A Cu-Zn nanoparticle promoter for selective carbon dioxide reduction and its application in visible-light-active Z-scheme systems using water as an electron donor.

PubMed

Yin, Ge; Sako, Hiroshi; Gubbala, Ramesh V; Ueda, Shigenori; Yamaguchi, Akira; Abe, Hideki; Miyauchi, Masahiro

2018-04-17

Selective carbon dioxide photoreduction to produce formic acid was achieved under visible light irradiation using water molecules as electron donors, similar to natural plants, based on the construction of a Z-scheme light harvesting system modified with a Cu-Zn alloy nanoparticle co-catalyst. The faradaic efficiency of our Z-scheme system for HCOOH generation was over 50% under visible light irradiation.

Biodegradation of Polychlorinated Methanes in Methanogenic Systems

DTIC Science & Technology

1991-01-01

occurring toxicant and C-1 growth substrate. J. General Microbiol. 132:1139-1142. 18. Hoover, S. R. and N. Porges. 1952. Assimilation of dairy wastes by...carbon and electron donor source; (3) to examine the level of micronutrients - provided as yeast extract (YE) - needed in the system feed; (4) to...provided the electron donor needed to consume oxygen and lower the redox potential in the precolumn; YE provided micronutrients . No reductant (Na2S

Electron shuttling in phosphorus donor qubit systems

NASA Astrophysics Data System (ADS)

Jacobson, N. Tobias; Gamble, John King; Nielsen, Erik; Muller, Richard P.; Witzel, Wayne M.; Montano, Ines; Carroll, Malcolm S.

2014-03-01

Phosphorus donors in silicon are a promising qubit architecture, due in large part to their long nuclear coherence times and the recent development of atomically precise fabrication methods. Here, we investigate issues related to implementing qubits with phosphorus donors in silicon, employing an effective mass theory that non-phenomenologically takes into account inter-valley coupling. We estimate the significant sources of decoherence and control errors in this system to compute the fidelity of primitive gates and gate timescales. We include the effects of valley repopulation during the process of shuttling an electron between a donor and nearby interface or between neighboring donors, evaluating the control requirements for ensuring adiabaticity with respect to the valley sector. This work was supported in part by the LDRD program at Sandia National Labs, a multi-program laboratory managed and operated by Sandia Corp, a wholly owned subsidiary of Lockheed Martin Corp, for the U.S. DOE NNSA under contract DE-AC04-94AL85000.

The adsorption properties of titanium dioxide

NASA Astrophysics Data System (ADS)

Lanin, S. N.; Vlasenko, E. V.; Kovaleva, N. V.; Zung, Fam Tien

2008-12-01

The adsorption properties of titanium dioxide were studied by gas chromatography. We used organic compounds from different classes, namely, n-alkanes, n-alkenes (C6-C8), and polar compounds (electron donors and acceptors) as test adsorbates. The differential heats of adsorption and the contributions of dispersion and specific intermolecular interaction energies were determined for the systems from the experimental retention data. The electron-donor and electron-acceptor characteristics of the ultimately hydroxylated surface of TiO2 were evaluated.

Density functional study of the electronic structure of dye-functionalized fullerenes and their model donor-acceptor complexes containing P3HT

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

Baruah, Tunna; Garnica, Amanda; Paggen, Marina

2016-04-14

We study the electronic structure of C{sub 60} fullerenes functionalized with a thiophene-diketo-pyrrolopyrrole-thiophene based chromophore using density functional theory combined with large polarized basis sets. As the attached chromophore has electron donor character, the functionalization of the fullerene leads to a donor-acceptor (DA) system. We examine in detail the effect of the linker and the addition site on the electronic structure of the functionalized fullerenes. We further study the electronic structure of these DA complexes with a focus on the charge transfer excitations. Finally, we examine the interface of the functionalized fullerenes with the widely used poly(3-hexylthiophene-2,5-diyl) (P3HT) donor. Ourmore » results show that all functionalized fullerenes with an exception of the C{sub 60}-pyrrolidine [6,6], where the pyrrolidine is attached at a [6,6] site, have larger electron affinities relative to the pristine C{sub 60} fullerene. We also estimate the quasi-particle gap, lowest charge transfer excitation energy, and the exciton binding energies of the functionalized fullerene-P3MT model systems. Results show that the exciton binding energies in these model complexes are slightly smaller compared to a similarly prepared phenyl-C{sub 61}-butyric acid methyl ester (PCBM)-P3MT complex.« less

The separation distance distribution in electron-donor-acceptor systems and the wavelength dependence of free ion yields

NASA Astrophysics Data System (ADS)

Zhou, Jinwei; Findley, Bret R.; Braun, Charles L.; Sutin, Norman

2001-06-01

We recently reported that free radical ion quantum yields for electron-donor-acceptor (EDA) systems of alkylbenzenes-tetracyanoethylene (TCNE) exhibit a remarkable wavelength dependence in dichloromethane, a medium polarity solvent. We proposed that weak absorption by long-distance, unassociated or "random" D⋯A pairs is mainly responsible for the free radical ion yield. Here a model for the wavelength dependence of the free ion yield is developed for four systems in which differing degrees of EDA complex formation are present: 1,3,5-tri-tert-butylbenzene-TCNE in which only random pairs exist due to the bulky groups on the electron donor, and toluene—TCNE, 1,3,5-triethylbenzene-TCNE and 1,3,5-trimethylbenzene-TCNE. Mulliken-Hush theory is used to determine the excitation distance distribution of unassociated, random pairs at different wavelengths. For each absorption distribution, free radical ion yields at different wavelengths are then calculated using Onsager's result for the ion separation probability. Encouraging agreement between the calculated yields and our experimental results is obtained. As far as we are aware, this is the first time that photoexcitation of unassociated donor/acceptor pairs has been invoked as the source of separated radical ion pairs.

Diamagnetic susceptibility of a hydrogenic donor in a group IV-VI quantum dot-quantum well heterostructure

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

Saravanamoorthy, S. N.; Peter, A. John, E-mail: a.john.peter@gmail.com

2016-05-23

Electronic properties of a hydrogenic donor impurity in a CdSe/Pb{sub 0.8}Cd{sub 0.2}Se/CdSe quantum dot quantum well system are investigated for various radii of core with shell materials. Confined energies are obtained taking into account the geometrical size of the system and thereby the donor binding energies are found. The diamagnetic susceptibility is estimated for a confined shallow donor in the well system. The results show that the diamagnetic susceptibility strongly depends on core and shell radii and it is more sensitive to variations of the geometrical size of the well material.

Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

NASA Astrophysics Data System (ADS)

Liyanage, Arawwawala Don Thilanga

After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the molecular self-assembly and (opto)-electronic properties. The body of this thesis mainly focuses on the substituent effects: how different substituents affect the (opto)-electronic properties of the donor-acceptor (D-A) conjugated polymers. The main priority goes to understand, how different alkyl substituent effect to the polymer solubility, crystallinity, thermal properties (e.g.: glass transition temperature) and morphological order. Three classes of D-A systems were extensively studied in this work. The second chapter mainly focuses on the synthesis and structure-property study of fluorinated arene (TFB) base polymers. Here we used commercially available 1,4-dibromo-2,3,5,6-tetrafluorobenzene (TFB) as the acceptor material and prepare several polymers using 3,3'-dialkyl(3,3'-R2T2) or 3,3'-dialkoxy bithiophene (3,3'-RO2T2) units as electron donors. A detail study was done using 3,3'-bithiophene donor units incorporating branched alkoxy-functionalities by systematic variation of branching position and chain length. The study allowed disentangling the branching effects on (i) aggregation tendency, intermolecular arrangement, (iii) solid state optical energy gaps, and (iv) electronic properties in an overall consistent picture, which might guide future polymer synthesis towards optimized materials for opto-electronic applications. The third chapter mainly focused on the structure-property study of imide functionalized D-A polymers. Here we used thiophene-imide (TPD) as the acceptor moiety and prepare several D-A polymers by varying the donor units. When selecting the donor units, more priority goes to the fused ring systems. One main reason to use imide functionality is due to the, open position of the imide nitrogen, which provides an attaching position to alkyl substituent. Through this we can easily manipulate solubility and solid state packing arrangement. Also these imide acceptors have low-lying LUMOs due to their electron deficient nature and this will allow tuning the optical energy gap by careful choice of donor materials with different electron donating ability. The fourth chapter mainly contribute to the synthesis and structure property study of a completely novel electron acceptor moiety consist of a unsaturated pyrrolidinone unit known as Pechmann dye (PD) core. Pechmann dyes are closely related to the Indigo family. This can refer as 3-butenolide dimer connected via an alkene bridge, containing a benzene ring at the 5 and 5' positions of the lactone rings. We have prepared several D-A polymers using this PD system with benzodithiophene (BDT) as the donor unit. Different to common D-A polymers the HOMO and LUMO of the PD acceptor moiety are energetically located within the gap of the BDT, so that the electronic and optical properties (HOMO-LUMO transition) are dictated by the PD properties. The promising electronic properties, band gaps, high absorption coefficients and broad absorption suggest this new D-A polymers as an interesting donor material for organic solar cell (OSC) applications. KEY WORDS: Organic semiconductor materials, Self assembly, (opto)-electronic properties, Donor-Acceptor conjugated polymers, Fluorinated arene, 3,3'-bithiophene donors, Thiophene-imide (TPD), Pechmann dye, benzodithiophene, organic solar cell.

