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1

Facile Interfacial Electron Transfer of Hemoglobin  

Directory of Open Access Journals (Sweden)

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

Chunhai Fan

2005-12-01

2

Interfacial Electron Transfer into Functionalized Crystalline Polyoxotitanate Nanoclusters  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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...

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.

2012-01-01

3

Single-molecule kinetics of interfacial electron transfer  

Energy Technology Data Exchange (ETDEWEB)

Measurements of single-molecule chemical reaction kinetics are demonstrated for interfacial electron transfer from excited cresyl violet molecules to the conduction band of indium tin oxide (ITO) or energetically accessible surface electronic states under ambient conditions by using a far-field fluorescence microscope. In this system, each single molecule exhibits a single-exponential electron transfer kinetics. A wide distribution of site-specific electron transfer rates is observed for many single cresyl violet molecules examined. This work reveals that the physical origin of multiexponential kinetics of electron transfer in this system is the inhomogeneity of molecular interactions on the semiconductor surface of ITO. We illustrate that the single-molecule experiments provide detailed information not obtainable from experiments conducted on large ensembles of molecules. Single-molecule kinetics is particularly useful in understanding multiexponential behavior of chemical reactions in heterogeneous systems. 42 refs., 4 figs.

Lu, H.P.; Xie, X.S. [Pacific Northwest National Lab., Richland, WA (United States)

1997-04-10

4

Intermittent Single-Molecule Interfacial Electron Transfer Dynamics  

Energy Technology Data Exchange (ETDEWEB)

We report on single molecule studies of photosensitized interfacial electron transfer (ET) processes in Coumarin 343 (C343)-TiO2 nanoparticle (NP) and Cresyl Violet (CV+)-TiO2 NP systems, using time-correlated single photon counting coupled with scanning confocal fluorescence microscopy. Fluorescence intensity trajectories of individual dye molecules adsorbed on a semiconductor NP surface showed fluorescence fluctuations and blinking, with time constrants distributed from sub-milliseconds to several seconds.

Biju, Vasudevan P.; Micic, Miodrag; Hu, Dehong; Lu, H. Peter

2004-08-04

5

Intermittent Single-Molecule Interfacial Electron Transfer Dynamics  

International Nuclear Information System (INIS)

We report on single molecule studies of photosensitized interfacial electron transfer (ET) processes in Coumarin 343 (C343)-TiO2 nanoparticle (NP) and Cresyl Violet (CV+)-TiO2 NP systems, using time-correlated single photon counting coupled with scanning confocal fluorescence microscopy. Fluorescence intensity trajectories of individual dye molecules adsorbed on a semiconductor NP surface showed fluorescence fluctuations and blinking, with time constraints distributed from sub-milliseconds to several seconds

6

Nanoscale and single-molecule interfacial electron transfer  

DEFF Research Database (Denmark)

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 scanning tunneling microscopy (STM) and single-electron tunneling (SET, or Coulomb blockade) in electrochemical. systems directly in aqueous electrolyte solution and at room temperature. We illustrate the new theoretical formalism and its perspectives by recent cases of electrochemical SET, negative differential resistance patterns, and by ET dynamics of organized assemblies of biological macromolecules, such as redox metalloproteins and oligonucleotides on single-crystal Au(III)-electrode surfaces.

Hansen, Allan Glargaard; Wackerbarth, Hainer

2003-01-01

7

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

International Nuclear Information System (INIS)

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

8

Remote interfacial electron transfer processes on nanocrystalline TiO2 sensitized with polynuclear complexes  

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The kinetic study of interfacial electron transfer in sensitized nanocrystalline semiconductor is essential to the design of molecular devices performing specific light induced functions in a microheterogeneous environment. A series of molecular assemblies performing direct and remote charge injection to the semiconductor have been discussed in the context of artificial photosynthesis. A particular attention in this article has been paid to the factors that control the interfacial electron tr...

Meyer, G. J.; Argazzi, R.; Kleverlaan, C. J.; Costa, E.; Alebbi, M.; Bignozzi, C. A.

1999-01-01

9

Remote interfacial electron transfer processes on nanocrystalline TiO2 sensitized with polynuclear complexes  

Directory of Open Access Journals (Sweden)

Full Text Available The kinetic study of interfacial electron transfer in sensitized nanocrystalline semiconductor is essential to the design of molecular devices performing specific light induced functions in a microheterogeneous environment. A series of molecular assemblies performing direct and remote charge injection to the semiconductor have been discussed in the context of artificial photosynthesis. A particular attention in this article has been paid to the factors that control the interfacial electron transfer processes in nanocrystalline TiO2 films sensitized with mononuclear and polynuclear transition metal complexes.

G. J. Meyer

1999-01-01

10

Single-molecule interfacial electron transfer dynamics manipulated by external electric current  

CERN Document Server

Interfacial electron transfer (IET) dynamics in 1,1'-dioctadecyl-3, 3, 3', 3'-tetramethylindodicarbocyanine (DiD) dye molecules / indium tin oxide (ITO) film system have been probed at the ensemble and single-molecule level by recording the change of fluorescence emission intensity. By comparing the difference of the external electric current (EEC) dependence of lifetime and intensity for enambles and single molecules, it is shown that the single-molecule probe can effcienly demonstrate the IET dynamics. The backward electron transfer and electron transfer of ground state induce the single molecules fluorescence quenching when an EEC is applied to ITO film.

Zhang, Guofeng; Chen, Ruiyun; Gao, Yan; Wang, Xiaobo; Jia, Suotang

2011-01-01

11

Interfacial Electron Transfer and Transient Photoconductivity Studied with Terahertz Spectroscopy  

Science.gov (United States)

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

Milot, Rebecca Lee

12

Dynamics of photoinduced interfacial electron transfer and charge transport in dye-sensitized mesoscopic semiconductors  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Molecular systems designed for the conversion of solar energy offer ideal models in the study of the kinetics of light-induced electron transfer at surfaces. Due to their high porosity, nanocrystalline oxide semiconductor films allow investigations of interfacial and lateral charge transfer processes that are barely detectable on flat surfaces. Although it has proven to be very promising, the redox photochemistry of the metal oxide I molecular monolayer I electrolyte interface is still a larg...

Thorsmolle, Vk; Wenger, B.; Teuscher, J.; Bauer, C.; Moser, J-e

2007-01-01

13

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

International Nuclear Information System (INIS)

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.

14

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

15

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

Energy Technology Data Exchange (ETDEWEB)

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.

Lian, Tianquan

2014-04-22

16

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

Science.gov (United States)

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 systems aimed at the production of solar fuels, creating a need for a better understanding and theoretical treatment of the dynamics and mechanisms of interfacial PET processes. We aim to achieve a fundamental understanding of these phenomena by designing experiments that can be used to test and alter modern theory and computational modeling. One example illustrating recent investigations into the details of the ultrafast processes that form the basis for photoinduced charge separation at a molecular/bulk interface relevant to dye-sensitized solar cells is briefly presented here: Kinetics of interfacial PET and charge recombination processes were measured by fs and ns transient spectroscopy in a heterogeneous donor-bridge-acceptor (D-B-A) system, where D is a Ru(II)(terpyridyl-PO3)(NCS)3 complex, B an oligo-p-phenylene bridge, and A nanocrystalline TiO2. The forward ET reaction was found to be faster than vibrational relaxation of the vibronic excited state of the donor. Instead, the back ET occurred on the micros time scale and involved fully thermalized species. The D-A distance dependence of the electron transfer rate was studied by varying the number of p-phenylene units contained in the bridge moiety. The remarkably low damping factor beta = 0.16 angstroms(-1) observed for the ultrafast charge injection from the dye excited state into the conduction band of TiO2 is attributed to the coupling of electron tunneling with nonequilibrium vibrations redistributed on the bridge, giving rise to polaronic transport of charges from the donor ligand to the acceptor solid oxide surface. PMID:22026184

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

2011-01-01

17

Transition metal polypyridyl compounds for the exploration of interfacial electron transfer dynamics  

Science.gov (United States)

The Re(I) coordination compounds, fac-Re(deeb)(CO)3(X) where (deeb) is 4,4'-(COOEt)2-2,2' -bipyridine and X is I-, Br-, Cl- or CN-, and [fac-Re(deeb)(CO) 3(py)](OTf) where OTf- is triflate anion and py is pyridine, have been prepared, characterized, and anchored to nanocrystalline (anatase) TiO 2. In regenerative solar cells with 0.5 M LiI--0.05 M I2 acetonitrile electrolyte, the Re(I) compounds convert absorbed photons into electrons efficiently. The rate of interfacial charge separation could not be time resolved, kcr > 108 s -1. Thermodynamically favorable recombination of the injected electron in TiO2 with the oxidized sensitizer requires milliseconds for completion. The charge recombination kinetics have been contrasted with other sensitized TiO2 materials and are insensitive to an ˜960 mV change in apparent driving force. The results suggest that charge recombination is rate limited by diffusional encounters of the injected electron with the oxidized sensitizer. New Ru(dcbH)(dcbH2)(L) sensitizers, where L is diethyldithiocarbamate, dibenzyldithiocarbamate, or pyrrolidinedithiocarbamate, dcbH is 4-(COOH)-4 '-(COO-)-2,2'-bipyridine and dcbH2 is 4,4'-(COOH)2-2,2 '-bipyridine, have been synthesized, characterized, and anchored to nanocrystalline TiO2 films for light to electrical energy conversion in regenerative photoelectrochemical cells with I-/I 2 acetonitrile electrolyte. The sensitizers have intense metal-to-ligand charge-transfer (MLCT) bands centered ˜380 and 535 nm that sensitize TiO 2 over a notably broad spectral range. The photophysical and photoelectrochemical studies of these materials are contrasted with cis-Ru(dcbH2) 2(NCS)2. Photophysical measurements show that the high photocurrent observed for cis-Ru(dcb)2(NCS)2/TiO 2 is due to efficient and rapid iodide oxidation. The sensitizer [(4,4'-(COOH)2-bpy)Re I(CO)3-CN-RuII(bpy) 2(CN)](PF6) and linkage isomer [(4,4'-(COOH) 2-bpy)ReI(CO)3-NC-Ru II(bpy)2(CN)](PF6), where bpy is 2,2 '-bipyridine, have been prepared, characterized, and anchored to porous nanocrystalline TiO2 surfaces for light-to-electrical energy conversion. The facial geometry about the ReI center orientates the RuII center proximate to the TiO2 surface. Long wavelength excitation is absorbed exclusively by the -RuII(bpy)2 group. Some implications for solar energy conversion are discussed.

Hasselmann, Georg Matthias

2000-10-01

18

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

DEFF Research Database (Denmark)

Interfacial electron transfer (ET) of biological macromolecules such as metalloproteins is the key process in bioelectrochemistry, enzymatic electrocatalysis, artificial ET chains, single-molecule electronic amplification and rectification, and other phenomena associated with the area of 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 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 ofcyt 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 and the protein molecule. When the nanoparticle-protein conjugates are assembled on Au(111) surfaces, long-range interfacial ET across a physical distance of over 50 A via the nanoparticle becomes feasible. Moreover, significant enhancement of the interfacial ET rate by more than an order of magnitude compared with that of cyt c in the absence of AuNPs is observed. AuNPs appear to serve as excellent ET relays, most likely by facilitating the electronic coupling between the protein redox center and the electrode surface.

Jensen, Palle Skovhus; Chi, Qijin

2007-01-01

19

Spectroelectrochemical investigation of intramolecular and interfacial electron-transfer rates reveals differences between nitrite reductase at rest and during turnover.  

Science.gov (United States)

A combined fluorescence and electrochemical method is described that is used to simultaneously monitor the type-1 copper oxidation state and the nitrite turnover rate of a nitrite reductase (NiR) from Alcaligenes faecalis S-6. The catalytic activity of NiR is measured electrochemically by exploiting a direct electron transfer to fluorescently labeled enzyme molecules immobilized on modified gold electrodes, whereas the redox state of the type-1 copper site is determined from fluorescence intensity changes caused by Fo?rster resonance energy transfer (FRET) between a fluorophore attached to NiR and its type-1 copper site. The homotrimeric structure of the enzyme is reflected in heterogeneous interfacial electron-transfer kinetics with two monomers having a 25-fold slower kinetics than the third monomer. The intramolecular electron-transfer rate between the type-1 and type-2 copper site changes at high nitrite concentration (?520 ?M), resulting in an inhibition effect at low pH and a catalytic gain in enzyme activity at high pH. We propose that the intramolecular rate is significantly reduced in turnover conditions compared to the enzyme at rest, with an exception at low pH/nitrite conditions. This effect is attributed to slower reduction rate of type-2 copper center due to a rate-limiting protonation step of residues in the enzyme's active site, gating the intramolecular electron transfer. PMID:21863850

Krzemi?ski, ?ukasz; Ndamba, Lionel; Canters, Gerard W; Aartsma, Thijs J; Evans, Stephen D; Jeuken, Lars J C

2011-09-28

20

Diffusion-limited interfacial electron transfer with large apparent driving forces  

Energy Technology Data Exchange (ETDEWEB)

The Re(I) coordination compounds fac-Re(deeb)(CO{sub 3})(X), where deeb is 4,4{prime}-(COOEt){sub 2}-2,2{prime}-bipyridine and X is I{sup {minus}}, Br{sup {minus}}, Cl{sup {minus}}, or CN{sup {minus}}, and [fac-Re(deeb)(CO{sub 3})(py)](OTf), where OTf{sup {minus}} is triflate anion and py is pyridine, have been prepared, characterized, and anchored to nanocrystalline (anatase) TiO{sub 2}. In regenerative solar cells with 0.5 M LiI-0.005 M I{sub 2} acetonitrile electrolyte, the Re(I) compounds convert absorbed photons into electrons efficiently. The rate of interfacial charge separation could not be time resolved, k{sub cr} > 10{sup 8} s{sup {minus}1}. Thermodynamically favorable recombination of the injected electron in TiO{sub 2} with the oxidized sensitizer requires milliseconds for completion. Charge recombination kinetics have been quantified on a 10{sup {minus}7}-s and longer time scale and are insensitive to the Re sensitizer employed. The charge recombination kinetics have been contrasted with other sensitized TiO{sub 2} materials and are insensitive to an {approximately} 960-mV change in apparent driving force. The results suggest that charge recombination is rate limited by diffusional encounters of the injected electron with the oxidized sensitizer.

Hasselmann, G.M.; Meyer, G.J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

1999-09-09

 
 
 
 
21

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

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...

Bauer, C.; Teuscher, J.; Brauer, Jc; Punzi, A.; Marchioro, A.; Ghadiri, E.; Jonghe, J.; Wielopolski, M.; Banerji, N.; Moser, Je

2011-01-01

22

Interfacial electron transfer in metal cyanide-sensitized TiO2 nanoparticles.  

Science.gov (United States)

Electroabsorption (Stark) spectroscopy has been used to study the charge-transfer absorption from a transition-metal-cyanide complex to a TiO2 nanoparticle. Transition-metal cyanide/TiO2(particle) systems were synthesized using FeII(CN)(6)4-, RuII(CN)6(4-), MoIV(CN)(8)4-, and WIV(CN)8(4-). On formation of the M(CN)n4-/TiO2(particle) system, a new metal-to-particle charge-transfer (MPCT) absorption band is observed in the 390-480 nm region. Analysis of the absorption spectra suggests that the TiO2 level involved in the MPCT transition resides at significantly higher energy than the bottom of the conduction band and that the electronic coupling between the two metal centers is the dominant factor determining the position of the MPCT band maximum. The average charge-transfer distances determined by Stark spectra range from 4.1-4.7 A. The observation of relatively short charge-transfer distances leads to the conclusion that the MPCT absorption is from the transition-metal cyanide center to a level that is localized on the Ti atom bound to a nitrogen end of the [O2Ti-N-C-M(CN)x] system. The electronic coupling, Hab, calculated for a two state model is similar to values observed in dinuclear metal complexes. PMID:17402776

Harris, James A; Trotter, Kevin; Brunschwig, Bruce S

2007-06-21

23

Hafnium metallocene compounds used as cathode interfacial layers for enhanced electron transfer in organic solar cells  

Digital Repository Infrastructure Vision for European Research (DRIVER)

We have used hafnium metallocene compounds as cathode interfacial layers for organic solar cells [OSCs]. A metallocene compound consists of a transition metal and two cyclopentadienyl ligands coordinated in a sandwich structure. For the fabrication of the OSCs, poly[3,4-ethylenedioxythiophene]:poly(styrene sulfonate), poly(3-hexylthiophene-2,5-diyl) + [6,6]-phenyl C61 butyric acid methyl ester, bis-(ethylcyclopentadienyl)hafnium(IV) dichloride, and aluminum were deposited as a hole transport ...

Park, Keunhee; Oh, Seungsik; Jung, Donggeun; Chae, Heeyeop; Kim, Hyoungsub; Boo, Jin-hyo

2012-01-01

24

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

Energy Technology Data Exchange (ETDEWEB)

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.

Zheng, Junwei

1999-11-08

25

Interfacial transfer in annular dispersed flow  

International Nuclear Information System (INIS)

The interfacial drag, droplet entrainment, droplet deposition and droplet-size distributions are important for detailed mechanistic modeling of annular dispersed two-phase flow. In view of this, recently developed correlations for these parameters are presented and discussed in this paper. The onset of droplet entrainment significantly alters the mechanisms of mass, momentum, and energy transfer between the film and gas core flow as well as the transfer between the two-phase mixture and the wall. By assuming the roll wave entrainment mechanism, the correlations for the amount of entrained droplet as well as for the droplet-size distribution have been obtained from a simple model in collaboration with a large number of data. Then the rate equations for entrainment and deposition have been developed. The drag correlations relevant to the droplet transfer is also presented. The comparison of the correlations to various data show satisfactory agreement

26

Approach to Interfacial and Intramolecular Electron Transfer of the Diheme Protein Cytochrome c(4) Assembled on Au(111) Surfaces  

DEFF Research Database (Denmark)

Intramolecular electron transfer (ET) between metal centers is a core feature of large protein complexes in photosynthesis, respiration, and redox enzyme catalysis. The number of microscopic redox potentials and ET rate constants is, however, prohibitive for experimental cooperative ET mapping, but two-center proteins are simple enough to offer complete communication networks. At the same time, multicenter redox proteins operate in membrane environments where conformational dynamics may lead to gated ET features different from conditions in homogeneous solution. The bacterial respiratory diheme 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-mercapto-alkanoic carboxylic acids. As evidenced by in situ STM, the strongly dipolar protein is immobilized in a close to vertical orientation at this surface with the positively charged high-potential heme domain adjacent to the electrode. This orientation gives asymmetric voltammograms with two one-ET peaks in the cathodic 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 is understandable due to the through-space, hydrogen-bonded electronic contact between the heme propionates which is highly sensitive to environmental configurational fluctuations.

Chi, Qijin; Zhang, Jingdong

2010-01-01

27

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

2002-07-01

28

Tunnel magnetoresistance and interfacial electronic state  

Digital Repository Infrastructure Vision for European Research (DRIVER)

We study the relation between tunnel magnetoresistance (TMR) and interfacial electronic states modified by magnetic impurities introduced at the interface of the ferromagnetic tunnel junctions, by making use of the periodic Anderson model and the linear response theory. It is indicated that the TMR ratio is strongly reduced depending on the position of the $d$-levels of impurities, based on reduction in the spin-dependent $s$-electron tunneling in the majority spin state. Th...

Inoue, J.; Itoh, H.

2002-01-01

29

Influence of surface adsorption on the interfacial electron transfer of flavin adenine dinucleotide and glucose oxidase at carbon nanotube and nitrogen-doped carbon nanotube electrodes.  

Science.gov (United States)

The adsorption of flavin adenine dinucleotide (FAD) and glucose oxidase (GOx) onto carbon nanotube (CNT) and nitrogen-doped CNT (N-CNT) electrodes was investigated and found to obey Langmuir adsorption isotherm characteristics. The amount adsorbed and adsorption maximum are dependent on exposure time, the concentration of adsorbate, and the ionic strength of the solution. The formal potentials measured for FAD and GOx are identical, indicating that the observed electroactivity is from FAD, the redox reaction center of GOx. When glucose is added to GOx adsorbed onto CNT/N-CNT electrodes, direct electron transfer (DET) from enzyme-active FAD is not observed. However, efficient mediated electron transfer (MET) occurs if an appropriate electron mediator is placed in solution, or the natural electron mediator oxygen is used, indicating that GOx is adsorbed and active on CNT/N-CNT electrodes. The observed surface-confined redox reaction at both CNT and N-CNT electrodes is from FAD that either specifically adsorbs from solution or adsorbs from the holoprotein subsequently inactivating the enzyme. The splitting of cathodic and anodic peak potentials as a function of scan rate provides a way to measure the heterogeneous electron-transfer rate constant (k(s)) using Laviron's method. However, the measured k(s) was found to be under ohmic control, not under the kinetic control of an electron-transfer reaction, suggesting that k(s) for FAD on CNTs is faster than the measured value of 7.6 s(-1). PMID:23289639

Goran, Jacob M; Mantilla, Sandra M; Stevenson, Keith J

2013-02-01

30

Interfacial charge transfer dynamics in small molecule-modified TiO2 nanoparticles  

Science.gov (United States)

Direct molecule-semiconductor interfacial charge transfer interactions have received considerable research attention for their applications in various fields. In this study, the dynamics of molecule-TiO2 interfacial charge transfer complexes is monitored with femtosecond fluorescence upconversion and transient absorption. Small molecules (catechol, dopamine, benzhydroxamic acid, acetyl acetonate and salicylate)-modified TiO2 nanoparticles are prepared and the complexation is followed with optical absorption measurements. Although little visible luminescence is observed from these molecule- TiO2 nanoparticles, ultrafast emission in broad range of wavelengths is detected with fluorescence upconversion which is ascribed to the interfacial charge transfer emission. The charge transfer emission arose out of the radiative recombination of the electrons in the conduction band of TiO2 with holes in the molecule. Femtosecond fluorescence anisotropy measurements have shown that the interfacial charge-transfer excitation is mostly a localized one for catechol, dopamine and benzhydroxamate modified TiO2 nanoparticles. However, the possibility of delocalized charge-transfer excitations is observed for salicylate and acetyl acetonate-TiO2 nanoparticles. The decay of the charge transfer emission is ascribed to the relaxation of the localized states to delocalized states in the TiO2 conduction band. Transient absorption measurements have shown long-lived charge separation in the case of surface-modified TiO2 nanoparticles. Further measurements on the influence of charge-transfer excitations on the interfacial electron transfer in surface-modified TiO2 nanoparticles are being carried out.

Varaganti, Shankar; Mghangha, Edwin; Hasan, Jameel A.; Ramakrishna, Guda

2010-08-01

31

Interfacial electron-transfer equilibria and flat-band potentials of ?-Fe2O3 and TiO2 colloids studied by pulse radiolysis  

International Nuclear Information System (INIS)

The kinetics and equilibria of electron transfer between methylviologen cation radicals and ?-Fe2O3 or TiO2 colloidal particles were studied with the pulse-radiolysis technique. The rates of electron transfer to both colloids are lower than those predicted for a diffusion-controlled reaction. For higher pHs (TiO2, pH > 2; ?-Fe2O3, pH > 9) the established equilibrium MV+ in equilibrium MV2+ + (e-)/sub coll/ is strongly influenced by the MV2+ concentration and pH. The MV+ equilibrium concentration can be exploited to derive the flat-band potential of the semiconductor colloids. The method for determining the flat-band potential of the particles is independent of whether the injected electrons are free or trapped, and whether the electrons raise the bulk Fermi level toward the conduction band or just produce a space charge. The flat-band potentials for both colloids appear to be somewhat more negative (-0.1 to -0.2 V) than the corresponding single-crystal electrodes. Also, the flat-band potentials become slightly more negative with increasing radiation dose (initial MV+ concentration). The effect of absorbed radiation dose is explained by the corresponding changes in the ratio of oxidized to reduced forms of the redox couple, which in turn changes the adsorbed ionic charge on the semiconductor surface. For colloidal particles of TiO22 stabilized by poly(vinyl alcohol) (PVA), the flat-band potentials were almost the same as those for PVA-free TiO2 sols. The decrease of particle diameter from 800 to 70 A does not affect the value of the flat-band potentials for TiO2 and ?-Fe2O3 colloids. 28 references, 9 figures

32

Multidimensional mechanistic modeling of interfacial heat and mass transfer  

International Nuclear Information System (INIS)

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 modacteristics 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)

33

Interfacial compatibility of polymer-based structures in electronics  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Interfacial compatibility of dissimilar materials was investigated to achieve a better understanding of interfacial adhesion in metal/polymer/metal systems. Surface modifications of polymers were applied to improve the adhesion. The modified surfaces were characterised by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements accompanied by surface free energy evaluations. The pull-off test was employed to asses...

Turunen, Markus P. K.

2004-01-01

34

Study of Interfacial Mass Transfer on Vapor Bubbles in Microgravity  

Directory of Open Access Journals (Sweden)

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.

Johannes Straub

2005-03-01

35

Interfacial load transfer in polymer/carbon nanotube nanocomposites with a nanohybrid shish kebab modification.  

Science.gov (United States)

Interfacial properties are known to have a critical effect on the mechanical properties of a nanocomposite material system. Here, the interfacial load transfer in a carbon nanotube (CNT)/nylon-11 composite was studied with a CNT/nylon-11 nanohybrid shish kebab (NHSK) structure modification using Raman spectroscopy. Characterization of the polymer crystal in the NHSK using differential scanning calorimetry (DSC) for the first time indicates that the NHSK structure formed a more perfect crystal structure than the bulk polymer. On the basis of transmission electron microscopy and DSC results, a new growth model for the NHSK crystal is hypothesized, indicating the formation of an initial uniform crystal layer on the CNT prior to the crystallization of the kebabs. Characterization of the nanocomposites using Raman spectroscopy, with the samples heated to introduce interfacial shear stress caused by thermal expansion mismatch, found that the D* band of the CNT in the NHSK/nylon-11 composite displayed a more pronounced shift with an increase in temperature, which is attributed to the NHSK structure being more effective at transferring load from the nylon matrix to the nanotube inclusions. The NHSK structure was also used to fabricate composites with two amorphous polymers, polycarbonate and poly(methyl methacrylate), to investigate the load transfer mechanism. It was found that when the compatibility between the polymer in the NHSK structure and the bulk polymer matrix at the molecular level is sufficiently high, the ensuing mechanical interlocking effect further enhances the interfacial load transfer for polymer nanocomposites. Additional mechanical characterization of polymer nanocomposites with 0.1 wt % NHSK reinforcement demonstrates how the moduli and ultimate tensile strength of the nanocomposites can be improved via this NHSK structure. PMID:25134606

Nie, Min; Kalyon, Dilhan M; Fisher, Frank T

2014-09-10

36

Electron transfer in peptides.  

Science.gov (United States)

In this review, we discuss the factors that influence electron transfer in peptides. We summarize experimental results from solution and surface studies and highlight the ongoing debate on the mechanistic aspects of this fundamental reaction. Here, we provide a balanced approach that remains unbiased and does not favor one mechanistic view over another. Support for a putative hopping mechanism in which an electron transfers in a stepwise manner is contrasted with experimental results that support electron tunneling or even some form of ballistic transfer or a pathway transfer for an electron between donor and acceptor sites. In some cases, experimental evidence suggests that a change in the electron transfer mechanism occurs as a result of donor-acceptor separation. However, this common understanding of the switch between tunneling and hopping as a function of chain length is not sufficient for explaining electron transfer in peptides. Apart from chain length, several other factors such as the extent of the secondary structure, backbone conformation, dipole orientation, the presence of special amino acids, hydrogen bonding, and the dynamic properties of a peptide also influence the rate and mode of electron transfer in peptides. Electron transfer plays a key role in physical, chemical and biological systems, so its control is a fundamental task in bioelectrochemical systems, the design of peptide based sensors and molecular junctions. Therefore, this topic is at the heart of a number of biological and technological processes and thus remains of vital interest. PMID:25619931

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

2015-02-10

37

Lead methylammonium triiodide perovskite-based solar cells: an interfacial charge-transfer investigation.  

Science.gov (United States)

This work reports on an investigation into interfacial charge transfer in CH3NH3PbI3 perovskite solar cells by using anatase TiO2 nanocuboids enclosed by active {100} and {001} facets. The devices show 6.0 and 8.0% power conversion efficiency with and without hole-transport material. Transient photovoltage/photocurrent decay and charge extraction, as well as impedance spectroscopy measurements, reveal that carbon materials are effective counter electrodes in perovskite solar cells. The photogenerated charges are observed to be stored in mesoporous TiO2 film under illumination and in the CH3NH3PbI3 layer in the dark. The use of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (spiro-MeOTAD) as a hole-transport material accelerates interfacial charge recombination between the photogenerated electrons and holes. PMID:25213607

Xu, Xiaobao; Zhang, Hua; Cao, Kun; Cui, Jin; Lu, Jianfeng; Zeng, Xianwei; Shen, Yan; Wang, Mingkui

2014-11-01

38

Interfacial heat transfer in countercurrent flows of steam and water  

International Nuclear Information System (INIS)

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

39

Fundamental studies of interfacial excited-state charge transfer in molecularly tethered semiconductor nanoassemblies  

Science.gov (United States)

The research presented in this dissertation focuses on elucidating the parameters affecting dynamics and yield of electron transfer reactions in semiconducting nanoparticle assemblies through the use of time-resolved spectroscopy. In particular, the dissertation focuses on photoinduced electron injection in assemblies of CdSe, CdS, or PbS quantum dots covalently bound to either metal oxide films or each other through the use of bifunctional molecular linkers. Chapter 2 elucidates the influence of electronic coupling on excited-state electron transfer from CdS quantum dots to TiO2 nanoparticles via molecular linkers with phenylene bridges. We establish that the efficiency of electron injection from CdS quantum dots to TiO2 nanoparticle varies dramatically with electronic coupling, which can be controlled by tuning the properties of molecular linkers. Chapter 3 presents the role of excitation energy on interfacial electron transfer in tethered assemblies of CdSe quantum dots and TiO2 nanoparticles. Through this work, we determined that injection efficiency from band-edge states is independent of excitation energy. However, the efficiency of injection from trap-states decreases at lower-energy excitation. We attribute the decrease to a lower energy distribution of emissive trap-states from which injection is less efficient. Chapter 4 presents the observation of multiphasic electron injection dynamics from photoexcited PbS quantum dots to TiO2 nanoparticles. In this collaborative study with Dr. Masumoto from the University of Tsukuba we observed electron injection on multiple timescales. We determined that electron injection occurred in this system through two different mechanisms. The first involved injection from thermalized PbS excited states and the second through injection of hot electrons through Auger recombination of biexcitons that creates high lying excitonic states. Chapter 5 investigates charge transfer in covalently bound quantum dot assemblies. We utilize established carbodiimide chemistry to tether quantum dots to each other through covalent bonds between capping groups. As a result of our controlled-covalent quantum dot attachment, we observe evidence of interfacial charge transfer from photoexcited CdS quantum dots to covalently-bound CdSe quantum dots.

Youker, Diane Greer

40

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

International Nuclear Information System (INIS)

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

 
 
 
 
41

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

Science.gov (United States)

The demand for clean energy will require the design of nanostructure-based light-harvesting assemblies for the conversion of solar energy into chemical energy (solar fuels) and electrical energy (solar cells). Semiconductor nanocrystals serve as the building blocks for designing next generation solar cells, and metal chalcogenides (e.g., CdS, CdSe, PbS, and PbSe) are particularly useful for harnessing size-dependent optical and electronic properties in these nanostructures. This Account focuses on photoinduced electron transfer processes in quantum dot sensitized solar cells (QDSCs) and discusses strategies to overcome the limitations of various interfacial electron transfer processes. The heterojunction of two semiconductor nanocrystals with matched band energies (e.g., TiO(2) and CdSe) facilitates charge separation. The rate at which these separated charge carriers are driven toward opposing electrodes is a major factor that dictates the overall photocurrent generation efficiency. The hole transfer at the semiconductor remains a major bottleneck in QDSCs. For example, the rate constant for hole transfer is 2-3 orders of magnitude lower than the electron injection from excited CdSe into oxide (e.g., TiO(2)) semiconductor. Disparity between the electron and hole scavenging rate leads to further accumulation of holes within the CdSe QD and increases the rate of electron-hole recombination. To overcome the losses due to charge recombination processes at the interface, researchers need to accelerate electron and hole transport. The power conversion efficiency for liquid junction and solid state quantum dot solar cells, which is in the range of 5-6%, represents a significant advance toward effective utilization of nanomaterials for solar cells. The design of new semiconductor architectures could address many of the issues related to modulation of various charge transfer steps. With the resolution of those problems, the efficiencies of QDSCs could approach those of dye sensitized solar cells (DSSC) and organic photovoltaics. PMID:22493938

Kamat, Prashant V

2012-11-20

42

Mass transfer and interfacial properties in two-phase microchannel flows  

Energy Technology Data Exchange (ETDEWEB)

Drop-based microfluidic devices are becoming more common, and molecular mass transfer and drop circulation are issues that often affect the performance of such devices. Moreover, interfacial properties and surfactant mass transfer rates govern emulsion behavior. Since these phenomena depend strongly on drop size, measurement methods using small drops and flow typical of applications are desired. Using mineral oil as a continuous phase, water droplets and an alcohol surfactant, we demonstrate here a microfluidic approach to measure the interrelated phenomena of dynamic interfacial tension, surfactant mass transfer and interfacial retardation that employs droplet flows in a microchannel with constrictions/expansions. Interfacial flow is influenced markedly by adsorption of surfactant: severe interfacial retardation (by a factor of 30) is observed at low surfactant concentrations and interface remobilization is observed at higher surfactant concentrations. The interfacial tension is described by Langmuir kinetics and the parameters for interfaces with mineral oil (studied here) compare closely with those previously found at air interfaces. For the conditions explored, the surfactant mass transfer is described well by a mixed kinetic-diffusion limited model, and the desorption rate coefficients are measured to be both approximately 70 s{sup -1}. The transition from a diffusion-controlled to mixed diffusion-kinetic mass transfer mechanism predicted with reducing drop size is verified. This experimental approach (i.e. adjustable geometry and drop size and height) can therefore probe interfacial dynamics in simple and complex flow.

