrons collide with neutral gas and the diffused low energy electrons generate the AuNPs by reducing Au ions of the gold chloride. On the other hand, in the core plasma region, the irradiated high energy electrons can dissociate the ionic liquid and generate the new compounds with oxidation effect, which inhibit the synthesis of the AuNPs

  6. Tunable Interfacial Thermal Conductance by Molecular Dynamics

    Shen, Meng

    We study the mechanism of tunable heat transfer through interfaces between solids using a combination of non-equilibrium molecular dynamics simulation (NEMD), vibrational mode analysis and wave packet simulation. We investigate how heat transfer through interfaces is affected by factors including pressure, interfacial modulus, contact area and interfacial layer thickness, with an overreaching goal of developing fundamental knowledge that will allow one to tailor thermal properties of interfacial materials. The role of pressure and interfacial stiffness is unraveled by our studies on an epitaxial interface between two Lennard-Jones (LJ) crystals. The interfacial stiffness is varied by two different methods: (i) indirectly by applying pressure which due to anharmonic nature of bonding, increases interfacial stiffness, and (ii) directly by changing the interfacial bonding strength by varying the depth of the potential well of the LJ potential. When the interfacial bonding strength is low, quantitatively similar behavior to pressure tuning is observed when the interfacial thermal conductance is increased by directly varying the potential-well depth parameter of the LJ potential. By contrast, when the interfacial bonding strength is high, thermal conductance is almost pressure independent, and even slightly decreases with increasing pressure. This decrease can be explained by the change in overlap between the vibrational densities of states of the two crystalline materials. The role of contact area is studied by modeling structures comprised of Van der Waals junctions between single-walled nanotubes (SWCNT). Interfacial thermal conductance between SWCNTs is obtained from NEMD simulation as a function of crossing angle. In this case the junction conductance per unit area is essentially a constant. By contrast, interfacial thermal conductance between multiwalled carbon nanotubes (MWCNTs) is shown to increase with diameter of the nanotubes by recent experimental studies [1]. To elucidate this behavior we studied a simplified model comprised of an interface between two stacks of graphene ribbons to mimic the contact between multiwalled nanotubes. Our results, in agreement with experiment, show that the interfacial thermal conductance indeed increases with the number of graphene layers, corresponding to larger diameter and larger number of walls in MWCNT. The role of interfacial layer thickness is investigated by modeling a system of a few layers of graphene sandwiched between two silicon slabs. We show, by wave packet simulation and by theoretical calculation of a spring-mass model, that the transmission coefficient of individual vibrational modes is strongly dependent on the frequency and the number of graphene layers due to coherent interference effects; by contrast, the interfacial thermal conductance obtained in NEMD simulation, which represents an integral over all phonons, is essentially independent of the number of graphene layers, in agreement with recent experiments. Furthermore, when we heat one atomic layer of graphene directly, the effective interfacial conductance associated with heat dissipation to the silicon substrate is very small. We attribute this to the resistance associated with heat transfer between high and low frequency phonon modes within graphene. Finally, we also replaced graphene layers by a few WSe2 sheets and observed that interfacial thermal resistance of a Si/n-WSe2/Si structure increases linearly with interface thickness at least for 1 transfer mechanism, in contrast to ballistic behavior of a few graphene layers. The corresponding thermal conductivity (0.048 W m-1 K-1) of a few WSe2 layers is rather small. By comparing phonon dispersion of graphene layers and WSe2 sheets, we attribute the diffusive behavior of a few WSe2 sheets to abundant optical phonons at low and medium frequencies leading to very short mean free path. Our computational studies of effects of pressure and structural properties on interfacial thermal conductance provide fundamental insights for tunable heat transfer in nanostructures. [1] Professor D. Y. Li from University of Vanderbilt, private communication (Nov. 14, 2011).

  7. Photoinduced electron transfer in fullerene triads bearing pyrene and fluorene

    Sandanayaka, Atula S. D.; Araki, Yasuyaki; Ito, Osamu; Deviprasad, Gollapalli R.; Smith, Phillip M.; Rogers, Lisa M.; Zandler, Melvin E.; D'Souza, Francis

    2006-06-01

    Photochemical properties of pyrene and fluorene appended fulleropyrrolidine triads (AH 1-C 60-AH 2; AH 1 = pyrene and fluorene; AH 2 = naphthalene and phenyl) are reported. Electrochemical studies using cyclic voltammetry technique and DFT calculations at B3LYP/3-21G( ∗) method revealed that the charge-separated states in pyrene and fluorene appended triads are pyrene-C60rad --AH2 and fluorene-C60rad --AH2, respectively; however, no such charge-separated states could be established for naphthalene and phenyl appended triads. As demonstrated from the time resolved fluorescence, upon excitation of AH moiety in nonpolar solvents, energy transfer predominantly occurred from the singlet excited fluorophore to the C 60 moiety, whereas in polar DMF charge-separation also contributed to the fluorescence quenching. Additionally, charge separation also occurred from the singlet excited C 60 to the pyrene or fluorene entities of the triads in DMF. The rates and quantum yields of charge separation obtained by time-resolved emission studies were around 10 9 s -1 and 0.9-0.6 for pyrene-C 60-AH 2 and fluorene-C 60-AH 2 triads. Nanosecond transient absorption spectral studies performed by using 355 nm laser light on the triads, exhibited transient bands corresponding to the C60rad - and pyrene rad + or fluorene rad + , thus establishing the occurrence of electron transfer in these triads in DMF. The rates of charge recombination obtained by monitoring the decay of the C60rad - were found to be around 10 6 s -1 in DMF which resulted in the lifetimes of the radical ion pairs up to 1000 ns indicating charge stabilization in pyrene-C 60-AH 2 and fluorene-C 60-AH 2 triads. The formations of long-lived charge-separated states, pyrene-C60rad --AH2 and fluorene-C60rad --AH2 in DMF, were rationalized by evaluating the Marcus parameters from the temperature dependence of the charge-recombination rate constants.

  8. Photoinduced electron transfer in fullerene triads bearing pyrene and fluorene

    Sandanayaka, Atula S.D. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai 980-8577 (Japan); Araki, Yasuyaki [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai 980-8577 (Japan); Ito, Osamu [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai 980-8577 (Japan)], E-mail: ito@tagen.tohoku.ac.jp; Deviprasad, Gollapalli R. [Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260-0051 (United States); Smith, Phillip M. [Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260-0051 (United States); Rogers, Lisa M. [Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260-0051 (United States); Zandler, Melvin E. [Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260-0051 (United States); D' Souza, Francis [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai 980-8577 (Japan)], E-mail: Francis.DSouza@wichita.edu

    2006-06-20

    Photochemical properties of pyrene and fluorene appended fulleropyrrolidine triads (AH{sub 1}-C{sub 60}-AH{sub 2}; AH{sub 1}=pyrene and fluorene; AH{sub 2}=naphthalene and phenyl) are reported. Electrochemical studies using cyclic voltammetry technique and DFT calculations at B3LYP/3-21G(*) method revealed that the charge-separated states in pyrene and fluorene appended triads are pyrene{sup dot+}-C{sub 60}{sup dot-}AH{sub 2} and fluorene{sup dot+}-C{sub 60}{sup dot-}AH{sub 2}, respectively; however, no such charge-separated states could be established for naphthalene and phenyl appended triads. As demonstrated from the time resolved fluorescence, upon excitation of AH moiety in nonpolar solvents, energy transfer predominantly occurred from the singlet excited fluorophore to the C{sub 60} moiety, whereas in polar DMF charge-separation also contributed to the fluorescence quenching. Additionally, charge separation also occurred from the singlet excited C{sub 60} to the pyrene or fluorene entities of the triads in DMF. The rates and quantum yields of charge separation obtained by time-resolved emission studies were around 10{sup 9}s{sup -1} and 0.9-0.6 for pyrene-C{sub 60}-AH{sub 2} and fluorene-C{sub 60}-AH{sub 2} triads. Nanosecond transient absorption spectral studies performed by using 355nm laser light on the triads, exhibited transient bands corresponding to the C{sub 60}{sup dot-} and pyrene{sup dot+} or fluorene{sup dot+}, thus establishing the occurrence of electron transfer in these triads in DMF. The rates of charge recombination obtained by monitoring the decay of the C{sub 60}{sup dot-} were found to be around 10{sup 6}s{sup -1} in DMF which resulted in the lifetimes of the radical ion pairs up to 1000ns indicating charge stabilization in pyrene-C{sub 60}-AH{sub 2} and fluorene-C{sub 60}-AH{sub 2} triads. The formations of long-lived charge-separated states, pyrene{sup dot+}-C{sub 60}{sup d}'o{sup t-}AH{sub 2} and fluorene{sup dot+}-C{sub 60}{sup dot-}AH{sub 2} in DMF, were rationalized by evaluating the Marcus parameters from the temperature dependence of the charge-recombination rate constants.