Effect of sulfate on anaerobic reduction of nitrobenzene with acetate or propionate as an electron donor.

PubMed

Huang, Jingang; Wen, Yue; Ding, Ning; Xu, Yue; Zhou, Qi

2012-09-15

Sulfate is frequently found in wastewaters that contain nitrobenzene. To reveal the effect of sulfate on the reductive transformation of nitrobenzene to aniline--with acetate or propionate as potential electron donors in anaerobic systems--an acetate series (R1-R5) and a propionate series (R6-R10) were set up. Each of these was comprised of five laboratory-scale sequence batch reactors. The two series were amended with the same amount of nitrobenzene and electron donor electron equivalents, whereas with increasing sulfate concentrations. Results indicated that the presence of sulfate could depress nitrobenzene reduction. Such depression is linked to the inhibition of nitroreductase activity and/or the shift of electron flow. In the acetate series, although sulfate did not strongly compete with nitrobenzene for electron donors, noncompetitive inhibition of specific nitrobenzene reduction rates by sulfate was observed, with an inhibition constant of 0.40 mM. Propionate, which can produce intermediate H₂ as preferred reducing equivalent, is a more effective primary electron donor for nitrobenzene reduction as compared to acetate. In the propionate series, sulfate was found to be a preferential electron acceptor as compared to nitrobenzene, resulting in a quick depletion of propionate and then a likely termination of H₂-releasing under higher sulfate concentrations (R9 and R10). In such a situation, nitrobenzene reduction slowed down, occurring two-stage zero-order kinetics. Copyright © 2012 Elsevier Ltd. All rights reserved.

All-electric control of donor nuclear spin qubits in silicon

NASA Astrophysics Data System (ADS)

Sigillito, Anthony J.; Tyryshkin, Alexei M.; Schenkel, Thomas; Houck, Andrew A.; Lyon, Stephen A.

2017-10-01

The electronic and nuclear spin degrees of freedom of donor impurities in silicon form ultra-coherent two-level systems that are potentially useful for applications in quantum information and are intrinsically compatible with industrial semiconductor processing. However, because of their smaller gyromagnetic ratios, nuclear spins are more difficult to manipulate than electron spins and are often considered too slow for quantum information processing. Moreover, although alternating current magnetic fields are the most natural choice to drive spin transitions and implement quantum gates, they are difficult to confine spatially to the level of a single donor, thus requiring alternative approaches. In recent years, schemes for all-electrical control of donor spin qubits have been proposed but no experimental demonstrations have been reported yet. Here, we demonstrate a scalable all-electric method for controlling neutral 31P and 75As donor nuclear spins in silicon. Using coplanar photonic bandgap resonators, we drive Rabi oscillations on nuclear spins exclusively using electric fields by employing the donor-bound electron as a quantum transducer, much in the spirit of recent works with single-molecule magnets. The electric field confinement leads to major advantages such as low power requirements, higher qubit densities and faster gate times. Additionally, this approach makes it possible to drive nuclear spin qubits either at their resonance frequency or at its first subharmonic, thus reducing device bandwidth requirements. Double quantum transitions can be driven as well, providing easy access to the full computational manifold of our system and making it convenient to implement nuclear spin-based qudits using 75As donors.

Tuning the Rectification Ratio by Changing the Electronic Nature (Open-Shell and Closed-Shell) in Donor-Acceptor Self-Assembled Monolayers.

PubMed

Souto, Manuel; Yuan, Li; Morales, Dayana C; Jiang, Li; Ratera, Imma; Nijhuis, Christian A; Veciana, Jaume

2017-03-29

This Communication describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor-acceptor systems consisting of a polychlorotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au and contacted by a eutectic alloy of gallium and indium top contacts. The electronic and supramolecular structures of these SAMs were well characterized. The PTM unit can be switched between the nonradical and radical forms, which influences the rectification behavior of the junction. Junctions with nonradical units rectify currents via the highest occupied molecular orbital (HOMO) with a rectification ratio R = 99, but junctions with radical units have a new accessible state, a single-unoccupied molecular orbital (SUMO), which turns rectification off and drops R to 6.

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE.

PubMed

Lee, Il-Su; Bae, Jae-Ho; McCarty, Perry L

2007-10-30

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

NASA Astrophysics Data System (ADS)

Lee, Il-Su; Bae, Jae-Ho; McCarty, Perry L.

2007-10-01

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H 2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H 2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H 2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H 2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.

Spectral engineering in π-conjugated polymers with intramolecular donor-acceptor interactions.

PubMed

Beaujuge, Pierre M; Amb, Chad M; Reynolds, John R

2010-11-16

With the development of light-harvesting organic materials for solar cell applications and molecular systems with fine-tuned colors for nonemissive electrochromic devices (e.g., smart windows, e-papers), a number of technical challenges remain to be overcome. Over the years, the concept of "spectral engineering" (tailoring the complex interplay between molecular physics and the various optical phenomena occurring across the electromagnetic spectrum) has become increasingly relevant in the field of π-conjugated organic polymers. Within the spectral engineering toolbox, the "donor-acceptor" approach uses alternating electron-rich and electron-deficient moieties along a π-conjugated backbone. This approach has proved especially valuable in the synthesis of dual-band and broadly absorbing chromophores with useful photovoltaic and electrochromic properties. In this Account, we highlight and provide insight into a present controversy surrounding the origin of the dual band of absorption sometimes encountered in semiconducting polymers structured using the "donor-acceptor" approach. Based on empirical evidence, we provide some schematic representations to describe the possible mechanisms governing the evolution of the two-band spectral absorption observed on varying the relative composition of electron-rich and electron-deficient substituents along the π-conjugated backbone. In parallel, we draw attention to the choice of the method employed to estimate and compare the absorption coefficients of polymer chromophores exhibiting distinct repeat unit lengths, and containing various extents of solubilizing side-chains along their backbone. Finally, we discuss the common assumption that "donor-acceptor" systems should have systematically lower absorption coefficients than their "all-donor" counterparts. The proposed models point toward important theoretical parameters which could be further explored at the macromolecular level to help researchers take full advantage of the complex interactions taking place in π-conjugated polymers with intramolecular "donor-acceptor" characteristics.

Organic electronic devices with multiple solution-processed layers

DOEpatents

Forrest, Stephen R.; Lassiter, Brian E.; Zimmerman, Jeramy D.