Martin, Jeffrey D; Hudson, Steven D [Complex Fluids Group, Polymers Division, National Institute of Standards and Technology, 100 Bureau Dr., Gaithersburg, MD 20899-8542 (United States)], E-mail: jeffrey.martin@nist.gov, E-mail: steven.hudson@nist.gov

2009-11-15

43

Mass transfer and interfacial properties in two-phase microchannel flows  

Science.gov (United States)

Drop-based microfluidic devices are becoming more common, and molecular mass transfer and drop circulation are issues that often affect the performance of such devices. Moreover, interfacial properties and surfactant mass transfer rates govern emulsion behavior. Since these phenomena depend strongly on drop size, measurement methods using small drops and flow typical of applications are desired. Using mineral oil as a continuous phase, water droplets and an alcohol surfactant, we demonstrate here a microfluidic approach to measure the interrelated phenomena of dynamic interfacial tension, surfactant mass transfer and interfacial retardation that employs droplet flows in a microchannel with constrictions/expansions. Interfacial flow is influenced markedly by adsorption of surfactant: severe interfacial retardation (by a factor of 30) is observed at low surfactant concentrations and interface remobilization is observed at higher surfactant concentrations. The interfacial tension is described by Langmuir kinetics and the parameters for interfaces with mineral oil (studied here) compare closely with those previously found at air interfaces. For the conditions explored, the surfactant mass transfer is described well by a mixed kinetic-diffusion limited model, and the desorption rate coefficients are measured to be both approximately 70 s-1. The transition from a diffusion-controlled to mixed diffusion-kinetic mass transfer mechanism predicted with reducing drop size is verified. This experimental approach (i.e. adjustable geometry and drop size and height) can therefore probe interfacial dynamics in simple and complex flow.

Martin, Jeffrey D.; Hudson, Steven D.

2009-11-01

44

Mass transfer and interfacial properties in two-phase microchannel flows  

International Nuclear Information System (INIS)

Drop-based microfluidic devices are becoming more common, and molecular mass transfer and drop circulation are issues that often affect the performance of such devices. Moreover, interfacial properties and surfactant mass transfer rates govern emulsion behavior. Since these phenomena depend strongly on drop size, measurement methods using small drops and flow typical of applications are desired. Using mineral oil as a continuous phase, water droplets and an alcohol surfactant, we demonstrate here a microfluidic approach to measure the interrelated phenomena of dynamic interfacial tension, surfactant mass transfer and interfacial retardation that employs droplet flows in a microchannel with constrictions/expansions. Interfacial flow is influenced markedly by adsorption of surfactant: severe interfacial retardation (by a factor of 30) is observed at low surfactant concentrations and interface remobilization is observed at higher surfactant concentrations. The interfacial tension is described by Langmuir kinetics and the parameters for interfaces with mineral oil (studied here) compare closely with those previously found at air interfaces. For the conditions explored, the surfactant mass transfer is described well by a mixed kinetic-diffusion limited model, and the desorption rate coefficients are measured to be both approximately 70 s-1. The transition from a diffusion-controlled to mixed diffusion-kinetic mass transfer mechanism predicted with reducing drop er mechanism predicted with reducing drop size is verified. This experimental approach (i.e. adjustable geometry and drop size and height) can therefore probe interfacial dynamics in simple and complex flow.

45

Determination of interfacial heat transfer coefficient and its application in high pressure die casting process  

Digital Repository Infrastructure Vision for European Research (DRIVER)

In this paper, the research progress of the interfacial heat transfer in high pressure die casting (HPDC) is reviewed. Results including determination of the interfacial heat transfer coefficient (IHTC), influence of casting thickness, process parameters and casting alloys on the IHTC are summarized and discussed. A thermal boundary condition model was developed based on the two correlations: (a) IHTC and casting solid fraction and (b) IHTC peak value and initial die surface temperature. The ...

Cao Yongyou; Guo Zhipeng; Xiong Shoumei

2014-01-01

46

Ultrafast interfacial charge transfer dynamics in dye-sensitized and quantum dot solar cell  

Science.gov (United States)

Dye sensitized solar cell (DSSC) appeared to be one of the good discovery for the solution of energy problem. We have been involved in studying ultrafast interfacial electron transfer dynamics in DSSC using femtosecond laser spectroscopy. However it has been realized that it is very difficult to design and develop higher efficient one, due to thermodynamic limitation. Again in DSSC most of the absorbed photon energy is lost as heat within the cell, which apart from decreasing the efficiency also destabilizes the device. It has been realized that quantum dot solar cell (QDSC) are the best bet where the sensitizer dye molecules can be replaced by suitable quantum dot (QD) materials in solar cell. The quantum-confinement effect in semiconductors modifies their electronic structure, which is a very important aspect of these materials. For photovoltaic applications, a long-lived charge separation remains one of the most essential criteria. One of the problems in using QDs for photovoltaic applications is their fast charge recombination caused by nonradiative Auger processes, which occur predominantly at lower particle sizes due to an increase in the Coulomb interaction between electrons and holes. Various approaches, such as the use of metal-semiconductor composites, semiconductor-polymer composite, and semiconductor core-shell heterostructures, have been attempted to minimize the fast recombination between electrons and holes. To make higher efficient solar devices it has been realised that it is very important to understand charge carrier and electron transfer dynamics in QD and QD sensitized semiconductor nanostructured materials. In the present talk, we are going to discuss on recent works on ultrafast electron transfer dynamics in dye-sensitized TiO2 nanoparticles/film [1-12] and charge (electron/hole) transfer dynamics in quantum dot core-shell nano-structured materials [13-17].

Ghosh, Hirendra N.

2013-02-01

47

Characterisation of interfacial segregation using Auger electron spectroscopy  

International Nuclear Information System (INIS)

Full text: Interfacial segregation is the collective term for the aggregation of atoms on both free surfaces and grain boundaries. It is different from adsorption as these atoms are not deposited from the gas phase but diffuse to the interfaces from the bulk of the material. Very often the segregating atoms are trace impurities present in ppm quantities. By accumulating in the interface in high concentrations, the enrichment factor, ie the ratio of interfacial concentration to the bulk concentration, is found to be of several orders of magnitude. The presence of these impurity atoms in the grain boundaries changes the mechanical properties of the alloy, sometimes with disastrous consequences. It was only after the advent of surface sensitive techniques, such as Auger electron spectroscopy (AES), that interfacial segregation could be studied in detail. Although the interfacial concentration is much higher than the bulk concentration, the thickness of the segregated layer is normally of the order of one atomic layer and the concentration within this monolayer varies between O and 1 as measured as a fraction of the monolayer. Surface segregation studies are thus confined to surface sensitive techniques such as the electron spectroscopies (AES, XPS) or static SIMS measurements. A brief introduction to the underlying principles of the phenomenon will be given. A striking characteristic is that the atoms diffuse 'uphill', ie from a low concentration in the bulk to a high colow concentration in the bulk to a high concentration on the surface/interface. This property presented some theoretical problems at first but it was shown that a Darken-type description provides a good description of the segregation process - also in multicomponent systems. Segregation studies on free surfaces are easier than interfacial studies: the segregated layer may be grown and monitored as a function of time. After one such run, the surface may be cleaned by argon ion sputtering and data at a different temperature may then be collected. Interfacial studies either involve in situ fracture to expose the grain boundaries or the preparation of thin specimens for TEM analysis. However, high temperature work in situ is not without some difficulties. The experimental setup, data and results for segregation to low index surfaces of single crystals will be discussed in some detail. It will also be shown that argon sputter cleaning at high temperature can influence the kinetic results while sputtering at low temperatures will change the surface concentration through preferential sputtering. Novel techniques where complete diffusion data is obtained in a single run will be discussed briefly and limitations will be highlighted. Copyright (2003) Australian Microbeam Analysis Society

48

Protein electron transfer: Dynamics and statistics  

Science.gov (United States)

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

Matyushov, Dmitry V.

2013-07-01

49

Nonadiabatic anharmonic electron transfer  

Energy Technology Data Exchange (ETDEWEB)

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

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

2013-03-28

50

Interfacial stress transfer and property mismatch in discontinuous nanofiber/nanotube composite materials.  

Science.gov (United States)

Novel nanotubes/nanofibers with high strength and stiffness did not lead to high failure strengths/strains of nanocomposite materials. Therefore, the interfacial stress transfer and possible stress singularities, arising at the interfacial ends of discontinuous nanofibers embedded in a matrix, subjected to tensile and shear loading, were investigated by finite element analysis. The effects of Young's moduli and volume fractions on interfacial stress distributions were studied. Round-ended nanofibers were proposed to remove the interfacial singular stresses, which were caused by high stiffness mismatch of the nanoscale reinforcement and the matrix. However, the normal stress induced in the nanofiber through interfacial stress transfer was still less than 2 times that in the matrix. This stress value is far below the high strength of the nanofiber. Therefore, the load transfer efficiency of discontinuous nanofibers or nanotube composites is very low. Hence, nanofibers or nanotubes in continuous forms, which also preclude the formation of singular interfacial stress zones, are recommended over discontinuous nanofibers to achieve high strengths in nanocomposite materials. PMID:16004129

Xu, L Roy; Sengupta, Sreeparna

2005-04-01

51

Transmission Electron Microscopy Characterization of Semiconductor Interfacial Structures  

Science.gov (United States)

The epitaxial structure and characterization of semiconductor/semiconductor interfacial systems have been studied using transmission electron microscopy as the primary investigative technique. Geometrical and elastic energy theories of epitaxy, as they relate to interfacial structure, have been reviewed to establish the framework necessary for analyzing experimental semiconductor heterostructures. The diffracted electron intensities for cross-sectional semiconductor single layer and superlattice structures have been derived based on the kinematical theory. The expression for the kinematical intensity for electron diffraction from a superlattice was observed to be analogous to the diffraction of light by a diffraction grating. The effects of surface relaxation, present in all strained-layer specimens prepared for the transmission electron microscope, have been investigated using elasticity theory. Conditions where surface relaxation effects can be ignored have also been presented. In order to quantify elastic strains at the nanometer level using high resolution electron microscopy (HREM) images, a new strain analysis technique, based on the cumulative sum of deviations (CUSUM) in lattice-fringe spacings from a target value, has been developed. This technique accurately reproduced the strain profiles in simulated and experimental HREM images and proved to be robust even in the presence of high levels of experimental noise. The above theory and techniques have been applied to three experimental systems, covering three distinct regimes of lattice mismatch (lattice mismatch ranged from -3.4% to +14.6%). These three systems were In_{1-x}Ga_ {x}Sb (0 <=q x <=q 1) single layers on (001) GaAs, rm In_{1-x}Al_{x}Sb/InSb single layers and superlattices on (001) InSb, and a 20 period AlAs/GaAs superlattice on (001) GaAs.

Robertson, Michael Dennis

52

Interplay of local and global interfacial electronic structure of a strongly coupled dipolar organic semiconductor  

Science.gov (United States)

We investigate the consequences of strong electronic coupling at the organic semiconductor/metal interface in both the ground and excited state manifold for the case of chloro-boron subphthalocyanine on Cu(111). Using a combination of low-temperature scanning tunneling microscopy and ultraviolet photoelectron spectroscopy and angle-resolved two-photon photoemission, we are able to connect local electronic interactions at the interface with thin film structure despite complex growth in the submonolayer regime. We show that strong coupling leads to charge transfer from the surface to the molecule, and we are able to correlate this observation with the specific molecular adsorption geometry. Strong coupling further results in molecular excited state anion resonances and is responsible for autoionization of highly excited image potential states, relating to the heterogeneous electronic environment in these thin films. This study provides a step towards disentangling interfacial electronic interactions at complex organic/metal interfaces.

Ilyas, Nahid; Monti, Oliver L. A.

2014-09-01

53

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

International Nuclear Information System (INIS)

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)

54

Determination of interfacial heat transfer coefficient and its application in high pressure die casting process  

Directory of Open Access Journals (Sweden)

Full Text Available In this paper, the research progress of the interfacial heat transfer in high pressure die casting (HPDC is reviewed. Results including determination of the interfacial heat transfer coefficient (IHTC, influence of casting thickness, process parameters and casting alloys on the IHTC are summarized and discussed. A thermal boundary condition model was developed based on the two correlations: (a IHTC and casting solid fraction and (b IHTC peak value and initial die surface temperature. The boundary model was then applied during the determination of the temperature field in HPDC and excellent agreement was found.

Cao Yongyou

2014-07-01

55

Nonequilibrium Structural Phase Transformation of Interfacial Water Assemblies Observed by Ultrafast Electron Crystallography  

Science.gov (United States)

Interfacial water, when compared with bulk phases, exhibits unique properties in various systems. By using ultrafast electron crystallography with atomic-scale spatiotemporal resolution, we report studies of structures and dynamics of interfacial ice assemblies on different surfaces. Structurally, ordered ice may be formed not only due to energetics of the water-surface interaction (commonly addressed as hydrophobicity and hydrophilicity), but also as a result of the surface morphology of the underlying substrate. The ultrafast dynamics also reveals new properties of a hydrogen-bond network. Following the photoexcitation of the substrate by a femtosecond infrared pulse, the interfacial ice structure undergoes, in few tens of picoseconds, nonequilibrium phase transformation identified through the observation of a structural isosbestic point in diffraction. This noncontinuous lattice expansion, from the unperturbed state to a highly expanded, nonthermal one, is caused by the structural vibration in the substrate and energy transfer across the interface. In addition, the cooperativeness of the hydrogen-bond network prevents a substantial evaporation lost of water molecules during repeated extreme expansion and recovery of the lattice. We provide the time scales involved and discuss the nature and implications of ice-substrate structural dynamics.

Yang, Ding-Shyue; Zewail, Ahmed H.

2010-03-01

56

Auger electron spectroscopy study on interfacial reactions in multilayer thin film systems  

Science.gov (United States)

Interfacial reactions at room temperature in multilayer thin film systems have been investigated by the Auger Electron Spectroscopy method. The multilayer thin film structure consists of metal, native oxide, and/or deposited interfacial layers on metal and semiconductor substrates. Various combinations of metals and interfacial layers on different substrates have been investigated. For the multilayer systems Au, Ag, Cu, and Cr were used as metals, GeO2, Bi2O3, SnO2, Sb2O3, Ga2O3, and As2O3 were used as interfacial layers, and GaAs, Si, and Fe were used as substrates. Only 'metal' atoms from the interfacial oxide layers (Ge from GeO2, Sb from Sb2O3, Bi from Bi2O3, Sn from SnO2, and Ga and As from the native oxide mixture of Ga2O3 and As2O3) were detected on the metal surface of Metal-Interfacial layer-Semiconductor and Metal-Interfacial layer-Metal-Semiconductor structures. This indicates that the interfacial reaction takes place only at the metal-interfacial layer interface. 'Drive-out' diffusion is present at all interfacial reactions. The interfacial reactions and the drive-out diffusion processes are thought to play an important role in the degradation of thin film multilayer structures.

Pandelišev, Kiril A.; Wang, Edward Y.

1982-06-01

57

Electron transfer: Lower tunnel barriers  

Science.gov (United States)

A better understanding of electron transfer through molecules could provide the basis for many technological breakthroughs. Now, the rate of electron transfer has been enhanced in a family of molecules by making them more rigid, and this phenomenon may be explained by the loss of electronic energy to vibrations.

Miller, John R.

2014-10-01

58

An extremely sensitive aptasensor based on interfacial energy transfer between QDS SAMs and GO  

Science.gov (United States)

In this work we designed a fluorescent self-assemblied multilayers, with thrombin aptamers and ssDNA as aptamer fixed onto the outermost layer, respectively. This multilayers can effectively sense biomolecules by interfacial florescence resonance energy transfer from multilayers to graphene oxide. High fluorescence quenching efficiency of graphene oxide and self-assemblied membrane' concentration results in good sensitivity for biosensing. A new interfacial sensing method with extremely high sensitivity for thrombin and DNA sequence was established, and the detection limit for thrombin and DNA was 16.2 pM and 72.6 fM, respectively.

Sun, Xiangying; Liu, Bin; Yang, Chuanxiao; Li, Congcong

2014-10-01

59

Hydrophobic ionic liquids/water interfacial phase transfer induced by direct current electric field  

International Nuclear Information System (INIS)

To investigate the affect of direct current electric field (DCEF) on the interfacial phase, in this paper, a hydrophobic ionic liquid (HIL)/water as liquid-liquid two-phase binary system is established by using the deionized water and l-butyl-3-methyl imidazolium hexafluorophosphate, and the topographies of the HIL nanodroplets and nanolayers in ambient water are observed by atomic force microscope (AFM). The results show the AFM exerting the DCEF can enhance the intersolubility of the HIL/water binary system and induce their interfacial phase transfer. (authors)

60

Time-resolved x-ray photoelectron spectroscopy techniques for real-time studies of interfacial charge transfer dynamics  

International Nuclear Information System (INIS)

X-ray based spectroscopy techniques are particularly well suited to gain access to local oxidation states and electronic dynamics in complex systems with atomic pinpoint accuracy. Traditionally, these techniques are applied in a quasi-static fashion that usually highlights the steady-state properties of a system rather than the fast dynamics that often define the system function on a molecular level. Novel x-ray spectroscopy techniques enabled by free electron lasers (FELs) and synchrotron based pump-probe schemes provide the opportunity to monitor intramolecular and interfacial charge transfer processes in real-time and with element and chemical specificity. Two complementary time-domain xray photoelectron spectroscopy techniques are presented that are applied at the Linac Coherent Light Source (LCLS) and the Advanced Light Source (ALS) to study charge transfer processes in N3 dye-sensitized ZnO semiconductor nanocrystals, which are at the heart of emerging light-harvesting technologies.

 
 
 
 
61

Core-concrete molten pool dynamics and interfacial heat transfer  

International Nuclear Information System (INIS)

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

62

Interfacial equilibrium and mass transfer from liquid CO2 disks through hydrate films  

International Nuclear Information System (INIS)

Dissolution behavior of CO2 in water is a key factor in the ocean sequestration of CO2 in deep sea. Studies have been reported on the mass transfer of CO2 into water through interfacial hydrate layer in convective conditions. Coupled with convective flows, such studies provide limited information on the mass transfer resistance at the interface. In the present study, liquid CO2 was injected into stagnant water to form disks at the center of a disk-like void in a deep sea condition (278 K, 20.0 MPa) and the decreasing radii of disks were photographed with a digital camera. The radius change of the CO2 disk was compared with moving boundary numerical solutions for diffusive dissolutions. The water side of the interfacial hydrate layer was found in equilibrium with aqueous phase and the slower dissolution in hydrate forming conditions is due to the decreased solubility. These findings are in accordance with previous studies in convective conditions.

63

Interfacial heat transfer in multiphase molten pools with gas injection  

Science.gov (United States)

In the very unlikely event of a severe reactor accident involving core meltdown and pressure vessel failure, it is vital to identify the circumstances that would allow the molten core material to cool down and resolidify, bringing core debris to a safe and stable state. In this type of accident, the molten material which escapes from the reactor pressure vessel will accumulate as a molten pool in the reactor cavity below. To achieve coolability of the corium in this configuration it has been proposed to flood the cavity with water from above forming a layered structure where upward heat loss from the molten pool to the water will cause the core material to quench and solidify. The effectiveness of this procedure depends largely on the rate of upward heat loss as well as on the formation and stability of an upper crust. In this situation the molten pool becomes a three phase mixture: the solid and liquid slurry formed by the molten pool cooled to a temperature below the temperature of liquidus, agitated by the gases formed in the concrete ablation process. The present work quantifies the partition of the heat losses upward and downward considering the influence of the solid fraction in the pool and the viscosity effects, and the rate of heat loss through a solid layer. To complete this task a intermediate scale experimental test section has been designed and built at the University of Wisconsin - Madison, in which simulant materials are used to model the process of heat and mass transfer which involves the molten pool, the solid layer atop and the coolant layer above. The design includes volumetric heating, gas injection from the bottom and solids within the pool. New experimental results showing the heat transfer behavior for pools with different viscosities and various solid fractions are presented. The current results indicate a power split which favors heat transfer upward to the coolant simulant above by a 2:1 or 3:1 ratio. In addition, the power split is unaffected by the viscosity of the pool, the solid fractions in the pool and the superficial velocity.

Bilbao Y Leon, Rosa Marina

1998-12-01

64

Characterization of interfacially electronic structures of gold-magnetite heterostructures using X-ray absorption spectroscopy.  

Science.gov (United States)

Gold-magnetite heterostructures are novel nanomaterials which can rapidly catalyze the reduction reaction of nitroaromatics. In this study, the interfacially structural and electronic properties of various morphologies of Au-Fe3O4 heterostructures were systematically investigated using X-ray absorbance spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The effect of change in electronic structure and charge transfer on electrochemically catalytic activity of Au-Fe3O4 heterostructures was further evaluated by oxygen reduction reaction (ORR). The shifts in binding energy of Au4f and Fe2p peaks in XPS spectra indicate the charge transfer between the Au and Fe3O4 nanoparticles. The increase in d-hole population of Au seeds after the conjugation with iron oxides follows the order flower-like Au-Fe3O4 (FLNPs)>dumbbell-like Au-Fe3O4 (DBNPs)>Au seeds. In addition, the Fe(2+) valence state increases in Au-Fe3O4 heterostructures, which provides evidence to support the hypothesis of charge transfer between Au and Fe3O4 nanoparticles. The theoretical simulation of Au L3-edge XAS further confirms the production of Au-Fe and Au-O bonds at the interface of Au/Fe3O4 and the epitaxial linkage relationship between Au and Fe3O4 nanoparticles. In addition, the electron deficient of Au seeds increases upon increasing Fe3O4 nanoparticles on a single Au seed, and subsequently decreases the catalytic activity of Au in the Au-Fe3O4 heterostructures. The catalytic activity of Au-Fe3O4 toward ORR follows the order Au seeds>Au-Fe3O4 DBNPs>Au-Fe3O4 FLNPs, which is positively correlated to the extent of electronic deficiency of Au in Au-Fe3O4 heterostructures. PMID:24407694

Lin, Fang-hsin; Doong, Ruey-an

2014-03-01

65

A Layer-by-Layer ZnO Nanoparticle-PbS Quantum Dot Self-Assembly Platform for Ultrafast Interfacial Electron Injection.  

Science.gov (United States)

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. PMID:25163799

Eita, Mohamed; Usman, Anwar; El-Ballouli, Ala'a O; Alarousu, Erkki; Bakr, Osman M; Mohammed, Omar F

2015-01-01

66

Interfacial misfit dislocation scattering effect in two-dimensional electron gas channel of GaN heterojunction  

International Nuclear Information System (INIS)

Interfacial misfit dislocation in AlxGa1?xN/GaN heterojunction was studied as a function of barrier layer thickness and lattice mismatch degree. The sheet charge density induced by interfacial dislocation was obtained. Based on the interfacial dislocation model, the mobility was calculated in two-dimensional electron gas channel. It was found that the mobility was dominated by the interfacial dislocation scattering at low temperature, and depended on the barrier layer thickness and lattice mismatch degree. -- Highlights: ? Interfacial misfit dislocation in AlxGa1?xN/GaN heterojunction was studied. ? The sheet charge density induced by interfacial dislocation was obtained. ? The mobility limited by interfacial dislocation was calculated. ? The mobility was dominated by interfacial dislocation scattering at low temperature.

67

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

2003-03-15

68

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

2003-03-15

69

Control of ferromagnetic relaxation in magnetic thin films through thermally induced interfacial spin transfer.  

Science.gov (United States)

Relaxation control in magnetic thin films via thermally induced interfacial spin transfers was demonstrated for the first time. The experiments used a trilayered structure that consisted of an yttrium iron garnet (YIG) thin film grown on a gadolinium gallium garnet substrate and capped with a nanometer-thick Pt layer. As a temperature gradient is applied across the thickness of the structure, there exists a spin angular momentum transfer across the YIG/Pt interface. This spin transfer results in a torque on YIG magnetic moments. The torque can either speed up or slow down the relaxation in the YIG film, depending on the sign of the temperature gradient with respect to the trilayered structure. PMID:23004648

Lu, Lei; Sun, Yiyan; Jantz, Michael; Wu, Mingzhong

2012-06-22

70

75 FR 31665 - Electronic Fund Transfers  

Science.gov (United States)

...implements the Electronic Fund Transfer...that overdraw a consumer's account...implements the Electronic Fund Transfer...without the consumer's affirmative...CFR Part 205 Consumer protection, Electronic fund...

2010-06-04

71

75 FR 9120 - Electronic Fund Transfers  

Science.gov (United States)

...implements the Electronic Fund Transfer...that overdraw a consumer's account...implements the Electronic Fund Transfer...without the consumer's affirmative...CFR Part 205 Consumer protection, Electronic fund...

2010-03-01

72

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

Energy Technology Data Exchange (ETDEWEB)

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)

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

73

Interfacial electronic properties of the heterojunctions C{sub 60}/rubrene/Au and rubrene/C{sub 60}/Au  

Energy Technology Data Exchange (ETDEWEB)

Using synchrotron-radiation photoemission, we have studied the electronic structures of rubrene:C{sub 60} heterojunctions on Au substrates. The photoelectron spectra show that the interfacial properties at the C{sub 60}/rubrene/Au and rubrene/C{sub 60}/Au interfaces are asymmetric and do not follow the commutation rule. In the C{sub 60}/rubrene case, a gap state appearing in the initial deposition stage results from negative charges transferred from rubrene to C{sub 60}, while in the inverse deposition process, no strong chemical reaction could be found. A significant shift of the vacuum level induced by alignment of the charge neutrality levels of the two materials was observed in both cases. Furthermore, the charge transfer strongly enhances the dipole potential of the C{sub 60}/rubrene interface. The energy level diagrams show that the C{sub 60}-on-rubrene process has a superior number of advantages in the photovoltaic applications.

Cheng, Chiu-Ping; Chan, Yi-Wei; Hsueh, Chih-Feng [Department of Electrophysics, National Chiayi University, 300 University Road, Chiayi 60004, Taiwan (China); Pi, Tun-Wen [National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China)

2012-07-15

74

Controlled interfacial electron dynamics in highly efficient Zn2 SnO4 -based dye-sensitized solar cells.  

Science.gov (United States)

Among ternary oxides, Zn2 SnO4 (ZSO) is considered for dye-sensitized solar cells (DSSCs) because of its wide bandgap, high optical transmittance, and high electrical conductivity. However, ZSO-based DSSCs have a poor performance record owing largely to the absence of systematic efforts to enhance their performance. Herein, general strategies are proposed to improve the performance of ZSO-based DSSCs involving interfacial engineering/modification of the photoanode. A conformal ZSO thin film (blocking layer) deposited at the fluorine-doped tin oxide-electrolyte interface by pulsed laser deposition suppressed the back-electron transfer effectively while maintaining a high optical transmittance, which resulted in a 22 % improvement in the short-circuit photocurrent density. Surface modification of ZSO nanoparticles (NPs) resulted in an ultrathin ZnO shell layer, a 9 % improvement in the open-circuit voltage, and a 4 % improvement in the fill factor because of the reduced electron recombination at the ZSO NPs-electrolyte interface. The ZSO-based DSSCs exhibited a faster charge injection and electron transport than their TiO2 -based counterparts, and their superior properties were not inhibited by the ZnO shell layer, which indicates their feasibility for highly efficient DSSCs. Each interfacial engineering strategy could be applied to the ZSO-based DSSC independently to lead to an improved conversion efficiency of 6 %, a very high conversion efficiency for a non-TiO2 based DSSC. PMID:24347268

Shin, Seong Sik; Kim, Dong Wook; Hwang, Daesub; Suk, Jae Ho; Oh, Lee Seul; Han, Byung Suh; Kim, Dong Hoe; Kim, Ju Seong; Kim, Dongho; Kim, Jin Young; Hong, Kug Sun

2014-02-01

75

75 FR 66644 - Electronic Fund Transfers  

Science.gov (United States)

...exceptions for any class of electronic fund transfers that in the...responsibilities of participants in electronic fund transfer systems...final rule, the Board found good cause under 5 U.S.C...205 Consumer protection, Electronic fund transfers, Federal...

2010-10-29

76

"Butterfly effect" in CuO/graphene composite nanosheets: a small interfacial adjustment triggers big changes in electronic structure and Li-ion storage performance.  

Science.gov (United States)

Generally speaking, excellent electrochemical performance of metal oxide/graphene nanosheets (GNSs) composite is attributed to the interfacial interaction (or "synergistic effect") between constituents. However, there are no any direct observations on how the electronic structure is changed and how the properties of Li-ion storage are affected by adjusting the interfacial interaction, despite of limited investigations on the possible nature of binding between GNSs and metal oxide. In this paper, CuO nanosheets/GNSs composites with a little Cu2O (ca. 4 wt %) were utilized as an interesting model to illustrate directly the changes of interfacial nature as well as its deep influence on the electronic structure and Li-ion storage performance of composite. The interfacial adjustment was successfully fulfilled by removal of Cu2O in the composite by NH3·H2O. Formation of Cu-O-C bonds on interfaces both between CuO and GNSs, and Cu2O and GNSs in the original CuO/GNSs composites was detected. The small interfacial alteration by removal of the little Cu2O results in the obvious changes in electronic structure, such as weakening of covalent Cu-O-C interfacial interaction and recovery of ? bonds in graphene, and simultaneously leads to variations in electrochemical performance of composites, including a 21% increase of reversible capacity, degradation of cyclic stability and rate-performance, and obvious increase of charge-transfer resistance, which can be called a "butterfly effect" in graphene-based metal oxide composites. These interesting phenomena could be helpful to design not only the high-performance graphene/metal oxide anode materials but also various advanced graphene-based composites used in the other fields such as sensors, catalysis, fuel cells, solar cells, etc. PMID:25226227

Zhang, Xiaoting; Zhou, Jisheng; Song, Huaihe; Chen, Xiaohong; Fedoseeva, Yu V; Okotrub, A V; Bulusheva, L G

2014-10-01

77

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

International Nuclear Information System (INIS)

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.

78

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

Science.gov (United States)

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.

Cao, Yongyou; Guo, Zhipeng; Xiong, Shoumei

2012-07-01

79

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

International Nuclear Information System (INIS)

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.

80

Quantum Plasmonics: Electron transfer processes  

Science.gov (United States)

Plasmon energies can be tuned across the spectrum by simply changing the geometrical shape of a nanostructure. Plasmons can efficiently capture incident light and focus it to nanometer sized hotspots which can enhance electronic and vibrational excitations in nearby structures.[1] Another important but still relatively unexplored property of plasmons, is that they can be efficient sources of hot energetic electrons which can transfer into nearby structures and induce a variety of processes. This process is a quantum mechanical effect: the decay of plasmon quanta into electron-hole pairs. I will discuss how plasmon induced hot electrons can be used in various applications: such as to induce chemical reactions in molecules physisorbed on a nanoparticle surface;[2] to inject electrons directly into the conduction band of a nearby substrate;[3] and to induce local doping of a nearby graphene sheet.[4] References [1] N.J. Halas et al., Adv. Mat. 24(2012)4842 [2] R. Huschka et al., JACS 133(2011)12247; S. Mukherjee et al. TBP 2012 [3] M. W. Knight et al., Science 332(2011)702, Z.Y. Fang et al., NL 12(2012)3808 [4] Z.Y. Fang et al., ACS Nano 6(2012)10.1021/nn304028b

Nordlander, Peter

2013-03-01

 
 
 
 
81

Inverse identification of interfacial heat transfer coefficient between the casting and metal mold using neural network  

International Nuclear Information System (INIS)

The effect of the heat transfer coefficient at the casting-mold interface is of prime importance to improve the casting quality, especially for castings in metal molds. However, it is difficult to determine the values of heat transfer coefficient from experiments due to the influence of various factors, such as contacting pressure, oxides on surfaces, roughness of surfaces, coating material, coating thickness and gap formation caused by the deformation of casting and mold, etc. In the present paper, the interfacial heat transfer coefficient (IHTC) between the casting and metal mold is identified by using the method of inverse analysis based on measured temperatures, neural network with back-propagation algorithm and numerical simulation. Then, by applying the identified IHTC in finite element analysis, the comparison between numerical calculated and experimental results is made to verify the correctness of method. The results show that the numerical calculated temperatures are in good agreement with experimental ones. These demonstrate that the method of inverse analysis is a feasible and effective tool for determination of the casting-mold IHTC. In addition, it is found that the identified IHTC varies with time during the casting solidification and varies in the range of about 100-3200 Wm-2K-1. The characteristics of the time-varying IHTC have also been discussed.

82

Interfacial electron transfer dynamics of photosensitized zinc oxide nanoclusters  

Energy Technology Data Exchange (ETDEWEB)

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.

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

83

Solar energy conversion dynamics of interfacial electron and excitation transfer  

CERN Document Server

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

Piotrowiak, Piotr

2013-01-01

84

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

Energy Technology Data Exchange (ETDEWEB)

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.

Hopkins, Patrick E.

2011-10-01

85

Interfacial charge transfer and hole injection in ?-NPD organic overlayer-CVD diamond substrate system  

International Nuclear Information System (INIS)

We have investigated interfacial charge transfers and hole injection characteristics between oxygen-terminated boron-doped homoepitaxial (1 0 0) chemical-vapor-deposited (CVD) diamond films and thermally deposited N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'biphenyl-4,4''diamine (?-NPD) mainly using X-ray photoelectron spectroscopy (XPS), Hall effect measurements and current-voltage (J-V) characteristic measurements. On one hand, no chemical shift was observed for C 1s and N 1s XPS spectra taken from the ?-NPD overlayer-CVD diamond substrate system. On the other hand, the low-temperature hole concentration of the diamond substrate decreased by ?10-17% after the ?-NPD depositions, verifying that small but substantial amounts of holes were transferred from the diamond substrates to the ?-NPD films. However, compared with those obtained from the specimens before the ?-NPD depositions, the sheet electrical conductivities of the specimens after the ?-NPD depositions increased at T ? 230 K while decreasing at T ? 200 K. In addition, J-V data measured from layered ?-NPD-diamond hetero-structures show evidence that the junction worked as a diode. These facts suggest that the ?-NPD-CVD diamond system may be useful for a transparent anode electrode with a hole transport layer appropriate for organic light emitting diodes

86

Spectral analysis of electron transfer kinetics II  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Electron transfer processes in Debye solvents are studied using a spectral analysis method recently proposed. Spectral structure of a nonadiabatic two-state diffusion equation is investigated to reveal various kinetic regimes characterized by a broad range of physical parameters; electronic coupling, energy bias, reorganization energy, and solvent relaxation rate. Within this unified framework, several kinetic behaviors of the electron transfer kinetics, including adiabatic ...

Jung, Younjoon; Cao, Jianshu

2002-01-01

87

Electron Transfer Dissociation of Oligonucleotide Cations  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Electron transfer dissociation (ETD) of multi-protonated 6 - 20-mer oligonucleotides and 12- and 14-mer duplexes is compared to collision activated dissociation (CAD). ETD causes efficient charge reduction of the multi-protonated oligonucleotides in addition to limited backbone cleavages to yield sequence ions of low abundance. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD)...

Smith, Suncerae I.; Brodbelt, Jennifer S.