  9. Photoinduced electron transfer in fullerene triads bearing pyrene and fluorene

    Photochemical properties of pyrene and fluorene appended fulleropyrrolidine triads (AH1-C60-AH2; AH1=pyrene and fluorene; AH2=naphthalene and phenyl) are reported. Electrochemical studies using cyclic voltammetry technique and DFT calculations at B3LYP/3-21G(*) method revealed that the charge-separated states in pyrene and fluorene appended triads are pyrenedot+-C60dot-AH2 and fluorenedot+-C60dot-AH2, respectively; however, no such charge-separated states could be established for naphthalene and phenyl appended triads. As demonstrated from the time resolved fluorescence, upon excitation of AH moiety in nonpolar solvents, energy transfer predominantly occurred from the singlet excited fluorophore to the C60 moiety, whereas in polar DMF charge-separation also contributed to the fluorescence quenching. Additionally, charge separation also occurred from the singlet excited C60 to the pyrene or fluorene entities of the triads in DMF. The rates and quantum yields of charge separation obtained by time-resolved emission studies were around 109s-1 and 0.9-0.6 for pyrene-C60-AH2 and fluorene-C60-AH2 triads. Nanosecond transient absorption spectral studies performed by using 355nm laser light on the triads, exhibited transient bands corresponding to the C60dot- and pyrenedot+ or fluorenedot+, thus establishing the occurrence of electron transfer in these triads in DMF. The rates of charge recombination obtained by monitoring the decay of the C60dot- were found to be around 106s-1 in DMF which resulted in the lifetimes of the radical ion pairs up to 1000ns indicating charge stabilization in pyrene-C60-AH2 and fluorene-C60-AH2 triads. The formations of long-lived charge-separated states, pyrenedot+-C60d'ot-AH2 and fluorenedot+-C60dot-AH2 in DMF, were rationalized by evaluating the Marcus parameters from the temperature dependence of the charge-recombination rate constants

  10. Unmediated by DNA electron transfer in redox-labeled DNA duplexes end-tethered to gold electrodes.

    Abi, Alireza; Ferapontova, Elena E

    2012-09-01

    Electron transfer (ET) between gold electrodes and redox-labeled DNA duplexes, immobilized onto the electrodes through the alkanethiol linker at the 3'-end and having internal either methylene blue (MB) or anthraquinone (AQ) redox labels, was shown to depend on the redox label charge and the way the redox label is linked to DNA. For loosely packed DNA monolayers, the conjugation of the positively charged MB to DNA through the long and flexible alkane linker provided ET whose kinetics was formally governed by the diffusion of the redox label to the negatively charged electrode surface. For the uncharged AQ label no ET signal was detected. The conjugation of AQ to DNA through the short and more conductive acetylene linker did not provide the anticipated DNA-mediated ET to the AQ-moiety: ET appeared to be low-efficient if any in the studied system, for which no intercalation of AQ within the DNA duplex occurred. The ET communication between the electrode and AQ, built in DNA through the acetylene linker, was achieved only when Ru(NH(3))(6)(3+) molecules were electrostatically attached to the DNA duplex, thus forming the electronic wire. These results are of particular importance both for the fundamental understanding of the interfacial behavior of the redox labeled DNA on electrodes and for the design of biosensors exploiting a variation of ET properties of DNA in the course of hybridization. PMID:22876831

  11. Poly (3,4-ethylenedioxythiophene) promotes direct electron transfer at the interface between Shewanella loihica and the anode in a microbial fuel cell

    Liu, Xing; Wu, Wenguo; Gu, Zhongze

    2015-03-01

    Anode modification is an effective method for enhancing extracellular electron transportation and improving the power density of microbial fuel cells (MFCs). In this study, a new conductive polymer called poly (3,4-ethylenedioxythiophene) (PEDOT) is electrochemically polymerized to modify the anode. The surface of the electrochemically polymerized PEDOT layer has a widespread porous structure. Both the anode electrochemical discharge experiment and MFC discharge test demonstrate the improved performance of the PEDOT-modified anode compared with a plain anode. Cyclic voltammetry and electrochemical impedance spectroscopy analyses show that the PEDOT modification increases the availability of redox active sites and reduces the interfacial electron transfer resistance of the anode. Compared with the unmodified anode, the PEDOT anodic modification improves the power density by 43%-140 mW m-2. Possible mechanisms are proposed to help understand the function of the PEDOT-modified anodic layer.

  12. Electron and hole transfer in DNA: the role of tunneling and environment

    Owing to the biological significance of radiation induced DNA damage, electron and hole transfer processes in DNA have attracted considerable interest. Various mechanisms for these processes have been proposed including tunneling and hopping. In our efforts we have investigated electron transfer for DNA in glasses, ices and solids at low temperatures via electron spin resonance (ESR) spectroscopy. Electrons and holes generated by irradiation at 77 K are trapped on DNA and transfer to a randomly interspersed intercalator, mitoxantrone (MX). Monitoring the changes of ESR signals of MX radicals, one electron oxidized guanine (G·+), one-electron reduced cytosine [C(N3)H·], and thymine anion radicals (T·-) with time at 77 K allows for the direct observation of electron and hole transfer. For DNA in aqueous glasses at low temperatures we are able to isolate the tunneling of excess electrons and we report overall distances of travel and the tunneling decay constant, beta. Studies with the duplexes polydAdT·polydAdT and polydIdC·polydIdC randomly intercalated with mitoxantrone (MX) show the excess electron transfer distances to be longer for pdAdT·pdAdT, than for for pdIdC·pdIdC. The beta value for DNA (0.9Angstroms-1) lies intermediate between that for pdAdT·pdAdT (0.75 Angstroms-1) and that for pdIdC·pdIdC (1.4 Angstroms-1). These results suggest that proton transfer from I to C·- forming CH· significantly slows but does not stop electron transfer. Similarly in DNA proton transfer in GC anion radical is not found to prevent electron transfer. Electron and hole transfer processes in frozen solutions (D2O ices) show that electron/hole transfer in polyA·polyU is significantly further than in DNA and transfer distances in polyC·polyG are substantially less than in DNA. These findings confirm our results in aqueous glasses. Our investigations of the effect of hydration, space filling lipid amine cation complexes, and temperature will also be discussed. Our modeling of electron transfer rates and distances of electron transfer in DNA-complexes allow for estimates of the spacing between DNA double stranded helices in each complex. This research was supported by the NIH NCI Grant RO1 CA45424

  13. 77 FR 10373 - Greenhouse Gas Reporting Program: Electronics Manufacturing: Revisions to Heat Transfer Fluid...

    2012-02-22

    ...The EPA is finalizing technical revisions to the electronics manufacturing source category of the Greenhouse Gas Reporting Rule related to fluorinated heat transfer fluids. More specifically, EPA is finalizing amendments to the definition of fluorinated heat transfer fluids and to the provisions to estimate and report emissions from fluorinated heat transfer fluids. This final rule is narrow......

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

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

    2015-01-01

    Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds new light on how oxidative enzymes present in plant degraders may act in concert. PMID:26686263

  15. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO3), 1-pyrenemethylamine salt (Py − Me-NH2) and Pluronic® P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr-LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr-LPE (the one prepared with Pluronic® P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (kET) using two different analytical approaches namely, linear sweep voltammetry and Laviron’s theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical wiring of the redox centers (with an increase in catalytic efficiency of Cyt c and Mb in the presence of GFNs attributed partially to the surface functional (carboxyl, epoxide and hydroxyl) groups on GO and rGO facilitating rapid charge transfer

  16. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    Sanju Gupta

    2015-03-01

    Full Text Available Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO3, 1-pyrenemethylamine salt (Py − Me-NH2 and Pluronic® P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr_LPE are characterized by a combination of analytical (microscopy and spectroscopy techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs namely, monolayer graphene, Gr_LPE (the one prepared with Pluronic® P-123, graphene oxide (GO and its reduced form (rGO on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c [for electron transfer], myoglobin (Mb [for oxygen storage] and horseradish peroxidase (HRP [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET kinetics and attempt to determine the rate constant (kET using two different analytical approaches namely, linear sweep voltammetry and Laviron’s theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical wiring of the redox centers (with an increase in catalytic efficiency of Cyt c and Mb in the presence of GFNs attributed partially to the surface functional (carboxyl, epoxide and hydroxyl groups on GO and rGO facilitating rapid charge transfer.