2015-08-04

A method of fabricating a tandem organic photosensitive device involves depositing a first layer of an organic electron donor type material film by solution-processing of the organic electron donor type material dissolved in a first solvent; depositing a first layer of an organic electron acceptor type material over the first layer of the organic electron donor type material film by a dry deposition process; depositing a conductive layer over the interim stack by a dry deposition process; depositing a second layer of the organic electron donor type material over the conductive layer by solution-processing of the organic electron donor type material dissolved in a second solvent, wherein the organic electron acceptor type material and the conductive layer are insoluble in the second solvent; depositing a second layer of an organic electron acceptor type material over the second layer of the organic electron donor type material film by a dry deposition process, resulting in a stack.

Quantum mechanical design of efficient second-order nonlinear optical materials based on heteroaromatic imido-substituted hexamolybdates: first theoretical framework of POM-based heterocyclic aromatic rings.

PubMed

Janjua, Muhammad Ramzan Saeed Ashraf

2012-11-05

This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 2009, 113, 3576-3587) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path of the ligand and the nature of hexamolybdates (polyoxometalates, POMs) was changed into a donor by altering the direction of charge transfer with a second aromatic ring. Herein, the first theoretical framework of POM-based heteroaromatic rings is found to be another class of excellent NLO materials having double heteroaromatic rings. First hyperpolarizabilities of a large number of push-pull-substituted conjugated systems with heteroaromatic rings have been calculated. The β components were computed at the density functional theory (DFT) level (BP86 geometry optimizations and LB94 time-dependent DFT). The largest β values are obtained with a donor (hexamolybdates) on the benzene ring and an acceptor (-NO(2)) on pyrrole, thiophene, and furan rings. The pyrrole imido-substituted hexamolybdate (system 1c) has a considerably large first hyperpolarizability, 339.00 × 10(-30) esu, and it is larger than that of (arylimido)hexamolybdate, calculated as 0.302 × 10(-30) esu (reference system 1), because of the double aromatic rings in the heteroaromatic imido-substituted hexamolybdates. The heteroaromatic rings act as a conjugation bridge between the electron acceptor (-NO(2)) and donor (polyanion). The introduction of an electron donor into heteroaromatic rings significantly enhances the first hyperpolarizabilities because the electron-donating ability is substantially enhanced when the electron donor is attached to the heterocyclic aromatic rings. Interposing five-membered auxiliary fragments between strong donor (polyanion) or acceptor (-NO(2)) groups results in a large computed second-order NLO response. The present investigation provides important insight into the NLO properties of (heteroaromatic) imido-substituted hexamolybdate derivatives because these compounds exhibit enhanced hyperpolarizabilities compared to typical NLO arylimido hexamolybdates and heterocyclic aromatic rings reported in the literature.

New organic superconductors beta-(BDA-TTP)2X [BDA-TTP + 2,5-bis(1,3-dithian-2ylidene)-1,3,4,6-tetrathiapentalene; X(-) = SbF6(-), AsF6(-), and PF6(-)].

PubMed

Yamada, J; Watanabe, M; Akutsu, H; Nakatsuji, S; Nishikawa, H; Ikemoto, I; Kikuchi, K

2001-05-09

The synthesis, electrochemical properties, and molecular structure of a new pi-electron donor, 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), is described. In contrast to the hitherto-known tetrachalcogenafulvalene pi-donors providing organic superconductors, this donor contains only the bis-fused 1,3-dithiole-2-ylidene unit as a pi-electron system, yet produces a series of ambient-pressure superconductors beta-(BDA-TTP)2X [X = SbF6 (magnetic T(c) = 6.9 K, resistive T(c) = 7.5 K), AsF6 (magnetic T(c) = 5.9 K, resistive T(c) = 5.8 K), and PF6 (magnetic T(c) = 5.9 K)], which are isostructural. The values of the intermolecular overlap integrals calculated on the donor layers of these superconductors suggest a two-dimensional (2D) electronic structure with loose donor packing. Tight-binding band calculations also indicate that these superconductors have the 2D band dispersion relations and closed Fermi surfaces.

Impact of Thermal Annealing on Organic Photovoltaic Cells Using Regioisomeric Donor-Acceptor-Acceptor Molecules.

PubMed

Zhang, Tao; Han, Han; Zou, Yunlong; Lee, Ying-Chi; Oshima, Hiroya; Wong, Ken-Tsung; Holmes, Russell J

2017-08-02

We report a promising set of donor-acceptor-acceptor (D-A-A) electron-donor materials based on coplanar thieno[3,2-b]/[2,3-b]indole, benzo[c][1,2,5]thiadiazole, and dicyanovinylene, which are found to show broadband absorption with high extinction coefficients. The role of the regioisomeric electron-donating thienoindole moiety on the physical and structural properties is examined. Bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on the thieno[2,3-b]indole-based electron donor NTU-2, using C 70 as an electron acceptor, show a champion power conversion efficiency of 5.2% under AM 1.5G solar simulated illumination. This efficiency is limited by a low fill factor (FF), as has previously been the case in D-A-A systems. In order to identify the origin of the limited FF, further insight into donor layer charge-transport behavior is realized by examining planar heterojunction OPVs, with emphasis on the evolution of film morphology with thermal annealing. Compared to as-deposited OPVs that exhibit insufficient donor crystallinity, crystalline OPVs based on annealed thin films show an increase in the short-circuit current density, FF, and power conversion efficiency. These results suggest that that the crystallization of D-A-A molecules might not be realized spontaneously at room temperature and that further processing is needed to realize efficient charge transport in these materials.

Photosystem I from plants as a bacterial cytochrome P450 surrogate electron donor: terminal hydroxylation of branched hydrocarbon chains.

PubMed

Jensen, Kenneth; Johnston, Jonathan B; de Montellano, Paul R Ortiz; Møller, Birger Lindberg

2012-02-01

The ability of cytochrome P450 enzymes to catalyze highly regio- and stereospecific hydroxylations makes them attractive alternatives to approaches based on chemical synthesis but they require expensive cofactors, e.g. NAD(P)H, which limits their commercial potential. Ferredoxin (Fdx) is a multifunctional electron carrier that in plants accepts electrons from photosystem I (PSI) and facilitates photoreduction of NADP(+) to NADPH mediated by ferredoxin-NAD(P)H oxidoreductase (FdR). In bacteria, the electron flow is reversed and Fdx accepts electrons from NADPH via FdR and serves as the direct electron donor to bacterial P450s. By combining the two systems, we demonstrate that irradiation of PSI can drive the activity of a bacterial P450, CYP124 from Mycobacterium tuberculosis. The substitution of the costly cofactor NADPH with sunlight illustrates the potential of the light-driven hydroxylation system for biotechnology applications.

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

Ran, Niva A.; Roland, Steffen; Love, John A.

Here, a long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting inmore » larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.« less

Novel High Efficient Organic Photovoltaic Materials

NASA Technical Reports Server (NTRS)

Sun, Sam; Haliburton, James; Fan, Zben; Taft, Charles; Wang, Yi-Qing; Maaref, Shahin; Mackey, Willie R. (Technical Monitor)

2001-01-01

In man's mission to the outer space or a remote site, the most abundant, renewable, nonpolluting, and unlimited external energy source is light. Photovoltaic (PV) materials can convert light into electrical power. In order to generate appreciable electrical power in space or on the Earth, it is necessary to collect sunlight from large areas due to the low density of sunlight, and this would be very costly using current commercially available inorganic solar cells. Future organic or polymer based solar cells seemed very attractive due to several reasons. These include lightweight, flexible shape, ultra-fast optoelectronic response time (this also makes organic PV materials attractive for developing ultra-fast photo detectors), tunability of energy band-gaps via molecular design, versatile materials synthesis and device fabrication schemes, and much lower cost on large-scale industrial production. It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks will facilitate the charge separation and migration due to improved electronic ultrastructure and morphology in comparison to current polymer composite photovoltaic system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel donor-bridge-acceptor block copolymer system for potential high-efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene, the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene, and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes the holes, the acceptor block stabilizes the electrons. The bridge block is designed to hinder the electron-hole recombination. Thus, improved charge separation is expected. In addition, charge migration will also be facilitated due to the expected nano-phase separated and highly ordered block copolymer ultrastructural. The combination of all these factors will result in significant overall enhancement of photovoltaic power conversion efficiency.