2009-01-01

88

Heteroepitaxial metallo-phthalocyanine (MPc, M = cobalt, nickel, copper) thin films on gold: Atomic and interfacial electronic structures  

Science.gov (United States)

Organic semiconductors have become a hot topic for research within the past few years. This work describes research into a family of organic semiconductors known as metallo-phthalocyanine (MPc) in which the electronic and optical properties can be easily tuned by the systematic modification of the metal cations and ligands. More specifically, thin films of CoPc, NiPc, and CuPc have been evaporated onto a "5 x 20" reconstructed Au(001) substrate and have been investigated by employing low energy electron diffraction and ultraviolet photoelectron spectroscopy. Low energy electron diffraction reveals that thin films of CuPc and NiPc are highly ordered with a square unit cell aligned along the substrate and axes. In addition, deposition of CuPc onto the Au(001) substrate when at room temperature and elevated temperatures reveal that the square unit cell is larger when the substrate is heated. On the other hand, CoPc thin films are not well ordered as evidenced by multiple rotationally equivalent square domains, which are separated by 16°. Even more interesting is that the contrast between NiPc and CoPc on Au(001) is further found in the interfacial electronic structure. Ultraviolet photoelectron spectroscopy studies of the interfacial layers of NiPc deposited on the reconstructed gold substrate indicate that NiPc physisorbs on the gold surface as verified by a uniform molecular orbital (MO) shift. However, similar studies of the interfacial layers of CoPc depict an interaction between the CoPc 13a1g MO and the Au surface suggesting a charge transfer between the two. In addition to the research into MPc thin films, this work also describes the development of a Low Energy Electron Diffraction Intensity versus Voltage (LEED-IV) system for the Laboratory for Surface Analysis and Modification. This development involved the merging of various hardware and software systems by means of LabVIEW environment. Characterization of the system performance was carried out through the use of a MoS2 sample with known LEED-IV characteristics. The results of the system characterization revealed that the fully operational and ready to be applied to other samples.

Ellis, Trinity S.

2005-12-01

89

Ground and excited state electron transfer dynamics  

Digital Repository Infrastructure Vision for European Research (DRIVER)

The focus of this work is the investigation of the factors controlling electron transfer in molecular electronic systems, in particular those affecting electron transfer to and from electronically excited states. To achieve this, a number of mono- and trimetallic osmium and ruthenium complexes were synthesised and characterised. Monolayers of an osmium polypyridyl complex bound to a platinum microelectrode via a ¿rara-l,2-bis-(4-pyridyl)ethylene bridge were formed to probe ground state elect...

Brennan, Jennifer L.

2002-01-01

90

Comparison of the intercondylar distance and the interfacial width as used with the electronic pantograph.  

Science.gov (United States)

The electronic pantograph (Pantronic) records mandibular movements and computes the articulator settings. The Pantronic pantograph does not determine the intercondylar distance but approximates it from the interfacial width at the condyles. An average distance of 12.5 mm is subtracted from each side to determine the intercondylar distance. This study recorded 45 patients' articulator intercondylar distances that had been set from a mechanical pantograph and they were compared with the Pantronic's approximation. The difference between the interfacial width and the actual intercondylar distance was 15.1 mm on the right side and 14.9 mm on the left side. A numerical value of 15.0 mm was statistically superior to the Pantronic's 12.5 mm in estimating the average distance between the intercondylar distance and the surface of the skin at the condyle. No statistically significant difference was found between the differences of interfacial width and intercondylar distance values for men and women (p greater than 0.05). The mean intercondylar distance was 56.5 mm on the right side and 56.7 mm on the left side. A statistically significant difference was found between the mean intercondylar distances of men and women (p less than 0.05). PMID:1507096

Mandilaris, C B; Beard, C C; Clayton, J A

1992-03-01

91

Electron transfer kinetics at single nanoparticles  

Digital Repository Infrastructure Vision for European Research (DRIVER)

The understanding and control of charge transfer at the very smallest scale is fundamental to nanoscience for applications such as catalysis and energy storage. However, the quantitative measurement of the kinetics of electron transfer at the nanoscale at individual free nanoparticles has not hitherto been possible. Here we describe experiments to unambiguously determine the electron transfer kinetics for the reduction of protons at single gold and silver nanoparticles of radii 7-15 nm. We sh...

Kahk, Jm; Rees, Nv; Pillay, J.; Tshikhudo, R.; Vilakazi, S.; Compton, Rg

2012-01-01

92

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

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 mon...

Mcewen, Gerald D.; Chen, Fan; Zhou, Anhong

2009-01-01

93

Manipulating NiFe/AlOx interfacial chemistry for the spin-polarized electrons transport  

International Nuclear Information System (INIS)

Through vacuum annealing, interfacial chemical composition of sputter-deposited AlOx/NiFe/AlOx can be controlled for electron transport manipulation. Chemical status change at the NiFe/AlOx interface was quantified by X-ray photoelectron spectroscopy and correlated to the structure and electron transport properties of the heterostructure. It is found that elemental Al existed in the insulting AlOx after annealing at intermediate temperature can improve the AlOx/NiFe interface and thus favor the electronic transport. Annealing at higher temperature will result in native AlOx formation and degrade transport properties due to the NiFe/AlOx interfaces deterioration caused by significant difference in thermal expansion coefficients of the two materials.

94

Fluorinated copper phthalocyanine nanowires for enhancing interfacial electron transport in organic solar cells.  

Science.gov (United States)

Zinc oxide is a promising candidate as an interfacial layer (IFL) in inverted organic photovoltaic (OPV) cells due to the n-type semiconducting properties as well as chemical and environmental stability. Such ZnO layers collect electrons at the transparent electrode, typically indium tin oxide (ITO). However, the significant resistivity of ZnO IFLs and an energetic mismatch between the ZnO and the ITO layers hinder optimum charge collection. Here we report that inserting nanoscopic copper hexadecafluorophthalocyanine (F(16)CuPc) layers, as thin films or nanowires, between the ITO anode and the ZnO IFL increases OPV performance by enhancing interfacial electron transport. In inverted P3HT:PC(61)BM cells, insertion of F(16)CuPc nanowires increases the short circuit current density (J(sc)) versus cells with only ZnO layers, yielding an enhanced power conversion efficiency (PCE) of ?3.6% vs ?3.0% for a control without the nanowire layer. Similar effects are observed for inverted PTB7:PC(71)BM cells where the PCE is increased from 8.1% to 8.6%. X-ray scattering, optical, and electrical measurements indicate that the performance enhancement is ascribable to both favorable alignment of the nanowire ?-? stacking axes parallel to the photocurrent flow and to the increased interfacial layer-active layer contact area. These findings identify a promising strategy to enhance inverted OPV performance by inserting anisotropic nanostructures with ?-? stacking aligned in the photocurrent flow direction. PMID:23181741

Yoon, Seok Min; Lou, Sylvia J; Loser, Stephen; Smith, Jeremy; Chen, Lin X; Facchetti, Antonio; Marks, Tobin J; Marks, Tobin

2012-12-12

95

Effects of turbulence on interfacial heat transfer: a priori test and filters evaluation  

International Nuclear Information System (INIS)

Full text of publication follows: Many applications involving multiphase flows (for instance: spray formation, oil transportation, sea aerosol formation,...) induce very high Reynolds numbers. In these turbulent regimes, non-linear effects mainly drive the behavior of such flows. Consequently, Direct Numerical Simulation (DNS) calculations have to entail a number of freedom degrees proportional to the third power of the Reynolds number to correctly describe the flow behavior. This extremely hard restraint makes it impossible to use DNS for industrial applications. However, the turbulent behavior of the flow is expected to widely favor the energy transfers through the interface and then to have a major effect on the energy balance of the flows. Until now, the great majority of numerical calculations for multiphase turbulent flows use RANS (Reynolds Averaged Navier-Stokes) and LES (Large-Eddy Simulation) modeling in order to add energy dissipation to the molecular diffusion terms. However, no theoretical or experimental justifications have been proposed. The impact of the local and instantaneous multiphase topology of the flow on the turbulent characteristics has never been carefully studied, and the modeling (RANS or LES) is mainly based on analytical considerations which needs additional terms when considering interfaces and turbulence. The Direct Numerical Simulation (DNS) calculation is used in this work to provide information for LES and RANS modeling thanks to a pon for LES and RANS modeling thanks to a priori tests. To correctly handle the challenging modeling process of the energy transfers, the final paper proposes a mathematical formalism of the filtered system of multiphase one-fluid equations, including the filtered energy equation. A general formulation for LES or RANS calculation is provided. Different filtering processes are discussed focusing on the concept of extensive (a.k.a. on the extensive variables) or intensive (a.k.a. on the intensive variables) filtering. Thus, this theoretical background is illustrated with two non-isothermal turbulent interfacial problems: a two-dimensional air bubble in water interacting with contra-rotative vortices using the Trio U calculation code and the water-oil phase separation in a square box submitted to a temperature gradient using Aquilon CFD library. These test cases exhibit for example the increase of energy transfers at the interface, for example when a bubble plunged into a temperature gradient is impacted by two vortices. The different sub-grid terms to close in the case of under-resolved (RANS or LES) calculations are identified and compared. Different definitions of the filtering are used and are shown to provide drastically different results. The present work highlights the modeling issues and the choice of the balance equations to solve. It is demonstrated that the order of magnitude of the sub-grid scale terms arising in the equations can vary from a factor of 100 depending on the filtering chosen and that neglecting the sub-grid scale terms leads to a widely over-estimated heat transfer at the interface. (authors)

96

Nuclear reorganization barriers to electron transfer  

International Nuclear Information System (INIS)

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

97

Nuclear reorganization barriers to electron transfer  

Energy Technology Data Exchange (ETDEWEB)

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

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

1988-01-01

98

Hierarchical control of electron-transfer  

DEFF Research Database (Denmark)

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

Westerhoff, Hans V.; Jensen, Peter Ruhdal

1997-01-01

99

Advances in electron transfer chemistry, v.6  

CERN Document Server

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.

Mariano, PS

1999-01-01

100

Coupled electron transfers in artificial photosynthesis  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Light-induced charge separation in molecular assemblies has been widely investigated in the context of artificial photosynthesis. Important progress has been made in the fundamental understanding of electron and energy transfer and in stabilizing charge separation by multi-step electron transfer. In the Swedish Consortium for Artificial Photosynthesis, we build on principles from the natural enzyme photosystem II and Fe-hydrogenases. An important theme in this biomimetic effort is that of cou...

Hammarstro?m, Leif; Styring, Stenbjörn

2008-01-01

 
 
 
 
101

Electron paramagnetic resonance of photocatalytic reaction which involve electron transfer  

Energy Technology Data Exchange (ETDEWEB)

Transient radicals generated under photocatalytic reactions in a polar solvent and their electronically spinned polarization were discussed under UV irradiation by using EPR and N2 gas pulse laser time-divided EPR. The reaction is a reaction of electron transfer from such amines as DABCO or electron donor molecules of SO3{sup -} to such electron accepting compounds as 1,4-benzoquinone and maleic anhydride under the presence of photocatalysts (triple photosensitizers) such as benzophenone and xanthone (XT). Spin polarized cation radicals of DABCO and radical anions of XT were detected in association with one electron transfer. A triple mechanism lies in the spinned polarization of both radicals, and transient XT in the triple state begin the electron transfer reaction. Photo-excited XT acts as a photocatalyst in one electron transfer reaction, the triple XT turns into an electron accepting body, and the transient anion radicals of XT become the electron donor. The XT(S) acts as a photocatalyst in the inter-molecular electron transfer from amine (D) to quinone (A). Its reaction is expressed by the following formula: D + S{sup *} + A{yields}D{sup dot +}+S+A{sup dot -} (where S{sup *} denotes a photo-excited state). 53 refs., 21 figs., 3 tabs.

Kaise, M. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1995-10-13

102

Heat Transfer Augmentation for Electronic Cooling  

Directory of Open Access Journals (Sweden)

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.

Suabsakul Gururatana

2012-01-01

103

Medium effects in photoinduced electron transfer reactions  

International Nuclear Information System (INIS)

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 ction some areas of particular importance for further research in this field are outlined. (author) 28 refs., 20 figs., 2 tabs

104

Convection heat transfer in electronic equipment cooling  

Science.gov (United States)

To maintain the best possible thermal environment in electronic packages, the engineer must establish the most efficient path for heat transfer from the electronic devices to an external cooling agent. The path is typically subdivided into internal and external components, representing, respectively, heat transfer by conduction through different materials and interfaces separating the devices from the package surface and heat transfer by convection from the surface to the coolant. Depending on the scale and speed of the electronic circuits, as well as on constraints imposed by nonthermal considerations, the coolant may be a gas or a liquid and heat transfer may be by natural, forced, or mixed convection or, in the case of a liquid, by pool or forced convection boiling. In this paper a comprehensive review of convection cooling options is provided.

Incropera, F. P.

1988-11-01

105

Chemical and electronic structure of SiO2/Si interfacial transition layer  

International Nuclear Information System (INIS)

The chemical and electronic structures of SiO2/Si(1 1 1) and SiO2/Si(1 0 0) interfacial transition layers are reviewed. It will be shown, considering the penetration of electronic states from the Si substrate into SiO2 in the analysis of the thickness dependence of the energy loss of O 1s photoelectrons measured with a probing depth of 0.41 nm, that energy barriers for valence electrons, which are almost comparable to those found in SiO2, were formed when the oxide layer formed on Si(1 1 1) and Si(1 0 0) was thicker than 0.61 and 0.51 nm, respectively. In other words, the SiO2/Si(1 1 1) and SiO2/Si(1 0 0) interface defined with electronic band structure exists, respectively, in the oxide located effectively 0.61 and 0.51 nm away from the nominal interface defined with the atomic structure. In other words, incorporation of one atomic layer of oxygen at the interface does not form an electronic barrier. The extreme uniformity of the oxide layer formed on Si(1 0 0) was verified using synchrotron radiation excited high resolution XPS

106

Spectral analysis of electron transfer kinetics II  

CERN Document Server

Electron transfer processes in Debye solvents are studied using a spectral analysis method recently proposed. Spectral structure of a nonadiabatic two-state diffusion equation is investigated to reveal various kinetic regimes characterized by a broad range of physical parameters; electronic coupling, energy bias, reorganization energy, and solvent relaxation rate. Within this unified framework, several kinetic behaviors of the electron transfer kinetics, including adiabatic Rabi oscillation, crossover from the nonadiabatic to adiabatic limits, transition from the incoherent to coherent kinetic limits, and dynamic bath effect, are demonstrated and compared with results from previous theoretical models. Dynamics of the electron transfer system is also calculated with the spectral analysis method. It is pointed out that in the large reorganization energy case the nonadiabatic diffusion equation exhibits a non-physical behavior, yielding a negative eigenvalue.

Jung, Y J; Jung, YounJoon; Cao, Jianshu

2002-01-01

107

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

Science.gov (United States)

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

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

2013-11-01

108

Intramolecular electron transfer in bipyridinium disulfides.  

Science.gov (United States)

Reductive cleavage of disulfide bonds is an important step in many biological and chemical processes. Whether cleavage occurs stepwise or concertedly with electron transfer is of interest. Also of interest is whether the disulfide bond is reduced directly by intermolecular electron transfer from an external reducing agent or mediated intramolecularly by internal electron transfer from another redox-active moiety elsewhere within the molecule. The electrochemical reductions of 4,4'-bipyridyl-3,3'-disulfide (1) and the di-N-methylated derivative (2(2+)) have been studied in acetonitrile. Simulations of the cyclic voltammograms in combination with DFT (density functional theory) computations provide a consistent model of the reductive processes. Compound 1 undergoes reduction directly at the disulfide moiety with a substantially more negative potential for the first electron than for the second electron, resulting in an overall two-electron reduction and rapid cleavage of the S-S bond to form the dithiolate. In contrast, compound 2(2+) is reduced at less negative potential than 1 and at the dimethyl bipyridinium moiety rather than at the disulfide moiety. Most interesting, the second reduction of the bipyridinium moiety results in a fast and reversible intramolecular two-electron transfer to reduce the disulfide moiety and form the dithiolate. Thus, the redox-active bipyridinium moiety provides a low energy pathway for reductive cleavage of the S-S bond that avoids the highly negative potential for the first direct electron reduction. Following the intramolecular two-electron transfer and cleavage of the S-S bond the bipyridinium undergoes two additional reversible reductions at more negative potentials. PMID:24528295

Hall, Gabriel B; Kottani, Rudresha; Felton, Greg A N; Yamamoto, Takuhei; Evans, Dennis H; Glass, Richard S; Lichtenberger, Dennis L

2014-03-12

109

Bioinspired electron-transfer systems and applications  

International Nuclear Information System (INIS)

Bioinspired electron-transfer systems including artificial photosynthesis and respiration are presented herein together with some of their applications. First, multi-step electron-transfer systems composed of electron donor-acceptor ensembles have been developed, mimicking functions of the photosynthetic reaction center. However, a significant amount of energy is lost during the multi-step electron-transfer processes. Then, as an alternative to conventional charge-separation functional molecular models based on multi-step long-range electron transfer within redox cascades, simple donor-acceptor dyads have been developed to attain along-lived and high energy charge-separated state without significant loss of excitation energy, by fine control of the redox potentials and of the geometry of donor-acceptor dyads that have small reorganization energies of electron transfer. Such simple molecular dyads, capable of fast charge separation but extremely slow charge recombination, have significant advantages with regard to synthetic feasibility, providing a variety of applications including construction of organic solar cells and development of efficient photo-catalytic systems for the solar energy conversion. An efficient four-electron reduction of dioxygen to water by one-electron reductants such as ferrocene derivatives as well as by an NADH analog has also been achieved as a respiration model by using a cofacial dicobalt porphyrin that can form the ?-peroxo Co(III)-O2hat can form the ?-peroxo Co(III)-O2Co(III) complex. The catalytic mechanism of the four-electron reduction of dioxygen has been clarified based on the detailed kinetic study and the detection of the intermediate. (author)

110

Photoinduced electron transfer in ordered polymers  

Energy Technology Data Exchange (ETDEWEB)

Long range photoinduced electron transfer between electron donor and acceptor groups is of considerable current interest in terms of strategies for artificial photosynthesis and studies regarding the redox properties of proteins. As part of an extensive study of long range electron transfer involving biopolymers, we have carried out this year investigations of the assembly of electron transfer agents in a system of model short peptides. Also studied is a polyelectrolyte that can adopt a helical conformation when electrostatically complexed with organic dye counter-ions. The principal interest in these systems has to do with the well ordered secondary structures adopted by peptide polymers, and the capabilities for synthetic modification of peptide side chains and end groups with chromophores or electroactive substituents. The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of the cationic organic dye to a peptide electrolyte, for which cooperative dye loading and helix formation is important; and (3) completion of the synthesis of a new series of acridinium chromophores that have rod-like'' arrangements of inked aryl rings for assembly of electron donor-acceptor systems that will exhibit especially long lived charge separation.

Jones, G. II.

1991-12-01

111

Hot-electron transfer from semiconductor nanocrystals.  

Science.gov (United States)

In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO2) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub-50-femtosecond charge separation across the PbSe-TiO2 interface excited coherent vibrations of the TiO2 surface atoms, whose motions could be followed in real time. PMID:20558714

Tisdale, William A; Williams, Kenrick J; Timp, Brooke A; Norris, David J; Aydil, Eray S; Zhu, X-Y

2010-06-18

112

Electron transfer dissociation of oligonucleotide cations  

Science.gov (United States)

Electron transfer dissociation (ETD) of multi-protonated 6-20-mer oligonucleotides and 12- and 14-mer duplexes is compared to collision activated dissociation (CAD). ETD causes efficient charge reduction of the multi-protonated oligonucleotides in addition to limited backbone cleavages to yield sequence ions of low abundance. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD), results in rich fragmentation in terms of w, a, z, and d products, with a marked decrease in the abundance of base loss ions and internal fragments. Complete sequencing was possible for nearly all oligonucleotides studied. ETcaD of an oligonucleotide duplex resulted in specific backbone cleavages, with conservation of weaker non-covalent bonds.

Smith, Suncerae I.; Brodbelt, Jennifer S.

2009-06-01

113

Cycloreversion of ?-lactams via photoinduced electron transfer.  

Science.gov (United States)

The radical anions of ?-lactams, photogenerated in the presence of DABCO as an electron donor, undergo cycloreversion via N-C4 bond cleavage, back electron transfer and final C2-C3 bond cleavage, leading to olefins. The involved intermediates are 1,4-radical anions and 1,4-biradicals. The experimental observations are consistent with the results of DFT calculations. PMID:25223340

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

2014-11-14

114

Interfacial electronic effects in functional biolayers integrated into organic field-effect transistors.  

Science.gov (United States)

Biosystems integration into an organic field-effect transistor (OFET) structure is achieved by spin coating phospholipid or protein layers between the gate dielectric and the organic semiconductor. An architecture directly interfacing supported biological layers to the OFET channel is proposed and, strikingly, both the electronic properties and the biointerlayer functionality are fully retained. The platform bench tests involved OFETs integrating phospholipids and bacteriorhodopsin exposed to 1-5% anesthetic doses that reveal drug-induced changes in the lipid membrane. This result challenges the current anesthetic action model relying on the so far provided evidence that doses much higher than clinically relevant ones (2.4%) do not alter lipid bilayers' structure significantly. Furthermore, a streptavidin embedding OFET shows label-free biotin electronic detection at 10 parts-per-trillion concentration level, reaching state-of-the-art fluorescent assay performances. These examples show how the proposed bioelectronic platform, besides resulting in extremely performing biosensors, can open insights into biologically relevant phenomena involving membrane weak interfacial modifications. PMID:22493224

Angione, Maria Daniela; Cotrone, Serafina; Magliulo, Maria; Mallardi, Antonia; Altamura, Davide; Giannini, Cinzia; Cioffi, Nicola; Sabbatini, Luigia; Fratini, Emiliano; Baglioni, Piero; Scamarcio, Gaetano; Palazzo, Gerardo; Torsi, Luisa

2012-04-24

115

Influence of the interfacial roughness on electron channelling in Fe/Au(001) multilayers  

Energy Technology Data Exchange (ETDEWEB)

Fe/Au(001) multilayers have been grown by molecular beam epitaxy using a new technique for the preparation of Au buffer layers on MgO(001) substrates. Scanning tunnelling microscopy and grazing incidence x-ray scattering reveal that the Au buffers have extremely low interface roughness and a long in-plane correlation length. X-ray scattering and diffraction show that multilayers grown on the new buffers, although having little difference in their crystalline structure, have much smoother interfaces than those grown on previous buffers. Compared with earlier multilayers with rougher interfaces, the giant magnetoresistance has increased by 20% due to more complete antiferromagnetic exchange coupling. Measurement of the saturation conductivity shows that the number of specular reflections occurring during electron channelling remains unchanged even though the interfacial roughness is reduced by a factor of six. It is postulated that the cause of this is either that spin-dependent scattering at the interface is being driven solely by the difference in the band structure, not by diffuse scatter at the interfaces, or that the wavelength of the transport electrons is such that the change in the roughness has no effect upon the specular scattering.

Cole, A [Department of Physics and Astronomy, EC Stoner Laboratory, University of Leeds, Leeds LS2 9JT (United Kingdom); Hickey, B J [Department of Physics and Astronomy, EC Stoner Laboratory, University of Leeds, Leeds LS2 9JT (United Kingdom); Hase, T P A [Department of Physics, University of Durham, Rochester Building, Science Laboratories, South Road, Durham DH1 3LE (United Kingdom); Buchanan, J D R [Department of Physics, University of Durham, Rochester Building, Science Laboratories, South Road, Durham DH1 3LE (United Kingdom); Tanner, B K [Department of Physics, University of Durham, Rochester Building, Science Laboratories, South Road, Durham DH1 3LE (United Kingdom)

2004-03-03

116

Self-Doping, O2-Stable, n-Type Interfacial Layer for Organic Electronics  

Energy Technology Data Exchange (ETDEWEB)

Solid films of a water-soluble dicationic perylene diimide salt, perylene bis(2-ethyltrimethylammonium hydroxide imide), Petma{sup +}OH{sup -}, are strongly doped n-type by dehydration and reversibly de-doped by hydration. The hydrated films consist almost entirely of the neutral perylene diimide, PDI, while the dehydrated films contain {approx}50% PDI anions. The conductivity increases by five orders of magnitude upon dehydration, probably limited by film roughness, while the work function decreases by 0.74 V, consistent with an n-type doping density increase of {approx}12 orders of magnitude. Remarkably, the PDI anions are stable in dry air up to 120 C. The work function of the doped film, {phi} (3.96 V vs. vacuum), is unusually negative for an O{sub 2}-stable contact. Petma{sup +} OH{sup -} is also characterized as an interfacial layer, IFL, in two different types of organic photovoltaic cells. Results are comparable to state of the art cesium carbonate IFLs, but may improve if film morphology can be better controlled. The films are stable and reversible over many months in air and light. The mechanism of this unusual self-doping process may involve the change in relative potentials of the ions in the film caused by their deshielding and compaction as water is removed, leading to charge transfer when dry.

Reilly, T. H. III; Hains, A. W.; Chen, H. Y.; Gregg, B. A.

2012-04-01

117

Measurement of the driving force dependence of interfacial charge-transfer rate constants in response to pH changes at n-ZnO/H2O interfaces  

International Nuclear Information System (INIS)

Changes in pH have been used to shift the band-edge positions of n-type ZnO electrodes relative to solution-based electron acceptors having pH-independent redox potentials. Differential capacitance vs. potential and current density vs. potential measurements using [Co(bpy)3]3+/2+ and [Ru(bpy)2(MeIm)2]3+/2+ (where bpy = 2,2'-bipyridyl and MeIm 1-methyl-imidazole) allowed investigation of the pH-induced driving-force dependence of the interfacial electron-transfer rate in the normal and inverted regions of electron transfer, respectively. All rate processes were observed to be kinetically first-order in the concentration of electrons at the ZnO surface and first-order in the concentration of dissolved redox acceptors. Measurements using [Co(bpy)3]3+/2+, which has a low driving force and a high reorganization energy in contact with ZnO electrodes, and measurements of [Ru(bpy)2(MeIm)2]3+/2+, which has a high driving force and a low reorganization energy in contact with ZnO electrodes, allowed for the evaluation of both the normal and inverted regions of interfacial electron-transfer processes, respectively. The rate constant at optimum exoergicity was observed to be approximately 5 x 10-17 cm4 s-1. The rate constant vs. driving-force dependence at n-type ZnO electrodes exhibited both normal and inverted regions, and the data were w and inverted regions, and the data were well-fitted by parabolas generated using classical electron-transfer theory

118

Interfacial Charge Transport in Organic Electronic Materials: the Key to a New Electronics Technology  

Energy Technology Data Exchange (ETDEWEB)

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The primary aim of this project is to obtain a basic scientific understanding of electrical transport processes at interfaces that contain an organic electronic material. Because of their processing advantages and the tunability of their electronic properties, organic electronic materials are revolutionizing major technological areas such as information display. We completed an investigation of the fundamental electronic excitation energies in the prototype conjugated polymer MEH-PPV. We completed a combined theoretical/experimental study of the energy relation between charged excitations in a conjugated polymer and the metal at a polymer/metal interface. We developed a theoretical model that explains injection currents at polymer/metal interfaces. We have made electrical measurements on devices fabricated using the conjugated polymer MEH-PPV a nd a series of metals.

Smith, D.L.; Campbell, I.H.; Davids, P.S.; Heller, C.M.; Laurich, B.K.; Crone, B.K.; Saxena, A.; Bishop, A.R.; Ferraris, J.P.; Yu, Z.G.

1999-06-04

119

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

DEFF Research Database (Denmark)

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2?,7?-dichlorofluorescein (DCF) anchored to the surface of iron(iii) oxide nanoparticles to create iron(ii) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115–310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2g vs. Fe eg).

Gilbert, Benjamin; Katz, Jordan E.

2013-01-01

120

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

Directory of Open Access Journals (Sweden)

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. .

Nikoli? Z.S.

2007-01-01

 
 
 
 
121

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

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. .

Nikoli? Z.S.; Yoshimura M.; Araki S; Fujiwara T.

2007-01-01

122

Atomic-scale calculations of interfacial structures and their properties in electronic materials  

Science.gov (United States)

With the tremendous increase in computational power over the last two decades as well as the continuous shrinkage of Si-based Metal Oxide Semiconductor Field Effect Transistors (MOSFET), quantum mechanically based ab initio methods become indispensable tools in nano-scale device engineering. In this work, atomistic simulations including ab initio, nudged elastic band (NEB) and kinetic Monte Carlo methods have been used to (1) calculate the dopant segregation energy at silicon/gate oxide interfaces; (2) characterize the Si:Ge/SiO2 interfacial structure; (3) study the effects of impurity atoms on the diffusion process at Al and Al(Cu) grain boundaries. Using VASP, an ab initio simulation package, we calculated B segregation energy at different atomic sites in perfect and defected Si/SiO 2 interfaces and arsenic segregation energy in Si/LaAlO3 structures. With the presence of O vacancies and H in B doped systems, the predicted segregation energy is 0.85 eV for neutral systems and 1.12 eV for negatively charged systems, which is consistent with experimental measurements (0.51 to 1.47 eV). Recent ab initio structure calculations have examined the stability of various Si(001)/LaAlO3 interfaces and find that a LaO terminated interface with La deficiency or perfect stoichiometry depending on oxygen partial pressure has the lowest energy. Focussing on the La deficient Si/LaAlO3 interfacial structure, we find that the arsenic prefers energetically not to segregate into LaAlO3 nor does it pile up in front of the interface. In combation of atomic-resolution Z-contrast imaging and electron energy loss spectroscopy (EELS), we theorectically calculated the band structure and EELS of a Ge/SiO2 interface. We actually found a chemically abrupt Ge/SiO2 interface, which has never been reported before and which is quite desirable for applications. Furthermore, we formulated a kinetic Monte Carlo model to simulate the oxidation process of Ge ion-implanted Si. Our modeling suggests the presence of small amounts of Ge in the oxide, which might be the major cause of worsened device performance of the 'perfect' Ge/SiO2 interface. Using nudged elastic band (NEB) method, we systematically calculate the vacancy formation, diffusion activation energy and pre-exponential diffusion factor at pure and Cu doped Al grain boundaries. Though grain boundary diffusion is still much faster than that of bulk, adding small amounts of Cu can dramatically improve the electromigration reliability of Al interconnects. (Abstract shortened by UMI.)

Liang, Tao

123

Reaction coordinates for electron transfer reactions  

International Nuclear Information System (INIS)

The polarization fluctuation and energy gap formulations of the reaction coordinate for outer sphere electron transfer are linearly related to the constant energy constraint Lagrangian multiplier m in Marcus' theory of electron transfer. The quadratic dependence of the free energies of the reactant and product intermediates on m and m+1, respectively, leads to similar dependence of the free energies on the reaction coordinates and to the same dependence of the activation energy on the reorganization energy and the standard reaction free energy. Within the approximations of a continuum model of the solvent and linear response of the longitudinal polarization to the electric field in Marcus' theory, both formulations of the reaction coordinate are expected to lead to the same results.

124

Resonant electron transfer between quantum dots  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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 superposi...

Openov, Leonid A.

1999-01-01

125

Promoting Interspecies Electron Transfer with Biochar  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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...

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

2014-01-01

126

Electron transfer theory revisit: Quantum solvation effect  

CERN Document Server

The effect of solvation on the electron transfer (ET) rate processes is investigated on the basis of the exact theory constructed in J. Phys. Chem. B Vol. 110, (2006); quant-ph/0604071. The nature of solvation is studied in a close relation with the mechanism of ET processes. The resulting Kramers' turnover and Marcus' inversion characteristics are analyzed accordingly. The classical picture of solvation is found to be invalid when the solvent longitudinal relaxation time is short compared with the inverse temperature.

Han, P; Cui, P; Mo, Y; He, G; Yan, Y J; Han, Ping; Xu, Rui-Xue; Cui, Ping; Mo, Yan; He, Guozhong; Yan, YiJing

2006-01-01

127

Quantum coherent contributions in biological electron transfer  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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, rec...

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

2011-01-01

128

Driving force dependent, photoinduced electron transfer at degenerately doped, optically transparent semiconductor nanoparticle interfaces.  

Science.gov (United States)

Photoinduced, interfacial electron injection and back electron transfer between surface-bound [Ru(II)(bpy)2(4,4'-(PO3H2)2-bpy)](2+) and degenerately doped In2O3:Sn nanoparticles, present in mesoporous thin films (nanoITO), have been studied as a function of applied external bias. Due to the metallic behavior of the nanoITO films, application of an external bias was used to vary the Fermi level in the oxide and, with it, the driving force for electron transfer (?G(o)'). By controlling the external bias, ?G(o)' was varied from 0 to -1.8 eV for electron injection and from -0.3 to -1.3 eV for back electron transfer. Analysis of the back electron-transfer data, obtained from transient absorption measurements, using Marcus-Gerischer theory gave an experimental estimate of ? = 0.56 eV for the reorganization energy of the surface-bound Ru(III/II) couple in acetonitrile with 0.1 M LiClO4 electrolyte. PMID:25330285

Farnum, Byron H; Morseth, Zachary A; Brennaman, M Kyle; Papanikolas, John M; Meyer, Thomas J

2014-11-12

129

Electron Transfer-Based Single Molecule Fluorescence as a Probe for Nano-Environment Dynamics  

Directory of Open Access Journals (Sweden)

Full Text Available Electron transfer (ET is one of the most important elementary processes that takes place in fundamental aspects of biology, chemistry, and physics. In this review, we discuss recent research on single molecule probes based on ET. We review some applications, including the dynamics of glass-forming systems, surface binding events, interfacial ET on semiconductors, and the external field-induced dynamics of polymers. All these examples show that the ET-induced changes of fluorescence trajectory and lifetime of single molecules can be used to sensitively probe the surrounding nano-environments.