  17. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    Gupta, Sanju, E-mail: sanju.gupta@wku.edu [Department of Physics and Astronomy, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States); Biotechnology Center, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States); Irihamye, Aline [Gatton Academy of Mathematics and Science in Kentucky, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States)

    2015-03-15

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO{sub 3}), 1-pyrenemethylamine salt (Py − Me-NH{sub 2}) and Pluronic{sup ®} P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr-LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr-LPE (the one prepared with Pluronic{sup ®} P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (k{sub ET}) using two different analytical approaches namely, linear sweep voltammetry and Laviron’s theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical wiring of the redox centers (with an increase in catalytic efficiency of Cyt c and Mb in the presence of GFNs attributed partially to the surface functional (carboxyl, epoxide and hydroxyl) groups on GO and rGO facilitating rapid charge transfer.

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

    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.

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

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

    , 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...

  20. 48 CFR 52.232-38 - Submission of Electronic Funds Transfer Information with Offer.

    2010-10-01

    ... CLAUSES Text of Provisions and Clauses 52.232-38 Submission of Electronic Funds Transfer Information with... information that is required to make payment by electronic funds transfer (EFT) under any contract that... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Submission of...

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

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

    adiabatic electron transfer reactions is elaborated. A new formula for the transition probability of non-adiabatic electron transfer reactions is obtained in an improved Condon approximation A regular method for the calculation of non-Condon corrections is suggested. The importance of these effects for some...

  2. MnO2-filled multiwalled carbon nanotube/polyaniline nanocomposites with enhanced interfacial interaction and electronic properties

    This paper reports the synthesis and characterization of new ternary nanocomposites combining polyaniline (PANI), multiwalled carbon nanotubes (MWCNTs) and manganese dioxide (MnO2). MnO2 was successfully incorporated within the MWCNTs. In situ polymerization of aniline in the presence of MWCNTs-MnO2 was carried out to form PANI/MWCNT-MnO2 nanocomposites, which were characterized by UV-visible and Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy with energy-dispersive X-ray analysis, and transmission electron microscopy, as well as electrical conductivity measurements. The PANI/MWCNT-MnO2 nanocomposites showed enhanced electrical conductivity compared to neat PANI and PANI/MWCNTs without MnO2 addition.

  3. Interfacial Al segregation limiting electron mobility at the inverted interface of AlGaAs/GaAs quantum well

    Low-temperature mobility spectrum of two-dimensional electron gas (2DEG) at the inverted interface of AlGaAs/GaAs quantum well has been evaluated theoretically taking into account nonabrupt composition profile due to segregation of Al atoms into the well. In this approach, the Al content profile at the inverted interface has been considered as exponential decay function, and transport mobility components were calculated in the Lindhard's framework and flat interface approximation. It was found that alloy scattering due to segregated Al atoms can be significant, and even limits electron mobility at high 2DEG densities. The segregation decay length is evaluated from comparing experimental mobility spectrum with theory. (paper)

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

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

    1999-01-01

    The polaron approach is used to treat long-range electron transfers between globular proteins. A rate expression for the polaron transfer model is given along with a description of appropriate conditions for its use. Assuming that electrons transfer via a superexchange coupling due to a polaron excitation, we have estimated the distance dependence of the rate constant for the self-exchange reactions between globular proteins in solutions. The distance dependence of the polaron coupling and so...

  5. An electron energy-loss study of picene and chrysene based charge transfer salts

    Mller, Eric; Mahns, Benjamin; Bchner, Bernd; Knupfer, Martin [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany)

    2015-05-14

    The electronic excitation spectra of charge transfer compounds built from the hydrocarbons picene and chrysene, and the strong electron acceptors F{sub 4}TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) and TCNQ (7,7,8,8-tetracyanoquinodimethan) have been investigated using electron energy-loss spectroscopy. The corresponding charge transfer compounds have been prepared by co-evaporation of the pristine constituents. We demonstrate that all investigated combinations support charge transfer, which results in new electronic excitation features at low energy. This might represent a way to synthesize low band gap organic semiconductors.

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

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

  7. An electron energy-loss study of picene and chrysene based charge transfer salts

    The electronic excitation spectra of charge transfer compounds built from the hydrocarbons picene and chrysene, and the strong electron acceptors F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) and TCNQ (7,7,8,8-tetracyanoquinodimethan) have been investigated using electron energy-loss spectroscopy. The corresponding charge transfer compounds have been prepared by co-evaporation of the pristine constituents. We demonstrate that all investigated combinations support charge transfer, which results in new electronic excitation features at low energy. This might represent a way to synthesize low band gap organic semiconductors

  8. In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter

    Grapes, Michael D., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Material Measurement Laboratory, Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); LaGrange, Thomas; Reed, Bryan W.; Campbell, Geoffrey H. [Lawrence Livermore National Laboratory, Materials Science and Technology Division, Livermore, California 94550 (United States); Woll, Karsten [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Institute of Applied Materials, Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen (Germany); LaVan, David A., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Material Measurement Laboratory, Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Weihs, Timothy P., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

    2014-11-01

    The Al/Ni formation reaction is highly exothermic and of both scientific and technological significance. In this report, we study the evolution of intermetallic phases in this reaction at a heating rate of 830 K/s. 100-nm-thick Al/Ni bilayers were deposited onto nanocalorimeter sensors that enable the measurement of temperature and heat flow during rapid heating. Time-resolved transmission electron diffraction patterns captured simultaneously with thermal measurements allow us to identify the intermetallic phases present and reconstruct the phase transformation sequence as a function of time and temperature. The results show a mostly unaltered phase transformation sequence compared to lower heating rates.

  9. Linker-free layer-by-layer self-assembly of gold nanoparticle multilayer films for direct electron transfer of horseradish peroxidase and H2O2 detection

    Highlights: ? Gold nanoparticle (AuNP) multilayer films were fabricated via a linker-free layer-by-layer assembly. ? Direct electron transfer of horseradish peroxidase (HRP) absorbed on as-prepared AuNP multilayer films was enhanced. ? The optimized HRP/AuNP multilayer film had a relatively rapid response and satisfactory selectivity for H2O2 detection. - Abstract: Au nanoparticle (AuNP) multilayer films were fabricated by combining interfacial assembly and layer-by-layer assembly. The key point is that the procedure does not require assistance of organic linker molecules, thus providing a suitable platform for the modification of biological molecules. Direct electron transfer can easily take place between a glassy carbon electrode and horseradish peroxidase (HRP) molecules adsorbed on AuNP films. The current density of direct electron transfer was closely related to the layer number, m, and reached a maximum value for m = 4. The optimized HRP/AuNP multilayer film had a relatively rapid response and satisfactory selectivity for H2O2 detection. The linear range and the detection limit were 9.8 x 10-6 to 6 x 10-3 mol/L and ?4.9 x 10-6 mol/L (S/N = 3), respectively.

  10. Approach to Interfacial and Intramolecular Electron Transfer of the Diheme Protein Cytochrome c(4) Assembled on Au(111) Surfaces

    Chi, Qijin; Zhang, Jingdong; Taner, Arslan; Borg, Lotte; Pedersen, G. W.; Christensen, Hans Erik Mølager; Nazmudtinov, R. R.; Ulstrup, Jens

    2010-01-01

    protein Pseudomonas stutzeri cytochrome c(4) has been a target for intramolecular, interheme ET. We report here voltammetric and in situ scanning tunneling microscopy (STM) data for P. stutzeri cyt c(4) at single-crystal, atomically planar Au(111)-electrode surfaces modified by variable-length omega...... direction and a single two-ET peak in the anodic direction. Intramolecular, interheme ET with high, 8,000-30,000 s(-1), rate constants is notably an essential part of this mechanism. The high rate constants are in striking contrast to ET reactions of P. stutzeri cyt c4 with small reaction partners in...... homogeneous solution for which kinetic analysis clearly testifies to electrostatic cooperative effects but no intramolecular, interheme ET higher than 0.1-10 s(-1). This difference suggests a strong gating feature of the process. On the basis of the three-dimensional structure of P. stutzeri cyt c(4), gating...