Organic photovoltaic cells based on unconventional electron donor fullerene and electron acceptor copper hexadecafluorophthalocyanine

NASA Astrophysics Data System (ADS)

Yang, J. L.; Sullivan, P.; Schumann, S.; Hancox, I.; Jones, T. S.

2012-01-01

We demonstrate organic discrete heterojunction photovoltaic cells based on fullerene (C60) and copper hexadecafluorophthalocyanine (F16CuPc), in which the C60 and F16CuPc act as the electron donor and the electron acceptor, respectively. The C60/F16CuPc cells fabricated with conventional and inverted architectures both exhibit comparable power conversion efficiencies. Furthermore, we show that the photocurrent in both cells is generated by a conventional exciton dissociation mechanism rather than the exciton recombination mechanism recently proposed for a similar C60/F16ZnPc system [Song et al., J. Am. Chem. Soc. 132, 4554 (2010)]. These results demonstrate that new unconventional material systems are a potential way to fabricate organic photovoltaic cells with inverted as well as conventional architectures.

Visible light water splitting using dye-sensitized oxide semiconductors.

PubMed

Youngblood, W Justin; Lee, Seung-Hyun Anna; Maeda, Kazuhiko; Mallouk, Thomas E

2009-12-21

Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

On vibrational circular dichroism chirality transfer in electron donor-acceptor complexes: a prediction for the quinine···BF3 system.

PubMed

Rode, Joanna E; Jamróz, Michał H; Dobrowolski, Jan Cz; Sadlej, Joanna

2012-08-02

Vibrational circular dichroism (VCD) chirality transfer occurs when an achiral molecule interacts with a chiral one and becomes VCD-active. Unlike for H-bonds, for organic electron donor-acceptor (EDA) complexes this phenomenon remains almost unknown. Here, the VCD chirality transfer from chiral quinine to achiral BF3 is studied at the B3LYP/aug-cc-pVDZ level. Accessibility of four quinine electron donor sites changes with conformation. Therefore, the quinine conformational landscape was explored and a considerable agreement between X-ray and the most stable conformer geometries was achieved. The BF3 complex through the aliphatic quinuclidine N atom is definitely dominating and is predicted to be easily recognizable in the VCD spectrum. Out of several VCD chirality transfer modes, the ν(s)(BF3) mode, the most intense in the entire VCD spectrum, satisfies the VCD mode robustness criterion and can be used for monitoring the chirality transfer phenomenon in quinine···BF3 system.

Design of butterfly type organic dye sensitizers with double electron donors: The first principle study

NASA Astrophysics Data System (ADS)

Yang, Zhenqing; Shao, Di; Li, Juan; Tang, Lian; Shao, Changjin

2018-05-01

In this work, we designed a series of butterfly type organic dyes, named ME07-ME13 by introducing such as triphenylamine, phenothiazine, coumarin groups etc. as electron donors and further investigated their absorption spectra using density functional theory (DFT) and time-dependent DFT (TDDFT). All designed dyes cover the entire visible absorption spectrum from 300 to 800 nm. It's fascinating that ME13 molecule has two absorption peak and the molar coefficient of two absorption peaks are above 4.645 × 104 M-1·cm-1. The light absorption area of ME13 exhibits an increment of 16.5-19.1% compared to ME07-ME12. Furthermore, we performed a detailed analysis on their geometrical and electronic properties, including molecular structures, energy levels, light harvesting efficiency (LHE), driving force (ΔGinject), regeneration (ΔGregen),electron dipole moments (μnormal), intermolecular electron transfer and dye/(TiO2)38 system electron transitions. The results of calculation reveal that double coumarin donors in ME13 are promising functional groups for butterfly type organic dye sensitizers. It is expected that the design of double donors can provide a new strategy and guidance for the investigation in high efficiency dye-sensitized devices.

Nuclear-driven electron spin rotations in a coupled silicon quantum dot and single donor system

NASA Astrophysics Data System (ADS)

Harvey-Collard, Patrick; Jacobson, Noah Tobias; Rudolph, Martin; Ten Eyck, Gregory A.; Wendt, Joel R.; Pluym, Tammy; Lilly, Michael P.; Pioro-Ladrière, Michel; Carroll, Malcolm S.

Single donors in silicon are very good qubits. However, a central challenge is to couple them to one another. To achieve this, many proposals rely on using a nearby quantum dot (QD) to mediate an interaction. In this work, we demonstrate the coherent coupling of electron spins between a single 31P donor and an enriched 28Si metal-oxide-semiconductor few-electron QD. We show that the electron-nuclear spin interaction can drive coherent rotations between singlet and triplet electron spin states. Moreover, we are able to tune electrically the exchange interaction between the QD and donor electrons. The combination of single-nucleus-driven rotations and voltage-tunable exchange provides all elements for future all-electrical control of a spin qubit, and requires only a single dot and no additional magnetic field gradients. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

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

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

McCusker, James

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

Electron charge and spin delocalization revealed in the optically probed longitudinal and transverse spin dynamics in n -GaAs

NASA Astrophysics Data System (ADS)

Belykh, V. V.; Kavokin, K. V.; Yakovlev, D. R.; Bayer, M.

2017-12-01

The evolution of the electron spin dynamics as consequence of carrier delocalization in n -type GaAs is investigated by the recently developed extended pump-probe Kerr/Faraday rotation spectroscopy. We find that isolated electrons localized on donors demonstrate a prominent difference between the longitudinal and transverse spin relaxation rates in a magnetic field, which is almost absent in the metallic phase. The inhomogeneous transverse dephasing time T2* of the spin ensemble strongly increases upon electron delocalization as a result of motional narrowing that can be induced by increasing either the donor concentration or the temperature. An unexpected relation between T2* and the longitudinal spin relaxation time T1 is found, namely, that their product is about constant, as explained by the magnetic field effect on the spin diffusion. We observe a two-stage longitudinal spin relaxation, which suggests the establishment of spin temperature in the system of exchange-coupled donor-bound electrons.

Comparison of Alternative Hydrogen Donors for Anaerobic Reductive Dechlorination of Tetrachloroethene

DTIC Science & Technology

1998-01-01

feature two - stage anaerobic reductive dechlorination of highly chlorinated compounds coupled with aerobic (sometimes co- metabolic) treatment of the...activity at some naturally attenuated sites. Fathepure and Vogel [76] used a two - stage anaerobic-aerobic reactor system to treat hexachlorobenzene, PCE...Complete removal of the chloroethenes by the two - stage system was observed using pyruvate, formate, or lactose as electron donor for the dechlorinating

Longitudinal and transverse spin dynamics of donor-bound electrons in fluorine-doped ZnSe: Spin inertia versus Hanle effect

NASA Astrophysics Data System (ADS)

Heisterkamp, F.; Zhukov, E. A.; Greilich, A.; Yakovlev, D. R.; Korenev, V. L.; Pawlis, A.; Bayer, M.

2015-06-01

The spin dynamics of strongly localized donor-bound electrons in fluorine-doped ZnSe epilayers is studied using pump-probe Kerr rotation techniques. A method exploiting the spin inertia is developed and used to measure the longitudinal spin relaxation time T1 in a wide range of magnetic fields, temperatures, and pump densities. The T1 time of the donor-bound electron spin of about 1.6 μ s remains nearly constant for external magnetic fields varied from zero up to 2.5 T (Faraday geometry) and in a temperature range 1.8-45 K. These findings impose severe restrictions on possible spin relaxation mechanisms. In our opinion they allow us to rule out scattering between free and donor-bound electrons, jumping of electrons between different donor centers, scattering between phonons and donor-bound electrons, and with less certainty charge fluctuations in the environment of the donors caused by the 1.5 ps pulsed laser excitation.

Impact of interfacial molecular orientation on radiative recombination and charge generation efficiency

DOE PAGES

Ran, Niva A.; Roland, Steffen; Love, John A.; ...

2017-07-19

Here, a long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting inmore » larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.« less

Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids.