Ruiyun Chen

2014-02-01

130

Direct contact heat exchange interfacial phenomena for liquid metal reactors : Part I - heat transfer  

International Nuclear Information System (INIS)

Experiments on direct-contact heat exchange between molten metal and water for steam production were conducted. These experiments involved the injection of water into molten lead-bismuth eutectic for heat transfer measurements in a 1-D geometry. Based on the initial results of the experiments, the effects of the water flow rate and the molten metal superheat (temperature difference between molten metal and saturated water) on the volumetric heat transfer coefficient were discussed

131

Identification of interfacial heat transfer between molten metal and green sand by inverse heat conduction method  

Science.gov (United States)

Heat flux and heat transfer coefficients at the interfaces of castings and molds are important parameters in the mold design and computer simulations of the solidification process in foundry operations. A better understanding of the heat flux and heat transfer coefficient between the solidifying casting and its mold can promote model design and improve the accuracy of computer simulation. The main purpose of the present dissertation involves the estimation of the heat flux and heat transfer coefficient at the interface of the molten metal and green sand. Since the inverse heat conduction method requires temperature measurement data to deduce the missing surface information, it is suitable for the present research. However, heat transfer inside green sand is complicated by the migration of water vapor and zonal temperature distribution results. This makes the solution of the inverse heat conduction problem more challenging. In this dissertation, Galerkin's method of Weighted Residual together with the front tracking technique is used in the development of a forward solver. Beck's future time step method incorporated with the Gaussian iterative minimization method is used as the inverse solver. The mathematical descriptions of the sensitivity coefficient for both the direct heat flux and direct heat transfer coefficient estimation are derived. The variations of the sensitivity coefficients with time are revealed. From the analysis of sensitivity coefficients, the concept of blank time period is proposed. This blank time period makes the inverse problem much more difficult. A total energy balance criterion is used to combat this. Numerical experiments confirmed the accuracy and robustness of both the direct heat flux estimation algorithm and the direct heat transfer coefficient estimation algorithm. Finally, some pouring experiments are carried out. The inverse algorithms are applied to the estimation of the heat flux and heat transfer coefficient at the interface of the molten metal and green sand with the input of measured temperature data from field experiments. The heat flux and heat transfer coefficient history at the interface of molten metal and green sand are obtained.

Ke, Quanpeng

132

Direct contact heat exchange interfacial phenomena for liquid metal reactors : Part I - heat transfer.  

Energy Technology Data Exchange (ETDEWEB)

Experiments on direct-contact heat exchange between molten metal and water for steam production were conducted. These experiments involved the injection of water into molten lead-bismuth eutectic for heat transfer measurements in a 1-D geometry. Based on the initial results of the experiments, the effects of the water flow rate and the molten metal superheat (temperature difference between molten metal and saturated water) on the volumetric heat transfer coefficient were discussed.

Cho, D.H.; Page, R.J.; Hurtault, D.; Abdulla, S.; Liu, X.; Anderson, M.H.; Bonazza, R.; Corradini, M.

2002-02-26

133

Electron transfer and reaction mechanism of laccases.  

Science.gov (United States)

Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme. PMID:25572295

Jones, Stephen M; Solomon, Edward I

2015-03-01

134

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

Science.gov (United States)

...Documents. Prices of new books are listed in the first FEDERAL...CFPB-2011-0009] RIN 3170-AA15 Electronic Fund Transfers (Regulation...6194), which implements the Electronic Fund Transfer Act, and the...in the interim final rule, Electronic Fund Transfers...

2012-07-10

135

Promoting Interspecies Electron Transfer with Biochar  

Science.gov (United States)

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

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

2014-01-01

136

Promoting interspecies electron transfer with biochar  

DEFF Research Database (Denmark)

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

Chen, Shanshan; Rotaru, Amelia-Elena

2014-01-01

137

Long-Range Electron Transfer and Electronic Transport Through Macromolecules  

CERN Document Server

A theory of electrical transport through molecular wires is used to estimate the electronic factor in the intramolecular electron transfer (ET) in porphyrin-nitrobenzene supermolecules, and to analyze its structure. The chosen molecules have complex donor and acceptor configurations, and relatively simple structure of the bridge, which enables us to concentrate our studies on the donor/acceptor coupling to the bridge. We present analytical and numerical results concerning the effect of donor/acceptor coupling to the bridge on the ET process in molecules with complex donor/acceptor subsystems. PACS 05.60.Gg, 36.20.-r

Zimbovskaya, N A; Zimbovskaya, Natalya; Gumbs, Godfrey

2002-01-01

138

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

Science.gov (United States)

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.

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

2009-12-01

139

Photoinduced electron transfer in ordered polymers  

Energy Technology Data Exchange (ETDEWEB)

The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and Photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of cationic organic dyes to a peptide electrolyte, for which cooperative dye loading and helix formation is important; (3) the completion of work on a new series of acridinium chromophores that have rod-like'' arrangements of linked aryl rings for assembly of electron donor-acceptor systems that exhibit long lived charge separation; and (4) use of the modified form of the peptide, poly-L-histidine, as a template for sulfide oxidation.

Jones, G. II.

1993-01-01

140

Interfacial wave effects on heat transfer to a falling liquid film  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Experiments were performed to provide insight into the heat transfer aspects of a wavy liquid film. Local film thickness and liquid temperature were measured simultaneously using a thermal conductance thickness probe and fast response thermocouples as the wavy film fell over an electrically heated wall. Liquid temperature at a fixed distance from the wall generally increased in the thin substrate portion of the film and decreased within the large waves. Temperature showed complex excursions w...

Lyu, Tae-hwan

1990-01-01

 
 
 
 
141

An approach for an advanced anode interfacial layer with electron-blocking ability to achieve high-efficiency organic photovoltaics.  

Science.gov (United States)

The interfacial properties of PEDOT:PSS, pristine r-GO, and r-GO with sulfonic acid (SR-GO) in organic photovoltaic are investigated to elucidate electron-blocking property of PEDOT:PSS anode interfacial layer (AIL), and to explore the possibility of r-GO as electron-blocking layers. The SR-GO results in an optimized power conversion efficiency of 7.54% for PTB7-th:PC71BM and 5.64% for P3HT:IC61BA systems. By combining analyses of capacitance-voltage and photovoltaic-parameters dependence on light intensity, it is found that recombination process at SR-GO/active film is minimized. In contrast, the devices using r-GO without sulfonic acid show trap-assisted recombination. The enhanced electron-blocking properties in PEDOT:PSS and SR-GO AILs can be attributed to surface dipoles at AIL/acceptor. Thus, for electron-blocking, the AIL/acceptor interface should be importantly considered in OPVs. Also, by simply introducing sulfonic acid unit on r-GO, excellent contact selectivity can be realized in OPVs. PMID:25343490

Yeo, Jun-Seok; Yun, Jin-Mun; Kang, Minji; Khim, Dongyoon; Lee, Seung-Hoon; Kim, Seok-Soon; Na, Seok-In; Kim, Dong-Yu

2014-11-26

142

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

Directory of Open Access Journals (Sweden)

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.

GUO Zhi-peng

2007-02-01

143

Electron transfer pathways in microbial oxygen biocathodes  

International Nuclear Information System (INIS)

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 ?M 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.

144

Mediated Electron Transfer at Redox Active Monolayers  

Directory of Open Access Journals (Sweden)

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.

Michael E.G. Lyons

2001-12-01

145

Quantum tunneling resonant electron transfer process in Lorentzian plasmas  

Energy Technology Data Exchange (ETDEWEB)

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

Hong, Woo-Pyo [Department of Electronics Engineering, Catholic University of Daegu, Hayang 712-702 (Korea, Republic of); Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr [Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New York 12180-3590 (United States); Department of Applied Physics and Department of Bionanotechnology, Hanyang University, Ansan, Kyunggi-Do 426-791 (Korea, Republic of)

2014-08-15

146

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

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 (I...

Guo, Zhi-peng; Xiong, Shou-mei

2007-01-01

147

Transfer line TT70 (electrons from PS to SPS)  

CERN Multimedia

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

1981-01-01

148

Electronic excitation transfer in concentrated micelle solutions  

International Nuclear Information System (INIS)

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. Followinsively 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

149

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

International Nuclear Information System (INIS)

The oxidative half-reaction of electron-transfer flavoprotein (ETF), electron transfer from ETF to electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO), is dependent on complementary surface charges on the two proteins. ETF is the positively charged member of the redox pair. The evidence is based on the pH and ionic strength dependencies of the comproportionation of oxidized ETF and ETF hydroquinone catalyzed by ETF-QO and on the effects of chemical modification of ETF on the comproportionation reaction. Acetylation of one and five epsilon-amino groups of lysyl residues results in 3- and 13-fold increases, respectively, in the K/sub m/ of ETF-QO for ETF but no change in V/sub max/. Amidination, which maintains positive charge at modified loci, has no effect on steady-state kinetic constants. These chemical modifications have no effect on the equilibrium constant for equilibration of ETF redox states. The K/sub m/ of ETF-QO for ETF is pH dependent above pH 8.5, suggesting titration of lysyl residues. The ionic strength dependence of TN/KmETF for the reaction follows the limiting Bronsted equation. The ETF-QO-catalyzed comproportionation reaction exhibits a primary deuterium isotope effect in D2O, perhaps indicating the participation of solvent water in the electron-transfer reaction

150

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

Science.gov (United States)

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.

Bascom, Willard D.; Lee, Ilzoo

1988-01-01

151

Interfacial Properties of Monolayer and Bilayer MoS2 Contacts with Metals: Depressed Many-electron Effects  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Although many devices based on MoS2 have been fabricated, where MoS2-metal contact plays a critical role, the nature of MoS2-metal contact has not been well established yet. We provide the first comparative study of the interfacial properties of a series of monolayer (ML) and bilayer (BL) MoS2-metal contacts (metal = Sc, Ti, Ag, Pt, Ni, and Au) with inclusion of many-electron effects based on a dual interface model. A comparison between the calculated and observed Schottky b...

Zhong, Hongxia; Ni, Zeyuan; Wang, Yangyang; Ye, Meng; Song, Zhigang; Pan, Yuanyuan; Quhe, Ruge; Yang, Jinbo; Yang, Li; Shi, Junjie; Lu, Jing

2015-01-01

152

Electron transfer in gas surface collisions  

International Nuclear Information System (INIS)

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.)

153

Charge transfer: An electronic bath approach  

International Nuclear Information System (INIS)

A charge transfer theory is developed for systems in which an atom, molecule, or ion interacts for a period of time with a substrate. The Hamiltonian of the system is taken to be one-electron and the nuclear motion of the substrate is ignored. The theory is structured so as to mimic generalized Langevin theory; namely, the equations of motion for annihilation operators of spin orbitals localized at the interaction site are developed such that a primary zone is defined with the remainder of the substrate being included through a memory kernel and a driving term. An electronic bath approximation is presented which leads to equations of motion for the occupation numbers of spin orbitals in the primary zone. These equations have the property that primary-zone occupation numbers damp to an equilibrium state at long time independent of their initial values. Specific application to a substrate modeled as a semi-infinite, Huckel chain is presented and numerical results are obtained. The electronic bath approximation is found to produce results in agreement with numerically exact data

154

Interfacial wicking dynamics and its impact on critical heat flux of boiling heat transfer  

Science.gov (United States)

Morphologically driven dynamic wickability is essential for determining the hydrodynamic status of solid-liquid interface. We demonstrate that the dynamic wicking can play an integral role in supplying and propagating liquid through the interface, and govern the critical heat flux (CHF) against surface dry-out during boiling heat transfer. For the quantitative control of wicking, we manipulate the characteristic lengths of hexagonally arranged nanopillars within sub-micron range through nanosphere lithography combined with top-down metal-assisted chemical etching. Strong hemi-wicking over the manipulated interface (i.e., wicking coefficients) of 1.28 mm/s0.5 leads to 164% improvement of CHF compared to no wicking. As a theoretical guideline, our wickability-CHF model can make a perfect agreement with improved CHF, which cannot be predicted by the classic models pertaining to just wettability and roughness effects, independently.

Kim, Beom Seok; Lee, Hwanseong; Shin, Sangwoo; Choi, Geehong; Cho, Hyung Hee

2014-11-01

155

Determination of the Magnitude of Interfacial Air-gap and Heat Transfer during Ingot Casting into Permanent Metal Moulds by Numerical and Experimental Techniques  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Numerically and experimentally the size of the casting-mould air-gap was investigated for the aluminium alloy LM25 cast into a cylindrical H13 steel mould. The air-gap significantly affects the magnitude of heat transfer. A numerical model has been developed to predict the size of the air-gap and the temperature distribution along the metal-mould interface given an initial Interfacial Heat Transfer Coefficient (IHTC), dependent on the mould surface roughness, and sufficient knowledge of the r...

Swan, J.; Ward, Rm; Reed, Rc

2013-01-01

156

Nanoparticles: toxicity, radicals, electron transfer, and antioxidants.  

Science.gov (United States)

In recent years, nanoparticles have received increasing attention in research and technology, including a variety of practical applications. The bioactivity appears to be related to the small particle size, in addition to inherent chemical activity as electron transfer (ET) agents, generators of reactive oxygen species (ROS) with subsequent oxidative stress (OS), and as antioxidants (AOs). The mechanism of toxicity, therapeutic action, and AO property is addressed based on the ET-ROS-OS approach. There are several main classes of ET functionalities, namely, quinones (or phenolic precursors), metal compounds, aromatic nitro compounds (or reduction products), and imine or iminium species. Most of the nanospecies fall within the metal category. Cell signaling is also discussed. This review discusses recent developments based on ET-ROS-OS-AO framework. PMID:23740111

Kovacic, Peter; Somanathan, Ratnasamy

2013-01-01

157

Direct electron transfer based enzymatic fuel cells  

International Nuclear Information System (INIS)

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

158

Dynamics of Electron Transfer Pathways in Cytochrome c Oxidase  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Cytochrome c oxidase mediates the final step of electron transfer reactions in the respiratory chain, catalyzing the transfer between cytochrome c and the molecular oxygen and concomitantly pumping protons across the inner mitochondrial membrane. We investigate the electron transfer reactions in cytochrome c oxidase, particularly the control of the effective electronic coupling by the nuclear thermal motion. The effective coupling is calculated using the Green's function technique with an ext...

Tan, Ming-liang; Balabin, Ilya; Onuchic, Jose? Nelson

2004-01-01

159

Single and Accumulative Electron Transfer – Prerequisites for Artificial Photosynthesis  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Photoinduced electron transfer is involved in a number of photochemical and photobiological processes. One example of this is photosynthesis, where the absorption of sunlight leads to the formation of charge-separated states by electron transfer. The redox equivalents built up by successive photoabsorption and electron transfer is further used for the oxidation of water and reduction of carbon dioxide to sugars. The work presented in this thesis is part of an interdisciplinary effort aiming a...

Karlsson, Susanne

2010-01-01

160

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

International Nuclear Information System (INIS)

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 ?1-like and ?5-like symmetries

 
 
 
 
161

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

Energy Technology Data Exchange (ETDEWEB)

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 ?{sub 1}-like and ?{sub 5}-like symmetries.

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

162

Evidence of short-range electron transfer of a redox enzyme on graphene oxide electrodes.  

Science.gov (United States)

Direct electron transfer (DET) between redox enzymes and electrode surfaces is of growing interest and an important strategy in the development of biofuel cells and biosensors. Among the nanomaterials utilized at electrode/enzyme interfaces to enhance the electronic communication, graphene oxide (GO) has been identified as a highly promising candidate. It is postulated that GO layers decrease the distance between the flavin cofactor (FAD/FADH2) of the glucose oxidase enzyme (GOx) and the electrode surface, though experimental evidence concerning the distance dependence of the rate constant for heterogeneous electron-transfer (k(het)) has not yet been observed. In this work, we report the experimentally observed DET of the GOx enzyme adsorbed on flexible carbon fiber (FCF) electrodes modified with GO (FCF-GO), where the k(het) between GO and electroactive GOx has been measured at a structurally well-defined interface. The curves obtained from the Marcus theory were used to obtain k(het), by using the model proposed by Chidsey. In agreement with experimental data, this model proved to be useful to systematically probe the dependence of electron transfer rates on distance, in order to provide an empirical basis to understand the origin of interfacial DET between GO and GOx. We also demonstrate that the presence of GO at the enzyme/electrode interface diminishes the activation energy by decreasing the distance between the electrode surface and FAD/FADH2. PMID:24676540

Martins, Marccus V A; Pereira, Andressa R; Luz, Roberto A S; Iost, Rodrigo M; Crespilho, Frank N

2014-09-01

163

Electron transfer reactions of metal complexes in solution  

International Nuclear Information System (INIS)

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

164

Reactions involving electron transfer at semiconductor surfaces  

International Nuclear Information System (INIS)

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)

165

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

Science.gov (United States)

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.

Krishna, Prasad

2001-08-01

166

Nanoscopic heterogeneities in adsorption and electron transfer processes of perylene diimide dye on TiO 2 nanoparticles studied by single-molecule fluorescence spectroscopy  

Science.gov (United States)

The interfacial electron transfer processes between a fluorescent water-soluble perylene diimide dye (WS-PDI) and TiO 2 nanoparticles were investigated using single-molecule fluorescence spectroscopy. Based on the single-molecule fluorescence spectral measurements, it was suggested that the local environment and/or the structural conformation of single WS-PDI molecules play important roles in the efficiency of the electron injection from WS-PDI in the singlet excited state to TiO 2. The observed single-molecule fluorescence blinking behavior was interpreted in terms of the interfacial electron-transfer dynamics between the single WS-PDI molecules and TiO 2 nanoparticles.

Tachikawa, Takashi; Cui, Shi-Cong; Tojo, Sachiko; Fujitsuka, Mamoru; Majima, Tetsuro

2007-08-01

167

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

Energy Technology Data Exchange (ETDEWEB)

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.

Fox, M.A.

1997-01-01

168

Electron transfer processes in photosynthetics biological systems  

International Nuclear Information System (INIS)

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 ondon 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

169

Electron and hole transfer from indium phosphide quantum dots.  

Science.gov (United States)

Electron- and hole-transfer reactions are studied in colloidal InP quantum dots (QDs). Photoluminescence quenching and time-resolved transient absorption (TA) measurements are utilized to examine hole transfer from photoexcited InP QDs to the hole acceptor N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) and electron transfer to nanocrystalline titanium dioxide (TiO2) films. Core-confined holes are effectively quenched by TMPD, resulting in a new approximately 4-ps component in the TA decay. It is found that electron transfer to TiO2 is primarily mediated through surface-localized states on the InP QDs. PMID:16851267

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

2005-02-24

170

Photoinduced Electron-transfer Reaction of Pentafluoroiodobenzene with Alkenes  

Directory of Open Access Journals (Sweden)

Full Text Available Irradiation of pentafluoroiodobenzene and alkenes gave the corresponding adducts. The presence of single electron-transfer scavengers, (p-dinitrobenzene and t-Bu2NO and the free radical inhibitor (hydroquinone suppressed the reaction. A photoinduced electron-transfer mechanism is proposed.

Qing-Yun Chen

1997-01-01

171

76 FR 29901 - Electronic Fund Transfers  

Science.gov (United States)

...often the consumer's country of origin. Traditional...transfers varies widely, in part because of the difficulty...subject population, and in part because of differences...transfers worldwide to developing countries reached $325...

2011-05-23

172

Correlation of interfacial electronic structures and transport properties in organic light emitting diodes  

Science.gov (United States)

Turn on voltage in the current density-voltage characteristics is one of the important factors to evaluate the performance of organic light emitting diodes (OLEDs). In this paper, we report investigation of the origins of turn-on voltage, defined at where log J (current density) has a sharp rise and starts to increase dramatically. In OLEDs with NPB as the hole transport layer (HTL) and Alq3 as the electron transport layer (ETL), we find that the turn on voltage is always at 2V, regardless the cathode structures, such as Ca, Al, LiF/Al, and Cs2CO3/Al, being used. The turn on voltage is also independent on the thickness of organic layers. Beside NPB and Alq3, we also study the J-V characteristics on OLEDs with various combinations of HTLs and ETLs. In all the devices investigated, the turn on voltage just equals to the difference between the LUMO of ETL and the HOMO of HTL, taking into consideration of vacuum level shift at organic interfaces measured from the ultraviolet photoemission spectroscopy (UPS). Combined with J-V characteristics of OLEDs and UPS measurement, we propose that the turn on voltage of organic light emitting devices is determined by the difference between LUMO of ETL and HOMO of HTL and is independent of the cathode and thickness of organic layers. We also found that the charge transfers at the interface of ETL/HTL play an important role to the turn on voltage of OLEDs.

Wu, I.-Wen; Chen, Yu-Hung; Wang, Chao-Kung; Wu, Chih-I.

2009-08-01

173

Activation entropy of electron transfer reactions  

International Nuclear Information System (INIS)

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

174

Electron transfer from cytochrome c to cupredoxins.  

Science.gov (United States)

Electron transfer (ET) through and between proteins is a fundamental biological process. The activation energy for an ET reaction depends upon the Gibbs energy change upon ET (DeltaG(0)) and the reorganization energy. Here, we characterized ET from Pseudomonas aeruginosa cytochrome c(551) (PA) and its designed mutants to cupredoxins, Silene pratensis plastocyanin (PC) and Acidithiobacillus ferrooxidans rusticyanin (RC), through measurement of pseudo-first-order ET rate constants (k(obs)). The influence of the DeltaG (0) value for ET from PA to PC or RC on the k(obs) value was examined using a series of designed PA proteins exhibiting a variety of E (m) values, which afford the DeltaG (0) variation range of 58-399 meV. The plots of the k(obs) values obtained against the DeltaG(0) values for both PA-PC and PA-RC redox pairs could be fitted well with a single Marcus equation. We have shown that the ET activity of cytochrome c can be controlled by tuning the E(m) value of the protein through the substitution of amino acid residues located in hydrophobic-core regions relatively far from the redox center. These findings provide novel insights into the molecular design of cytochrome c, which could be utilized for controlling its ET activity by means of protein engineering. PMID:19294434

Takayama, Shin-ichi J; Irie, Kiyofumi; Tai, Hulin; Kawahara, Takumi; Hirota, Shun; Takabe, Teruhiro; Alcaraz, Luis A; Donaire, Antonio; Yamamoto, Yasuhiko

2009-08-01

175

Kinetics of electron transfer between semiquinones and stable radicals  

International Nuclear Information System (INIS)

The interaction of semiquinone and stable nitroxyl radicals has been studied in modeling radiosensitization processes. Bimolecular radical reactions which proceed through one-electron transfer are of interest for the information which they furnish concerning radical reactions, in general, and charge-transfer processes, in particular. The present work used flash photolysis to study the kinetics of electron transfer between semiquinone (Q-/sup ./, QH/sup ./), nitroxyl, and triphenylverdazyl radicals in aqueous and aqueous organic solution

176

Electron Transfer in Porphyrin Complexes in Different Solvents  

CERN Document Server

The electron transfer in different solvents is investigated for systems consisting of donor, bridge and acceptor. It is assumed that vibrational relaxation is much faster than the electron transfer. Electron transfer rates and final populations of the acceptor state are calculated numerically and in an approximate fashion analytically. In wide parameter regimes these solutions are in very good agreement. The theory is applied to the electron transfer in ${\\rm H_2P-ZnP-Q}$ with free-base porphyrin (${\\rm H_2P}$) being the donor, zinc porphyrin (${\\rm ZnP}$) the bridge, and quinone (${\\rm Q}$) the acceptor. It is shown that the electron transfer rates can be controlled efficiently by changing the energy of the bridging level which can be done by changing the solvent. The effect of the solvent is determined for different models.

Kilin, D S; Schreiber, M

2000-01-01

177

Condensation of two-dimensional oxide-interfacial charges into one-dimensional electron chains by the misfit-dislocation strain field.  

Science.gov (United States)

The success of semiconductor technology is largely ascribed to controlled impacts of strains and defects on the two-dimensional interfacial charges. Interfacial charges also appear in oxide heterojunctions such as LaAlO3/SrTiO3 and (Nd0.35Sr0.65)MnO3/SrTiO3. How the localized strain field of one-dimensional misfit dislocations, defects resulting from the intrinsic misfit strains, would affect the extended oxide-interfacial charges is intriguing and remains unresolved. Here we show the atomic-scale observation of one-dimensional electron chains formed in (Nd0.35Sr0.65)MnO3/SrTiO3 by the condensation of characteristic two-dimensional interfacial charges into the strain field of periodically arrayed misfit dislocations, using chemical mapping and quantification by scanning transmission electron microscopy. The strain-relaxed inter-dislocation regions are readily charge depleted, otherwise decorated by the pristine charges, and the corresponding total-energy calculations unravel the undocumented charge-reservoir role played by the dislocation-strain field. This two-dimensional-to-one-dimensional electronic condensation represents a novel electronic-inhomogeneity mechanism at oxide interfaces and could stimulate further studies of one-dimensional electron density in oxide heterostructures. PMID:24663109

Chang, C-P; Chu, M-W; Jeng, H T; Cheng, S-L; Lin, J G; Yang, J-R; Chen, C H

2014-01-01

178

Influence of the electron-phonon interfacial conductance on the thermal transport at metal/dielectric interfaces.  

Science.gov (United States)

Thermal boundary conductance at a metal-dielectric interface is a quantity of prime importance for heat management at the nanoscale. While the boundary conductance is usually ascribed to the coupling between metal phonons and dielectric phonons, in this work we examine the influence of a direct coupling between the metal electrons and the dielectric phonons. The effect of electron-phonon processes is generally believed to be resistive and tends to decrease the overall thermal boundary conductance as compared to the phonon-phonon conductance ?p. Here, we find that the effect of a direct electron-phonon interfacial coupling ?e is to enhance the effective thermal conductance between the metal and the dielectric. Resistive effects turn out to be important only for thin films of metals that have a low electron-phonon coupling strength. Two approaches are explored to reach these conclusions. First, we present an analytical solution of the two-temperature model to compute the effective conductance which accounts for all the relevant energy channels, as a function of ?e, ?p and the electron-phonon coupling factor G. Second, we use numerical resolution to examine the influence of ?e on two realistic cases: a gold film on silicon or silica substrates. We point out the implications for the interpretation of time-resolved thermoreflectance experiments. PMID:25425559

Lombard, J; Detcheverry, F; Merabia, S

2015-01-14

179

Influence of the electron–phonon interfacial conductance on the thermal transport at metal/dielectric interfaces  

Science.gov (United States)

Thermal boundary conductance at a metal-dielectric interface is a quantity of prime importance for heat management at the nanoscale. While the boundary conductance is usually ascribed to the coupling between metal phonons and dielectric phonons, in this work we examine the influence of a direct coupling between the metal electrons and the dielectric phonons. The effect of electron–phonon processes is generally believed to be resistive and tends to decrease the overall thermal boundary conductance as compared to the phonon–phonon conductance ?p. Here, we find that the effect of a direct electron-phonon interfacial coupling ?e is to enhance the effective thermal conductance between the metal and the dielectric. Resistive effects turn out to be important only for thin films of metals that have a low electron–phonon coupling strength. Two approaches are explored to reach these conclusions. First, we present an analytical solution of the two-temperature model to compute the effective conductance which accounts for all the relevant energy channels, as a function of ?e, ?p and the electron–phonon coupling factor G. Second, we use numerical resolution to examine the influence of ?e on two realistic cases: a gold film on silicon or silica substrates. We point out the implications for the interpretation of time-resolved thermoreflectance experiments.

Lombard, J.; Detcheverry, F.; Merabia, S.

2015-01-01

180

Electron transfer in organic glass. Distance and energy dependence  

International Nuclear Information System (INIS)

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

 
 
 
 
181

Interfacial Chemistry and the Design of Solid-Phase Nucleic Acid Hybridization Assays Using Immobilized Quantum Dots as Donors in Fluorescence Resonance Energy Transfer  

Directory of Open Access Journals (Sweden)

Full Text Available The use of quantum dots (QDs as donors in fluorescence resonance energy transfer (FRET offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD and enabling the regeneration and reuse of solid-phase QD-FRET hybridization assays. FRET-sensitized emission from acceptor dyes associated with hybridization events at immobilized QD donors provides the analytical signal in these assays. The minimization of active sensing area reduces background from QD donor PL and allows the resolution of smaller amounts of acceptor emission, thus lowering the LOD. The association of multiple acceptor dyes with each hybridization event can enhance FRET efficiency, thereby improving sensitivity. Many previous studies have used interfacial protein layers to generate selectivity; however, transient destabilization of these layers is shown to prevent efficient regeneration. To this end, we report a protein-free interfacial chemistry and demonstrate the specific detection of as little as 2 pmol of target, as well as an improved capacity for regeneration.

Ulrich J. Krull

2011-06-01

182

Electron transfer in proteins : in search of preferential pathways  

DEFF Research Database (Denmark)

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 distance and nature of the microenvironment separating the reactants) thermodynamic driving force and the configurational changes required upon reaction. Several of these aspects are addressed in this review, which is based primarily on recent work performed by the authors on model systems of blue copper-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.

Farver, O; Pecht, I

1991-01-01

183

Charge Transfer, Energy-level ''Lineup'' and Transmission in Molecular Electronic Devices  

Science.gov (United States)

There has been strong interest and significant progress in measuring electron transport through single molecules, due to their potential use in future molecular nanotechnology. Such molecular electronic devices usually involve the adsorption of single or a small group of molecules onto two large metallic electrodes. Understanding the electronic property of such metal-molecule-metal systems at equilibrium therefore provides the starting point for understanding their property under nonzero bias. We present first-principle based calculation of some equilibrium properties of the molecular device formed by a phenyldithiolate molecule bridging two gold electrodes, i.e., charge transfer, energy-level ''lineup'' and transmission. In contrast to previous works, we have used local-spin-density-functional theory with a Gaussian-type orbital basis, which not only allows us to use established techniques in molecular electronic structure theory but also to rationalize the result of computation in terms of the familiar language of bonding and orbital interactions in chemistry. We show that significant charge transfer from the metal to the molecule occurs, involving mostly the end sulfur atoms and localized in the interfacial region. Such charge transfer increases the electrostatic potential in the molecule thus changing the energy level structure and the corresponding charge distribution within the molecule. The interaction between the resulting molecular orbitals and the surface metal states determines the lineup of molecular levels relative to the metal Fermi-level and the transmission through the molecule. Our work also points to the importance of interface ''engineering'' for controlling the charge transfer and therefore the energy-level ''lineup'' in molecular electronic devices.

Xue, Yongqiang; Datta, Supriyo; Ratner, Mark

2001-03-01

184

Photoinduced electron transfer from a fundamental understanding to potential applications  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Although the transfer of an electron from a donor to an acceptor after one of them has been electronically excited by the absorption of light appears to be a very simple reaction, there are still many open questions concerning the detailed mechanism of photoinduced electron transfer. It is nevertheless a fascinating and very important reaction, given its key importance in photosynthesis and many modern approaches to solar energy conversion. The objective of this PhD thesis was thus to use ult...

Banerji, Nathalie Renuka

2009-01-01

185

Shewanella secretes flavins that mediate extracellular electron transfer  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Bacteria able to transfer electrons to metals are key agents in biogeochemical metal cycling, subsurface bioremediation, and corrosion processes. More recently, these bacteria have gained attention as the transfer of electrons from the cell surface to conductive materials can be used in multiple applications. In this work, we adapted electrochemical techniques to probe intact biofilms of Shewanella oneidensis MR-1 and Shewanella sp. MR-4 grown by using a poised electrode as an electron acc...

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

2008-01-01

186

A Simple Marcus-Theory Type Model for Hydrogen Atom Transfer/Proton-Coupled Electron Transfer  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Hydrogen atom transfer reactions are the simplest class of proton-coupled electron transfer (PCET) processes. These reactions involve transfer of one electron and one proton from one reagent to another, in the same kinetic step: XH + Y ? X + HY. A predictive model for these reactions based on the Marcus cross relation is described. The model predicts rate constants within one or two orders of magnitude in most cases, over a very wide range of reactants and solvents. This remarkable result i...

Mayer, James M.

2011-01-01

187

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

Science.gov (United States)

Well-designed hierarchical nanostructures with one dimensional (1D) TiO(2) nanofibers (120-350 nm in diameter and several micrometers in length) and ultrathin hexagonal SnS(2) nanosheets (40-70 nm in lateral size and 4-8 nm in thickness) were successfully synthesized by combining the electrospinning technique (for TiO(2) nanofibers) and a hydrothermal growth method (for SnS(2) nanosheets). The single-crystalline SnS(2) nanosheets with a 2D layered structure were uniformly grown onto the electrospun TiO(2) nanofibers consisted of either anatase (A) phase or anatase-rutile (AR) mixed phase TiO(2) nanoparticles. The definite heterojunction interface between SnS(2) nanosheets and TiO(2) (A or R) nanoparticles were investigated by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Moreover, the as-prepared SnS(2)/TiO(2) 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 TiO(2) nanofibers and the SnS(2) nanosheets, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the SnS(2)/TiO(2) heterojunction. Significantly, the SnS(2)/TiO(2) (AR) hierarchical nanostructures as the tricomponent heterojunction system possessed stronger photocatalytic activity than the bicomponent heterojunction system of SnS(2)/TiO(2) (A) hierarchical nanostructures or TiO(2) (AR) nanofibers, which was discussed in terms of the three-way photosynergistic effect between SnS(2), TiO(2) (A) and TiO(2) (R) component in the SnS(2)/TiO(2) (AR) heterojunction resulting in the high separation efficiency of photoinduced electron-hole pairs, as evidenced by photoluminescence (PL) and surface photovoltage spectra (SPS). PMID:23202888

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

2013-01-21

188

Heat Transfer Augmentation for Electronic Cooling  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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 impingeme...

Suabsakul Gururatana

2012-01-01

189

Electronic Publishing and the Information Transfer Process.  

Science.gov (United States)

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)

Aveney, Brian

1983-01-01

190

Dissociative electron attachment and charge transfer in condensed matter  

International Nuclear Information System (INIS)

Experiments using energy-selected beams of electrons incident from vacuum upon thin vapour deposited solids show that, as in the gas-phase, scattering cross sections at low energies are dominated by the formation of temporary negative ions (or resonances) and that molecular damage may be effected via dissociative electron attachment (DEA). Recent results also show that charge transfer between anionic states of target molecules and their environment is often crucial in determining cross sections for electron driven processes. Here, we review recent work from our laboratory, in which charge transfer is observed. For rare gas solids, electron exchange between the electron-exciton complex and either a metal substrate or co-adsorbed molecule enhances the desorption of metastable atoms and/or molecular dissociation. We discuss how transient electron capture by surface electron states of a substrate and subsequent electron transfer to a molecular adsorbate enhances the effective cross sections for DEA. We also consider the case of DEA to CF2Cl2 condensed on water and ammonia ices, where electron exchange between pre-solvated electron states of ice and transient molecular anions can also increase DEA cross sections. Electron transfer from molecular resonances into pre-solvated electron states of ice is also discussed

191

Understanding the mechanism of short-range electron transfer using an immobilized cupredoxin.  

Science.gov (United States)

The hydrophobic patch of azurin (AZ) from Pseudomonas aeruginosa is an important recognition surface for electron transfer (ET) reactions. The influence of changing the size of this region, by mutating the C-terminal copper-binding loop, on the ET reactivity of AZ adsorbed on gold electrodes modified with alkanethiol self-assembled monolayers (SAMs) has been studied. The distance-dependence of ET kinetics measured by cyclic voltammetry using SAMs of variable chain length, demonstrates that the activation barrier for short-range ET is dominated by the dynamics of molecular rearrangements accompanying ET at the AZ-SAM interface. These include internal electric field-dependent low-amplitude protein motions and the reorganization of interfacial water molecules, but not protein reorientation. Interfacial molecular dynamics also control the kinetics of short-range ET for electrostatically and covalently immobilized cytochrome c. This mechanism therefore may be utilized for short-distance ET irrespective of the type of metal center, the surface electrostatic potential, and the nature of the protein-SAM interaction. PMID:22788731

Monari, Stefano; Battistuzzi, Gianantonio; Bortolotti, Carlo A; Yanagisawa, Sachiko; Sato, Katsuko; Li, Chan; Salard, Isabelle; Kostrz, Dorota; Borsari, Marco; Ranieri, Antonio; Dennison, Christopher; Sola, Marco

2012-07-25

192

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

Energy Technology Data Exchange (ETDEWEB)

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.)