  11. Anode interfacial tuning via electron-blocking/hole-transport layers and indium tin oxide surface treatment in bulk-heterojunction organic photovoltaic cells

    Hains, Alexander W.; Liu, Jun; Martinson, Alex B.F.; Irwin, Michael D.; Marks, Tobin J. [Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, Illinois (United States)

    2010-02-22

    The effects of anode/active layer interface modification in bulk-heterojunction organic photovoltaic (OPV) cells is investigated using poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and/or a hole-transporting/electron-blocking blend of 4,4'-bis[(p-trichlorosilylpropylphenyl)-phenylamino]biphenyl (TPDSi{sub 2}) and poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB) as interfacial layers (IFLs). Current-voltage data in the dark and AM1.5G light show that the TPDSi{sub 2}:TFB IFL yields MDMO-PPV:PCBM OPVs with substantially increased open-circuit voltage (V{sub oc}), power conversion efficiency, and thermal stability versus devices having no IFL or PEDOT:PSS. Using PEDOT:PSS and TPDSi{sub 2}:TFB together in the same cell greatly reduces dark current and produces the highest V{sub oc} (0.91 V) by combining the electron-blocking effects of both layers. ITO anode pre-treatment was investigated by X-ray photoelectron spectroscopy to understand why oxygen plasma, UV ozone, and solvent cleaning markedly affect cell response in combination with each IFL. O{sub 2} plasma and UV ozone treatment most effectively clean the ITO surface and are found most effective in preparing the surface for PEDOT:PSS deposition; UV ozone produces optimum solar cells with the TPDSi{sub 2}:TFB IFL. Solvent cleaning leaves significant residual carbon contamination on the ITO and is best followed by O{sub 2} plasma or UV ozone treatment. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  12. Final Report for completed IPP-0110 and 0110A Projects: 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications'

    The DOE-supported IPP (Initiatives for Proliferation Prevention) Project, IPP-0110, and its accompanying 'add-on project' IPP-0110A, entitled 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications' was a collaborative project involving the Lawrence Berkeley National Laboratory (LBNL) as the U.S. DOE lab; the US surface modification company, Phygen, Inc., as the US private company involved; and the High Current Electronics Institute (HCEI) of the Russian Academy of Sciences, Tomsk, Siberia, Russia, as the NIS Institute involved. Regular scientific research progress meetings were held to which personnel came from all participating partners. The meetings were held mostly at the Phygen facilities in Minneapolis, Minnesota (with Phygen as host) with meetings also held at Tomsk, Russia (HCEI as host), and at Berkeley, California (LBNL as host) In this way, good exposure of all researchers to the various different laboratories involved was attained. This report contains the Final Reports (final deliverables) from the Russian Institute, HCEI. The first part is that for IPP-0110A (the 'main part' of the overall project) and the second part is that for the add-on project IPP-0110A. These reports are detailed, and contain all aspects of all the research carried out. The project was successful in that all deliverables as specified in the proposals were successfully developed, tested, and delivered to Phygen. All of the plasma hardware was designed, made and tested at HCEI, and the performance was excellent. Some of the machine and performance parameters were certainly of 'world class'. The goals and requirements of the IPP Project were well satisfied. I would like to express my gratitude to the DOE IPP program for support of this project throughout its entire duration, and for the unparalleled opportunity thereby provided for all of the diverse participants in the project to join in this collaborative research. The benefits are superb, as measured in quite a number of different ways.

  13. Coulomb effects in polarization transfer in elastic antiproton and proton electron scattering at low energies

    Arenhoevel, H.

    2007-01-01

    The influence of Coulomb distortion on the polarization transfer in elastic proton and antiproton electron scattering at low energies is calculated in a distorted wave Born approximation. For antiproton electron scattering Coulomb effects reduce substantially the spin transfer cross section compared to the plane wave Born approximation whereas for proton electron scattering they lead to a dramatic increase for kinetic proton lab energies below about 20 keV.

  14. Interfacial microstructure and strength of the dissimilar joint Ti3Al/TC4 welded by the electron beam process

    Dissimilar weld joints in Ti3Al/TC4 were welded using the electron beam (EB) process. The microstructure evolution characterizations of the joints was investigated by means of OM, SEM, XRD, TEM and the tensile strengths of the joints were tested. The microstructure of the weld metal of every joint was identical. The structures were characterized by martensite, appearing coarse equiaxed grains. There existed grain coarsening and martensitic transformation in Ti3Al/HAZ and TC4/HAZ. With the increase of heat input, the grain size was significantly raised, yet the composition of the weld metal was independent of heat input. The highest tensile strength of the joints can reach 831 MPa, equaled almost to 92% of that of Ti3Al-based alloy

  15. Influences of interfacial terminations on electronic structure and magnetoelectric coupling in Fe/KNbO3 superlattices

    Zhang, Hu; Dai, Jian-Qing; Song, Yu-Min

    2015-01-01

    We study the electronic structures and the magnetoelectric (ME) effect in Fe/KNbO3 superlattices theoretically. The interior KNbO3 layers in superlattices with the NbO2 terminations are insulating. While they are metallic for the KO terminations. The interface Fesbnd Nb and Fesbnd O bonds induce large magnetic moments on Nb and O atoms. The magnitude of the induced magnetic moments is related to the polarization direction of the KNbO3 layers. We obtain a large ME effect in NbO2-terminated superlattices. However the ME effect is negligible in KO-terminated superlattices due to the opposite sign of variations of magnetic moments on O and Fe at two interfaces.

  16. Role of 2-mercaptoethanol in direct electron transfer-type bioelectrocatalysis of fructose dehydrogenase at Au electrodes

    Highlights: • The state of FDH on the Au electrode is voltammetrically monitored with DET catalytic current, O2 reduction current, and [Fe(CN)6]3−/4− redox signal. • FDH shows the highest activity at around the pzc of Au electrode. • The DET activity of FDH decreases with time at positive electrode potentials due to the strong positive electric field. • Mercaptoethanol-Au binding located in the gap of the adsorbed FDH plays a significant role in the stability of the adsorbed FDH on the Au electrode. -- Abstract: Effects of the electrode potential on a direct electron transfer (DET)-type bioelectrocatalysis of fructose dehydrogenase (FDH) at Au electrodes were investigated. Adsorbed FDH showed the highest DET activity at an adsorption potential (Ead) around the point of zero charge (Epzc). Since FDH stock solution contains 2-mercaptoethanol (ME) for stabilization, ME is partially bound to the Au electrode. However, the DET activity drastically decreased at Ead >> Epzc. Au oxide layer is formed at the positive potentials to hinder the interfacial electron transfer. In contrast, only slight decrease in the DET activity was observed at sufficiently negative Ead (<

  17. Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation

    Pulse radiolysis has been used to investigate intramolecular electron transfer in a series of molecules in which dimethoxynapththalene (M2N) and dicyanovinyl (DCV) groups are held at fixed distance and orientation by rigid saturated hydrocarbon bridges. Electron transfer from M2N- to DCV is faster than 1 x 109 s-1 for compounds in which the two groups are separated by 4, 6, 8, 10, or 12 saturated carbon-carbon bonds. For the 4-, 6-, and 8-bond compounds, optical electron transfer bands are present in the visible - near-infrared absorption spectra of the anions. The positions shift to higher energies with increasing solvent polarity. Their intensities are large (epsilon ? 2000 M-1 cm-1 for the 4-bond compound) and decrease rapidly as the length of the bridge increases. It is clear that exceptionally large, long-distance electronic coupling of the two ? systems occurs through the saturated bonds of the bridge. These electronic couplings are 0.16, 0.06, and 0.03 eV across 4-, 6-, and 8-bond bridges. Even larger couplings have been observed previously by photoelectron spectroscopy, but not for such large ? systems. With these large electronic couplings, long-distance electron transfer in the 4- and 6-bond compounds is expected to be adiabatic. Even for the 8-bond compound with a center-to-center distance of ?12 A the electron-transfer rate reduced from the optical electron-transfer absorption band is > 1012 s-1

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

    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.

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

    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. Interfacial electronic structure-modulated magnetic anisotropy in Ta/CoFeB/MgO/Ta multilayers

    We have observed several unexpected phenomena when a trace amount of Fe atoms is deposited onto the CoFeB/MgO interface in Ta/CoFeB/MgO/Ta multilayers. With the nominal thickness of the introduced Fe atoms (tFe) varying from 0 to 0.1 Å, the effective magnetic anisotropy energy (Keff) of annealed multilayers is remarkably enhanced from 1.28 × 106 erg/cm3 to 2.14 × 106 erg/cm3. As tFe further increasing, the Keff decreases and even becomes negative when tFe > 1 Å, indicating the change from perpendicular magnetic anisotropy to in-plane magnetic anisotropy. The analysis by X-ray photoelectron spectrometer reveals that the Fe atoms at annealed CoFeB/MgO interface show different electronic structures as tFe increasing, which combine with O atoms to form FeOx (x 2O3, and Fe3O4, respectively, leading to modulation of Fe 3d-O 2p orbital hybridization and thus the Keff. On the other hand, we find that the introduction of Fe atoms also helps to reduce the multilayers' magnetic damping.