PubMed

Arellano, Luis M; Martín-Gomis, Luis; Gobeze, Habtom B; Molina, Desiré; Hermosa, Cristina; Gómez-Escalonilla, María J; Fierro, José Luis G; Sastre-Santos, Ángela; D'Souza, Francis; Langa, Fernando

2018-03-15

Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor-acceptor nanohybrids was determined by systematic studies involving AFM, TGA, XPS, optical and Raman techniques. Intramolecular interactions in MPc-SWCNT nanohybrids were probed by studies involving optical absorbance, Raman, luminescence and electrochemical studies. Different degrees of interactions were observed depending on the type of MPc and mode of attachment. Substantial quenching of MPc fluorescence in these hybrids was observed from steady-state and three-dimensional fluorescence mapping, which suggests the occurrence of excited state events. Evidence for the occurrence of excited state charge transfer type interactions was subsequently secured from femtosecond transient absorption studies covering both the visible and near-infrared regions. Furthermore, electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor revealed accumulation of one-electron reduced product upon continuous irradiation of the nanohybrids. In such experiments, the ZnPc-SWCNT (6,5) nanohybrid outperformed other nanohybrids and this suggests that this is a superior donor-acceptor system for photocatalytic applications.

A single molecule rectifier with strong push-pull coupling

NASA Astrophysics Data System (ADS)

Saraiva-Souza, Aldilene; Macedo de Souza, Fabricio; Aleixo, Vicente F. P.; Girão, Eduardo Costa; Filho, Josué Mendes; Meunier, Vincent; Sumpter, Bobby G.; Souza Filho, Antônio Gomes; Del Nero, Jordan

2008-11-01

We theoretically investigate the electronic charge transport in a molecular system composed of a donor group (dinitrobenzene) coupled to an acceptor group (dihydrophenazine) via a polyenic chain (unsaturated carbon bridge). Ab initio calculations based on the Hartree-Fock approximations are performed to investigate the distribution of electron states over the molecule in the presence of an external electric field. For small bridge lengths (n =0-3) we find a homogeneous distribution of the frontier molecular orbitals, while for n >3 a strong localization of the lowest unoccupied molecular orbital is found. The localized orbitals in between the donor and acceptor groups act as conduction channels when an external electric field is applied. We also calculate the rectification behavior of this system by evaluating the charge accumulated in the donor and acceptor groups as a function of the external electric field. Finally, we propose a phenomenological model based on nonequilibrium Green's function to rationalize the ab initio findings.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Comparison of nitrogen removal and microbial distribution in wastewater treatment process under different electron donor conditions.

PubMed

Park, Sora; Seon, Jiyun; Byun, Imgyu; Cho, Sunja; Park, Taejoo; Lee, Taeho

2010-05-01

The applicability of modified spent caustic (MSC) as an electron donor for denitrification was evaluated in a lab-scale reactor for the Bardenpho process under various electron donor conditions: (A) no electron donor, (B) methanol, (C) thiosulfate and (D) MSC conditions. TN removal efficiency varied in each condition, 23.1%, 87.8%, 83.7% and 71.7%, respectively. The distribution ratio of nitrifying bacteria and DGGE profile including sulfur-reducing or oxidizing bacteria also varied depending on the conditions. These results indicated that the MSC would be used as an efficient electron donor for denitrification by autotrophic denitrifier in wastewater treatment process. Copyright 2009 Elsevier Ltd. All rights reserved.

Simplified charge separation energetics in a two-dimensional model for polymer-based photovoltaic cells.

PubMed

Sylvester-Hvid, Kristian O; Ratner, Mark A

2005-01-13

An extension of our two-dimensional working model for photovoltaic behavior in binary polymer and/or molecular photoactive blends is presented. The objective is to provide a more-realistic description of the charge generation and charge separation processes in the blend system. This is achieved by assigning an energy to each of the possible occupation states, describing the system according to a simple energy model for exciton and geminate electron-hole pair configurations. The energy model takes as primary input the ionization potential, electron affinity and optical gap of the components of the blend. The underlying photovoltaic model considers a nanoscopic subvolume of a photoactive blend and represents its p- and n-type domain morphology, in terms of a two-dimensional network of donor and acceptor sites. The nearest-neighbor hopping of charge carriers in the illuminated system is described in terms of transitions between different occupation states. The equations governing the dynamics of these states are cast into a linear master equation, which can be solved for arbitrary two-dimensional donor-acceptor networks, assuming stationary conditions. The implications of incorporating the energy model into the photovoltaic model are illustrated by simulations of the short circuit current versus thickness of the photoactive blend layer for different choices of energy parameters and donor-acceptor topology. The results suggest the existence of an optimal thickness of the photoactive film in bulk heterojunctions, based on kinetic considerations alone, and that this optimal thickness is very sensitive to the choice of energy parameters. The results also indicate space-charge limiting effects for interpenetrating donor-acceptor networks with characteristic domain sizes in the nanometer range and high driving force for the photoinduced electron transfer across the donor-acceptor internal interface.

Revealing electronic open quantum systems with subsystem TDDFT

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

Krishtal, Alisa, E-mail: alisa.krishtal@rutgers.edu; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu

2016-03-28

Open quantum systems (OQSs) are perhaps the most realistic systems one can approach through simulations. In recent years, describing OQSs with Density Functional Theory (DFT) has been a prominent avenue of research with most approaches based on a density matrix partitioning in conjunction with an ad-hoc description of system-bath interactions. We propose a different theoretical approach to OQSs based on partitioning of the electron density. Employing the machinery of subsystem DFT (and its time-dependent extension), we provide a novel way of isolating and analyzing the various terms contributing to the coupling between the system and the surrounding bath. To illustratemore » the theory, we provide numerical simulations on a toy system (a molecular dimer) and on a condensed phase system (solvated excimer). The simulations show that non-Markovian dynamics in the electronic system-bath interactions are important in chemical applications. For instance, we show that the superexchange mechanism of transport in donor-bridge-acceptor systems is a non-Markovian interaction between the donor-acceptor (OQS) with the bridge (bath) which is fully characterized by real-time subsystem time-dependent DFT.« less

Revealing electronic open quantum systems with subsystem TDDFT.

PubMed

Krishtal, Alisa; Pavanello, Michele

2016-03-28

Open quantum systems (OQSs) are perhaps the most realistic systems one can approach through simulations. In recent years, describing OQSs with Density Functional Theory (DFT) has been a prominent avenue of research with most approaches based on a density matrix partitioning in conjunction with an ad-hoc description of system-bath interactions. We propose a different theoretical approach to OQSs based on partitioning of the electron density. Employing the machinery of subsystem DFT (and its time-dependent extension), we provide a novel way of isolating and analyzing the various terms contributing to the coupling between the system and the surrounding bath. To illustrate the theory, we provide numerical simulations on a toy system (a molecular dimer) and on a condensed phase system (solvated excimer). The simulations show that non-Markovian dynamics in the electronic system-bath interactions are important in chemical applications. For instance, we show that the superexchange mechanism of transport in donor-bridge-acceptor systems is a non-Markovian interaction between the donor-acceptor (OQS) with the bridge (bath) which is fully characterized by real-time subsystem time-dependent DFT.

Revealing electronic open quantum systems with subsystem TDDFT

NASA Astrophysics Data System (ADS)

Krishtal, Alisa; Pavanello, Michele

2016-03-01

Open quantum systems (OQSs) are perhaps the most realistic systems one can approach through simulations. In recent years, describing OQSs with Density Functional Theory (DFT) has been a prominent avenue of research with most approaches based on a density matrix partitioning in conjunction with an ad-hoc description of system-bath interactions. We propose a different theoretical approach to OQSs based on partitioning of the electron density. Employing the machinery of subsystem DFT (and its time-dependent extension), we provide a novel way of isolating and analyzing the various terms contributing to the coupling between the system and the surrounding bath. To illustrate the theory, we provide numerical simulations on a toy system (a molecular dimer) and on a condensed phase system (solvated excimer). The simulations show that non-Markovian dynamics in the electronic system-bath interactions are important in chemical applications. For instance, we show that the superexchange mechanism of transport in donor-bridge-acceptor systems is a non-Markovian interaction between the donor-acceptor (OQS) with the bridge (bath) which is fully characterized by real-time subsystem time-dependent DFT.