Staehler, A.J.

2007-05-15

193

Quinone methide generation via photoinduced electron transfer.  

Science.gov (United States)

Photochemical activation of water-soluble 1,8-naphthalimide derivatives (NIs) as alkylating agents has been achieved by irradiation at 310 and 355 nm in aqueous acetonitrile. Reactivity in aqueous and neat acetonitrile has been extensively investigated by laser flash photolysis (LFP) at 355 nm, as well as by steady-state preparative irradiation at 310 nm in the presence of water, amines, thiols, and ethyl vinyl ether. Product distribution analysis revealed fairly efficient benzylation of the amines, hydration reaction, and 2-ethoxychromane generation, in the presence of ethyl vinyl ether, resulting from a [4 + 2] cycloaddition onto a transient quinone methide. Remarkably, we found that the reactivity was dramatically suppressed under the presence of oxygen and radical scavengers, such as thiols, which was usually associated with side product formation. In order to unravel the mechanism responsible for the photoreactivity of these NI-based molecules, a detailed LFP study has been carried out with the aim to characterize the transient species involved. LFP data suggest a photoinduced electron transfer (PET) involving the NI triplet excited state (?(max) 470 nm) of the NI core and the tethered quinone methide precursor (QMP) generating a radical ions pair NI(•-) (?(max) 410 nm) and QMP(•+). The latter underwent fast deprotonation to generate a detectable phenoxyl radical (?(max) 390 and 700 nm), which was efficiently reduced by the radical anion NI(•-), generating detectable QM. The mechanism proposed has been validated through a LFP investigation at 355 nm exploiting an intermolecular reaction between the photo-oxidant N-pentylnaphthalimide (NI-P) and a quaternary ammonium salt of a Mannich base as QMP (2a), in both neat and aqueous acetonitrile. Remarkably, these experiments revealed the generation of the model o-QM (?(max) 400 nm) as a long living transient mediated by the same reactivity pathway. Negligible QM generation has been observed under the very same conditions by irradiation of the QMP in the absence of the NI. Owing to the NIs redox and recognition properties, these results represent the first step toward new molecular devices capable of both biological target recognition and photoreleasing of QMs as alkylating species, under physiological conditions. PMID:21425810

Percivalle, Claudia; La Rosa, Andrea; Verga, Daniela; Doria, Filippo; Mella, Mariella; Palumbo, Manlio; Di Antonio, Marco; Freccero, Mauro

2011-05-01

194

Versatile electron-collecting interfacial layer by in situ growth of silver nanoparticles in nonconjugated polyelectrolyte aqueous solution for polymer solar cells.  

Science.gov (United States)

Novel PEIE-Ag composites by in situ growth of silver nanoparticles in poly(ethylenimine)-ethoxylated (PEIE) aqueous solution are explored as an efficient interfacial layer for improving inverted polymer solar cells (PSCs) performance. The hybrid PEIE-Ag interfacial material is simple to fabricate only via ultraviolet irradiation with good water-solubility and unique film formation. The generated Ag nanoparticles can anchor in the PEIE polymer chains to form a conductive continuous interpenetrating network structure. Combining of the advantages of PEIE and Ag nanoparticles, the PEIE-Ag shows enhanced charge transport, electron selective and collection, and improved light-harvesting, mainly due to the surface plasmon resonance effect, better energy alignment induced by the formation of ideal dipole layer, as well as the improved conductivity. These distinguished interfacial properties result in the power conversion efficiency of inverted PSCs based on poly[4,8-bis(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b]dithiophene-2,6-diyl]-alt-[2-(2-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl] (PBDTTT-C-T) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) photoactive layer substantially improved up to 7.66% from 6.11%. Moreover, the device performance is insensitively dependent on the thickness of the PEIE-Ag interfacial layer, broadening the thicknesses selection window for interfacial materials. These results demonstrate that PEIE-Ag is a potential interfacial material compatible with roll-to-roll techniques and suitable for printed electronic devices. PMID:25207753

Yuan, Kai; Chen, Lie; Chen, Yiwang

2014-10-01

195

Electron transfer dynamics using projected modes  

Digital Repository Infrastructure Vision for European Research (DRIVER)

For electron-phonon Hamiltonians with the couplings linear in the phonon operators we construct a class of unitary transformations that separate the normal modes into two groups. The modes in the first group interact with the electronic degrees of freedom directly. The modes in the second group interact directly only with the modes in the first group but not with the electronic system. We show that for the $n$-level electronic system the minimum number of modes in the first ...

Pereverzev, Andrey; Bittner, Eric R.

2008-01-01

196

Electronic Properties of MoS2/HfO2 Interface: Impact of Interfacial Impurities during Atomic Layer Deposition Growth  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Using ab-initio calculations within the framework of Density Functional Theory (DFT), atomic structures and electronic properties of MoS2/HfO2 interface are investigated. The impact of interfacial oxygen concentration on the MoS2/HfO2 interface electronic structure is examined in order to mimic the atomic layer deposition growth at ambient conditions. Then, the effect on band offsets and the thermodynamic stability of those interfaces is investigated and compared with availa...

Kc, Santosh; Longo, Roberto C.; Wallace, Robert M.; Cho, Kyeongjae

2014-01-01

197

Theory of electron transfer and ionization  

International Nuclear Information System (INIS)

The main effort reported is directed toward charge transfer and ionization in high energy atomic collisions. The research may be divided into classical trajectory calculations, quantum - mechanical collision theory, and phenomenological treatments of quantal interference effects in heavy ion collisions

198

27 CFR 25.165 - Payment of tax by electronic fund transfer.  

Science.gov (United States)

... false Payment of tax by electronic fund transfer. 25.165...ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE...165 Payment of tax by electronic fund transfer. (a) Eligible...bank in making payment by electronic fund transfer...

2010-04-01

199

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

Science.gov (United States)

... false Payment of tax by electronic fund transfer. 19.524...ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE...524 Payment of tax by electronic fund transfer. (a) General...bank in making payment by electronic fund transfer...

2010-04-01

200

27 CFR 53.158 - Payment of tax by electronic fund transfer.  

Science.gov (United States)

... false Payment of tax by electronic fund transfer. 53.158...ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE...158 Payment of tax by electronic fund transfer. (a) In...the taxes (taxpayments) by electronic fund transfer...

2010-04-01

 
 
 
 
201

12 CFR 205.15 - Electronic fund transfer of government benefits.  

Science.gov (United States)

...device to a consumer for use in initiating an electronic fund transfer...means of an electronic fund transfer...identity of the consumer receiving the...time of an electronic fund transfer...history of the consumer's...

2010-01-01

202

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

Science.gov (United States)

...2010-01-01 false Electronic fund transfer...not holding consumer's account...provides an electronic fund transfer service to a consumer but that does...describes each electronic fund transfer initiated by the consumer with...

2010-01-01

203

Electronic Structure and Vibrational Mode Study of Nafion Membrane Interfacial Water Interactions.  

Science.gov (United States)

The structural, energetic, and mid-infrared spectral properties of water clusters interacting with a model perfluorosulfonate (Nafion) ionomer segment have been investigated by means of quantum chemical calculations. Density functional theory calculations were conducted to model interfacial water condensed in pores and channels of Nafion and helped shedding light on the structural and vibrational properties of hydrated Nafion membranes. The computational models consisted of a sodium counterion, the Nafion ionomer, and a cluster of water molecules positioned in three different regions of the ionomer. The orientations of the water molecules in the vicinity of the ionomer were examined to understand the appearance of O-H stretching bands that deviated from the typical bulk water values as well as the appearance of multiple free O-H stretching bands. The calculations revealed insights into the structure, orientation, and energetics of Nafion and water clusters in and around the membrane interface; the results show that hydrogen atoms at the water-ionomer interface hydrogen bond to the hydrophilic sulfonate group as well as to the hydrophobic fluorinated backbone. PMID:25412259

Kabrane, Joseph; Aquino, Adelia J A

2014-12-01

204

Electron attachment step in electron capture dissociation (ECD) and electron transfer dissociation (ETD).  

Science.gov (United States)

We have made use of classical dynamics trajectory simultions and ab initio electronic structure calculations to estimate the cross sections with which electrons are attached (in electron capture dissociation (ECD)) or transferred (in electron transfer dissociation (ETD)) to a model system that contained both an S-S bond that is cleaved and a -NH(3)(+) positively charged site. We used a Landau-Zener-Stueckelberg curve-crossing approximation to estimate the ETD rates for electron transfer from a CH(3)(-) anion to the -NH(3)(+) Rydberg orbital or the S-S sigma* orbital. We draw conclusions about ECD from our ETD results and from known experimental electron-attachment cross sections for cations and sigma-bonds. We predict the cross section for ETD at the positive site of our model compound to be an order of magnitude larger than that for transfer to the Coulomb-stabilized S-S bond site. We also predict that, in ECD, the cross section for electron capture at the positive site will be up to 3 orders of magnitude larger than that for capture at the S-S bond site. These results seem to suggest that attachment to such positive sites should dominate in producing S-S bond cleavage in our compound. However, we also note that cleavage induced by capture at the positive site will be diminished by an amount that is related to the distance from the positive site to the S-S bond. This dimunition can render cleavage through Coulomb-assisted S-S sigma* attachment competitive for our model compound. Implications for ECD and ETD of peptides and proteins in which SS or N-C(alpha) bonds are cleaved are also discussed, and we explain that such events are most likely susceptible to Coulomb-assisted attachment, because the S-S sigma* and C=O pi* orbitals are the lowest-lying antibonding orbitals in most peptides and proteins. PMID:16833914

Anusiewicz, Iwona; Berdys-Kochanska, Joanna; Simons, Jack

2005-07-01

205

Theory of interrelated electron and proton transfer processes  

DEFF Research Database (Denmark)

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 nonadiabatic reactions are derived.

Kuznetsov, A.M.; Ulstrup, Jens

2003-01-01

206

Thermodynamics of electron transfer in Escherichia coli cytochrome bo3  

Digital Repository Infrastructure Vision for European Research (DRIVER)

The proton translocation mechanism of the Escherichia coli cytochrome bo3 complex is intimately tied to the electron transfers within the enzyme. Herein we evaluate two models of proton translocation in this enzyme, a cytochrome c oxidase-type ion-pump and a Q-cycle mechanism, on the basis of the thermodynamics of electron transfer. We conclude that from a thermodynamic standpoint, a Q-cycle is the more favorable mechanism for proton translocation and is likely occ...

Schultz, Brian E.; Chan, Sunney I.

1998-01-01

207

Single-molecule electron transfer reactions in nanomaterials  

Energy Technology Data Exchange (ETDEWEB)

Here we report the study of single molecule electron transfer dynamics by coupling fluorescence microscopy at a conventional electrochemical cell. The single-molecule fluorescence spectroelectrochemistry of cresyl violet in aqueous solution and on nanoparticle surface were studied. We observed that the single-molecule fluorescence intensity of cresyl violet is modulated synchronously with the cyclic voltammetric potential scanning. We attribute the fluorescence intensity change of single cresyl violet molecules to the electron transfer reaction driven by the electrochemical potential.

Hu, Dehong; Lei, Chenghong; Ackerman, Eric J.

2009-07-26

208

Photoinduced electron transfer from DABCO to trans-nitrostilbenes  

Science.gov (United States)

The anion radical of the trans isomers of 4-nitro-, 4,4'-dinitro-, and 4-nitro-4'-methoxystilbene was generated by triplet quenching with 1,4-diazabicyclo[2.2.2]octane (DABCO) in polar solvents at room temperature using laser flash photolysis. Electron transfer and trans ? cis photoisomerization are competing processes. The radical ions decay by electron back-transfer yielding the initial ground states.

Görner, Helmut; Schulte-Frohlinde, Dietrich

209

Laser pulse control of bridge mediated heterogeneous electron transfer  

International Nuclear Information System (INIS)

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.

210

Laser pulse control of bridge mediated heterogeneous electron transfer  

Science.gov (United States)

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.

Wang, Luxia; May, Volkhard

2009-06-01

211

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

International Nuclear Information System (INIS)

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

212

A self-doping, O{sub 2}-stable, n-type interfacial layer for organic electronics  

Energy Technology Data Exchange (ETDEWEB)

Solid films of a water-soluble dicationic perylene diimide salt, perylene bis(2-ethyltrimethylammonium hydroxide imide), Petma{sup +}OH{sup -}, are strongly doped n-type by dehydration and reversibly de-doped by hydration. The hydrated films consist almost entirely of the neutral perylene diimide, PDI, while the dehydrated films contain {proportional_to}50% PDI anions. The conductivity increases by five orders of magnitude upon dehydration, probably limited by film roughness, while the work function decreases by 0.74 V, consistent with an n-type doping density increase of {proportional_to}12 orders of magnitude. Remarkably, the PDI anions are stable in dry air up to 120 C. The work function of the doped film, {phi} (3.96 V vs. vacuum), is unusually negative for an O{sub 2}-stable contact. Petma{sup +}OH{sup -} is also characterized as an interfacial layer, IFL, in two different types of organic photovoltaic cells. Results are comparable to state of the art cesium carbonate IFLs, but may improve if film morphology can be better controlled. The films are stable and reversible over many months in air and light. The mechanism of this unusual self-doping process may involve the change in relative potentials of the ions in the film caused by their deshielding and compaction as water is removed, leading to charge transfer when dry. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Reilly, Thomas H. III; Hains, Alexander W.; Chen, Hsiang-Yu; Gregg, Brian A. [National Renewable Energy Laboratory, Golden, CO (United States)

2012-04-15

213

Electron Transfer in Ferritin as Probed by Muon Spin Relaxation  

Science.gov (United States)

Electron-transfer processes play a vital role in many biological phenomena, from energy storage to photosynthesis. Positive muons allow such transfer processes in macromolecules, such as proteins, to be probed on a microscopic level. We have used this probe via muon spin relaxation (?SR) to investigate electron-transfer processes in ferritin; the normal iron storage protein. Data collected at finite fields is well described using the Risch-Kehr model at all measured temperatures with inter and intra-chain diffusion rates of 109 and 1011 rad s-1 being determined respectively. The results are compared to similar measurements on other proteins.

Telling, Mark T. F.; Kilcoyne, Susan H.

214

Theoretical investigation on intramolecular electron transfer in polypeptides  

Science.gov (United States)

Theoretical investigations on the intramolecular electron transfer between the intermediate residues of different secondary structures of an oligopeptide have been carried out. Density functional theory calculations have been performed to calculate the charge transfer integral, spatial overlap integral and site-energies for the optimized secondary structures of the glycine oligopeptide by varying the dihedral angles ( ? and ?) along the ?-carbon atom of amino acid subgroups. The reorganization energy has been calculated in the presence of an excess negative charge. The electron transfer rates for the model peptide have been estimated and the dependence of the rate on secondary structures is discussed.

Santhanamoorthi, N.; Kolandaivel, P.; Senthilkumar, K.

2007-06-01

215

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

International Nuclear Information System (INIS)

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

216

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

217

Evaluating zirconium–zirconium hydride interfacial strains by nano-beam electron diffraction  

International Nuclear Information System (INIS)

Nano-beam electron diffraction has been used to quantify the elastic strain field associated with ?-hydride needles embedded in an ?-Zr matrix. It has been found that the volume misfit associated with precipitation results in elastic strains that are ?4× greater in the matrix than the hydride. Electron energy loss spectroscopy was used to detect hydrogen enrichment at the matrix–hydride interface by a shift in the zirconium plasmon peak. This work highlights that ?-hydride is metastable and acts as a precursor to equilibrium ?-hydride and that compositional variations within the hydride can be detected using electron energy loss spectroscopy.

218

Graphene field effect transistor as a probe of electronic structure and charge transfer at organic molecule-graphene interfaces  

Science.gov (United States)

The electronic structure of physisorbed molecules containing aromatic nitrogen heterocycles (triazine and melamine) on graphene is studied using a combination of electronic transport, X-ray photoemission spectroscopy and density functional theory calculations. The interfacial electronic structure and charge transfer of weakly coupled molecules on graphene is found to be governed by work function differences, molecular dipole moments and polarization effects. We demonstrate that molecular depolarization plays a significant role in these charge transfer mechanisms even at submonolayer coverage, particularly for molecules which possess strong dipoles. Electronic transport measurements show a reduction of graphene conductivity and charge carrier mobility upon the adsorption of the physisorbed molecules. This effect is attributed to the formation of additional electron scattering sites in graphene by the molecules and local molecular electric fields. Our results show that adsorbed molecules containing polar functional groups on graphene exhibit different coverage behaviour to nonpolar molecules. These effects open up a range of new opportunities for recognition of different molecules on graphene-based sensor devices.The electronic structure of physisorbed molecules containing aromatic nitrogen heterocycles (triazine and melamine) on graphene is studied using a combination of electronic transport, X-ray photoemission spectroscopy and density functional theory calculations. The interfacial electronic structure and charge transfer of weakly coupled molecules on graphene is found to be governed by work function differences, molecular dipole moments and polarization effects. We demonstrate that molecular depolarization plays a significant role in these charge transfer mechanisms even at submonolayer coverage, particularly for molecules which possess strong dipoles. Electronic transport measurements show a reduction of graphene conductivity and charge carrier mobility upon the adsorption of the physisorbed molecules. This effect is attributed to the formation of additional electron scattering sites in graphene by the molecules and local molecular electric fields. Our results show that adsorbed molecules containing polar functional groups on graphene exhibit different coverage behaviour to nonpolar molecules. These effects open up a range of new opportunities for recognition of different molecules on graphene-based sensor devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05390g

Cervenka, Jiri; Budi, Akin; Dontschuk, Nikolai; Stacey, Alastair; Tadich, Anton; Rietwyk, Kevin J. Schenk, Alex; Edmonds, Mark T.; Yin, Yuefeng; Medhekar, Nikhil; Kalbac, Martin; Pakes, Chris I.

2015-01-01

219

Interfacial tension phenomenon and mass transfer process in the reservoir brine-CO2 system at high pressures and elevated temperatures. Paper no. IGEC-1-090  

International Nuclear Information System (INIS)

In this paper, an experimental technique is developed to study the dynamic interfacial tension (IFT) phenomenon and the mass transfer process in a reservoir brine-CO2 system at high pressures and elevated temperatures, based on the axisymmetric drop shape analysis (ADSA) for the pendant drop case. More specifically, the dynamic IFT between the reservoir brine and CO2 is measured under different pressures at two constant temperatures. It is found that the dynamic IFT gradually reduces to a constant value, which is referred to as the equilibrium IFT. The equilibrium IFT decreases as the pressure increases, whereas it increases as the temperature increases. It is also found that there exists two-way mass transfer between the brine phase and CO2. This two-way mass transfer results in the so-called brine swelling effect, shrinking effect and the reservoir brine-CO2 interface disappearance. The brine swelling effect is observed at all the pressures and temperatures tested, while the brine shrinking effect occurs only at high pressures and a lower temperature (T=27oC). Furthermore, at an elevated temperature (T=58oC), no pendant brine drop can be observed in CO2 phase at P. 12.238 MPa. The observed two-way mass transfer between the reservoir brine and CO2 phase may significantly affect accurate determination of the maximum sequestrable CO2 in a depleted reservoir or in a salineub> in a depleted reservoir or in a saline aquifer. (author)

220

Electron transfer, ionization, and excitation in atomic collisions: Progress report  

International Nuclear Information System (INIS)

The fundamental processes of electron transfer, ionization, and excitation in ion-atom collisions are being studied at Penn State by Winter. (The related work of Alston, who recently came to Penn State, is not described here since he is not at present funded by DOE.) These collision processes are treated in the context of simple one- or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. Three coupled-state calculations are being carried out over the present three-year period and are discussed here: a Sturmian-pseudostate study of electron transfer in collisions between protons and the hydrogenic ions He+, Li2+, Be3+, ...; a triple-center, atomic-state study of ionization in collisions between ? particles and H(ls) atoms and between protons and He+(ls) ions; and a coupled-state study of electron transfer and excitation in collisions between protons and neutral He atoms

 
 
 
 
221

Electron transfer properties of organic dye-sensitized solar cells based on indoline sensitizers with ZnO nanoparticles  

International Nuclear Information System (INIS)

Two indoline dyes, coded D149 and D205, were used as the sensitizers of ZnO dye-sensitized solar cells (DSCs) with optimal energy conversion efficiencies of more than 5%, under AM 1.5 full sunlight illumination (100 mW cm-2). Higher interfacial charge transfer rate and retardant fluorescence decay confirmed from transient fluorescence illustrated that D205-sensitized ZnO DSCs could possess better electron transport than D149-sensitized ZnO DSCs. The enhancement of Voc and Jsc for D205-sensitized ZnO DSCs was ascribed to the effective suppression of electron recombination by extending the alkyl chain on the terminal rhodanine moiety from ethyl to octyl. The evidence of enhanced electron diffusion coefficient was further shown by electrochemical impedance spectroscopy (EIS).

222

Electron transfer properties of organic dye-sensitized solar cells based on indoline sensitizers with ZnO nanoparticles  

Energy Technology Data Exchange (ETDEWEB)

Two indoline dyes, coded D149 and D205, were used as the sensitizers of ZnO dye-sensitized solar cells (DSCs) with optimal energy conversion efficiencies of more than 5%, under AM 1.5 full sunlight illumination (100 mW cm{sup -2}). Higher interfacial charge transfer rate and retardant fluorescence decay confirmed from transient fluorescence illustrated that D205-sensitized ZnO DSCs could possess better electron transport than D149-sensitized ZnO DSCs. The enhancement of V{sub oc} and J{sub sc} for D205-sensitized ZnO DSCs was ascribed to the effective suppression of electron recombination by extending the alkyl chain on the terminal rhodanine moiety from ethyl to octyl. The evidence of enhanced electron diffusion coefficient was further shown by electrochemical impedance spectroscopy (EIS).

Cheng, Hsin-Ming; Hsieh, Wen-Feng, E-mail: SMCheng@itri.org.tw, E-mail: wfhsieh@mail.nctu.edu.tw [Department of Photonics and Institute of Electro-Optical Engineering, National Chiao Tung University, Hsinchu 300, Taiwan (China)

2010-12-03

223

Electron transfer properties of organic dye-sensitized solar cells based on indoline sensitizers with ZnO nanoparticles  

Science.gov (United States)

Two indoline dyes, coded D149 and D205, were used as the sensitizers of ZnO dye-sensitized solar cells (DSCs) with optimal energy conversion efficiencies of more than 5%, under AM 1.5 full sunlight illumination (100 mW cm - 2). Higher interfacial charge transfer rate and retardant fluorescence decay confirmed from transient fluorescence illustrated that D205-sensitized ZnO DSCs could possess better electron transport than D149-sensitized ZnO DSCs. The enhancement of Voc and Jsc for D205-sensitized ZnO DSCs was ascribed to the effective suppression of electron recombination by extending the alkyl chain on the terminal rhodanine moiety from ethyl to octyl. The evidence of enhanced electron diffusion coefficient was further shown by electrochemical impedance spectroscopy (EIS).

Cheng, Hsin-Ming; Hsieh, Wen-Feng

2010-12-01

224

Photoinduced Interfacial Electron Injection Dynamics in Dye-Sensitized Solar Cells under Photovoltaic Operating Conditions  

Digital Repository Infrastructure Vision for European Research (DRIVER)

We report a pump–probe spectroscopy study of electron injection rates in dye-sensitized solar cell (DSSC) devices. We examine the case of working devices employing an N719 ruthenium sensitizer and an iodide electrolyte. Electron injection is found to occur mainly on a sub-100 fs time scale, followed by a slower component with a lifetime of 26.9 ps, in accordance with previous reports on model samples. The amplitude of this latter component varies with electrolyte composition from 25 to 9%. ...

Teuscher, Joe?l; De?coppet, Jean-david; Punzi, Angela; Zakeeruddin, Shaik M.; Moser, Jacques-e; Grätzel, Michael

2012-01-01

225

Improved heterogeneous electron transfer kinetics of fluorinated graphene derivatives.  

Science.gov (United States)

Though graphitic carbons are commercially available for various electrochemical processes, their performance is limited in terms of various electrochemical activities. Recent experiments on layered carbon materials, such as graphene, demonstrated an augmented performance of these systems in all electrochemical activities due to their unique electronic properties, enhanced surface area, structure and chemical stabilities. Moreover, flexibility in controlling electronic, as well as electrochemical activities by heteroatom doping brings further leverage in their practical use. Here, we study the electron transfer kinetics of fluorinated graphene derivatives, known as fluorinated graphene oxide (FGO) and its reduced form, RFGO. Enhanced electron transfer kinetics (heterogeneous electron transfer (HET)) is observed from these fluorinated systems in comparison to their undoped systems such as graphene oxide (GO) and reduced GO. A detailed study has been conducted using standard redox probes and biomolecules revealing the enhanced electro-catalytic activities of FGO and RFGO, and electron transfer rates are simulated theoretically. This study reveals that fluorine not only induces defects in graphitic lattice leading to an enhanced HET process but also can modify the electronic structure of graphene surface. PMID:25042554

Boopathi, Sidhureddy; Narayanan, Tharangattu N; Senthil Kumar, Shanmugam

2014-09-01

226

pH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films.  

Science.gov (United States)

Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L(P))(CO)3Cl (or ReC1P) [L(P) = 2,2'-bipyridine-4,4'-bis-CH2PO(OH)2] and Re(L(A))(CO)3Cl (or ReC1A) [L(A) = 2,2'-bipyridine-4,4'-bis-CH2COOH] sensitized TiO2 and ReC1P sensitized SnO2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position. PMID:16853498

She, Chunxing; Anderson, Neil A; Guo, Jianchang; Liu, Fang; Goh, Wan-Hee; Chen, Dai-Tao; Mohler, Debra L; Tian, Zhong-Qun; Hupp, Joseph T; Lian, Tianquan

2005-10-20

227

Interfacial and bulk electronic properties of complex oxides and buried interfaces probed by HAXPES  

International Nuclear Information System (INIS)

Highlights: ? Analysis of well screened satellites and electron screening in complex oxides ? Identification of DOS electronic character in LSMO ? Analysis of s-states contribution in organic spintronics systems. -- Abstract: Designing, understanding and controlling the properties of engineered and functional materials, based on oxides and buried interfaces, is one of the most flourishing research fields and one of the major challenges faced by contemporary solid state science and technology. Often, a reliable spectroscopic analysis of such systems is hindered by surface effects, as structural distortion, stoichiometry changes, strong reactivity to external agent and major atomic and/or electronic reconstruction to name but a few. Hard X-Ray PhotoEmission Spectroscopy (HAXPES) is a powerful technique to overcome such limitations, allowing to monitor truly bulk sensitive properties. We report selected HAXPES results for manganese-based oxides, both in films and crystal forms, and for buried metal–organic interfaces, with the aim of highlighting some of the important features such technique brings in the analysis of electronic properties of the solids

228

Interfacial and bulk electronic properties of complex oxides and buried interfaces probed by HAXPES  

Energy Technology Data Exchange (ETDEWEB)

Highlights: ? Analysis of well screened satellites and electron screening in complex oxides ? Identification of DOS electronic character in LSMO ? Analysis of s-states contribution in organic spintronics systems. -- Abstract: Designing, understanding and controlling the properties of engineered and functional materials, based on oxides and buried interfaces, is one of the most flourishing research fields and one of the major challenges faced by contemporary solid state science and technology. Often, a reliable spectroscopic analysis of such systems is hindered by surface effects, as structural distortion, stoichiometry changes, strong reactivity to external agent and major atomic and/or electronic reconstruction to name but a few. Hard X-Ray PhotoEmission Spectroscopy (HAXPES) is a powerful technique to overcome such limitations, allowing to monitor truly bulk sensitive properties. We report selected HAXPES results for manganese-based oxides, both in films and crystal forms, and for buried metal–organic interfaces, with the aim of highlighting some of the important features such technique brings in the analysis of electronic properties of the solids.

Borgatti, F. [CNR – Istituto per lo Studio dei Materiali Nanostrutturati (ISMN),Via Piero Gobetti 101, 40129 Bologna (Italy); Offi, F. [CNISM and Dipartimento di Fisica, Università Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Torelli, P. [CNR, Istituto Officina dei Materiali (IOM), Lab. TASC, in Area Science Park, S.S. 14 km 163.5, I-34149 Trieste (Italy); Monaco, G. [European Synchrotron Radiation Facility, BP 220, 38043 Grenoble (France); Panaccione, G., E-mail: panaccioneg@elettra.trieste.it [CNR, Istituto Officina dei Materiali (IOM), Lab. TASC, in Area Science Park, S.S. 14 km 163.5, I-34149 Trieste (Italy)

2013-10-15

229

Plugging in or Going Wireless: Strategies for Interspecies Electron Transfer  

Directory of Open Access Journals (Sweden)

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.

PravinMallaShrestha

2014-05-01

230

Electrochemical proton-coupled electron transfer: Beyond the golden rule  

International Nuclear Information System (INIS)

Electrochemical proton-coupled electron transfer rate constant expressions that interpolate between the golden rule and solvent-controlled limits are derived. These expressions include the effects of solvent dynamics and thus are applicable for a wide range of vibronic couplings and solvent relaxation times. The golden rule limit is defined in terms of weak vibronic coupling and fast solvent relaxation, and the solvent-controlled limit is defined in terms of strong vibronic coupling and slow solvent relaxation. In the golden rule limit, the rate constant is proportional to the square of the vibronic coupling and is independent of the solvent relaxation time. In the solvent-controlled limit, the rate constant is independent of the vibronic coupling and increases as the solvent relaxation time decreases. The interconversion between the solvent-controlled and golden rule limits can be induced by altering the proton donor-acceptor mode frequency and the overlap between the reactant and product proton vibrational wave functions, as well as the electronic coupling, the solvent relaxation time, and the overpotential. The kinetic isotope effect behaves differently in the solvent-controlled and golden rule limits and thus provides a unique probe for characterizing electrochemical proton-coupled electron transfer processes. The analogous rate constant expressions for electrochemical electron transfer and homogeneous proton-coupled electron transfer are also presented. The impacron transfer are also presented. The impact of electrode overpotential, solvent relaxation time, and proton donor-acceptor mode frequency on the rate constants are analyzed for model systems.

231

Plugging in or Going Wireless : Strategies for Interspecies Electron Transfer  

DEFF Research Database (Denmark)

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 contact 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. 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.

Shrestha, Pravin; Rotaru, Amelia-Elena

2014-01-01

232

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

Energy Technology Data Exchange (ETDEWEB)

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 strengt

Janke, C.J.

2005-10-17

233

Efficient light-to-current conversion by organic-inorganic interfacial charge-transfer transitions in TiO2 chemically adsorbed with 2-anthroic acid  

Science.gov (United States)

Organic-inorganic interfacial charge-transfer (ICT) transitions provide the concepts that organic-inorganic interfaces serve as a field for light absorption and charge separation directly occurs without energy loss. Here, we report efficient light-to-current conversion due to the ICT transitions in TiO2 chemically adsorbed with 2-anthroic acid. The incident photon-to-current conversion efficiency (IPCE) surpasses 85%, showing the significant improvement as compared to the reported results. Density functional analysis shows that the ICT absorption arises from strong d?-?* interactions at the inorganic-organic interface. In addition, we examined the density of states (DOS) of unoccupied surface states on TiO2 from the absorption and IPCE spectra.

Fujisawa, Jun-ichi; Nagata, Morio

2015-01-01

234

Mathematics and electronics - the conceptual transfer problem  

Science.gov (United States)

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.

Waks, S.

1988-07-01

235

[Electron transfer, ionization, and excitation in atomic collisions  

International Nuclear Information System (INIS)

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

236

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)  

International Nuclear Information System (INIS)

Highlights: • Design, preparation, testing and characterization of uniform sputtered films. • Interfacial charge transfer from the Ag2O (cb) to the lower laying Ta2O5 (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 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 Ag0, 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

237

Photoinduced electron transfer processes in homogeneous and microheterogeneous solutions  

Energy Technology Data Exchange (ETDEWEB)

The focus of the work described in this report is on single electron transfer reactions of excited states which culminate in the formation of stable or metastable even electron species. For the most part the studies have involved even electron organic substrates which are thus converted photochemically to odd electron species and then at some stage reconvert to even electron products. These reactions generally fall into two rather different categories. In one set of studies we have examined reactions in which the metastable reagents generated by single electron transfer quenching of an excited state undergo novel fragmentation reactions, chiefly involving C-C bond cleavage. These reactions often culminate in novel and potentially useful chemical reactions and frequently have the potential for leading to new chemical products otherwise unaffordable by conventional reaction paths. In a rather different investigation we have also studied reactions in which single electron transfer quenching of an excited state is followed by subsequent reactions which lead reversibly to metastable two electron products which, often stable in themselves, can nonetheless be reacted with each other or with other reagents to regenerate the starting materials with release of energy. 66 refs., 9 figs., 1 tab.

Whitten, D.G.

1991-10-01

238

Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri.  

Science.gov (United States)

Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri to participate in DIET was evaluated in coculture with Geobacter metallireducens. Cocultures formed aggregates that shared electrons via DIET during the stoichiometric conversion of ethanol to methane. Cocultures could not be initiated with a pilin-deficient G. metallireducens strain, suggesting that long-range electron transfer along pili was important for DIET. Amendments of granular activated carbon permitted the pilin-deficient G. metallireducens isolates to share electrons with M. barkeri, demonstrating that this conductive material could substitute for pili in promoting DIET. When M. barkeri was grown in coculture with the H2-producing Pelobacter carbinolicus, incapable of DIET, M. barkeri utilized H2 as an electron donor but metabolized little of the acetate that P.carbinolicus produced. This suggested that H2, but not electrons derived from DIET, inhibited acetate metabolism. P. carbinolicus-M. barkeri cocultures did not aggregate, demonstrating that, unlike DIET, close physical contact was not necessary for interspecies H2 transfer. M. barkeri is the second methanogen found to accept electrons via DIET and the first methanogen known to be capable of using either H2 or electrons derived from DIET for CO2 reduction. Furthermore, M. barkeri is genetically tractable,making it a model organism for elucidating mechanisms by which methanogens make biological electrical connections with other cells. PMID:24837373

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

2014-08-01

239

Electron transfer through rigid organic molecular wires enhanced by electronic and electron–vibration coupling  

Science.gov (United States)

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

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

2014-10-01

240

Dynamics of electron transfer pathways in cytochrome C oxidase.  