  1. Effect of excess charge of cadmium sulfide colloid particles on interphase rate of electron transfer

    Kinetics of photodecolorization relaxation of aqueous solutions containing CdS colloid with particle size approx 50 A, L-cysteine as electron donor and oxygen as electron acceptor, has been studied. Photodecolorization relaxation kinetics reflects of nonequilibrium electron transfer from CdS particles to oxygen molecules in solution. The regularities defined are explained proceeding from the assumption on the effect of excess electrons charge on potential of colloid particles double layer, i.e. on apparent activation energy of electron interphase transfer

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

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

    2016-02-10

    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. PMID:26820105

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

    Horáček, Miroslav

    2005-01-01

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

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

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

    2016-03-14

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, 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. PMID:26979698

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

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

    2003-01-01

    Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have...

  6. Electron-transfer reactions between viologen radical cations and quinones in AOT reverse micelles studied by electron pulse radiolysis

    Electron-transfer reactions between viologen radical cations (CnVsm-bullet+, n = 1-18) and various quinones have been studied in aqueous and reverse micellar (AOT/isooctane/H2O) solution by use of the electron pulse radiolysis technique. By use of dynamic light scattering measurements, the concentration of water pools was determined and the number of electron-transfer reactants per water pool could be calculated. Rate constants measured for the reaction between CnVsm-bullet+ radicals and anthraquinonesulfonate ions (AQS-) decreased with increasing length of the aliphatic chain of the viologens, caused by association of the viologen with the surfactant interface

  7. Study of intermediates from transition metal excited-state electron-transfer reactions

    Hoffman, M. Z.

    1992-07-01

    Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes.

  8. Photo-induced electron transfer at nanostructured semiconductor-zinc porphyrin interface

    Hakola, Hanna; Pyymaki Perros, Alexander; Myllyperkiö, Pasi; Kurotobi, Kei; Lipsanen, Harri; Imahori, Hiroshi; Lemmetyinen, Helge; Tkachenko, Nikolai V.

    2014-01-01

    Electron transfer at metal oxide-organic dye interface on ZnO nanorod (ZnOr) templates was studied by femtosecond absorption spectroscopy method. Further confirmation of the electron transfer was obtained from photoelectrical studies. The fastest electron transfer from zinc porphyrin (ZnP) to semiconductor was observed for ZnOr modified by a 5 nm layer of TiO2 (nanoparticle and ZnP. This indicates that the charge recombination depends mainly on semiconductor bulk properties whereas the charge separation is determined by the organic-semiconductor interface.

  9. Reversible electron transfer reaction between polyaniline and thiol/disulfide couples

    Tatsuma, Tetsu; Matsui, Hiroshi; Shouji, Eiichi; Oyama, Noboru [Tokyo Univ. of Agriculture and Technology (Japan)

    1996-08-15

    Reversible electron transfer was observed between polyaniline (PAn) and thiol/disulfide couples of 2,5-dimercapto-1,3,4-thiadazole (DMcT), 2-mercapto-5-methyl-1,3,4-thiadiazole, 2-mercaptopyridine, and thiophenol. Thus, PAn can be used as a molecular current collector for those insulating organosulfur compounds, which are promising high-capacity energy storage materials. Among those couples, DMc Tex hibits the fastest reversible electron transfer. Electron transfer from other aromatic and aliphatic thiols to oxidized PAn is also observed. Effects of protons on the reactions and reaction kinetics are discussed. 10 refs., 10 figs., 1 tab.

  10. Explicitly Time-Dependent Electron Transfer in Donor-Bridge-Acceptor Systems

    Psiachos, Demetra

    2016-01-01

    We discuss electron transfer in benchmark donor-bridge-acceptor systems using time-dependent methods based on exact diagonalizations. For the small bridge sizes studied, the exact solution leads to results far different from perturbation theory. Notably, we do not obtain destructive interferences in the electron transfer for the arrangements of the bridge molecules which lead to this result using the perturbation theory. The calculated currents for various donor-bridge-acceptor configurations attached to electrodes show two distinct regimes: hopping and tunnelling, where in the latter, the current increases as a function of the energy of the transferred electron, a regime inaccessible by conventional scattering theory.

  11. Electron Transfer and Proton-Coupled Electron Transfer Reactivity and Self-Exchange of Synthetic [2Fe–2S] Complexes: Models for Rieske and mitoNEET Clusters

    Saouma, Caroline T.; Pinney, Margaux M.; Mayer, James M.

    2014-01-01

    This report describes the thermochemistry, proton-coupled electron transfer (PCET) reactions and self-exchange rate constants for a set of bis-benzimidazolate-ligated [2Fe–2S] clusters. These clusters serve as a model for the chemistry of biological Rieske and mitoNEET clusters. PCET from [Fe2S2(Prbbim)(PrbbimH)]2– (4) and [Fe2S2(Prbbim)(PrbbimH2)]1– (5) to TEMPO occurs via concerted proton–electron transfer (CPET) mechanisms (PrbbimH2 = 4,4-bis-(benzimidazol-2-yl)heptane). Intermolecular ele...

  12. Near-IR excitation transfer and electron transfer in a BF2-chelated dipyrromethane-azadipyrromethane dyad and triad.

    El-Khouly, Mohamed E; Amin, Anu N; Zandler, Melvin E; Fukuzumi, Shunichi; D'Souza, Francis

    2012-04-23

    A molecular dyad and triad, comprised of a known photosensitizer, BF(2)-chelated dipyrromethane (BDP), covalently linked to its structural analog and near-IR emitting sensitizer, BF(2)-chelated tetraarylazadipyrromethane (ADP), have been newly synthesized and the photoinduced energy and electron transfer were examined by femtosecond and nanosecond laser flash photolysis. The structural integrity of the newly synthesized compounds has been established by spectroscopic, electrochemical, and computational methods. The DFT calculations revealed a molecular-clip-type structure for the triad, in which the BDP and ADP entities are separated by about 14 Å with a dihedral angle between the fluorophores of around 70°. Differential pulse voltammetry studies have revealed the redox states, allowing estimation of the energies of the charge-separated states. Such calculations revealed a charge separation from the singlet excited BDP ((1)BDP*) to ADP (BDP(.+)-ADP(.-)) to be energetically favorable in nonpolar toluene and in polar benzonitrile. In addition, the excitation transfer from the singlet BDP to ADP is also envisioned due to good spectral overlap of the BDP emission and ADP absorption spectra. Femtosecond laser flash photolysis studies provided concrete evidence for the occurrence of energy transfer from (1)BDP* to ADP (in benzonitrile and toluene) and electron transfer from BDP to (1)ADP* (in benzonitrile, but not in toluene). The kinetic study of energy transfer was measured by monitoring the rise of the ADP emission and revealed fast energy transfer (ca. 10(11) s(-1)) in these molecular systems. The kinetics of electron transfer via (1)ADP*, measured by monitoring the decay of the singlet ADP at λ=820 nm, revealed a relatively fast charge-separation process from BDP to (1)ADP*. These findings suggest the potential of the examined ADP-BDP molecules to be efficient photosynthetic antenna and reaction center models. PMID:22416038

  13. Extracellular electron transfer mechanism in Shewanella loihica PV-4 biofilms formed at indium tin oxide and graphite electrodes

    Jain, A.; Connolly, J.O.; Woolley, R.; Krishnamurthy, S.; Marsili, E.

    , secreted redox mediators accumulated at biofilm/graphite interface, thus increasing mediated electron transfer as the biofilm grows over five days. Our results showed that the electrode material determined the prevalent electron transfer mechanism...