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems

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

Wasielewski, Michael R.

In natural photosynthesis, organisms optimize solar energy conversion through organized assemblies of photofunctional chromophores and catalysts within proteins that provide specifically tailored environments for chemical reactions. As with their natural counterparts, artificial photosynthetic systems for practical solar fuels production must collect light energy, separate charge, and transport charge to catalytic sites where multielectron redox processes will occur. While encouraging progress has been made on each aspect of this complex problem, researchers have not yet developed self-ordering and self-assembling components and the tailored environments necessary to realize a fully-functional artificial system. Previously researchers have used complex, covalent molecular systems comprised ofmore » chromophores, electron donors, and electron acceptors to mimic both the light-harvesting and the charge separation functions of photosynthetic proteins. These systems allow for study of the dependencies of electron transfer rate constants on donor?acceptor distance and orientation, electronic interaction, and the free energy of the reaction. The most useful and informative systems are those in which structural constraints control both the distance and the orientation between the electron donors and acceptors. Self-assembly provides a facile means for organizing large numbers of molecules into supramolecular structures that can bridge length scales from nanometers to macroscopic dimensions. The resulting structures must provide pathways for migration of light excitation energy among antenna chromophores, and from antennas to reaction centers. They also must incorporate charge conduits, that is, molecular 'wires' that can efficiently move electrons and holes between reaction centers and catalytic sites. The central scientific challenge is to develop small, functional building blocks with a minimum number of covalent linkages, which also have the appropriate molecular recognition properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving ?-stacking can be used to integrate light harvesting with charge separation and transport.« less

Disorder-driven metal-insulator-transition assisted by interband Coulomb repulsion in a surface transfer doped electron system

NASA Astrophysics Data System (ADS)

Francisco Sánchez-Royo, Juan

2012-12-01

The two-dimensional conducting properties of the Si(111) \\sqrt {3} \\times \\sqrt {3} surface doped by the charge surface transfer mechanism have been calculated in the frame of a semiclassical Drude-Boltzmann model considering donor scattering mechanisms. To perform these calculations, the required values of the carrier effective mass were extracted from reported angle-resolved photoemission results. The calculated doping dependence of the surface conductance reproduces experimental results reported and reveals an intricate metallization process driven by disorder and assisted by interband interactions. The system should behave as an insulator even at relatively low doping due to disorder. However, when doping increases, the system achieves to attenuate the inherent localization effects introduced by disorder and to conduct by percolation. The mechanism found by the system to conduct appears to be connected with the increasing of the carrier effective mass observed with doping, which seems to be caused by interband interactions involving the conducting band and deeper ones. This mass enhancement reduces the donor Bohr radius and, consequently, promotes the screening ability of the donor potential by the electron gas.

Chemical Bonding and Thermodynamics in Superconductivity and Superfluidity

NASA Astrophysics Data System (ADS)

Love, Peter

2012-05-01

Superconductivity and superfluidity are physical states that occur in a variety of chemical and physical systems. These physical states share a common type of real, or virtual, chemical bonding. Each of the systems discussed herein contain at least one real, or effective, coordinate covalent bond. This is formed from an electron pair donor species and an electron pair acceptor species. When the electronegativity difference between the electron pair donor and acceptor species is sufficiently small, the resultant coordinate covalent bond density can be substantial. If delocalized, this bond density can result in a significant increase in the electron pair orbital volume relative to that of the parent species, and an increase in the valence shell orbital entropy. In terms of the normalized Gibbs-Helmholtz equation, this results in a concomitant decrease in free energy of the delocalized electronic system. A decrease in free energy to negative values can support a boson state, and superconductivity. A clear example of these principles is the occurrence of superconductivity in the ceramic material, MgB2. These generalizations apply to superconducting elements, high temperature superconductors, superconducting alloys, and equivalently to superfluid 4He.

Effect of two intermediate electron donors, NADPH and FADH(2), on Spirulina Delta (6)-desaturase co-expressed with two different immediate electron donors, cytochrome b (5) and ferredoxin, in Escherichia coli.

PubMed

Kurdrid, Pavinee; Subudhi, Sanjukta; Cheevadhanarak, Supapon; Tanticharoen, Morakot; Hongsthong, Apiradee

2007-12-01

When the gene desD encoding Spirulina Delta(6)-desaturase was heterologously expressed in E. coli, the enzyme was expressed without the ability to function. However, when this enzyme was co-expressed with an immediate electron donor, i.e. the cytochrome b (5) domain from Mucor rouxii, the results showed the production of GLA (gamma-linolenic acid), the product of the reaction catalyzed by Delta(6)-desaturase. The results revealed that in E. coli cells, where cytochrome b (5) is absent and ferredoxin, a natural electron donor of Delta(6)-desaturase, is present at a very low level, the cytochrome b (5) domain can complement for the function of ferredoxin in the host cells. In the present study, the Spirulina-ferredoxin gene was cloned and co-expressed with the Delta(6)-desaturase in E. coli. In comparison to the co-expression of cytochrome b ( 5 ) with the Delta(6)-desaturase, the co-expression with ferredoxin did not cause any differences in the GLA level. Moreover, the cultures containing the Delta(6)-desaturase co-expressed with cytochrome b (5) and ferredoxin were exogenously supplied with the intermediate electron donors, NADPH (nicotinamide adenine dinucleotide phosphate, reduced form) and FADH(2) (flavin adenine dinucleotide, reduced form), respectively. The GLA level in these host cells increased drastically, by approximately 50%, compared to the cells without the intermediate electron donors. The data indicated that besides the level of immediate electron donors, the level of intermediate electron donors is also critical for GLA production. Therefore, if the pools of the immediate and intermediate electron donors in the cells are manipulated, the GLA production in the heterologous host will be affected.

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

PubMed

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

2007-01-08

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

Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

NASA Astrophysics Data System (ADS)

Dillon, Robert John

The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the prime consideration is avoiding loss due to recombination of the electron and hole. In this study, four samples of core-shell Au-TiO 2 nanostructures are analyzed for their photocatalytic activity and spectroscopic properties. The samples were made with increasingly crystalline TiO2 shells. The more crystalline samples had higher photocatalytic activities, attributed to longer carrier lifetimes. The observed photophysics of these samples vary with excitation wavelength and detection method used. We find the time-resolved photoluminescence correlates with the samples' photocatalytic activities only when high energy, excitation wavelength less than or equal to 300 nm is used, while transient absorption experiments show no correlation regardless of excitation source. The results imply that photoexcitation with high energy photons can generate both reactive surface sites and photoluminescent surface sites in parallel. Both types of sites then undergo similar electron-hole recombination processes that depend on the crystallinity of the TiO2 shell. Surface sites created by low energy photons, as well as bulk TiO2 carrier dynamics that are probed by transient absorption, do not appear to be sensitive to the same dynamics that determine chemical reactivity.

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

PubMed Central

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

2016-01-01

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

Picosecond Control of Photogenerated Radical Pair Lifetimes Using a Stable Third Radical.

PubMed

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

2016-05-12

Photoinduced electron transfer reactions in organic donor-acceptor systems leading to long-lived radical ion pairs (RPs) have attracted broad interest for their potential applications in fields as diverse as solar energy conversion and spintronics. We present the photophysics and spin dynamics of an electron donor - electron acceptor - stable radical system consisting of a meta-phenylenediamine (mPD) donor covalently linked to a 4-aminonaphthalene-1,8-dicarboximide (ANI) electron-accepting chromophore as well as an α,γ-bisdiphenylene-β-phenylallyl (BDPA) stable radical. Selective photoexcitation of ANI produces the BDPA-mPD(+•)-ANI(-•) triradical in which the mPD(+•)-ANI(-•) RP spins are strongly exchange coupled. The presence of BDPA is found to greatly increase the RP intersystem crossing rate from the initially photogenerated BDPA-(1)(mPD(+•)-ANI(-•)) to BDPA-(3)(mPD(+•)-ANI(-•)), resulting in accelerated RP recombination via the triplet channel to produce BDPA-mPD-(3*)ANI as compared to a reference molecule lacking the BDPA radical. The RP recombination rates observed are much faster than those previously reported for weakly coupled triradical systems. Time-resolved EPR spectroscopy shows that this process is also associated with strong spin polarization of the stable radical. Overall, these results show that RP intersystem crossing rates can be strongly influenced by stable radicals nearby strongly coupled RP systems, making it possible to use a third spin to control RP lifetimes down to a picosecond time scale.