Science.gov (United States)

Cytochrome c oxidase mediates the final step of electron transfer reactions in the respiratory chain, catalyzing the transfer between cytochrome c and the molecular oxygen and concomitantly pumping protons across the inner mitochondrial membrane. We investigate the electron transfer reactions in cytochrome c oxidase, particularly the control of the effective electronic coupling by the nuclear thermal motion. The effective coupling is calculated using the Green's function technique with an extended Huckel level electronic Hamiltonian, combined with all-atom molecular dynamics of the protein in a native (membrane and solvent) environment. The effective coupling between Cu(A) and heme a is found to be dominated by the pathway that starts from His(B204). The coupling between heme a and heme a(3) is dominated by a through-space jump between the two heme rings rather than by covalent pathways. In the both steps, the effective electronic coupling is robust to the thermal nuclear vibrations, thereby providing fast and efficient electron transfer. PMID:14990507

Tan, Ming-Liang; Balabin, Ilya; Onuchic, José Nelson

2004-03-01

 
 
 
 
241

The role of excited Rydberg States in electron transfer dissociation.  

Science.gov (United States)

Ab initio electronic structure methods are used to estimate the cross sections for electron transfer from donor anions having electron binding energies ranging from 0.001 to 0.6 eV to each of three sites in a model disulfide-linked molecular cation. The three sites are (1) the S-S sigma(*) orbital to which electron attachment is rendered exothermic by Coulomb stabilization from the nearby positive site, (2) the ground Rydberg orbital of the -NH(3)(+) site, and (3) excited Rydberg orbitals of the same -NH(3)(+) site. It is found that attachment to the ground Rydberg orbital has a somewhat higher cross section than attachment to either the sigma orbital or the excited Rydberg orbital. However, it is through attachment either to the sigma(*) orbital or to certain excited Rydberg orbitals that cleavage of the S-S bond is most likely to occur. Attachment to the sigma(*) orbital causes prompt cleavage because the sigma energy surface is repulsive (except at very long range). Attachment to the ground or excited Rydberg state causes the S-S bond to rupture only once a through-bond electron transfer from the Rydberg orbital to the S-S sigma(*) orbital takes place. For the ground Rydberg state, this transfer requires surmounting an approximately 0.4 eV barrier that renders the S-S bond cleavage rate slow. However, for the excited Rydberg state, the intramolecular electron transfer has a much smaller barrier and is prompt. PMID:16599533

Sobczyk, Monika; Simons, Jack

2006-04-13

242

Electron transfer, ionization, and excitation atomic collisions  

International Nuclear Information System (INIS)

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

243

Front-End Electron Transfer Dissociation: A New Ionization Source  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Electron transfer dissociation (ETD), a technique that provides efficient fragmentation while depositing little energy into vibrational modes, has been widely integrated into proteomics workflows. Current implementations of this technique, as well as other ion–ion reactions like proton transfer, involve sophisticated hardware, lack robustness, and place severe design limitations on the instruments to which they are attached. Described herein is a novel, electrical discharge-based reagent io...

Earley, Lee; Anderson, Lissa C.; Bai, Dina L.; Mullen, Christopher; Syka, John E. P.; English, A. Michelle; Dunyach, Jean-jacques; Stafford, George C.; Shabanowitz, Jeffrey; Hunt, Donald F.; Compton, Philip D.

2013-01-01

244

Photoinduced interfacial electron transfer and lateral charge transport in molecular donor–acceptor photovoltaic systems  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Nanostructured liquid|solid and solid|solid bulk heterojunctions designed for the conversion of solar energy offer ideal models for the investigation of light-induced ET dynamics at surfaces. Despite significant study of processes leading to charge generation in third-generation solar cells, a conclusive picture of the photophysics of these photovoltaic converters is still missing. More specifically searched is the link between the molecular structure of the interface and the kinetics of surf...

Punzi, Angela; Brauer, Jan C.; Marchioro, Arianna; Ghadiri, Elham; Jonghe, Jelissa; Moser, Jacques-e

2011-01-01

245

Theoretical analysis of electron transfer cross reactions between complex ions  

International Nuclear Information System (INIS)

Cross redox-systems are considered which contain cobalt and ruthenium ethylene diamine (en) complexed as one of reactants and as another one - hexaaqua- and hexamine complexes of vanadium, chromium, iron and ruthenium. To obtain the kinetic parameters of the abovesaid complexes two symmetric redox-systems: Co(en)sub(3)sup(3+/2+) and Ru(en)sub(3)sup(3+/2+) are also considered. The calculated values of rate constants and activation enthalpies of electron transfer reactions are given. A comparison of transmission coefficients for electron transfer in the redox-systems of Co and Ru complexes is made which permits to draw a conclusion on the delocalization degree of the transferred electron in the compared complexes

246

Auger-assisted electron transfer from photoexcited semiconductor quantum dots.  

Science.gov (United States)

Although quantum confined nanomaterials, such as quantum dots (QDs) have emerged as a new class of light harvesting and charge separation materials for solar energy conversion, theoretical models for describing photoinduced charge transfer from these materials remain unclear. In this paper, we show that the rate of photoinduced electron transfer from QDs (CdS, CdSe, and CdTe) to molecular acceptors (anthraquinone, methylviologen, and methylene blue) increases at decreasing QD size (and increasing driving force), showing a lack of Marcus inverted regime behavior over an apparent driving force range of ?0-1.3 V. We account for this unusual driving force dependence by proposing an Auger-assisted electron transfer model in which the transfer of the electron can be coupled to the excitation of the hole, circumventing the unfavorable Franck-Condon overlap in the Marcus inverted regime. This model is supported by computational studies of electron transfer and trapping processes in model QD-acceptor complexes. PMID:24359156

Zhu, Haiming; Yang, Ye; Hyeon-Deuk, Kim; Califano, Marco; Song, Nianhui; Wang, Youwei; Zhang, Wenqing; Prezhdo, Oleg V; Lian, Tianquan

2014-03-12

247

Theoretical aspects of electron transfer reactions of complex molecules  

DEFF Research Database (Denmark)

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 vibrational frequency changes, local mode anharmonicity, and rotational reorganization, in both diabatic and adiabatic limits. Systems for which this formalism is appropriate are discussed.

Kuznetsov, A. M.; Ulstrup, Jens

2001-01-01

248

Surface ion transfer growth of ternary CdS1-xSex quantum dots and their electron transport modulation  

Science.gov (United States)

We report a surface ion transfer method to synthesise ternary alloy CdS1-xSex (0 nanoparticles. By tuning the content of selenium in such quantum dots, the optical absorption spectra can be controllably widened to cover the most of the visible light range. The electron transport of such QDs can be modulated by changing the interfacial electronic energy between CdS1-xSex QDs and TiO2 nanoparticles. The QDs with optimized selenium content (x = 0.72) give a balance between a broad optical absorption and a suitable energy band alignment. The homogenous alloy CdS1-xSex QDs achieve a maximum light-harvesting efficiency over 90%, and generate a photocurrent density larger than 10 mA cm-2, which is 2.6- and 1.4-times that of binary CdS and CdSe QDs sensitized photovoltaic devices.We report a surface ion transfer method to synthesise ternary alloy CdS1-xSex (0 nanoparticles. By tuning the content of selenium in such quantum dots, the optical absorption spectra can be controllably widened to cover the most of the visible light range. The electron transport of such QDs can be modulated by changing the interfacial electronic energy between CdS1-xSex QDs and TiO2 nanoparticles. The QDs with optimized selenium content (x = 0.72) give a balance between a broad optical absorption and a suitable energy band alignment. The homogenous alloy CdS1-xSex QDs achieve a maximum light-harvesting efficiency over 90%, and generate a photocurrent density larger than 10 mA cm-2, which is 2.6- and 1.4-times that of binary CdS and CdSe QDs sensitized photovoltaic devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr31703f

Chen, Zhenhua; Peng, Wenqin; Zhang, Kun; Zhang, Jing; Yanagida, Masatoshi; Han, Liyuan

2012-11-01

249

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

Science.gov (United States)

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.

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

1996-01-01

250

Comparing Electron Recombination via Interfacial Modifications in Dye-Sensitized Solar Cells.  

Science.gov (United States)

Establishing a blocking layer between the interfaces of the photoanode is an effective approach to improve the performance of dye-sensitized solar cells (DSSCs). In this work, HfO2 blocking layers are deposited via atomic layer deposition (ALD) onto tin-doped indium oxide (ITO) and TiO2. In both cases, addition of the blocking layer increases cell efficiencies to greater than 7%. The improved performance for a HfO2 layer inserted between the ITO/TiO2 interface is associated with an energy barrier that reduces electron recombination. HfO2 blocking layers between the TiO2/dye interface show more complex behavior and are more sensitive to the number of ALD cycles. For thin blocking layers on TiO2, the improved device performance is attributed to the passivation of surface states in TiO2. A distinct transition in dark current and electron lifetime are observed after 4 ALD cycles. These changes to performance indicate thick HfO2 layers on TiO2 formed an energy barrier that significantly hinders cell performance. PMID:25412271

Li, Luping; Chen, Shikai; Xu, Cheng; Zhao, Yang; Rudawski, Nicholas G; Ziegler, Kirk J

2014-12-10

251

Reactant-Product Quantum Coherence in Electron Transfer Reactions  

CERN Document Server

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

Kominis, I K

2012-01-01

252

A role for excreted quinones in extracellular electron transfer  

Science.gov (United States)

Respiratory processes in bacteria are remarkable because of their ability to use a variety of compounds, including insoluble minerals, as terminal electron acceptors. Although much is known about microbial electron transport to soluble electron acceptors, little is understood about electron transport to insoluble compounds such as ferric oxides. In anaerobic environments, humic substances can serve as electron acceptors and also as electron shuttles to ferric oxides. To explore this process, we identified mutants in Shewanella putrefaciens that are unable to respire on humic substances. Here we show that these mutants contain disruptions in a gene that is involved in the biosynthesis of menaquinone. During growth, the wild type releases a menaquinone-related redox-active small molecule into the medium that complements the mutants. This finding raises the possibility that electron transfer to a variety of oxidants, including poorly soluble minerals, may be mediated by microbially excreted quinones that have yet to be identified.

Newman, Dianne K.; Kolter, Roberto

2000-05-01

253

Intramolecular electron transfer in nitrite reductase studied by pulse radiolysis  

International Nuclear Information System (INIS)

We report the evidence for the electron-transfer reaction between two copper sites in nitrite reductase from Achromobacter cycloclastes IAM 1013 by pulse radiolysis. Type 1 Cu sites in native (type 1 Cu : type 2 Cu = 1 : 0.5) and type 2 Cu-depleted (T2D) nitrite reductase are reduced with N-methylnicotinamide radical generated by the hydrated electron. The reductions of the coppers in the both enzymes give second-order rate constants of (3.4 - 3.5) x 108 M-1s-1. In the case of the native enzyme, moreover, the recovery of the absorbance of reduced type 1 Cu is observed (about 35 %). This finding suggests the intramolecular electron transfer from type 1 Cu to type 2 Cu, because T2D nitrite reductase does not show the recovery of the absorption band at all. The electron-transfer occurs with an observed first order rate constant of 1400 s-1. The incomplete electron transfer from type 1 Cu to type 2 Cu are due to the difference between the redox potential of two Cu sites. (author)

254

Modification of interfacial electronic structure as a function of organic overlayer stereochemistry  

Science.gov (United States)

Hydrogen bonding interactions involving molecular chiral centers control the organizational structure at the tartaric acid/Ag(111) interface. Specifically, for enantiopure tartaric acid films, a single molecule basis adsorbs with the molecular axis orientated parallel to the surface plane. Conversely, a paired basis unit composed of opposite enantiomers adsorbs with the combined molecular axis perpendicular to the surface plane for racemic tartaric acid films. Here, the unique electronic structure of each interface will be discussed. Scanning tunneling spectroscopy results give quantitative shifts of the Ag(111) Shockley-type surface state (67 meV below the Fermi level) of 881 meV and 55 meV for enantiopure and racemic films, respectively. Density functional theory computations have also been carried out in support of the experimental results. The respective energetic shifts will be discussed in terms of a modified surface potential, film polarizability, and work function changes.

Santagata, N. M.; Andrews, K. M.; Calzolari, A.; Buongiorno Nardelli, M.; Pearl, T.

2010-03-01

255

Optical and interfacial electronic properties of diamond-like carbon films  

Science.gov (United States)

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.

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

256

Mechanism of back electron transfer in an intermolecular photoinduced electron transfer reaction: solvent as a charge mediator.  

Science.gov (United States)

Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4-dicyanobenzene (DCB) in acetonitrile (ACN) by using time-resolved near- and mid-IR spectroscopy. The Py dimer radical cation (Py2(·+)) and DCB radical anion (DCB(·-)) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB(·-) to the solvent and charge recombination between the resulting ACN dimer anion and Py2(·+). The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye-sensitized solar cells. PMID:25044892

Narra, Sudhakar; Nishimura, Yoshifumi; Witek, Henryk A; Shigeto, Shinsuke

2014-10-01

257

Universal nanopatternable interfacial bonding.  

Science.gov (United States)

A nanopatternable polydimethylsiloxane (PDMS) oligomer layer is demonstrated as an interfacial adhesive for its intrinsic transferability and universal adhesiveness. Utilizing the well-established surface modification and bonding techniques of PDMS surfaces, irreversible bonding is formed (up to 400 kPa) between a wide range of substrate pairs, representing ones within and across different materials categories, including metals, ceramics, thermoset, and thermoplastic polymers. PMID:22028210

Ding, Yuzhe; Garland, Shaun; Howland, Michael; Revzin, Alexander; Pan, Tingrui

2011-12-01

258

Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis*  

Digital Repository Infrastructure Vision for European Research (DRIVER)

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...

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

2011-01-01

259

Inelastic electron photon scattering at moderate four momentum transfers  

International Nuclear Information System (INIS)

We present new high statistics data on hadron production in photon photon reactions. The data are analyzed in terms of an electron photon scattering formalism. The dependence of the total cross section on Q2, the four momentum transfer squared of the scattered electron, and on the mass W of the hadronic system is investigated. The data are compared to predictions from Vector Dominance and the quark model. (orig.)

260

Study of the interfacial reactions between a bioactive apatite-mullite glass-ceramic coating and titanium substrates using high angle annular dark field transmission electron microscopy.  

Science.gov (United States)

Glass of generic composition SiO(2) . Al(2)O(3) . P(2)O(5) . CaO . CaF(2) will crystallise predominantly to apatite and mullite upon heat-treatment. Such ceramics are bioactive, osseoconductive, and have a high resistance to fracture. As a result, they are under investigation for use as biomedical device coatings, and in particular for orthopaedic implants. Previous work has shown that the material can be successfully enamelled to titanium with an interfacial reaction zone produced during heat treatment. The present study uses high angle annular dark field transmission electron microscopy (HAADF-TEM) to conduct a detailed examination of this region. Results show evidence of complex interfacial reactions following the diffusion of titanium into an intermediate layer and the production of titanium silicides and titanium phosphides. These results confirm previously hypothesised mechanisms for the bonding of silicate bioceramics with titanium alloys. PMID:19034617

Stanton, Kenneth T; O'Flynn, Kevin P; Nakahara, Shohei; Vanhumbeeck, Jean-François; Delucca, John M; Hooghan, Bobby

2009-04-01

 
 
 
 
261

Photoinitiated electron transfer in multi-chromophoric species: Synthetic tetrads and pentads  

Energy Technology Data Exchange (ETDEWEB)

This research project involves the design, synthesis and study of the molecules which mimic many of the important aspects of photosynthetic electron and energy transfer. Specifically, the molecules are designed to mimic the following aspects of natural photosynthetic multistep electron transfer: electron donation from a tetrapyrrole excited singlet state, electron transfer between tetrapyrroles, electron transfer from tetrapyrroles to quinones, and electron transfer between quinones with different redox properties. In addition, they model carotenoid antenna function in photosynthesis (singlet-singlet energy transfer from carotenoid polyenes to chlorophyll) and carotenoid photoprotection from singlet oxygen damage (triplet-triplet energy transfer from chlorophyll to carotenoids).

1990-02-14

262

Interfacial electronic structure of copper phthalocyanine on a gold surface studied by synchrotron radiation photoemission  

Science.gov (United States)

We have studied copper phthalocyanine (CuPc) molecules deposited on a clean gold surface via synchrotron radiation photoemission. The persistent appearance of Au4f surface core-level emission in a series of depositions suggests columnar growth of the adsorbed molecules covering only one-fifth of the surface. Molecular adsorption reduced the line intensity of emission from the Au surface slightly and also produced a shortened core-level shift, which demonstrates weakened s-d hybridization of the surface band. Moreover, manifestation of excess charge in the C1s core, along with an induced component in the Au4f core, indicates that charge polarization occurred at the organic/metal contact. The interface introduces an electronic state 1.09 eV below the Fermi level. Further analysis reveals that only the carbon atoms in the benzene rings are affected upon adsorption, suggesting that the molecular plane lies flat on the surface without changing the nominal bent configuration.

Pi, Tun-Wen; Lee, Guan-Ru; Wei, Ching-Hsuan; Chen, Wen-Yen; Cheng, Chiu-Ping

2009-12-01

263

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

International Nuclear Information System (INIS)

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

264

D Simulation for Maximizing Electron Transfer Efficiency in Thick GEMS  

Science.gov (United States)

Thick GEM for UV detector applications must provide high detection efficiency for a single photoelectron produced by UV light. Electron Transfer Efficiency (ETE) of GEM detector determines the detection efficiency. We have used GARFIELD simulation for estimation of ETE at various operating parameters, which are to be optimized for high detection efficiency.

Garai, Baishali; Rajanna, K.; Radhakrishna, V.

2012-08-01

265

Electron transfer kinetics on mono- and multilayer graphene.  

Science.gov (United States)

Understanding of the electrochemical properties of graphene, especially the electron transfer kinetics of a redox reaction between the graphene surface and a molecule, in comparison to graphite or other carbon-based materials, is essential for its potential in energy conversion and storage to be realized. Here we use voltammetric determination of the electron transfer rate for three redox mediators, ferricyanide, hexaammineruthenium, and hexachloroiridate (Fe(CN)(6)(3-), Ru(NH3)(6)(3+), and IrCl(6)(2-), respectively), to measure the reactivity of graphene samples prepared by mechanical exfoliation of natural graphite. Electron transfer rates are measured for varied number of graphene layers (1 to ca. 1000 layers) using microscopic droplets. The basal planes of mono- and multilayer graphene, supported on an insulating Si/SiO(2) substrate, exhibit significant electron transfer activity and changes in kinetics are observed for all three mediators. No significant trend in kinetics with flake thickness is discernible for each mediator; however, a large variation in kinetics is observed across the basal plane of the same flakes, indicating that local surface conditions affect the electrochemical performance. This is confirmed by in situ graphite exfoliation, which reveals significant deterioration of initially, near-reversible kinetics for Ru(NH3)(6)(3+) when comparing the atmosphere-aged and freshly exfoliated graphite surfaces. PMID:25290250

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

2014-10-28

266

Observation of pH-dependent back-electron-transfer dynamics in alizarin/TiO2 adsorbates: importance of trap states.  

Science.gov (United States)

The dependence of the interfacial electron transfer in alizarin-sensitized TiO2 nanoparticles on the sample pH has been examined via transient absorbance spectroscopy in the visible spectral region (443-763 nm). Excitation of the alizarin/TiO2 system with visible pump pulses (lambdaexc = 500 nm) leads to a very fast electron injection (tauinj band energy. Indeed, a variation of pH values over 7 units leads to a approximately 0.42 eV change of the conduction band edge position (i.e., the nominal free energy of the electron in the electrode). Assuming a pH-independent redox potential of the dye, this change was sufficient to push the system to a condition where direct photoinitiated electron injection to intraband gap surface states could be investigated. The existence of an electron-transfer pathway via surface trap states is supported by the similarity of the observed back-electron-transfer kinetics of alizarin/TiO2 at pH 9 and alizarin/ZrO2 reported in earlier work (J. Phys. Chem. B 2000, 104, 8995), where the conduction band edge is approximately 1 eV above the excited state of the dye. The influence of surface trap states on interfacial electron transfer has been studied, and a detailed analysis of their population, depopulation, and relaxation kinetics is performed. Therefore, alizarin adsorbed on the surface of TiO2 nanoparticles is an ideally suited system, where pH-dependent investigations allow a detailed study of the electron dynamics in trap states of TiO2 nanoparticles. PMID:16623522

Matylitsky, V V; Lenz, M O; Wachtveitl, J

2006-04-27

267

Electron-transfer reactions at the plasma-liquid interface.  

Science.gov (United States)

Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions. PMID:21985430

Richmonds, Carolyn; Witzke, Megan; Bartling, Brandon; Lee, Seung Whan; Wainright, Jesse; Liu, Chung-Chiun; Sankaran, R Mohan

2011-11-01

268

Polymer dielectric materials for organic thin-film transistors: Interfacial control and development for printable electronics  

Science.gov (United States)

Organic thin-film transistors (OTFTs) have been extensively studied for organic electronics. In these devices, organic semiconductor-dielectric interface characteristics play a critical role in influencing OTFT operation and performance. This study begins with exploring how the physicochemical characteristics of the polymer gate dielectric affects the thin-film growth mode, microstructure, and OTFT performance parameters of pentacene films deposited on bilayer polymer (top)-SiO2 (bottom) dielectrics. Pentacene growth mode varies considerably with dielectric substrate, and correlations are established between pentacene film deposition temperature, the thin-film to bulk microstructural phase transition, and OTFT device performance. Furthermore, the primary influence of the polymer dielectric layer glass transition temperature on pentacene film microstructure and OTFT response is shown for the first time. Following the first study, the influence of the polymer gate dielectric viscoelastic properties on overlying organic semiconductor film growth, film microstructure, and TFT response are investigated in detail. From the knowledge that nanoscopically-confined thin polymer films exhibit glass transition temperatures that deviate substantially from those of the corresponding bulk materials, pentacene (p-channel) and cyanoperylene (n-channel) films grown on polymer gate dielectrics at temperatures well-below their bulk glass transition temperatures (Tg(b)) have been shown to exhibit morphological/microstructural transitions and dramatic OTFT performance discontinuities at well-defined temperatures (defined as the polymer "surface glass transition temperature," or Tg(s)). These transitions are characteristic of the particular polymer architecture and independent of film thickness or overall film cooperative chain dynamics. Furthermore, by analyzing the pentacene films grown on UV-curable polymer dielectrics with different curing times (hence, different degrees of crosslinking), clear correlations between pentacene film deposition temperature, degree of polymer dielectric film crosslinking, and the corresponding pentacene film growth mode, phase composition, and carrier mobilities are established. Based on the results, TFT measurements have been demonstrated to represent a new and sensitive methodology to probe polymer surface viscoelastic properties as well as the degree of polymer dielectric film crosslinking. In the final study, the synthesis and dielectric properties of optimized crosslinked polymer blend (CPB) dielectrics for printable TFTs are reported. Novel silane crosslinking reagents with tuned reactivity enable the fabrication of CPB films having excellent quality and tunable thickness, fabricated both by spin-coating and gravure-printing. The CPB dielectric films fabricated by blending crosslinking reagent with poly(4-vinyl)phenol (PVP) require very low-curing temperatures (˜110°C), tenaciously adhere to a variety of TFT gate contact materials and exhibit excellent insulating properties with tunable capacitance values. The CPB film quality is correlated with the PVP-crosslinking reagent reactivity. Devices fabricated with both p- and n-channel organic semiconductors on the CPB dielectrics function at low operating voltages and the device performance is strongly correlated with the morphology and microstructure of the representative semiconductor films.

Kim, Choongik

269

Spin selectivity in electron transfer in photosystem I.  

Science.gov (United States)

Photosystem I (PSI) is one of the most studied electron transfer (ET) systems in nature; it is found in plants, algae, and bacteria. The effect of the system structure and its electronic properties on the electron transfer rate and yield was investigated for years in details. In this work we show that not only those system properties affect the ET efficiency, but also the electrons' spin. Using a newly developed spintronic device and a technique which enables control over the orientation of the PSI monolayer relative to the device (silver) surface, it was possible to evaluate the degree and direction of the spin polarization in ET in PSI. We find high-spin selectivity throughout the entire ET path and establish that the spins of the electrons being transferred are aligned parallel to their momenta. The spin selectivity peaks at 300?K and vanishes at temperatures below about 150?K. A mechanism is suggested in which the chiral structure of the protein complex plays an important role in determining the high-spin selectivity and its temperature dependence. Our observation of high light induced spin dependent ET in PSI introduces the possibility that spin may play an important role in ET in biology. PMID:24989350

Carmeli, Itai; Senthil Kumar, Karuppannan; Heifler, Omri; Carmeli, Chanoch; Naaman, Ron

2014-08-18

270

Efficient electron transfer in a protein network lacking specific interactions.  

Science.gov (United States)

In many biochemical processes, proteins need to bind partners amidst a sea of other molecules. Generally, partner selection is achieved by formation of a single-orientation complex with well-defined, short-range interactions. We describe a protein network that functions effectively in a metabolic electron transfer process but lacks such specific interactions. The soil bacterium Paracoccus denitrificans oxidizes a variety of compounds by channeling electrons into the main respiratory pathway. Upon conversion of methylamine by methylamine dehydrogenase, electrons are transported to the terminal oxidase to reduce molecular oxygen. Steady-state kinetic measurements and NMR experiments demonstrate a remarkable number of possibilities for the electron transfer, involving the cupredoxin amicyanin as well as four c-type cytochromes. The observed interactions appear to be governed exclusively by the electrostatic nature of each of the proteins. It is concluded that Paracoccus provides a pool of cytochromes for efficient electron transfer via weak, ill-defined interactions, in contrast with the view that functional biochemical interactions require well-defined molecular interactions. It is proposed that the lack of requirement for specificity in these interactions might facilitate the integration of new metabolic pathways. PMID:21916462

Meschi, Francesca; Wiertz, Frank; Klauss, Linda; Blok, Anneloes; Ludwig, Bernd; Merli, Angelo; Heering, Hendrik A; Rossi, Gian Luigi; Ubbink, Marcellus

2011-10-26

271

Temperature dependence of electron transfer in coupled quantum wells  

Science.gov (United States)

We report on the temperature dependence of electron transfer between coupled quantum wells in a voltage tunable two-color quantum-well infrared photodetector (QWIP). The detection peak of this QWIP switches from 7.1 ?m under positive bias to 8.6 ?m under negative bias for temperatures T?40 K. For T?40 K, the 7.1 ?m peak is present under both bias polarities and increases significantly with T while the 8.6 ?m peak decreases correspondingly. We determine the temperature dependence of electron densities in the two QWs from the detector absorption spectra that are deduced using corrugated QWIPs and find that electron transfer is efficient only when thermionic emission is not significant.

Majumdar, Amlan; Choi, K. K.; Reno, J. L.; Rokhinson, L. P.; Tsui, D. C.

2003-02-01

272

Microstructure, phase transition, and interfacial chemistry of Gd2O3/Si(111) grown by electron-beam physical vapor deposition  

International Nuclear Information System (INIS)

The effects of growth temperature, film thickness, and oxygen flux on the microstructure, phase transition, and interfacial chemistry of gadolinium oxide (Gd2O3) films grown on Si(111) substrates by electron-beam physical vapor deposition were investigated using a combination of transmission electron microscopy (TEM), electron diffraction, scanning TEM, x-ray energy dispersive spectrometry, and electron energy loss spectrometry. The authors find that a low growth temperature (250 °C) and a high oxygen flux (200 sccm) led to a small grain size and a high porosity of the Gd2O3 film. Lowering the oxygen flux to 50 sccm led to reduced film porosity, presumably due to the increased diffusion length of the Gd atoms on the surface. Increasing the growth temperature to 650 °C resulted in a film with large columnar grains and elongated pores at the grain boundaries. Thin films grown at 250 °C consisted of cubic Gd2O3, but thermodynamically less stable monoclinic phase formed as the film thickness increased. Lowering the oxygen flux apparently further promoted the formation of the monoclinic phase. Furthermore, monoclinic phase dominated in the films grown at 650 °C. Such phase transitions may be related to the stress evolution of the films at different temperatures, thicknesses, and oxygen fluxes. Enhanced Gd2O3/Si interfacial reaction was observed as the growth temperature, film thicknas the growth temperature, film thickness, and oxygen flux increased. Moreover, oxygen was found to play a crucial role in the Gd2O3/Si interfacial reaction and the formation of Gd-Si-O interface layers, which proceeded by the reaction of excess oxygen with Si followed by the intermixing of SiOx and Gd2O3.

273

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  

Directory of Open Access Journals (Sweden)

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.

Manoranjan Reddy,

2011-07-01

274

Evaluation of mass transfer coefficient of rare earth elements with interfacial agitation in LiCl-KCl/Cd system  

International Nuclear Information System (INIS)

Reductive-extraction is one of the main process of pyro-chemical reprocessing for metallic fuel. Mass transfer coefficient of rare earth elements was evaluated in LiCl-KCl/Cd system at 450 and 500 degree C. The interface between the salt and the Cd was agitated with a fun turbine blade at 30 to 500 rpm. In case of 300 or 500 rpm, the system reached at equilibrium condition within 10 minutes. The evaluated mass transfer coefficient was 0.0008 to 0.05 cm/sec, which depended on the agitation speed or Reynolds number. The mass transfer coefficients became larger at 500 degree C than at 450 degree C, and in case of upward stream than in case of downward stream. Evaluation of recovery yield and separation efficiency of each solute were carried out in single-stage continuous-flow extraction and in multi-stages counter-current extraction in LiCl-KCl/Cd system. The mass transfer coefficients obtained in these experiments should be enough for separation and recovery in pyro-reprocessing by using counter-current extraction with 6 stages in case that the flow rare of both salt and Cd controlled within 2%/min. (author)

275

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

DEFF Research Database (Denmark)

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 transfer (ET). Image interpretation requires, however, theoretical support, as STM represents both electronic and topographic features. Molecules with accessible redox levels offer other insight into electron tunneling mechanisms, addressed in detail for ET metalloproteins. We present here in situ STM of the blue redox metalloenzyme copper nitrite reductase (Achromobacter xylosoxidans, AxCuNiR) on Au(111) electrode surfaces modified by a self-assembled cysteamine monolayer. AxCuNiR displays strong nitrite reduction waves in this environment. AxCuNiR/cysteamine/ Au(111) surfaces were imaged at KNO2 concentrations where most of the enzyme is in the enzyme-substrate bound state. Molecular resolution for both cysteamine/Au(111) and AxCuNiR/cysteamine/ Au(111) electrode surfaces was achieved. The enzyme coverage is about 1.5 x 10(-13) Mol cm(-2), which is low compared with an ideal close-packed monolayer. The adlayer behaves as an assembly of individual molecules, reflected in distributions of molecular appearance, although a number of molecules do show the triangular shape of the trimeric AxCuNiR structure. The apparent average molecular height is about 11 Angstrom. This suggests that details of electronic structures and larger assemblies are needed to disentangle enzyme mechanisms at the single-molecule level.

Hansen, Allan Glargaard; Zhang, Jingdong

2004-01-01

276

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

DEFF Research Database (Denmark)

Smell is a vital sense for animals. The mainstream explanation of smell is based on recognition of the odorant molecules through characteristics of their surface, e.g., shape, but certain experiments suggest that such recognition is complemented by recognition of vibrational modes. According to this suggestion an olfactory receptor is activated by electron transfer assisted through odorant vibrational excitation. The hundreds to thousands of different olfactory receptors in an animal recognize odorants over a discriminant landscape with surface properties and vibrational frequencies as the two major dimensions. In the present paper we introduce the vibrationally assisted mechanism of olfaction and demonstrate for several odorants that, indeed, a strong enhancement of an electron tunneling rate due to odorant vibrations can arise. We discuss in this regard the influence of odorant deuteration and explain, 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 characteristics which olfactory receptors and odorants must obey for the vibrationally assisted electron transfer mechanism to function. We argue that the stated characteristics are feasible for realistic olfactory receptors, noting, though, that the receptor structure presently is still unknown, but can be studied through homology modeling.

Solov'yov, Ilia; Chang, Po-Yao

2012-01-01

277

Structures of protein-protein complexes involved in electron transfer.  

Science.gov (United States)

Electron transfer reactions are essential for life because they underpin oxidative phosphorylation and photosynthesis, processes leading to the generation of ATP, and are involved in many reactions of intermediary metabolism. Key to these roles is the formation of transient inter-protein electron transfer complexes. The structural basis for the control of specificity between partner proteins is lacking because these weak transient complexes have remained largely intractable for crystallographic studies. Inter-protein electron transfer processes are central to all of the key steps of denitrification, an alternative form of respiration in which bacteria reduce nitrate or nitrite to N2 through the gaseous intermediates nitric oxide (NO) and nitrous oxide (N2O) when oxygen concentrations are limiting. The one-electron reduction of nitrite to NO, a precursor to N2O, is performed by either a haem- or copper-containing nitrite reductase (CuNiR) where they receive an electron from redox partner proteins a cupredoxin or a c-type cytochrome. Here we report the structures of the newly characterized three-domain haem-c-Cu nitrite reductase from Ralstonia pickettii (RpNiR) at 1.01?Å resolution and its M92A and P93A mutants. Very high resolution provides the first view of the atomic detail of the interface between the core trimeric cupredoxin structure of CuNiR and the tethered cytochrome c domain that allows the enzyme to function as an effective self-electron transfer system where the donor and acceptor proteins are fused together by genomic acquisition for functional advantage. Comparison of RpNiR with the binary complex of a CuNiR with a donor protein, AxNiR-cytc551 (ref. 6), and mutagenesis studies provide direct evidence for the importance of a hydrogen-bonded water at the interface in electron transfer. The structure also provides an explanation for the preferential binding of nitrite to the reduced copper ion at the active site in RpNiR, in contrast to other CuNiRs where reductive inactivation occurs, preventing substrate binding. PMID:23535590

Antonyuk, Svetlana V; Han, Cong; Eady, Robert R; Hasnain, S Samar

2013-04-01

278

Electron donor-acceptor quenching and photoinduced electron transfer for coumarin dyes  

Science.gov (United States)

The fluorescence of 7-aminocoumarins is quenched by a variety of organic electron donors or acceptors in acetonitrile. In general, donors with half-wave oxidation potentials less positive than 1.0 V vs SCE and acceptors with reduction potentials less negative than -1.5 V vs SCE are candidates for diffusion limited quenching of coumarin singlet states. Profiles of quenching rates are consistent with calculated free energies for electron transfer between excited coumarins and donors or acceptors. In flash photolysis experiments electron transfer for several dyes and quenchers (e.g., methyl viologen) is demonstrated. Relatively low yields of net electron transfer are consistently obtained due to inefficient ionic photodissociation via singlet quenching or a low yield of more photoactive coumarin triplets. Electrochemical properties of the coumarins have been investigated by cyclic voltammetry with the indications of reversible oxidation and irreversible reduction as important processes.