  14. Near-interfacial thermal donor generation during processing of (100)Si/low-κ Si-oxycarbide insulator structures revealed by electron spin resonance

    A low-temperature multifrequency electron spin resonance (ESR) study has been carried out on Cz-(110)Si/insulator structures with organosilicate films of low dielectric constant κ grown at 300 °C using the plasma-enhanced chemical vapor deposition method (PECVD). After subjection to a short-term UV-irradiation-assisted thermal curing treatment at 430 °C to remove the organic component from the low-κ film and obtain optimal porosity, the NL8 ESR spectrum of C2v symmetry is observed, characterized by g1 (//[100] = 1.999 83(8), g2(//[011] = 1.992 74(8), g3 = (//[1 1-bar 0]) = 2.001 15(8). Based on previous insight, this reveals the generation in the c-Si substrate of singly ionized thermal double donor (TDD) defects with a core containing oxygen atoms. Remarkably, the generation is found to be highly nonuniform, and the defect density depth profile shows an exponential-like decay (decay length ∼3.8 μm) from the oxide/Si interface inward the Si substrate, thus exposing the defect formation as an interface-administered effect. Upon analysis, the strain induced by interfacial stress in the c-Si beneath the interface is suggested as the major driving component in the enhancement of TDD formation during thermal treatment, suggesting that substantial stress is involved with PECVD organosilicate low-κ glasses. The result represents a different and affirmative illustration of the influence of strain on TDD formation. Based on the principal g values, the observed TDD is closest to the NL81 type, the one formed first in bulk c-Si through oxygen agglomeration during short-term thermal treatment. (paper)

  15. Electron transfer of nitrogen, oxygen and silicon in vanadium

    In order to assess the possibility of refining vanadium by the electricity transfer method, the process of electricity transfer of impurities of nitrogen, oxygen and silicon in vanadium is studied. The diffusion coefficients for these impurities in the temperature range of 1565-16650C are determined. The distribution of impurities over the length of a specimen is determined by methods of potentials and eddy currents. The electricity transfer is performed in a hermetically sealed flask in argon atmosphere. The diffusion coefficient values for O2, N2, Si in V at 16650C are measured to be 1.0x10-5; 0.38x10-5; 4.7x10-5cm.g/sec, respectively, which corresponds to an activation energy of 12, 20 and 24 kcal/mol. Also estimated are their effective valence and charge carrier density per atom of vanadium. The data obtained stubstantiate the ''hole'' mechanism of vanadium conductivity

  16. Direct Delocalization for Calculating Electron Transfer in Fullerenes

    Arntsen, Christopher D.; Reslan, Randa; Hernandez, Samuel; Gao, Yi; Neuhauser, Daniel

    2013-08-05

    A method is introduced for simple calculation of charge transfer between very large solvated organic dimers (fullerenes here) from isolated dimer calculations. The individual monomers in noncentrosymmetric dimers experience different chemical environments, so that the dimers do not necessarily represent bulk-like molecules. Therefore, we apply a delocalizing bias directly to the Fock matrix of the dimer system, and verify that this is almost as accurate as self-consistent solvation. As large molecules like fullerenes have a plethora of excited states, the initially excited state orbitals are thermally populated, so that the rate is obtained as a thermal average over Marcus thermal transfers.

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

    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.

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

    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.

  19. Impact of electron delocalization on the nature of the charge-transfer states in model pentacene/C60 Interfaces: A density functional theory study

    Yang, Bing

    2014-12-04

    Electronic delocalization effects have been proposed to play a key role in photocurrent generation in organic photovoltaic devices. Here, we study the role of charge delocalization on the nature of the charge-transfer (CT) states in the case of model complexes consisting of several pentacene molecules and one fullerene (C60) molecule, which are representative of donor/acceptor heterojunctions. The energies of the CT states are examined by means of time-dependent density functional theory (TD-DFT) using the long-range-corrected functional, ωB97X, with an optimized range-separation parameter, ω. We provide a general description of how the nature of the CT states is impacted by molecular packing (i.e., interfacial donor/acceptor orientations), system size, and intermolecular interactions, features of importance in the understanding of the charge-separation mechanism.

  20. Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

    Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields 3TMB* after rapid intersystem crossing from 1TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), α-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property (π-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the kqT values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants kqS have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic kq values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation

  1. Dynamic modulation of electron correlation by intramolecular modes in charge transfer compounds

    Meneghetti, M

    1999-01-01

    Electron-phonon and electron-electron interactions are in competition in determining the properties of molecular charge transfer conductors and superconductors. The direct influence of phonons on the electron-electron interaction was not before considered and in the present work the coupling of intramolecular modes to electron-electron interaction (U-vib interaction) is investigated.The effect of this coupling on the frequency of the normal modes of a dimer model is obtained and it is shown that frequency shifts of the Raman active modes are directly related to this coupling. The results are used to obtain the values of the U-vib coupling constants of intramolecular modes of a representative molecule of charge transfer conductors, like tetramethyltetratiafulvalene. Consequences of this coupling on the electron pairing are also suggested.

  2. Bi-directional magnetic resonance based wireless power transfer for electronic devices

    Kar, Durga P.; Nayak, Praveen P.; Bhuyan, Satyanarayan; Mishra, Debasish

    2015-09-01

    In order to power or charge electronic devices wirelessly, a bi-directional wireless power transfer method has been proposed and experimentally investigated. In the proposed design, two receiving coils are used on both sides of a transmitting coil along its central axis to receive the power wirelessly from the generated magnetic fields through strongly coupled magnetic resonance. It has been observed experimentally that the maximum power transfer occurs at the operating resonant frequency for optimum electric load connected across the receiving coils on both side. The optimum wireless power transfer efficiency is 88% for the bi-directional power transfer technique compared 84% in the one side receiver system. By adopting the developed bi-directional power transfer method, two electronic devices can be powered up or charged simultaneously instead of a single device through usual one side receiver system without affecting the optimum power transfer efficiency.

  3. Bi-directional magnetic resonance based wireless power transfer for electronic devices

    In order to power or charge electronic devices wirelessly, a bi-directional wireless power transfer method has been proposed and experimentally investigated. In the proposed design, two receiving coils are used on both sides of a transmitting coil along its central axis to receive the power wirelessly from the generated magnetic fields through strongly coupled magnetic resonance. It has been observed experimentally that the maximum power transfer occurs at the operating resonant frequency for optimum electric load connected across the receiving coils on both side. The optimum wireless power transfer efficiency is 88% for the bi-directional power transfer technique compared 84% in the one side receiver system. By adopting the developed bi-directional power transfer method, two electronic devices can be powered up or charged simultaneously instead of a single device through usual one side receiver system without affecting the optimum power transfer efficiency

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

    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.

  5. 77 FR 6310 - Electronic Fund Transfers (Regulation E)

    2012-02-07

    ... information on whether it should revise these threshold numbers in Regulation Z. See 76 FR 75825 (Dec. 5, 2011... would complete the rulemaking process. 76 FR 29902 (May 23, 2011). This proposal has two parts. First... disclosure and two receipts) for each transfer described above would create information overload...

  6. Rhodamine-6G can photosensitize folic acid decomposition through electron transfer

    Hirakawa, Kazutaka; Ito, Hiroki

    2015-05-01

    Rhodamine-6G photosensitized folic acid decomposition in aqueous solution, and its quantum yield in the presence of 10 ?M folic acid was 9.9 10-6. A possible mechanism of this photodecomposition is direct oxidation through an electron transfer from folic acid to rhodamine-6G. The fluorescence lifetime of rhodamine-6G was slightly decreased by folic acid, suggesting electron transfer in the excited singlet state of rhodamine-6G. The quenching rate coefficient estimated from the Stern-Volmer plot of the fluorescence quenching supported that this electron transfer proceeds as a diffusion-controlled reaction. The quantum yields of the electron transfer and the following reaction could be determined.

  7. Radiation and photo induced electron transfer processes: Exciting possibilities for basic research and applications

    Radiation and/or photo induced electron transfer reaction results in retrievable storage of information, with extensive applications ranging from dosimetry, efficient light conversion molecular devices (LCMD), photo refraction, optical phase conjunction and holography. These areas gives ample new opportunities to conduct basic investigations to elucidate the mechanistic aspects of photo (radiation) induced electron transfer, and to translate the acquired knowledge into making a device. The talk will focus on the investigation by the author on photo induced electron transfer reaction in photorefractive systems and also on the radiation induced electron transfer processes in dosimetric materials. Furthermore, the recent trends in the light conversion molecular devices using rare earth complexes and the fluorescent molecular sensors for cation recognition will be discussed. (author)

  8. Model-free Investigation of Ultrafast Bimolecular Chemical Reactions: Bimolecular Photo Induced Electron Transfer

    Rosspeintner Arnulf; Lang Bernhard; Vauthey Eric

    2013-01-01

    Using photoinduced bimolecular electron transfer reactions as example we demonstrate how diffusion controlled bimolecular chemical reactions can be studied in a model-free manner by quantitatively combining different ultrafast spectroscopical tools.