Single-electron quantization at room temperature in a-few-donor quantum dot in silicon nano-transistors

NASA Astrophysics Data System (ADS)

Samanta, Arup; Muruganathan, Manoharan; Hori, Masahiro; Ono, Yukinori; Mizuta, Hiroshi; Tabe, Michiharu; Moraru, Daniel

2017-02-01

Quantum dots formed by donor-atoms in Si nanodevices can provide a breakthrough for functionality at the atomic level with one-by-one control of electrons. However, single-electron effects in donor-atom devices have only been observed at low temperatures mainly due to the low tunnel barriers. If a few donor-atoms are closely coupled as a molecule to form a quantum dot, the ground-state energy level is significantly deepened, leading to higher tunnel barriers. Here, we demonstrate that such an a-few-donor quantum dot, formed by selective conventional doping of phosphorus (P) donors in a Si nano-channel, sustains Coulomb blockade behavior even at room temperature. In this work, such a quantum dot is formed by 3 P-donors located near the center of the selectively-doped area, which is consistent with a statistical analysis. This finding demonstrates practical conditions for atomic- and molecular-level electronics based on donor-atoms in silicon nanodevices.

Uranium reduction and microbial community development in response to stimulation with different electron donors.

PubMed

Barlett, Melissa; Moon, Hee Sun; Peacock, Aaron A; Hedrick, David B; Williams, Kenneth H; Long, Philip E; Lovley, Derek; Jaffe, Peter R

2012-07-01

Stimulating microbial reduction of soluble U(VI) to less soluble U(IV) shows promise as an in situ bioremediation strategy for uranium contaminated groundwater, but the optimal electron donors for promoting this process have yet to be identified. The purpose of this study was to better understand how the addition of various electron donors to uranium-contaminated subsurface sediments affected U(VI) reduction and the composition of the microbial community. The simple electron donors, acetate or lactate, or the more complex donors, hydrogen-release compound (HRC) or vegetable oil, were added to the sediments incubated in flow-through columns. The composition of the microbial communities was evaluated with quantitative PCR probing specific 16S rRNA genes and functional genes, phospholipid fatty acid analysis, and clone libraries. All the electron donors promoted U(VI) removal, even though the composition of the microbial communities was different with each donor. In general, the overall biomass, rather than the specific bacterial species, was the factor most related to U(VI) removal. Vegetable oil and HRC were more effective in stimulating U(VI) removal than acetate. These results suggest that the addition of more complex organic electron donors could be an excellent option for in situ bioremediation of uranium-contaminated groundwater.

The spin relaxation of nitrogen donors in 6H SiC crystals as studied by the electron spin echo method

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

Savchenko, D., E-mail: dariyasavchenko@gmail.com; National Technical University of Ukraine “Kyiv Polytechnic Institute,” Kyiv 03056; Shanina, B.

2016-04-07

We present the detailed study of the spin kinetics of the nitrogen (N) donor electrons in 6H SiC wafers grown by the Lely method and by the sublimation “sandwich method” (SSM) with a donor concentration of about 10{sup 17 }cm{sup −3} at T = 10–40 K. The donor electrons of the N donors substituting quasi-cubic “k1” and “k2” sites (N{sub k1,k2}) in both types of the samples revealed the similar temperature dependence of the spin-lattice relaxation rate (T{sub 1}{sup −1}), which was described by the direct one-phonon and two-phonon processes induced by the acoustic phonons proportional to T and to T{sup 9}, respectively. Themore » character of the temperature dependence of the T{sub 1}{sup −1} for the donor electrons of N substituting hexagonal (“h”) site (N{sub h}) in both types of 6H SiC samples indicates that the donor electrons relax through the fast-relaxing centers by means of the cross-relaxation process. The observed enhancement of the phase memory relaxation rate (T{sub m}{sup −1}) with the temperature increase for the N{sub h} donors in both types of the samples, as well as for the N{sub k1,k2} donors in Lely grown 6H SiC, was explained by the growth of the free electron concentration with the temperature increase and their exchange scattering at the N donor centers. The observed significant shortening of the phase memory relaxation time T{sub m} for the N{sub k1,k2} donors in the SSM grown sample with the temperature lowering is caused by hopping motion of the electrons between the occupied and unoccupied states of the N donors at N{sub h} and N{sub k1,k2} sites. The impact of the N donor pairs, triads, distant donor pairs formed in n-type 6H SiC wafers on the spin relaxation times was discussed.« less

Understanding biogeobatteries: Where geophysics meets microbiology

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

Revil, A.; Mendonca, C.A.; Atekwana, E.A.

2009-08-15

Although recent research suggests that contaminant plumes behave as geobatteries that produce an electrical current in the ground, no associated model exists that honors both geophysical and biogeochemical constraints. Here, we develop such a model to explain the two main electrochemical contributions to self-potential signals in contaminated areas. Both contributions are associated with the gradient of the activity of two types of charge carriers, ions and electrons. In the case of electrons, bacteria act as catalysts for reducing the activation energy needed to exchange the electrons between electron donor and electron acceptor. Possible mechanisms that facilitate electron migration include ironmore » oxides, clays, and conductive biological materials, such as bacterial conductive pili or other conductive extracellular polymeric substances. Because we explicitly consider the role of biotic processes in the geobattery model, we coined the term 'biogeobattery'. After theoretical development of the biogeobattery model, we compare model predictions with self-potential responses associated with laboratory and field-scale conducted in contaminated environments. We demonstrate that the amplitude and polarity of large (>100 mV) self-potential signatures requires the presence of an electronic conductor to serve as a bridge between electron donors and acceptors. Small self-potential anomalies imply that electron donors and electron acceptors are not directly interconnected, but instead result simply from the gradient of the activity of the ionic species that are present in the system.« less

Electrobioremediation of oil spills.

PubMed

Daghio, Matteo; Aulenta, Federico; Vaiopoulou, Eleni; Franzetti, Andrea; Arends, Jan B A; Sherry, Angela; Suárez-Suárez, Ana; Head, Ian M; Bestetti, Giuseppina; Rabaey, Korneel

2017-05-01

Annually, thousands of oil spills occur across the globe. As a result, petroleum substances and petrochemical compounds are widespread contaminants causing concern due to their toxicity and recalcitrance. Many remediation strategies have been developed using both physicochemical and biological approaches. Biological strategies are most benign, aiming to enhance microbial metabolic activities by supplying limiting inorganic nutrients, electron acceptors or donors, thus stimulating oxidation or reduction of contaminants. A key issue is controlling the supply of electron donors/acceptors. Bioelectrochemical systems (BES) have emerged, in which an electrical current serves as either electron donor or acceptor for oil spill bioremediation. BES are highly controllable and can possibly also serve as biosensors for real time monitoring of the degradation process. Despite being promising, multiple aspects need to be considered to make BES suitable for field applications including system design, electrode materials, operational parameters, mode of action and radius of influence. The microbiological processes, involved in bioelectrochemical contaminant degradation, are currently not fully understood, particularly in relation to electron transfer mechanisms. Especially in sulfate rich environments, the sulfur cycle appears pivotal during hydrocarbon oxidation. This review provides a comprehensive analysis of the research on bioelectrochemical remediation of oil spills and of the key parameters involved in the process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhancement in Organic Photovoltaic Efficiency through the Synergistic Interplay of Molecular Donor Hydrogen Bonding and -Stacking

DOE PAGES

Shewmon, Nathan; Watkins, Davita; Galindo, Johan; ...