Jones, G., II; Griffin, S. F.; Choi, C. Y.; Bergmark, W. R.

1983-10-01

279

Electron Transfer in DNA through magnetic bound states  

CERN Document Server

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.

Cox, D L; Pati, S K

2000-01-01

280

Large scale oil lease automation and electronic custody transfer  

International Nuclear Information System (INIS)

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

 
 
 
 
281

Laser decal transfer of electronic materials with thin film characteristics  

Science.gov (United States)

We describe a novel technique, called laser decal transfer, for the laser forward transfer of electronic inks that allows the non-contact direct writing of thin film-like patterns and structures on glass and plastic substrates. This technique allows the direct printing of materials such as metallic nano-inks from a donor substrate to the receiving substrate while maintaining the size and shape of the area illuminated by the laser transfer pulse. That is, the area of the donor substrate or ribbon exposed to the laser pulse releases an identical area of nano-ink material which retains its shape while it travels across the gap between the ribbon and the receiving substrate forming a deposited pattern of the same dimensions. As a result, this technique does not exhibit the limited resolution, non-uniform thickness, irregular edge features and surrounding debris associated with earlier laser forward transfer techniques. Continuous and uniform metallic lines typically 5 micrometers or less in width, and a few hundred nanometers in thickness were fabricated by laser decal transfer. These lines are of similar scale as patterns generated by lithographic techniques. Once transferred, the lines are laser-cured in-situ using a CW laser beam, becoming electrically conductive with resistivities as low as 3.4 ?? cm. This novel laser direct-write technique is a significant improvement in terms of quality and fidelity for directwrite processes and offers great promise for electronic applications such as in the development, customization, modification, and/or repair of microelectronic circuits.

Piqué, Alberto; Auyeung, Raymond C. Y.; Metkus, Kristin M.; Kim, Heungsoo; Mathews, Scott; Bailey, Thomas; Chen, Xianhai; Young, Lydia J.

2008-02-01

282

Electron transfer between cytochrome c and metalloporphyrins at high exothermicities  

Science.gov (United States)

The electron-transfer rates between cytochrome c and the anion radical of two metalloporphyrins ZnTPPS and ZnTPPC (? E for the reaction is 1.42eV) have been measured by laser flash spectroscopy. The anion radicals were produced by reaction of the porphyrins with hydrated electrons which resulted from the photoionization of ferrocyanide ions. Together with results obtained previously, a reorganization energy of ? 1.1 eV was deduced for the cytochrome c-porphyrin system.

Cho, K. C.; Ng, K. M.; Choy, C. L.; Che, C. M.

1986-09-01

283

Photophysical and electron transfer studies of a stable carbocation  

Science.gov (United States)

Photophysical and electron transfer properties of the stable trioxatriangulenium carbocation ( 1) are reported. Photophysical studies include absorption, fluorescence and phosphorescence spectra, singlet and triplet state quantum yields and lifetimes. Both the singlet and triplet excited states of 1 can accept an electron from donor molecules leading to the formation of the donor radical cation and the radical of 1. In aqueous solution, 1 can photo-oxidize DNA nucleosides such as guanosine and adenosine indicating that 1 may have potential use as a DNA cleaving agent.

Dileesh, S.; Gopidas, K. R.

2000-11-01

284

PROTON COUPLED ELECTRON TRANSFER AND BOND BREAKING IN ELECTROCATALYTIC PROCESSES  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Proton Coupled Electron Transfer are involved in a huge number of processes, especially in catalytic activation of small molecules such as H2O or CO2. The actual ecological background requires the use of alternative nonpolluting resources. The production of energy thanks to natural flow implies storage to permit a use on demand. Chemical bonds seem to be a solution through the activation of small molecules by using metal transition complexes as catalysts in electrocatalytic reactions. The mec...

Passard, Guillaume

2014-01-01

285

Direct and indirect electron transfer between electrodes and redox proteins.  

Digital Repository Infrastructure Vision for European Research (DRIVER)

The direct electrochemistry of redox proteins has been achieved at a variety of electrodes, including modified gold, pyrolytic graphite and metal oxides. Careful design of electrode surfaces and electrolyte conditions are required for the attainment of rapid and reversible protein-electrode interaction. The electron transfer reactions of more complex systems, such as redox enzymes, are now being examined. The 'well-behaved' electrochemistry of redox proteins can be usefully exploited by coupl...

Frew, Je; Hill, Ha

1988-01-01

286

Structures of Protein-Protein Complexes involved in electron transfer  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Electron transfer (ET) reactions are essential for life since they underpin oxidative phosphorylation and photosynthesis, processes leading to the generation of ATP, and are involved in many reactions of intermediary metabolism1. Key to these roles is the formation of transient inter-protein ET complexes. The structural basis for the control of specificity between partner proteins is lacking since these weak transient complexes have remained largely intractable for crystallographic studies2,3...

Antonyuk, Svetlana V.; Cong, Han; Eady, Robert R.; Hasnain, S. Samar

2013-01-01

287

Low activation barriers characterize intramolecular electron transfer in ascorbate oxidase  

DEFF Research Database (Denmark)

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 over a range of reactant concentrations, pH, and temperature. The direct bimolecular reduction of type 1 [Cu(II)] [(1.2 +/- 0.2) x 10(9) M-1.s-1] was followed by its subsequent reoxidation in three distinct phases, all found to be unimolecular processes with the respective specific rates of 201 +/- 8, 20 +/- 4, and 2.3 +/- 0.2 s-1 at pH 5.5 and 298 K. While at this pH no direct bimolecular reduction was resolved in the 330-nm band, at pH 7.0 such a direct process was observed [(6.5 +/- 1.2) x 10(8) M-1.s-1]. In the same slower time domains where type 1 [Cu(I)] reoxidation was monitored, reduction of type 3 [Cu(II)] was observed, which was also concentration independent and with identical rate constants and amplitudes commensurate with those of type 1 [Cu(II)] reoxidation. These results show that after electron uptake by type 1 [Cu(II)], its reoxidation takes place by intramolecular electron 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 +/- 9 and -215 +/- 16 J.K-1.mol-1. The exceptionally low enthalpy barriers imply the involvement of highly optimized electron transfer pathways for internal electron transfer.

Farver, O; Pecht, I

1992-01-01

288

Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface  

Energy Technology Data Exchange (ETDEWEB)

Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA{sup +}) or ClO{sub 4}{sup -} is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k{sub 12}, is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K{sub 4}Fe(CN){sub 6} in water when the concentration of TCNQ in the DCE phase is in excess. The k{sub 12} dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ{sup -} and ferricyanide, k{sub 21}, is also obtained by SECM and these results cannot be explained by the same manner.

Bai Yamin; Sun Peng; Zhang Meiqin; Gao Zhao; Yang Zhengyu; Shao Yuanhua

2003-10-15

289

Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface  

International Nuclear Information System (INIS)

Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA+) or ClO4- is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k12, is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K4Fe(CN)6 in water when the concentration of TCNQ in the DCE phase is in excess. The k12 dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ- and ferricyanide, k21, is also obtained by SECM and these results cannot be explained by the same manner

290

The electron transfer system of syntrophically grown Desulfovibrio vulgaris  

Energy Technology Data Exchange (ETDEWEB)

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.

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

291

The Electron Transfer System of Syntrophically Grown Desulfovibrio vulgaris  

Energy Technology Data Exchange (ETDEWEB)

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.

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

292

Nanoparticle facilitated extracellular electron transfer in microbial fuel cells.  

Science.gov (United States)

Microbial fuel cells (MFCs) have been the focus of substantial research interest due to their potential for long-term, renewable electrical power generation via the metabolism of a broad spectrum of organic substrates, although the low power densities have limited their applications to date. Here, we demonstrate the potential to improve the power extraction by exploiting biogenic inorganic nanoparticles to facilitate extracellular electron transfer in MFCs. Simultaneous short-circuit current recording and optical imaging on a nanotechnology-enabled platform showed substantial current increase from Shewanella PV-4 after the formation of cell/iron sulfide nanoparticle aggregates. Detailed characterization of the structure and composition of the cell/nanoparticle interface revealed crystalline iron sulfide nanoparticles in intimate contact with and uniformly coating the cell membrane. In addition, studies designed to address the fundamental mechanisms of charge transport in this hybrid system showed that charge transport only occurred in the presence of live Shewanella, and moreover demonstrated that the enhanced current output can be attributed to improved electron transfer at cell/electrode interface and through the cellular-networks. Our approach of interconnecting and electrically contacting bacterial cells through biogenic nanoparticles represents a unique and promising direction in MFC research and has the potential to not only advance our fundamental knowledge about electron transfer processes in these biological systems but also overcome a key limitation in MFCs by constructing an electrically connected, three-dimensional cell network from the bottom-up. PMID:25310721

Jiang, Xiaocheng; Hu, Jinsong; Lieber, Alexander M; Jackan, Charles S; Biffinger, Justin C; Fitzgerald, Lisa A; Ringeisen, Bradley R; Lieber, Charles M

2014-11-12

293

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

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2010-04-01

294

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

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...agency make all payments via electronic funds transfer? 102-118...agency make all payments via electronic funds transfer? Yes...must make all payments for goods and services via EFT (this includes goods and services ordered...

2010-07-01

295

A New Formulation of the Frequency Factor in the Expression for the Rate Constant of Interfacial Charge Transfers  

Scientific Electronic Library Online (English)

Full Text Available SciELO Portugal | Language: English Abstract in english A new way for deriving the fundamental equation of the electrochemistry has been developed in the potential range in which Butler-Volmer behaviour is found. In this approach the frequency factor is considered to be a function of the potential instead of the activation energy. The frequency factor is [...] calculated by means of a classical statistical mechanics treatment giving rise to a new definition for the symmetry factor. A new expression for the standard rate constant in adiabatic heterogeneous charge transfer reactions has been derived.

Jaime González, Velasco.

296

A New Formulation of the Frequency Factor in the Expression for the Rate Constant of Interfacial Charge Transfers  

Directory of Open Access Journals (Sweden)

Full Text Available A new way for deriving the fundamental equation of the electrochemistry has been developed in the potential range in which Butler-Volmer behaviour is found. In this approach the frequency factor is considered to be a function of the potential instead of the activation energy. The frequency factor is calculated by means of a classical statistical mechanics treatment giving rise to a new definition for the symmetry factor. A new expression for the standard rate constant in adiabatic heterogeneous charge transfer reactions has been derived.

Jaime González Velasco

2007-01-01

297

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

International Nuclear Information System (INIS)

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/oxidizedzed 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.

298

Long range electron transfer across $\\pi$-conjugated systems: role of electron correlations  

CERN Document Server

We consider a prototype polyene chain: donor-$\\pi$(bridge)-acceptor. The distance between the donor and the acceptor is varied by increasing the number of bridged atoms and rate of electron transfer, k$_{et}$ is studied for a series of different donors, D=NH$_2$, SH, OH, and a fixed acceptor, A=NO$_2$. We observe a large k$_{et}$ even at a very large D-A separation of $\\sim$ 45 $\\AA$, unexpected from the well-known and standard theories like the Forster theory. Such a long range electron transfer is due to the strong electron-electron interactions in the bridged orbitals that result in deconfinment of electrons in donor orbitals. Calculations at various levels: semi-empirical and many-body exact, have been performed to accurately account for such correlations.

Lakshmi, S; Pati, S K; Datta, Ayan; Pati, Swapan K.

2005-01-01

299

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

DEFF Research Database (Denmark)

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.

Zhang, Jingdong; Grubb, Mikala

2003-01-01

300

Understanding interfacial charge transfer between metallic PEDOT counter electrodes and a cobalt redox shuttle in dye-sensitized solar cells.  

Science.gov (United States)

Conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with iron(III) tris-p-toluenesulfonate (PEDOT:Tos) having metallic conductivity was coated onto fluorine-doped tin oxide (FTO) glass and plain glass substrates and used as a counter electrode (CE) in a dye-sensitized solar cell (DSC) with a [Co(bpy)3](3+/2+) complex redox shuttle. DSCs with PEDOT:Tos/glass CE yielded power conversion efficiencies (PCE) of 6.3%, similar to that of DSCs with platinized FTO glass CE (6.1%). The PEDOT:Tos-based counter electrodes had 5 to 10 times lower charge-transfer resistance than the Pt/FTO CE in DSCs, as analyzed by impedance spectroscopy. More detailed studies in symmetrical CE-CE cells showed that the PEDOT:Tos layers are nanoporous. Not all internal area can be used catalytically under solar cell conditions and effective charge-transfer resistance was similar to that of Pt/FTO. PMID:24410094

Park, Byung-wook; Pazoki, Meysam; Aitola, Kerttu; Jeong, Seunghee; Johansson, Erik M J; Hagfeldt, Anders; Boschloo, Gerrit

2014-02-12

 
 
 
 
301

Electron Transfer Dissociation (ETD) of Peptides Containing Intrachain Disulfide Bonds  

Science.gov (United States)

The fragmentation chemistry of peptides containing intrachain disulfide bonds was investigated under electron transfer dissociation (ETD) conditions. Fragments within the cyclic region of the peptide backbone due to intrachain disulfide bond formation were observed, including: c (odd electron), z (even electron), c-33 Da, z + 33 Da, c + 32 Da, and z-32 Da types of ions. The presence of these ions indicated cleavages both at the disulfide bond and the N-C? backbone from a single electron transfer event. Mechanistic studies supported a mechanism whereby the N-C? bond was cleaved first, and radical-driven reactions caused cleavage at either an S-S bond or an S-C bond within cysteinyl residues. Direct ETD at the disulfide linkage was also observed, correlating with signature loss of 33 Da (SH) from the charge-reduced peptide ions. Initial ETD cleavage at the disulfide bond was found to be promoted amongst peptides ions of lower charge states, while backbone fragmentation was more abundant for higher charge states. The capability of inducing both backbone and disulfide bond cleavages from ETD could be particularly useful for sequencing peptides containing intact intrachain disulfide bonds. ETD of the 13 peptides studied herein all showed substantial sequence coverage, accounting for 75%-100% of possible backbone fragmentation.

Cole, Scott R.; Ma, Xiaoxiao; Zhang, Xinrong; Xia, Yu

2012-02-01

302

27 CFR 24.272 - Payment of tax by electronic fund transfer.  

Science.gov (United States)

... false Payment of tax by electronic fund transfer. 24.272...ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE...272 Payment of tax by electronic fund transfer. (a) General...institution in making payment by electronic fund transfer (EFT)...

2010-04-01

303

27 CFR 26.112a - Payment of tax by electronic fund transfer.  

Science.gov (United States)

... false Payment of tax by electronic fund transfer. 26.112a...ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE...112a Payment of tax by electronic fund transfer. (a) General...bank in making payment by electronic fund transfer...

2010-04-01

304

Noise-assisted quantum electron transfer in photosynthetic complexes  

CERN Document Server

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...

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

2013-01-01

305

Mechanisms for control of biological electron transfer reactions.  

Science.gov (United States)

Electron transfer (ET) through and between proteins is a fundamental biological process. The rates and mechanisms of these ET reactions are controlled by the proteins in which the redox centers that donate and accept electrons reside. The protein influences the magnitudes of the ET parameters, the electronic coupling and reorganization energy that are associated with the ET reaction. The protein can regulate the rates of the ET reaction by requiring reaction steps to optimize the system for ET, leading to kinetic mechanisms of gated or coupled ET. Amino acid residues in the segment of the protein through which long range ET occurs can also modulate the ET rate by serving as staging points for hopping mechanisms of ET. Specific examples are presented to illustrate these mechanisms by which proteins control rates of ET reactions. PMID:25085775

Williamson, Heather R; Dow, Brian A; Davidson, Victor L

2014-12-01

306

Effects of electrostatic interactions on electron transfer reactions  

International Nuclear Information System (INIS)

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

307

Charge amplification and transfer processes in the gas electron multiplier  

CERN Document Server

We report the results of systematic investigations on the operating properties of detectors based on the gas electron multiplier (GEM). The dependence of gain and charge collection efficiency on the external fields has been studied in a range of values for the hole diameter and pitch. The collection efficiency of ionization electrons into the multiplier, after an initial increase, reaches a plateau extending to higher values of drift field the larger the GEM voltage and its optical transparency. The effective gain, fraction of electrons collected ba an electrode following the multiplier, increases almost linearly with the collection field, until entering a steeper parallel plate multiplication regime. The maximum effective gain attainable increases with the reduction in the hole diameter, stabilizing to a constant value at a diameter approximately corresponding to the foil thickness. Charge transfer properties appear to depend only on ratios of fields outside mad and the channels, with no interaction between ...

Bachmann, S; Ropelewski, Leszek; Sauli, Fabio; Sharma, A; Mörmann, D

1999-01-01

308

DNA Damage Induced by Low-Energy Electrons: Electron Transfer and Diffraction  

Science.gov (United States)

Thin films of the short single strand of DNA, GCAT, in which guanine (G) or adenine (A) have been removed, were bombarded under vacuum by 4 to 15 eV electrons. The fragments corresponding to base release and strand breaks (SB) were analyzed by high performance liquid chromatography and their yields compared with those obtained from unmodified GCAT. From such a comparison, it is shown that, using GCAT as a model system, (1) most SB result from electron capture by DNA bases followed by electron transfer to the phosphate group and (2) the initial capture probability depends on the coherence of the electron wave within the tetramer.

Zheng, Yi; Wagner, J. Richard; Sanche, Léon

2006-05-01

309

Electron transfer reactions involving acridine and related compounds  

International Nuclear Information System (INIS)

Acridine is rapidly reduced by e/sub sol/- (k = 3 x 1010 M-1 s-1) and by (CH3)2CO- (k = 3 x 109 M-1 s-1 in water and 1.4 x 109 M-1 s-1 in i-PrOH). Reduction by (CH3)2COH and CO2- is rapid and efficient only when the acridine is protonated (pK/sub a/ = 5.6). With neutral acridine, however, the slow reduction is accompanied by addition of these radicals to acridine. Both forms of acridine are reduced by pyridinyl radicals, although the acid more rapidly than the neutral form. In all these one-electron reductions the anion radical of acridine is produced, which in aqueous and alcoholic solutions undergoes rapid protonation on the nitrogen to form a neutral radical, with a pK/sub a/ apparently above 14. Related heterocyclic compounds, such as 1,10-phenanthroline and phenazine, behave in a similar fashion. The radicals produced by reduction of acridine and other heterocycles can transfer an electron to 9,10-anthraquinone in nonaqueous media or to anthraquinonesulfonate in aqueous solutions (k approx. 109 M-1 s-1). The spectra of the resulting semiquinone radicals were found, in all cases examined, to be identical with those obtained by direct reduction of the quinone under similar conditions without the intermediacy of the heterocycle. This is in contrast w of the heterocycle. This is in contrast with previous findings with a porphyrin-anthraqinone system. It is concluded that, despite the previous suggestion that an intermediate complex is formed upon electron transfer from tetraphenylporphyrin radical to anthraquinone, no such complex appears to be formed in the electron transfer reactions involving acridine and related heterocycles

310

Reduced density matrix hybrid approach: Application to electronic energy transfer  

International Nuclear Information System (INIS)

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

311

Hetero-cycloreversions mediated by photoinduced electron transfer.  

Science.gov (United States)

Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the preferred route depends on the substitution pattern of the ring, the type of heteroatom, and various experimental conditions. To better accommodate spin and charge, C-X cleavage happens more frequently, especially in the radical anionic version of the reaction. The addition or withdrawal of a single electron provides a new complementary synthetic strategy to activate hetero-cycloreversions. Despite its potential, this strategy remains largely unexplored. However, it offers a useful method to achieve C?X/olefin metathesis or, upon ring expansion, to construct six-membered heterocyclic rings. PMID:24702062

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

2014-04-15

312

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

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 fragment...

Khan, Yaser R.; Brumer, Paul

2012-01-01

313

Single Electron Transfer Living Radical Polymerization via a New Initiator  

Science.gov (United States)

Research and development of novel initiating system such as single electron transfer living radical polymerization (SET-LRP) is of high importance in polymer chemistry. A new SET-LRP initiator was synthesized and applied to prepare end-functionalized poly(methyl methacrylate) (PMMA) in this study. ?-Trichloromethyl benzyl alcohol was firstly synthesized, followed by preparation of PMMA under SET-LRP conditions. Conversion of MMA was 81.9%, and the molecular weight of PMMA was about 2.5 kDa at 60 °C for 1 h. Consistency of the number-average molecular weight of PMMA from NMR, GPC and theoretical calculation indicated that the polymerization featured controllable property. Broad molecular weight distribution (MWD) may be ascribed to branched polymers formed by initiation and chain transfer.

Bai, Xiongxiong; Hu, Ying; Zhang, Xu; Ai, Lingling; Cheng, Chuanjie

2014-08-01

314

A stochastic reorganizational bath model for electronic energy transfer  

CERN Document Server

The fluctuations of optical gap induced by the environment play crucial roles 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 model, in which the energy-gap fluctuation is approximated as a white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to take the thermal fluctuation of excitation energies into account. 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 equ...

Fujita, Takatoshi; Aspuru-Guzik, Alan

2014-01-01

315

Modeling biofilms with dual extracellular electron transfer mechanisms  

Energy Technology Data Exchange (ETDEWEB)

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

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

2013-11-28

316

Extracting electron transfer coupling elements from constrained density functional theory  

International Nuclear Information System (INIS)

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

317

Mechanisms of bridge-mediated electron transfer: A TDDFT electronic dynamics study  

Science.gov (United States)

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

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

2012-12-01

318

Transcriptomic and genetic analysis of direct interspecies electron transfer.  

Science.gov (United States)

The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens was the electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7-fold lower in cocultures with G. metallireducens than in cocultures with P. carbinolicus, consistent with DIET and HIT, respectively, in the two cocultures. Transcript abundance for the pilus-associated cytochrome OmcS, which is essential for DIET but not for HIT, was 240-fold higher in the cocultures with G. metallireducens than in cocultures with P. carbinolicus. The pilin gene pilA was moderately expressed despite a mutation that might be expected to repress pilA expression. Lower transcript abundance for G. sulfurreducens genes associated with acetate metabolism in the cocultures with P. carbinolicus was consistent with the repression of these genes by H2 during HIT. Genes for the biogenesis of pili and flagella and several c-type cytochrome genes were among the most highly expressed in G. metallireducens. Mutant strains that lacked the ability to produce pili, flagella, or the outer surface c-type cytochrome encoded by Gmet_2896 were not able to form cocultures with G. sulfurreducens. These results demonstrate that there are unique gene expression patterns that distinguish DIET from HIT and suggest that metatranscriptomics may be a promising route to investigate interspecies electron transfer pathways in more-complex environments. PMID:23377933

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

2013-04-01

319

Artificial photosynthesis: from nanosecond electron transfer to catalytic water oxidation.  

Science.gov (United States)

Human society faces a fundamental challenge as energy consumption is projected to increase due to population and economic growth as fossil fuel resources decrease. Therefore the transition to alternative and sustainable energy sources is of the utmost importance. The conversion of solar energy into chemical energy, by splitting H2O to generate molecular O2 and H2, could contribute to solving the global energy problem. Developing such a system will require the combination of several complicated processes, such as light-harvesting, charge separation, electron transfer, H2O oxidation, and reduction of the generated protons. The primary processes of charge separation and catalysis, which occur in the natural photosynthetic machinery, provide us with an excellent blueprint for the design of such systems. This Account describes our efforts to construct supramolecular assemblies capable of carrying out photoinduced electron transfer and to develop artificial water oxidation catalysts (WOCs). Early work in our group focused on linking a ruthenium chromophore to a manganese-based oxidation catalyst. When we incorporated a tyrosine unit into these supramolecular assemblies, we could observe fast intramolecular electron transfer from the manganese centers, via the tyrosine moiety, to the photooxidized ruthenium center, which clearly resembles the processes occurring in the natural system. Although we demonstrated multi-electron transfer in our artificial systems, the bottleneck proved to be the stability of the WOCs. Researchers have developed a number of WOCs, but the majority can only catalyze H2O oxidation in the presence of strong oxidants such as Ce(IV), which is difficult to generate photochemically. By contrast, illumination of ruthenium(II) photosensitizers in the presence of a sacrificial acceptor generates [Ru(bpy)3](3+)-type oxidants. Their oxidation potentials are significantly lower than that of Ce(IV), but our group recently showed that incorporating negatively charged groups into the ligand backbone could decrease the oxidation potential of the catalysts and, at the same time, decrease the potential for H2O oxidation. This permitted us to develop both ruthenium- and manganese-based WOCs that can operate under neutral conditions, driven by the mild oxidant [Ru(bpy)3](3+). Many hurdles to the development of viable systems for the production of solar fuels remain. However, the combination of important features from the natural photosynthetic machinery and novel artificial components adds insights into the complicated catalytic processes that are involved in splitting H2O. PMID:23957573

Kärkäs, Markus D; Johnston, Eric V; Verho, Oscar; Akermark, Björn

2014-01-21

320

Effect of electron transfer on contact fusion kinetics  

International Nuclear Information System (INIS)

The effect of electric current on the kinetics of contact fusion (CF) is investigated. It is revealed that electric current can not only retard or accelerate CF in the diffusion regime at constant temperature T, but it can result in the process of ''contact crysllization''. CF may be used to study electron transfer in liquid solutions of eutectic systems. The results obtained may be applied in problems of the so-called contact-reactive soldering. In-Bi, Pb-Bi and Cd-Bi systems were used for investigations

 
 
 
 
321

Long-range intramolecular electron transfer in azurins  

DEFF Research Database (Denmark)

The Cu(II) sites of azurins, the blue single copper proteins, isolated from Pseudomonas aeruginosa and Alcaligenes spp. (Iwasaki) are reduced by CO2- radicals, produced by pulse radiolysis, in two distinct reaction steps: (i) a fast bimolecular phase, at the rates (5.0 +/- 0.8) x 10(8) M-1.s-1 (P. aeruginosa) and (6.0 +/- 1.0) x 10(8) M-1.s-1 (Alcaligenes); (ii) a slow unimolecular phase with specific rates of 44 +/- 7 s-1 in the former and 8.5 +/- 1.5 s-1 for the latter (all at 298 K, 0.1 M ionic strength). Concomitant with the fast reduction of Cu(II), the single disulfide bridge linking cysteine-3 to -26 in these proteins is reduced to the RSSR- radical ion as evidenced by its characteristic absorption band centered at 410 nm. This radical ion decays in a unimolecular process with a rate identical to that of the slow Cu(II) reduction phase in the respective protein, thus clearly suggesting that a long-range intramolecular electron transfer occurs between the RSSR- radicals and the Cu(II) site. The temperature dependence of the internal electron transfer process in both proteins was measured over the 4 degrees C to 42 degrees C range. The activation parameters derived are delta H* = 47.5 +/- 4.0 and 16.7 +/- 1.5 kJ.mol-1; and delta S not equal to = -56.5 +/- 7.0 and -171 +/- 18 J.K-1.mol-1, respectively. Using the Marcus theory, we found that the intramolecular electron transfer rates and their activation parameters observed for the two azurins correlate well with the distances between the reactive sites, their redox potential, and the nature of the separating medium. Thus, azurins with distinct structural and reactivity characteristics isolated from different bacteria or modified by site-directed mutagenesis can be used in comparing long-range electron transfer process between their conserved disulfide bridge and the Cu(II) sites.

Farver, O; Pecht, I

1989-01-01

322

Light induced electron transfer reactions of metal complexes  

Energy Technology Data Exchange (ETDEWEB)

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.

Sutin, N; Creutz, C

1980-01-01

323

Quantum simulation of nuclear rearrangement in electron transfer reactions  

Digital Repository Infrastructure Vision for European Research (DRIVER)

A quantum simulation scheme based on the path integral molecular dynamics technique has been used to calculate the effective activation energies associated with nuclear rearrangement in the electron transfer reactions Co(NH3)62+ + Co(NH3)63+ ? Co(NH3)63+ + Co(NH3)62+ and Ru(NH3)62+ + Ru(NH3)63+ ? Ru(NH3)63+ + Ru(NH3)62+. Even with a simple Hamiltonian and short time dynamic simulations, the results are in satisfactory agreement with other theoretical calculations. This simulation approach...

Zheng, Chong; Mccammon, J. Andrew; Wolynes, Peter G.

1989-01-01

324

Light induced electron transfer reactions of metal complexes  

International Nuclear Information System (INIS)

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

325

Photoinduced dissociative electron transfer (DET) interactions in methoxycalixarene chloroalkane systems  

Science.gov (United States)

Fluorescence quenching of methoxycalixarenes (MOCX) by chloroalkanes (CA) has been investigated in acetonitrile solutions. Observed quenching is attributed to photoinduced dissociative electron transfer (DET) interaction, which is supported by the characterization of the Cl - ions and by the radical scavenging experiments. Comparing the Cl - yields with different DET systems, it is inferred that both concerted and stepwise DET mechanisms operate simultaneously in MOCX-CA systems. A correlation of the quenching constants with the free-energy changes following a suitable DET theory supports the above inference.

Mohanty, J.; Pal, H.; Nayak, S. K.; Chattopadhyay, S.; Sapre, A. V.

2003-03-01

326

Linear Energy Relationships in Ground State Proton Transfer and Excited State Proton-Coupled Electron Transfer.  

Science.gov (United States)

Proton-coupled electron transfer (PCET) processes are elementary chemical reaction involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects and reaction barriers of both ground state proton transfer (pT) and photo-induced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photo-excitation leads to a PCET reaction, for which we find that the non-adiabatic excited state reaction barrier depend on the thermodynamic driving force with a Brønsted slope of ½. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes. PMID:25485993

Gámiz-Hernández, Ana-Patricia; Magomedov, Artiom; Hummer, Gerhard; Kaila, Ville R I

2014-12-01

327

Effect of electrostatic interactions on electron-transfer reactions  

International Nuclear Information System (INIS)

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

328

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

Science.gov (United States)

...requirements apply to electronic records? 1235...Property NATIONAL ARCHIVES AND RECORDS ADMINISTRATION...the transfer of electronic records other than...with the National Archives and Records Administration, Electronic/Special...

2010-07-01

329

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

Science.gov (United States)

...3170-AA33 Electronic Fund Transfers...Bureau of Consumer Financial Protection...participants in electronic fund and remittance...individual consumer rights...Banking, banks, Consumer protection, Credit unions, Electronic fund...

2013-01-29

330

ATP-induced electron transfer by redox-selective partner recognition.  

Science.gov (United States)

Thermodynamically unfavourable electron transfers are enabled by coupling to an energy-supplying reaction. How the energy is transduced from the exergonic to the endergonic process is largely unknown. Here we provide the structural basis for an energy transduction process in the reductive activation of B12-dependent methyltransferases. The transfer of one electron from an activating enzyme to the cobalamin cofactor is energetically uphill and relies on coupling to an ATPase reaction. Our results demonstrate that the key to coupling is, besides the oxidation state-dependent complex formation, the conformational gating of the electron transfer. Complex formation induces a substitution of the ligand at the electron-accepting Co ion. Addition of ATP initiates electron transfer by provoking conformational changes that destabilize the complex. We show how remodelling of the electron-accepting Co(2+) promotes ATP-dependent electron transfer; an efficient strategy not seen in other electron-transferring ATPases. PMID:25109607

Hennig, Sandra E; Goetzl, Sebastian; Jeoung, Jae-Hun; Bommer, Martin; Lendzian, Friedhelm; Hildebrandt, Peter; Dobbek, Holger

2014-01-01

331

Interfacial forces  

International Nuclear Information System (INIS)

The past few years have witnessed tremendous advances in experimental and theoretical techniques for probing both the static and dynamic properties of surfaces at the angstrom level. Here we review how these advances have furthered our fundamental understanding of adhesion-particularly those processes that contribute to energy dissipation during adhesion and separation (loading--unloading cycles), and friction-particularly how the dynamic (e.g., viscous and rheological) properties of liquids in ultrathin films differ from the bulk liquid properties, and how this affects the friction forces of lubricated contacts. The emphasis will be on ''ideal'' surfaces and interfaces, i.e., surfaces that are molecularly smooth, and interfacial films that are no more than a few molecular layers thick

332

Determination of the electronics transfer function for current transient measurements  

CERN Document Server

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...

Scharf, Christian

2014-01-01

333

Solvent-controlled electron transfer in crystal violet lactone.  

Science.gov (United States)

Steady-state and picosecond time-resolved emission experiments are used to examine the excited-state charge transfer reaction of crystal violet lactone (CVL) in aprotic solvents. Solvatochromic analysis using a dielectric continuum model suggests dipole moments of 9-12 D for the initially excited (LE) state and ?24 D for the charge-transfer (CT) state. Intensities of steady-state emission as well as kinetic data provide free energies for the LE ? CT reaction that range from +12 kJ/mol in nonpolar solvents to -10 kJ/mol in highly polar solvents at 25 °C. Reaction rates constants, which lie in the range of 10-100 ns(-1) in most solvents, depend on both solvent polarity and solvent friction. In highly polar solvents, rates are correlated to solvation times in a manner that indicates that the reaction is a solvent-controlled electron transfer on an adiabatic potential surface having a modest barrier. PMID:20831148

Li, Xiang; Maroncelli, Mark

2011-04-28

334

Photoinduced electron transfer in rhenium(I)-oligotriarylamine molecules.  