  9. Facilitation of Electron Transfer in the Presence of Mitochondria-Targeting Molecule SS31

    Nosach, Tetiana; Ebrahim, Mark; Ren, Yuhang; Darrah, Shaun; Szeto, Hazel

    2010-03-01

    Electron transfer (ET) processes in mitochondria are very important for the production of adenosine triphosphate (ATP), the common source of the chemical energy. The inability to transfer electrons efficiently in mitochondrial ET chain plays a major role in age associated diseases, including diabetes and cancer. In this work, we used the time dependent absorption and photoluminescence spectroscopy to study the electron transfer kinetics along the ET chain of mitochondria. Our spectroscopic results suggest that SS31, a small peptide molecule targeting to the mitochondrial inner membrane, can facilitate electron transfer and increase ATP production. We show that SS31 targets cytochrome c to both increase the availability of state and also potentially reduce the energy barrier required to reduce cytochrome c.

  10. An Electron Transfer Approach to the Preparation of Highly Functionalized Anthraquinones

    Patrice Vanelle

    2005-01-01

    Full Text Available A series of highly functionalized quinones was prepared by an original reaction of 2,3-bis(chloromethyl-1,4-dimethoxyanthraquinone (6 with various nitronate anions under electron transfer reaction conditions.

  11. Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

    Patrice Vanelle

    2002-12-01

    Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

  12. Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

    Patrice Vanelle; Vincent Rémusat; Pascal Rathelot

    2002-01-01

    A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

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

    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...

  14. Experimental insights on the electron transfer and energy transfer processes between Ce3+-Yb3+ and Ce3+-Tb3+ in borate glass

    Sontakke, Atul D.; Ueda, Jumpei; Katayama, Yumiko; Dorenbos, Pieter; Tanabe, Setsuhisa

    2015-03-01

    A facile method to describe the electron transfer and energy transfer processes among lanthanide ions is presented based on the temperature dependent donor luminescence decay kinetics. The electron transfer process in Ce3+-Yb3+ exhibits a steady rise with temperature, whereas the Ce3+-Tb3+ energy transfer remains nearly unaffected. This feature has been investigated using the rate equation modeling and a methodology for the quantitative estimation of interaction parameters is presented. Moreover, the overall consequences of electron transfer and energy transfer process on donor-acceptor luminescence behavior, quantum efficiency, and donor luminescence decay kinetics are discussed in borate glass host. The results in this study propose a straight forward approach to distinguish the electron transfer and energy transfer processes between lanthanide ions in dielectric hosts, which is highly advantageous in view of the recent developments on lanthanide doped materials for spectral conversion, persistent luminescence, and related applications.

  15. Experimental insights on the electron transfer and energy transfer processes between Ce3+-Yb3+ and Ce3+-Tb3+ in borate glass

    A facile method to describe the electron transfer and energy transfer processes among lanthanide ions is presented based on the temperature dependent donor luminescence decay kinetics. The electron transfer process in Ce3+-Yb3+ exhibits a steady rise with temperature, whereas the Ce3+-Tb3+ energy transfer remains nearly unaffected. This feature has been investigated using the rate equation modeling and a methodology for the quantitative estimation of interaction parameters is presented. Moreover, the overall consequences of electron transfer and energy transfer process on donor-acceptor luminescence behavior, quantum efficiency, and donor luminescence decay kinetics are discussed in borate glass host. The results in this study propose a straight forward approach to distinguish the electron transfer and energy transfer processes between lanthanide ions in dielectric hosts, which is highly advantageous in view of the recent developments on lanthanide doped materials for spectral conversion, persistent luminescence, and related applications

  16. 48 CFR 52.232-35 - Designation of Office for Government Receipt of Electronic Funds Transfer Information.

    2010-10-01

    ... Government Receipt of Electronic Funds Transfer Information. 52.232-35 Section 52.232-35 Federal Acquisition... Electronic Funds Transfer Information. As prescribed in 32.1110(c), insert the following clause: Designation of Office for Government Receipt of Electronic Funds Transfer Information (MAY 1999) (a) As...

  17. Electron transfer from CO2lg-bullet- to perylene in cyclohexane

    CO2lg-bullet- formed by the reactions of the electron with CO2 in cyclohexane transfers an electron to perylene with a rate constant of 2.9 x 1010 M-1s-1. Gε580nm for the perylene radical anion is 9 x 103 molecules (100 eV)-1 M -1 cm-1. The transfer of an electron from CO2lg-bullet+ to an aromatic molecule is a significant process when CO2 is used as an electron scavenger in solution where the production of excited states of the aromatic molecule is studied. 24 refs., 6 figs

  18. Microbe-electrode interactions: The chemico-physical environment and electron transfer

    Gardel, Emily Jeanette

    2013-01-01

    This thesis presents studies that examine microbial extracellular electron transfer that an emphasis characterizing how environmental conditions influence electron flux between microbes and a solid-phase electron donor or acceptor. I used bioelectrochemical systems (BESs), fluorescence and electron microscopy, chemical measurements, 16S rRNA analysis, and qRT-PCR to study these relationships among chemical, physical and biological parameters and processes.

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

    Sjulstok, Emil; Olsen, Jgvan 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 to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome-a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor. PMID:26689792

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

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

    2015-12-01

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

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

    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.

  2. Electronic transfer of prescription-related information: comparing views of patients, general practitioners, and pharmacists.

    Porteous, Terry; Bond, Christine; Robertson, Roma; Hannaford, Philip; Reiter, Ehud

    2003-01-01

    BACKGROUND: The National Health Service (NHS) intends to introduce a system of electronic transfer of prescription-related information between general practitioners (GPs) and community pharmacies. The NHS Plan describes how this will be achieved. AIM: To gather opinions of patients, GPs, and community pharmacists on the development of a system of electronic transfer of prescription-related information between GPs and community pharmacies. DESIGN OF STUDY: Survey combining interviews, focus gr...

  3. Electron transfer and photophosphorylation in mitochondria of buckwheat after irradiation of seeds with ?-rays

    Pre-sowing irradiation of seeds at 500 R activates the transfer of electrons by photosynthetic electron transfer path of isolated buchwheat chloroplasts in the ontogenesis and stimulates the conjugated photosynthetic phosphorilation. An increased content of NADPxH2 is observed along with an elevated level of ATP production. Intensification of oxidative phosphorilation and growth of the P/O ratio of mitochondria has been shown in the ''irradiated'' plants, together with a concomitant increase of ATPhase activity in chloroplasts and mitochondria

  4. Synthesis and photoinduced electron transfer studies of a tri(phenothiazine)-subphthalocyanine-fullerene pentad.

    KC, Chandra B; Lim, Gary N; Zandler, Melvin E; D'Souza, Francis

    2013-09-01

    A novel donor-acceptor pentad featuring subphthalocyanine and fullerene as the primary electron donor and acceptor, and three phenothiazine entities as secondary hole transferring agents, have been newly synthesized and characterized as an photosynthetic reaction center model compound. Occurrences of ultrafast photoinduced electron transfer (PET) and slower charge recombination are witnessed in the pentad from the femtosecond and nanosecond transient absorption studies. PMID:23981125

  5. Microbial Electrochemical System: extracellular electron transfer from photosynthesis and respiration to electrode

    Hasan, Kamrul

    2016-01-01

    The electrochemical communication between microorganisms and electrodes has substantial implications both for basic understanding of biological electron transfer as well as in diverse applications, such as, microbial electrochemical system (MES), microbial biosensors and in production of valuable chemicals. In these systems the extracellular electron transfer (EET) from microbial metabolism to electrodes is restricted due to the insulated cellular exterior made of lipid structures. To obtain ...

  6. FinalReport for completed IPP-0110 and 0110A Projects:"High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications"

    Brown, Ian

    2009-09-01

    The DOE-supported IPP (Initiatives for Proliferation Prevention) Project, IPP-0110, and its accompanying 'add-on project' IPP-0110A, entitled 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications' was a collaborative project involving the Lawrence Berkeley National Laboratory (LBNL) as the U.S. DOE lab; the US surface modification company, Phygen, Inc., as the US private company involved; and the High Current Electronics Institute (HCEI) of the Russian Academy of Sciences, Tomsk, Siberia, Russia, as the NIS Institute involved. Regular scientific research progress meetings were held to which personnel came from all participating partners. The meetings were held mostly at the Phygen facilities in Minneapolis, Minnesota (with Phygen as host) with meetings also held at Tomsk, Russia (HCEI as host), and at Berkeley, California (LBNL as host) In this way, good exposure of all researchers to the various different laboratories involved was attained. This report contains the Final Reports (final deliverables) from the Russian Institute, HCEI. The first part is that for IPP-0110A (the 'main part' of the overall project) and the second part is that for the add-on project IPP-0110A. These reports are detailed, and contain all aspects of all the research carried out. The project was successful in that all deliverables as specified in the proposals were successfully developed, tested, and delivered to Phygen. All of the plasma hardware was designed, made and tested at HCEI, and the performance was excellent. Some of the machine and performance parameters were certainly of 'world class'. The goals and requirements of the IPP Project were well satisfied. I would like to express my gratitude to the DOE IPP program for support of this project throughout its entire duration, and for the unparalleled opportunity thereby provided for all of the diverse participants in the project to join in this collaborative research. The benefits are superb, as measured in quite a number of different ways.