Science.gov (United States)

Two molecular triads with an oligotriarylamine multielectron donor were synthesized and investigated with a view to obtaining charge-separated states in which the oligotriarylamine is oxidized 2-fold. Such photoinduced accumulation of multiple redox equivalents is of interest for artificial photosynthesis. The first triad was comprised of the oligotriarylamine and two rhenium(I) tricarbonyl diimine photosensitizers each of which can potentially accept one electron. In the second triad the oligotriarylamine was connected to anthraquinone, in principle an acceptor of two electrons, via a rhenium(I) tricarbonyl diimine unit. With nanosecond transient absorption spectroscopy (using an ordinary pump-probe technique) no evidence for the generation of 2-fold oxidized oligotriarylamine or 2-fold reduced anthraquinone was found. The key factors limiting the photochemistry of the new triads to simple charge separation of one electron and one hole are discussed, and the insights gained from this study are useful for further research in the area of charge accumulation in purely molecular (nanoparticle-free) systems. An important problem of the rhenium-based systems considered here is the short wavelength required for photoexcitation. In the second triad, photogenerated anthraquinone monoanion is protonated by organic acids, and the resulting semiquinone species leads to an increase in lifetime of the charge-separated state by about an order of magnitude. This shows that the proton-coupled electron transfer chemistry of quinones could be beneficial for photoinduced charge accumulation. PMID:25271567

Bonn, Annabell G; Neuburger, Markus; Wenger, Oliver S

2014-10-20

335

Electron-transfer functionality of synthetic coiled-coil metalloproteins  

Scientific Electronic Library Online (English)

Full Text Available SciELO Brazil | Language: English Abstract in portuguese O campo emergente da engenharia molecular de metaloproteínas visa preparar proteínas artificiais, cujas propriedades podem imitar e talvez até mesmo melhorar várias características encontradas nas metaloenzimas naturais. Este artigo de revisão resume nossos esforços recentes na preparação de metalop [...] roteínas sintéticas, construídas a partir de "coiled-coils" alfa-hélices, e na incorporação de grupos de transferência de elétrons nesses sistemas. Recentemente, concebemos uma cisteína contendo um peptídeo com hélice randômica, o qual forma uma estrutura "coiled-coil" alfa-helicoidal ao se ligar a vários metais. O aduto de CuI pode atuar como agente fotoindutor de transferência de elétrons para receptores exógenos, e transfere elétrons por colisão na região invertida de Marcus para várias aminas de rutênio, as quais atuam como receptores. Especula-se que este resultado inesperado advenha do posicionamento do cofator de CuI no interior da porção hidrofóbica da proteína, o qual proíbe a aproximação entre o doador e o receptor, diminuindo a velocidade de transferência eletrônica daquelas reações termodinamicamente muito favorecidas, para velocidades inferiores à do limite difusional. Abstract in english The emerging field of metalloprotein design seeks to prepare artificial proteins whose properties can mimic, enhance, and perhaps improve upon many features found in natural metalloenzymes. This review summarizes our recent efforts to prepare synthetic metalloproteins built from alpha-helical coiled [...] -coils and to incorporate electron-transfer functionality within these systems. We have recently designed a cysteine-containing random-coil peptide which forms a alpha-helical coiled-coil upon binding various metals. The CuI adduct can serve as photoinduced electron-transfer agent to exogenous acceptors and undergoes collisional electron-transfer in the inverted Marcus region to various ruthenium ammine acceptors. It is speculated that this unexpected result might be due to the positioning of the CuI cofactor within the hydrophobic core of the protein which prohibits close approach between the donor and acceptor to slow the high driving force reaction rates below the diffusion limit.

Michael Y., Ogawa; Jiufeng, Fan; Anna, Fedorova; Jing, Hong; Olesya A., Kharenko; Anna Y., Kornilova; Robin C., Lasey; Fei, Xie.

1516-15-01

336

ELECTRONIC FUNDS TRANSFER: EXPLORING THE DIFFICULTIES OF SECURITY  

Directory of Open Access Journals (Sweden)

Full Text Available 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.

MPAKWANA ANNASTACIA MTHEMBU

2010-10-01

337

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

Science.gov (United States)

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. In contrast to carbon double bonds, nitrogen double bonds can react via two possible mechanisms; rotation or inversion. To determine which pathway is predominant, I studied an azobenzene derivative using both FSRS and impulsive stimulated Raman spectroscopy (ISRS). The FSRS experiments demonstrated that the photochemical reaction occurs concomitantly with the 700 fs non-radiative decay of the excited state; because no major change in N=N stretching frequency was measured, I surmised that the reaction proceeds through an inversion pathway. My subsequent ISRS experiments confirmed this hypothesis; I observed a highly displaced, low frequency, inversion-like mode, indicating that initial movement out of the Franck-Condon region proceeds along an inversion coordinate. To probe which nuclear motions facilitate electron transfer and charge recombination, I used FSRS and the newly developed 2D-FSRS techniques to study two model systems, triphenylamine dyes bound to TiO2 nanoparticles and a molecular charge transfer (CT) dimer. In the dye-nanoparticle system I discovered that charge separation persists much longer (> 100 ps) than previously thought by using the juxtaposition of the FSRS and transient absorption data to separate the dynamics of the dye from that of the injected electron. Additionally, I discovered that dye constructs with an added vinyl group were susceptible to quenching via isomerization. The CT dimer offered an opportunity to study a system in which charge recombination occurred on a shorter timescale (˜10 ps). Here I found that impulsively excited coherent nuclear motion in the excited state survived for more than 5 ps. These long lived coherences enabled the performance of 2D-FSRS to identify the coupling and tuning modes of the conical intersection that connects the charge transfer excited state with the neutral ground state and therefore the nuclear motions responsible for charge recombination. Furthermore, these data demonstrate that the photochemical reactivity is not mediated by phase-space randomization but rather by specific, coherent, nuclear trajectories. In this thesis I have demonstrated the power and utility of FSRS in probing condensed phase chemical reaction dynamics and provided a glimpse of the capabilities of 2D-FSRS. In general, 2D-FSRS provides a direct measure of the anharmonic coupling that controls reactivity. Looking forward, higher time resolution (broader band) 2D-FSRS will open up a whole new approach for characterizing transition states and energy transfer processes.

Hoffman, David Paul

338

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

Science.gov (United States)

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 ? = 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

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

2013-06-01

339

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

DEFF Research Database (Denmark)

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

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

2001-01-01

340

Collisional electron transfer to photoexcited acceptor radical anions  

DEFF Research Database (Denmark)

In this article, we show that photoexcitation of radical anions facilitates electron transfer from sodium atoms in femtosecond encounters. Thus, excitation of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and fluorinated TCNQ (TCNQ-F(4)) anions to the second optically active state at 478 nm led to increases in the yields of dianions of about 20% and 10%, respectively. Photoexcitation with a nanosecond-long laser pulse was done a few microseconds before the ions entered the sodium collision cell so that none of the ions would be in any of the initially reached doublet-excited states. We suggest an explanation for the higher electron capture cross section based on the formation of long-lived quartet state anions. Excitation of TCNQ anions within the lowest-energy absorption band, where there are no accessible quartet states, led instead to a lower yield of dianions. There are at least three explanations for the lower dianion yields: (1) Depletion of the monoanion beam due to photodetachment after the absorption ofminimum two photons; (2) Formation of short-lived vibrationally excited dianions that decay by electron autodetachment prior to identification; and (3) Lower electron capture cross sections of vibrationally excited monoanions. Similar losses in dianion signal can occur at 478 nm so the actual yield of dianions at this wavelength due to the population of quartet states is therefore greater than that observed. Our methodology devises a more efficient route for the production of molecular dianions, and at the same time it may provide information on long-lived electronic states.

Wyer, Jean Ann; StØchkel, Kristian

2012-01-01

 
 
 
 
341

Cluster PEACE observations of electrons during magnetospheric flux transfer events  

Directory of Open Access Journals (Sweden)

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

C. J. Owen

342

Interfacial microstructure and defect analysis in Cu(In,Ga)Se([sub]2)-based multilayered film by analytical transmission electron microscopy and focused ion beam  

International Nuclear Information System (INIS)

Interfacial microstructures of Cu(In,Ga)Se2(CIGS)-based multilayered film are closely characterized by TEM (transmission electron microscopy), SEM (scanning electron microscopy) and FIB (focused ion beam). A cross-sectional TEM, energy dispersive X-ray spectroscopy and energy-filtered TEM reveal that a pronounced Cu diffusion occurs across the interface of the CdS/CIGS, which leads to a large amount of Cu rich in the CdS layer and a Cu-deficient sub-surface in the CIGS layer as well as a rough interfacial structure. TEM studies further reveal that the interface microstructures in the multilayered film are dissimilar, both ZnO/CdS and CdS/CIGS interfaces are strongly bonded whereas the CIGS/Mo interface is weakly bonded and interface separation occasionally occurs. Mo back contact layer shows a well adhesion to glass substrate. Detailed observation on defects in the CIGS-based multilayered film is carried out by 3D (3-dimensional) FIB and SEM techniques. Sequential 2D (2-demensional) cross-sectioning shows that dominant growth-defects in the CIGS and top SiO2 layers are micro-scale crack, appearing as diversified morphologies. The micro-scale crack in the CIGS layer is possibly released by propagating into the adjacent layer while the crack in the SiO2 layer is relieved usually by forming a small particle behind. It is noted that in the multilayered film the interface frequently acts as crack initiation sites due to distinct thermal expitiation sites due to distinct thermal expansion coefficients.

343

Correlation properties of surface and percolation transfer of electrons  

International Nuclear Information System (INIS)

In this work was received equation, connecting correlatively properties of surface with electrons distribution function. Usually for equilibrium is necessary a large number of collisions. Collisions are 'destroying' correlations. In case rare collisions large importance have correlations and 'memory' effects. Non-Markov's character of emitting particles by surface lead to strongly nonequilibrium condition of 'gas'. Here kinetic equation of diffusive form does not apply. Classical kinetic equation are described only conditions near to equilibrium. This work offers to use ideas anomal diffusion in phase-space. The correlation properties of surface describe by correlations of velocities of emitting electrons: B(t). We offer to use functional equation for probability collision instead of kinetic equation: ?0?0WnoncollF(?) 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(?) ? 1/?? exp(-1/?). The solution of this form can not be get with help asymptotic methods of kinetic theory. Asymptotics of solution have scale-invariant character F(V) ? 1/V?. This indicate on fractal properties phase-space. (author)

344

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

Science.gov (United States)

... (a) Method of payment. (1) All payments by the Government...contract shall be made by electronic funds transfer (EFT...may also include the payment information transfer...Clearing House (ACH) network, subject to...

2010-10-01

345

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

DEFF Research Database (Denmark)

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 molecular and solvent reorganisation Gibbs energy, E-r. However, a large V-bias is frequently needed for stable imaging. This applies particularly to in situ STM of redox metalloproteins, emerging as a new approach to imaging of biological processes directly in aqueous medium. We provide first an extension of previous theoretical work on in situ STM of redox molecules, to large bias voltages, \\eV(bias)\\ > E-r. Large bias voltages give tunnelling contrasts independent of the overpotential over a broad range, as both the oxidised and reduced redox levels are located within the 'energy tip' between 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 cover a broad tunnelling current-overpotential range at a constant (large) bias voltage of +0.2 V. The current is found to be constant over a 0.25 V overpotential range, which covers roughly the range where the oxidised and reduced redox levels are located within the energy tip. STM contrast and apparent adsorbate coverage decrease outside this range. This could reflect in part redox processes of azurin, but also tip-induced disassembly of the azurin monolayer.

Zhang, Jingdong; Kuznetsov, A.M.

2003-01-01

346

Reorganization energy of electron transfer at the solvent glass transition  

CERN Document Server

We present a molecular-dynamics study of the solvent reorganization energy of electron transfer in supercooled water. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect as discussed by the mode coupling theory. Both the heat capacity and dielectric susceptibility of the pure water show sharp drops at about the same temperature. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the break-down of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to Debye relaxation of the solvent dipolar polarization.

Ghorai, P K; Ghorai, Pradip K.; Matyushov, Dmitry V.

2005-01-01

347

Facile direct electron transfer in glucose oxidase modified electrodes  

Energy Technology Data Exchange (ETDEWEB)

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 {mu}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.

Wang Dan [Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701 (United States); Chen Liwei [Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701 (United States); Suzhou Institute of Nano Tech and Nano Bionics, Chinese Academy of Sciences, 398 Ruoshui Road, Suzhou Industrial Park, Suzhou, Jiangsu 215125 (China)], E-mail: lwchen2008@sinano.ac.cn

2009-07-15

348

Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase  

Science.gov (United States)

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

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

2003-06-01

349

Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase  

DEFF Research Database (Denmark)

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

Farver, Ole; Kroneck, Peter M H

2003-01-01

350

A stochastic reorganizational bath model for electronic energy transfer.  

Science.gov (United States)

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. PMID:24985614

Fujita, Takatoshi; Huh, Joonsuk; Aspuru-Guzik, Alán

2014-06-28

351

A stochastic reorganizational bath model for electronic energy transfer  

International Nuclear Information System (INIS)

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

352

Steric guided change of electron transfer mechanism in benzene  

Science.gov (United States)

In fluorescence quenching study via electron transfer (ET), the quenching rate constant ( kq) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, kq values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C 12H 9N) with decrease in concentration of DCB, kq values can even reach the order of energy transfer (10 11 s -1). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET ( kq) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882].

Chatterjee, Suchandra; Basu, Samita; Ghosh, Nandita; Chakrabarty, Manas

2005-06-01

353

Analyses of donor-acceptor distance-dependent rates of photo-induced electron transfer in flavoproteins with three kinds of electron transfer theories  

International Nuclear Information System (INIS)

Reported donor-acceptor distance-dependent rates of photo-induced electron transfer from tryptophan (Trp), tyrosine (Tyr), and benzoate (Bz) to the excited isoalloxazine in ten flavoprotein systems were analyzed with three kinds of electron transfer theories by Marcus, by Bixon and Jortner, and also by Kakitani, Yoshimori, and Mataga. Average donor-acceptor distances that were obtained from X-ray structures of flavoproteins were used for the analysis, rather than the edge-to-edge distance. The observed photo-induced electron transfer rates were best reproduced by the Kakitani, Yoshimori, and Mataga theory

354

Proton-coupled electron transfer: the mechanistic underpinning for radical transport and catalysis in biology  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Charge transport and catalysis in enzymes often rely on amino acid radicals as intermediates. The generation and transport of these radicals are synonymous with proton-coupled electron transfer (PCET), which intrinsically is a quantum mechanical effect as both the electron and proton tunnel. The caveat to PCET is that proton transfer (PT) is fundamentally limited to short distances relative to electron transfer (ET). This predicament is resolved in biology by the evolution of enzymes to contr...

Reece, Steven Y.; Hodgkiss, Justin M.; Stubbe, Joanne; Nocera, Daniel G.

2006-01-01

355

Characterization of electron transfer dissociation in the Orbitrap Velos HCD cell.  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Electron transfer dissociation (ETD) is commonly employed in ion traps utilizing rf fields that facilitate efficient electron transfer reactions. Here, we explore performing ETD in the HCD collision cell on an Orbitrap Velos instrument by applying a static DC gradient axially to the rods. This gradient enables simultaneous three dimensional, charge sign independent, trapping of cations and anions, initiating electron transfer reactions in the center of the HCD cell where oppositely charged io...

Frese, Ck; Nolting, D.; Altelaar, Af; Griep-raming, J.; Mohammed, S.; Heck, Aj

2013-01-01

356

Control of electron transfer from lead-salt nanocrystals to TiO?.  

Science.gov (United States)

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. PMID:21506588

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

2011-05-11

357

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

International Nuclear Information System (INIS)

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+

358

Transfer of spectral weight in spectroscopies of correlated electron systems  

CERN Document Server

We study the transfer of spectral weight in the photoemission and optical spectra of strongly correlated electron systems. Within the LISA, that becomes exact in the limit of large lattice coordination, we consider and compare two models of correlated electrons, the Hubbard model and the periodic Anderson model. The results are discussed in regard of recent experiments. In the Hubbard model, we predict an anomalous enhancement optical spectral weight as a function of temperature in the correlated metallic state which is in qualitative agreement with optical measurements in V_2O_3. We argue that anomalies observed in the spectroscopy of the metal are connected to the proximity to a crossover region in the phase diagram of the model. In the insulating phase, we obtain an excellent agreement with the experimental data and present a detailed discussion on the role of magnetic frustration by studying the k-resolved single particle spectra. The results for the periodic Anderson model are discussed in connection to ...

Rozenberg, M J; Kajueter, H

1995-01-01

359

The chemical basis for interfacial activation of monomeric phospholipases A2. Autocatalytic derivatization of the enzyme by acyl transfer from substrate.  

Science.gov (United States)

A basic monomeric phospholipase A2 from the venom of the American water moccasin, Agkistrodon piscivorus piscivorus, undergoes Ca2+-dependent, autocatalytic acylation during the course of hydrolysis of both model and natural phospholipid substrates. Acylation occurs at 2 lysine residues, Lys-7 and Lys-10, in the NH2-terminal alpha-helical segment of the enzyme, and when both positions are fully derivatized, the stable bisacylphospholipase A2 becomes a dimer in solution. The acylated enzyme is fully activated toward monomolecular layers of lecithins. Similar studies applied to the monomeric phospholipases A2 from porcine pancreas and from the venom of Agkistrodon contortrix contortrix also showed irreversible activation of the enzymes by substrate with the same kinetic consequences and formation of dimers. Acylation thus enables these enzymes to overcome the lag period observed under such conditions with native monomeric phospholipases, a phenomenon referred to as interfacial activation. Activation of the enzyme by acylation potentiates the phospholipase for interfacial recognition via formation of a dimeric enzyme. The naturally occurring phospholipase A2 dimer from Crotalus atrox venom displays no lag in the hydrolysis of lecithin monolayers nor does it undergo substrate level acylation. These facts support our proposal that dimerization concomitant with acylation is responsible for the large rate enhancements seen in the hydrolysis of aggregated phospholipids by monomeric phospholipases. Our findings demonstrate for the first time a chemical mechanism for interfacial activation of and interfacial recognition by phospholipases A2. PMID:3403524

Cho, W; Tomasselli, A G; Heinrikson, R L; Kézdy, F J

1988-08-15

360

Theory of Electron-Transfer Reactions and of Related Phenomena  

International Nuclear Information System (INIS)

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 appad 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 ?F°'' 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)

 
 
 
 
361

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

Digital Repository Infrastructure Vision for European Research (DRIVER)

Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide variety of electron donors; in addition, fullerenes in the ground state also act as good electron acceptors in the presence of light-absorbing electron donors such as porphyrins. Wi...

Osamu Ito; Francis D’Souza

2012-01-01

362

Photoinitiated electron transfer in multi-chromophoric species: Synthetic tetrads and pentads. Technical progress report, 1987--1990  

Energy Technology Data Exchange (ETDEWEB)

This research project involves the design, synthesis and study of the molecules which mimic many of the important aspects of photosynthetic electron and energy transfer. Specifically, the molecules are designed to mimic the following aspects of natural photosynthetic multistep electron transfer: electron donation from a tetrapyrrole excited singlet state, electron transfer between tetrapyrroles, electron transfer from tetrapyrroles to quinones, and electron transfer between quinones with different redox properties. In addition, they model carotenoid antenna function in photosynthesis (singlet-singlet energy transfer from carotenoid polyenes to chlorophyll) and carotenoid photoprotection from singlet oxygen damage (triplet-triplet energy transfer from chlorophyll to carotenoids).

1990-02-14

363

77 FR 22066 - Proposed Collection of Information: “Notice of Reclamation Electronic Funds Transfer, Federal...  

Science.gov (United States)

...Service solicits comments concerning forms FMS-I33, ``Notice of Reclamation. Electronic...Transfer, Federal Recurring Payment'' and FMS-135, ``Request for Debit. Electronic...OMB Number: 1510-0043. Form Number: FMS 133, FMS 135. [[Page 22067

2012-04-12

364

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

Science.gov (United States)

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

365

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

2014-12-16

366

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

Energy Technology Data Exchange (ETDEWEB)

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

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

2011-11-30

367

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

International Nuclear Information System (INIS)

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

368

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

International Nuclear Information System (INIS)

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

369

Structural factors influencing the intramolecular charge transfer and photoinduced electron transfer in tetrapyrazinoporphyrazines.  

Science.gov (United States)

A series of unsymmetrical tetrapyrazinoporphyrazines (TPyzPzs) from the group of azaphthalocyanines with one peripherally attached amino substituent (donor) were synthesized, and their photophysical properties (fluorescence quantum yield and singlet oxygen quantum yield) were determined. The synthesized TPyzPzs were expected to undergo intramolecular charge transfer (ICT) as the main pathway for deactivating their excited states. Several structural factors were found to play a critical role in ICT efficiency. The substituent in the ortho position to the donor center significantly influences the ICT, with tert-butylsulfanyl and butoxy substituents inducing the strongest ICTs, whereas chloro, methyl, phenyl, and hydrogen substituents in this position reduce the efficiency. The strength of the donor positively influences the ICT efficiency and correlates well with the oxidation potential of the amines used as the substituents on the TPyzPz as follows: n-butylamine < N,N-diethylamine < aniline < phenothiazine. The ICT (with conjugated donors and acceptors) in the TPyzPz also proved to be much stronger than a photoinduced electron transfer in which the donor and the acceptor are connected through an aliphatic linker. PMID:24509513

Novakova, Veronika; Hladík, Petr; Filandrová, Tereza; Zajícová, Ivana; Krepsová, Veronika; Miletin, Miroslav; Len?o, Juraj; Zimcik, Petr

2014-03-21

370

Dynamic modeling of interfacial structures via interfacial area transport equation  

International Nuclear Information System (INIS)

Full text of publication follows:In the current thermal-hydraulic system analysis codes using the two-fluid model, the empirical correlations that are based on the two-phase flow regimes and regime transition criteria are being employed as closure relations for the interfacial transfer terms. Due to its inherent shortcomings, however, such static correlations are inaccurate and present serious problems in the numerical analysis. In view of this, a new dynamic approach employing the interfacial area transport equation has been studied. The interfacial area transport equation dynamically models the two-phase flow regime transitions and predicts continuous change of the interfacial area concentration along the flow field. Hence, when employed in the thermal-hydraulic system analysis codes, it eliminates artificial bifurcations stemming from the use of the static flow regime transition criteria. Therefore, the interfacial area transport equation can make a leapfrog improvement in the current capability of the two-fluid model from both scientific and practical point of view. Accounting for the substantial differences in the transport phenomena of various sizes of bubbles, the two-group interfacial area transport equations have been developed. The group 1 equation describes the transport of small-dispersed bubbles that are either distorted or spherical in shapes, and the group 2 equation describes the transport of large cap, slug or churn-turbulent bubbles. The source and s churn-turbulent bubbles. The source and sink terms in the right hand-side of the transport equations have been established by mechanistically modeling the creation and destruction of bubbles due to major bubble interaction mechanisms. The coalescence mechanisms include the random collision driven by turbulence, and the entrainment of trailing bubbles in the wake region of the preceding bubble. The disintegration mechanisms include the break-up by turbulence impact, shearing-off at the rim of large cap bubbles and the break-up of large cap bubbles due to surface instability. In the present paper, the interfacial area transport equations currently available are reviewed to address the feasibility and reliability of the model. Results from extensive benchmark experiments for the model evaluation are also present. These include the data from adiabatic upward air-water two-phase flow in round tubes of various sizes, from a rectangular duct, and from adiabatic co-current downward air-water two-phase flow in round pipes of two different sizes. Furthermore, some guidelines for the future study on interfacial area transport equation are discussed. (authors)

371

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

International Nuclear Information System (INIS)

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

372

Long-distance fluorescence quenching by electron transfer in rigid solutions  

International Nuclear Information System (INIS)

Fluorescence of aromatic molecules in solid solutions at room temperature and low temperature is quenched by addition of strong electron donors. The efficiency of quenching correlates well with calculated energetics for electron transfer (ET) from the added donors to the excited molecules, D + A* ? D+ + A-. The quencher (D) always had a substantially higher-lying excited state than did A to prevent electronic energy transfer (e.g., Foerster transfer). The A* fluorescence decreased exponentially with D concentration, being halved by addition of about 0.1 M D in cases with favorable energetics for electron transfer. These quenching measurements are interpreted as indicating electron transfer over distances up to 15 A (center to center). These maximum quenching distances are in excellent agreement with electron tunneling distances measured for ion-molecule reactions by pulse radiolysis. Formation of donor-acceptor complexes during sample preparation is a possible alternate interpretattion, but several features of the data provide evidence against this alternative

373

Coherent transfer of light polarization to electron spins in a semiconductor  

Digital Repository Infrastructure Vision for European Research (DRIVER)

We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g-factors of electrons and light holes. The result encourages us to make a quantum med...

Kosaka, Hideo; Shigyou, Hideki; Mitsumori, Yasuyoshi; Rikitake, Yoshiaki; Imamura, Hiroshi; Kutsuwa, Takeshi; Arai, Koichiro; Edamatsu, Keiichi

2007-01-01

374

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

DEFF Research Database (Denmark)

Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly on the electrode charge. The slope is smaller the more negative the charge density due to enhanced extension of the surface electronic density profile on the solution side, and thereby better electronic overlap with the reacting molecule. The effect is sensitive to the bulk electron density of the metal and the localization of the electronic state at the molecular reactant site. Effects similar to these have been observed experimentally and could be common for electronically light metals.

Kornyshev, A. A.; Kuznetsov, A. M.

2000-01-01

375

Electron transfer reactions of macrocyclic compounds of cobalt  

Energy Technology Data Exchange (ETDEWEB)

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.

Heckman, R.A.

1978-08-01

376

ELECTRONIC FUNDS TRANSFER: EXPLORING THE DIFFICULTIES OF SECURITY  

Directory of Open Access Journals (Sweden)

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.

MPAKWANA ANNASTACIA MTHEMBU

2010-09-01

377

Theoretical study on the electronic structure of triphenyl sulfonium salts: Electronic excitation and electron transfer processes  

Science.gov (United States)

Density functional theory (DFT) and Time Dependent DFT calculations on triphenyl sulfonium cation (TPS) and the salts of TPS with triflate, nonaflate, perfluoro-1-octanesulfonate and hexafluoro antimonate anions are presented. These systems are widely used as cationic photoinitiators and as electron ejection layer for polymer light-emitting diodes. While some differences exist in the electronic structure of the different salts, their lowest energy intense absorption maxima are calculated at nearly the same energy for all systems. The first excited state of TPS and of the TPS salts is dissociating. Electron addition to the TPS salts lowers their energy by 1.0-1.33 eV.

Petsalakis, Ioannis D.; Theodorakopoulos, Giannoula; Lathiotakis, Nektarios N.; Georgiadou, Dimitra G.; Vasilopoulou, Maria; Argitis, Panagiotis

2014-05-01

378

The electron transfer complex between nitrous oxide reductase and its electron donors.  

Science.gov (United States)

Identifying redox partners and the interaction surfaces is crucial for fully understanding electron flow in a respiratory chain. In this study, we focused on the interaction of nitrous oxide reductase (N(2)OR), which catalyzes the final step in bacterial denitrification, with its physiological electron donor, either a c-type cytochrome or a type 1 copper protein. The comparison between the interaction of N(2)OR from three different microorganisms, Pseudomonas nautica, Paracoccus denitrificans, and Achromobacter cycloclastes, with their physiological electron donors was performed through the analysis of the primary sequence alignment, electrostatic surface, and molecular docking simulations, using the bimolecular complex generation with global evaluation and ranking algorithm. The docking results were analyzed taking into account the experimental data, since the interaction is suggested to have either a hydrophobic nature, in the case of P. nautica N(2)OR, or an electrostatic nature, in the case of P. denitrificans N(2)OR and A. cycloclastes N(2)OR. A set of well-conserved residues on the N(2)OR surface were identified as being part of the electron transfer pathway from the redox partner to N(2)OR (Ala495, Asp519, Val524, His566 and Leu568 numbered according to the P. nautica N(2)OR sequence). Moreover, we built a model for Wolinella succinogenes N(2)OR, an enzyme that has an additional c-type-heme-containing domain. The structures of the N(2)OR domain and the c-type-heme-containing domain were modeled and the full-length structure was obtained by molecular docking simulation of these two domains. The orientation of the c-type-heme-containing domain relative to the N(2)OR domain is similar to that found in the other electron transfer complexes. PMID:21739254

Dell'acqua, Simone; Moura, Isabel; Moura, José J G; Pauleta, Sofia R

2011-12-01

379

Linker-free layer-by-layer self-assembly of gold nanoparticle multilayer films for direct electron transfer of horseradish peroxidase and H2O2 detection  

International Nuclear Information System (INIS)

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.

380

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

Science.gov (United States)

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.

Khan, Jafar I.; Abbas, Abdullah Saud; Aly, Shawkat M.; Usman, Anwar; Melnikov, Vasily A.; Alarousu, Erkki; Mohammed, Omar F.

2014-11-01

 
 
 
 
381

Application of electron-transfer theory to several systems of biological interest  

Energy Technology Data Exchange (ETDEWEB)

Electron-transfer reaction rates are compared with theoretically calculated values for several reactions in the bacterial photosynthetic reaction center. A second aspect of the theory, the cross-relation, is illustrated using protein-protein electron transfers. 22 refs., 3 tabs.

Marcus, R.A.; Sutin, N.

1985-01-01

382

Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer–fullerene blends  

Science.gov (United States)

The conversion of photoexcitations into charge carriers in organic solar cells is facilitated by the dissociation of excitons at the donor/acceptor interface. The ultrafast timescale of charge separation demands sophisticated theoretical models and raises questions about the role of coherence in the charge-transfer mechanism. Here, we apply two-dimensional electronic spectroscopy to study the electron transfer process in poly(3-hexylthiophene)/PCBM (P3HT/PCBM) blends. We report dynamics maps showing the pathways of charge transfer that clearly expose the significance of hot electron transfer. During this ultrafast electron transfer, vibrational coherence is directly transferred from the P3HT exciton to the P3HT hole polaron in the crystalline domain. This result reveals that the exciton converts to a hole with a similar spatial extent on a timescale far exceeding other photophysical dynamics including vibrational relaxation.

Song, Yin; Clafton, Scott N.; Pensack, Ryan D.; Kee, Tak W.; Scholes, Gregory D.

2014-09-01

383

Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer-fullerene blends.  

Science.gov (United States)

The conversion of photoexcitations into charge carriers in organic solar cells is facilitated by the dissociation of excitons at the donor/acceptor interface. The ultrafast timescale of charge separation demands sophisticated theoretical models and raises questions about the role of coherence in the charge-transfer mechanism. Here, we apply two-dimensional electronic spectroscopy to study the electron transfer process in poly(3-hexylthiophene)/PCBM (P3HT/PCBM) blends. We report dynamics maps showing the pathways of charge transfer that clearly expose the significance of hot electron transfer. During this ultrafast electron transfer, vibrational coherence is directly transferred from the P3HT exciton to the P3HT hole polaron in the crystalline domain. This result reveals that the exciton converts to a hole with a similar spatial extent on a timescale far exceeding other photophysical dynamics including vibrational relaxation. PMID:25215959

Song, Yin; Clafton, Scott N; Pensack, Ryan D; Kee, Tak W; Scholes, Gregory D

2014-01-01

384

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

Science.gov (United States)

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

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

2015-02-01

385

Electron transfer precedes ATP hydrolysis during nitrogenase catalysis  

Science.gov (United States)

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

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

2013-01-01

386

Electron transfer of peroxidase assemblies at tailored nanocarbon electrodes  

International Nuclear Information System (INIS)

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 adsorbenondoped CNTs and N-CNTs with adsorbed HRP for unmediated, quantitative H2O2 sensing

387

Diameter dependent electron transfer kinetics in semiconductor-enzyme complexes.  

Science.gov (United States)

Excited state electron transfer (ET) is a fundamental step for the catalytic conversion of solar energy into chemical energy. To understand the properties controlling ET between photoexcited nanoparticles and catalysts, the ET kinetics were measured for solution-phase complexes of CdTe quantum dots and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) using time-resolved photoluminescence spectroscopy. Over a 2.0-3.5 nm diameter range of CdTe nanoparticles, the observed ET rate (kET) was sensitive to CaI concentration. To account for diameter effects on CaI binding, a Langmuir isotherm and two geometric binding models were created to estimate maximal CaI affinities and coverages at saturating concentrations. Normalizing the ET kinetics to CaI surface coverage for each CdTe diameter led to k(ET) values that were insensitive to diameter, despite a decrease in the free energy for photoexcited ET (?GET) with increasing diameter. The turnover frequency (TOF) of CaI in CdTe-CaI complexes was measured at several molar ratios. Normalization for diameter-dependent changes in CaI coverage showed an increase in TOF with diameter. These results suggest that k(ET) and H2 production for CdTe-CaI complexes are not strictly controlled by ?G(ET) and that other factors must be considered. PMID:25244026

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

2014-10-28

388

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

2014-01-01

389

Electronic coulombic coupling of excitation-energy transfer in xanthorhodopsin.  

Science.gov (United States)

Electronic coupling of excitation-energy transfer (EET) in a retinal (RET) protein, xanthorhodopsin (xR), was studied theoretically. The protein, functioning as a light driven proton pump, contains a carotenoid antenna, salinixanthin (SXN), to collect light energy for an RET chromophore through EET. The pseudo-Coulombic interaction (PCI) between the donor SXN and the acceptor RET molecules was calculated by a transition density fragment interaction (TDFI) method, which overcomes difficulty arising in the evaluation of PCI in xR by a conventional dipole-dipole (dd) method, at the ab initio TDDFT/SAC-CI level of theory. The result nicely agrees with the experimentally observed PCI. To examine the correlation between the SXN-RET alignment and the EET efficiency, we computed PCIs for SXN conformations that are virtually generated around the protein. The calculation shows that the optimal SXN alignment for the maximally tuned efficiency of EET is attained in the native xR. PCI in another retinal protein, archaerhodopsin-2, which also binds a carotenoid but lacks EET activity, was also evaluated. The computed PCI is negligibly small, well explaining the lack of EET efficiency. PMID:19772318

Fujimoto, Kazuhiro J; Hayashi, Shigehiko

2009-10-14

390

SO2?· Electron Transfer Ion/Ion Reactions with Disulfide Linked Polypeptide Ions  

Digital Repository Infrastructure Vision for European Research (DRIVER)

Multiply-charged peptide cations comprised of two polypeptide chains (designated A and B) bound via a disulfide linkage have been reacted with SO2?· in an electrodynamic ion trap mass spectrometer. These reactions proceed through both proton transfer (without dissociation) and electron transfer (with and without dissociation). Electron transfer reactions are shown to give rise to cleavage along the peptide backbone, loss of neutral molecules, and cleavage of the cystine bond. Disulfide bon...

Chrisman, Paul A.; Pitteri, Sharon J.; Hogan, Jason M.; Mcluckey, Scott A.

2005-01-01

391

Tunable Interfacial Thermal Conductance by Molecular Dynamics  

Science.gov (United States)

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 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 in

Shen, Meng

392

Probing the ultrafast electron transfer at the CuPc/Au(111) interface  

International Nuclear Information System (INIS)

Core-hole clock spectroscopy and near-edge x-ray-absorption fine structure measurements have been used to investigate the ultrafast electron transfer dynamics at the Copper(II) phthalocyanine (CuPc)/Au(111) interface. It was found that the strong electronic coupling between the first layer of CuPc molecules and Au(111) substrate favors ultrafast electron transfer from the lowest unoccupied molecular orbital of the CuPc molecules to the conduction band of Au(111) in the time scale of ?6 fs. In contrast, the intermolecular electron transfer within multilayers of CuPc molecules via the weak van der Waals interaction was much slower

393

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

International Nuclear Information System (INIS)

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 ?s) 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