  7. Electron Transfer Between Colloidal ZnO Nanocrystals

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

    2011-01-01

    Colloidal ZnO nanocrystals, capped with dodecylamine and dissolved in toluene, can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals with a solution of uncharged large nanocrystals, e-CB:ZnO–S + ZnO–L, causes changes in the EPR spectrum i...

  8. Average electron tunneling route of the electron transfer in protein media.

    Nishioka, Hirotaka; Kakitani, Toshiaki

    2008-08-14

    We present a new theoretical method to determine and visualize the average tunneling route of the electron transfer (ET) in protein media. In this, we properly took into account the fluctuation of the tunneling currents and the quantum-interference effect. The route was correlated with the electronic factor in the case of ET by the elastic tunneling mechanism. We expanded by the interatomic tunneling currents 's. Incorporating the quantum-interference effect into the mean-square interatomic tunneling currents, denoted as , we could express as a sum of variant Planck's over 2pi(2). Drawing the distribution of on the protein structure, we obtain the map which visually represents which parts of bonds and spaces most significantly contribute to . We applied this method to the ET from the bacteriopheophytin anion to the primary quinone in the bacterial photosynthetic reaction center of Rhodobacter sphaeroides. We obtained 's by a combined method of molecular dynamics simulations and quantum chemical calculations. In calculating , we found that much destructive interference works among the interatomic tunneling currents even after taking the average. We drew the map by a pipe model where atoms a and b are connected by a pipe with width proportional to the magnitude of . We found that two groups of 's, which are mutually coupled with high correlation in each group, have broad pipes and form the average tunneling routes, called Trp route and Met route. Each of the two average tunneling routes is composed of a few major pathways in the Pathways model which are fused at considerable part to each other. We also analyzed the average tunneling route for the ET by the inelastic tunneling mechanism. PMID:18630851

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

    Scharf, Christian, E-mail: Christian.Scharf@desy.de; Klanner, Robert

    2015-04-11

    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. The charge carriers in the sensor are 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 laser light of both wavelengths. The method has been applied successfully for the simulation of current transients of several different silicon pad diodes. It can also be applied for the analysis of transient-current measurements of radiation-damaged solid state sensors, as long as sensors properties, like high-frequency capacitance, are not too different.

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

    Efficiency of current drive by electron-cyclotron waves is investigated numerically by a bounce-average Fokker-Planck code to elucidate the effects of momentum transfer from resonant to bulk electrons, finite bulk temperature relative to the energy of resonant electrons, and trapped electrons. Comparisons are made with existing theories to assess their validity and quantitative difference between theory and code results. Difference of nearly a factor of 2 was found in efficiency between some theory and code results. 4 refs., 4 figs

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

    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.

  12. Use of electron-excitation energy transfer in dye laser active media

    Rodchenkova, V.V.; Reva, M.G.; Akimov, A.I.; Uzhinov, B.M.

    1984-01-01

    A study was made of the spectral luminescence and lasing characteristics of two-component dye mixtures, and of the use of electron-excitation energy transfer to improve the laser emission parameters. A considerable increase in the lasing efficiencyu was found on exciting Trypaflavine by energy transfer from coumarin dyes. The use of electron-excitation energy transfer enabled the laser emission spectrum to be broadened. It was found that by varying the energy donor and acceptor concentrations one could produce laser emission of constant intensity in the spectral range between the donor and acceptor lasing regions.

  13. Enhancing interfacial conductivity and spatial charge confinement of LaAlO{sub 3}/SrTiO{sub 3} heterostructures via strain engineering

    Nazir, Safdar; Behtash, Maziar; Yang, Kesong, E-mail: kesong@ucsd.edu [Department of NanoEngineering, University of California, San Diego, 9500 Gilman Drive, Mail Code 0448, La Jolla, California 92093-0448 (United States)

    2014-10-06

    We explored the possibility of enhancing interfacial conductivity and spatial charge confinement of LaAlO{sub 3}/SrTiO{sub 3} (LAO/STO) heterostructure (HS) via strain engineering using first-principles electronic structure calculations. We found that applying a tensile strain on the STO substrate along the ab-plane can significantly enhance the interfacial conductivity, magnetic moments, and the spatial charge confinement of the HS system. In contrast, a compressive strain can dilute the interfacial charge carrier density, make the mobile charges transfer to deep STO substrate, and weaken the spatial charge confinement along the c-axis. Hence, we propose that applying a tensile strain can be an effective way to enhance the interfacial conductivity and magnetism of STO-based HS systems.

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

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

    2011-05-24

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

  15. Exclusive electron scattering from deuterium at high momentum transfer

    Cross sections are presented for the reaction 2H(e,e'p)n for momentum transfers in the range 1.2≤Q2≤6.8(GeV/c)2 and for missing momenta from 0 to 250 MeV/c. The longitudinal-transverse interference structure function has been separated at Q2=1.2(GeV/c)2. The observables are compared to calculations performed in nonrelativistic and relativistic frameworks. The data are best described by a fully relativistic calculation

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

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

    2015-06-01

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

  17. Vibrational coherence transfer in an electronically decoupled molecular dyad

    Schweighfer, Felix; Dworak, Lars; Braun, Markus; Zastrow, Marc; Wahl, Jan; Burghardt, Irene; Rck-Braun, Karola; Wachtveitl, Josef

    2015-03-01

    The ring opening of a dithienylethene photoswitch incorporated in a bridged boron-dipyrromethene - dithienylethene molecular dyad was investigated with ultrafast spectroscopy. Coherent vibrations in the electronic ground state of the boron-dipyrromethene are triggered after selective photoexcitation of the closed dithienylethene indicating vibrational coupling although the two moieties are electronically isolated. A distribution of short-lived modes and a long-lived mode at 143 cm-1 are observed. Analysis of the theoretical frequency spectrum indicates two modes at 97 cm-1 and 147 cm-1 which strongly modulate the electronic transition energy. Both modes exhibit a characteristic displacement of the bridge suggesting that the mechanical momentum of the initial geometry change after photoexcitation of the dithienylethene is transduced to the boron-dipyrromethene. The relaxation to the dithienylethene electronic ground state is accompanied by significant heat dissipation into the surrounding medium. In the investigated dyad, the boron-dipyrromethene acts as probe for the ultrafast photophysical processes in the dithienylethene.

  18. Cellular electron transfer and radical mechanisms for drug metabolism

    Aerobic and anaerobic reductions of various nitroaromatic compounds by mammalian cells result in the production of reactive intermediates. Drug reduction is dependent upon glucose, nonprotein thiols, endogenous enzyme levels, and drug electron affinity. Drugs with electron affinities approaching that of oxygen are reduced, in the presence of oxygen, beyond a one-electron radical anion. Nitroaromatic radical anion inactivation occurs by reaction with cellular ferricytochrome c, endogenous thiols, and with oxygen. In the latter case the reaction results in the production of peroxide. Drugs that are substrates for the enzyme glutathione-S-transferase remove endogeneous thiols and demonstrate peroxide production without prior thiol removal. Less electron affinic drugs such as misonidazole require thiol removal as well as the presence of cyanide or azide for maximal peroxide production. Under anaerobic conditions radical anion and nitroso intermediates are reactive with glutathione. Removal of endogenous thiols by hypoxic preincubation with misonidazole may be related to the enhanced radiation response and cytotoxicity of this drug. Reduction of nitro compounds in the presence of DNA and chemicals such as dithionite, zinc dust, or polarographic techniques causes binding to macromolecules and DNA breaks. Chemical-reduction of nitro compounds by ascorbate in the presence of cells enhances drug cytotoxic effects

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

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

  20. Electron-Vibron Coupling at Metal-Organic Interfaces from Theory and Experiment

    Rosenow, Phil; Jakob, Peter; Tonner, Ralf

    2015-01-01

    We study the significance and characteristics of interfacial dynamical charge transfer at metal-organic interfaces for the organic semiconductor model system 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111) quantitatively. We combine infrared absorption spectroscopy and dispersion-corrected density functional theory calculations to analyze dynamic dipole moments and electron-vibron coupling at the interface. We demonstrate that interfacial dynamical charge transfer is the do...