2015-07-20

For organic photovoltaic (OPV) cells based on the bulk heterojunction (BHJ) structure, it remains challenging to rationally control the degree of phase separation and percolation within blends of donors and acceptors to secure optimal charge separation and transport. Reported is a bottom-up, supramolecular approach to BHJ OPVs wherein tailored hydrogen bonding (H-bonding) interactions between π-conjugated electron donor molecules encourage formation of vertically aligned donor π-stacks while simultaneously suppressing lateral aggregation; the programmed arrangement facilitates fine mixing with fullerene acceptors and efficient charge transport. The approach is illustrated using conventional linear or branched quaterthiophene donor chromophores outfitted with terminal functional groupsmore » that are either capable or incapable of self-complementary H-bonding. When applied to OPVs, the H-bond capable donors yield a twofold enhancement in power conversion efficiency relative to the comparator systems, with a maximum external quantum efficiency of 64%. H-bond promoted assembly results in redshifted absorption (in neat films and donor:C 60 blends) and enhanced charge collection efficiency despite disparate donor chromophore structure. Both features positively impact photocurrent and fill factor in OPV devices. Film structural characterization by atomic force microscopy, transmission electron microscopy, and grazing incidence wide angle X-ray scattering reveals a synergistic interplay of lateral H-bonding interactions and vertical π-stacking for directing the favorable morphology of the BHJ.« less

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

Ponomarenko, N. S.; Poluektov, O. G.; Bylina, E. J.

High-field electron paramagnetic resonance (HF EPR) has been employed to investigate the primary electron donor electronic structure of Blastochloris viridis heterodimer mutant reaction centers (RCs). In these mutants the amino acid substitution His(M200)Leu or His(L173)Leu eliminates a ligand to the primary electron donor, resulting in the loss of a magnesium in one of the constituent bacteriochlorophylls (BChl). Thus, the native BChl/BChl homodimer primary donor is converted into a BChl/bacteriopheophytin (BPhe) heterodimer. The heterodimer primary donor radical in chemically oxidized RCs exhibits a broadened EPR line indicating a highly asymmetric distribution of the unpaired electron over both dimer constituents. Observed tripletmore » state EPR signals confirm localization of the excitation on the BChl half of the heterodimer primary donor. Theoretical simulation of the triplet EPR lineshapes clearly shows that, in the case of mutants, triplet states are formed by an intersystem crossing mechanism in contrast to the radical pair mechanism in wild type RCs. Photooxidation of the mutant RCs results in formation of a BPhe anion radical within the heterodimer pair. The accumulation of an intradimer BPhe anion is caused by the substantial loss of interaction between constituents of the heterodimer primary donor along with an increase in the reduction potential of the heterodimer primary donor D/D{sup +} couple. This allows oxidation of the cytochrome even at cryogenic temperatures and reduction of each constituent of the heterodimer primary donor individually. Despite a low yield of primary donor radicals, the enhancement of the semiquinone-iron pair EPR signals in these mutants indicates the presence of kinetically viable electron donors.« less

Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors

NASA Astrophysics Data System (ADS)

Sivakumar, V.; Ponnamma, Deepalekshmi; Hussein, Yasser H. A.

2017-02-01

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQT) but not the triplets AQT or AQST. However in aqueous medium, AN quenches AQST and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQT or AQST while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications.

Estimation of electronic coupling in π-stacked donor-bridge-acceptor systems: Correction of the two-state model

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.

2006-02-01

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽda=(E2-E1)μ12/Rda+(2E3-E1-E2)2μ13μ23/Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model.

Estimation of electronic coupling in pi-stacked donor-bridge-acceptor systems: correction of the two-state model.

PubMed

Voityuk, Alexander A

2006-02-14

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of V(da) because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a pi stack, where donor and acceptor are separated by a bridging unit, can be obtained as V(da) = (E(2)-E(1))mu(12)R(da) + (2E(3)-E(1)-E(2))2mu(13)mu(23)R(da) (2), where E(1), E(2), and E(3) are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, mu(ij) is the transition dipole moments between the states i and j, and R(da) is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model.

Magneto-ionic phase control in a quasi-layered donor/acceptor metal-organic framework by means of a Li-ion battery system

NASA Astrophysics Data System (ADS)

Taniguchi, Kouji; Narushima, Keisuke; Yamagishi, Kayo; Shito, Nanami; Kosaka, Wataru; Miyasaka, Hitoshi

2017-06-01

Electrical magnetism control is realized in a Li-ion battery system through a redox reaction involving ion migrations; “magneto-ionic control”. A quasi-layered metal-organic framework compound with a cross-linked π-conjugated/unconjugated one-dimensional chain motifs composed of electron-donor/acceptor units is developed as the cathode material. A change in magnetic phase from paramagnetic to ferrimagnetic is demonstrated by means of electron-filling control for the acceptor units via insertion of Li+-ions into pores in the material. The transition temperature is as high as that expected for highly π-conjugated layered systems, indicating an extension of π-conjugated exchange paths by rearranging coordination bonds in the first discharge process.

Carbon dot-Au(i)Ag(0) assembly for the construction of an artificial light harvesting system.

PubMed

Jana, Jayasmita; Aditya, Teresa; Pal, Tarasankar

2018-03-06

Artificial light harvesting systems (LHS) with inorganic counterparts are considered to be robust as well as mechanistically simple, where the system follows the donor-acceptor principle with an unchanged structural pattern. Plasmonic gold or silver nanoparticles are mostly chosen as inorganic counterparts to design artificial LHS. To capitalize on its electron accepting capability, Au(i) has been considered in this work for the synergistic stabilization of a system with intriguingly fluorescing silver(0) clusters produced in situ. Thus a stable fluorescent Au(i)Ag(0) assembly is generated with electron accepting capabilities. On the other hand, carbon dots have evolved as new fluorescent probes due to their unique physicochemical properties. Utilizing the simple electronic behavior of carbon dots, an electronic interaction between the fluorescent Au(i)Ag(0) and a carbon dot has been investigated for the construction of a new artificial light harvesting system. This coinage metal assembly allows surface energy transfer where it acts as an acceptor, while the carbon dot behaves as a good donor. The energy transfer efficiency has been calculated experimentally to be significant (81.3%) and the Au(i)Ag(0)-carbon dot assembly paves the way for efficient artificial LHS.

Ternary bulk heterojunction for wide spectral range organic photodetectors

NASA Astrophysics Data System (ADS)

Shin, Hojung; Kim, Jaehoon; Lee, Changhee

2017-08-01

Ternary bulk heterojunction (BHJ) system, dual electron donors and an acceptor, was studied for developing wide spectral range organic photodetectors (OPDs). With two electron donor polymers with different bandgaps and an efficient electron acceptor of [6,6]-Phenyl-C71-butyric acid methyl ester (PC70BM), different blend ratios for ternary BHJ OPD were examined to achieve high photoresponsivity over a wide spectral range. OPDs based on ternary BHJ showed improved photovoltage response compared to binary BHJ. Current-voltage (J-V) characteristics as a function of external bias and light illumination were measured to reveal the underlying charge recombination mechanism which is found to be dominantly ruled by space charge limit (SCL) effect. Additional in-depth analyses including absorbance, cross-section scanning electron microscope (SEM), incident photon-to-electron conversion efficiency (IPCE) were performed.

Biophotolysis systems for hydrogen production

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

Rao, K.K.; Adams, M.W.W.; Gisby, P.E.

1981-01-01

Model systems containing natural and synthetic catalysts were constructed for the production of H/sub 2/ from water using visible solar radiation as the energy source. The authors have investigated the use of aqueous systems with proflavine as the light activator and artificial electron donors for subsequent production of H/sub 2/ when coupled to electron mediators and hydrogenase (or Pt). The characteristics, relative merits and defects of these systems are discussed. 22 refs.

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

PubMed

Jakowetz, Andreas C; Böhm, Marcus L; Zhang, Jiangbin; Sadhanala, Aditya; Huettner, Sven; Bakulin, Artem A; Rao, Akshay; Friend, Richard H

2016-09-14

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

Enhanced reduction of an azo dye using henna plant biomass as a solid-phase electron donor, carbon source, and redox mediator.

PubMed

Huang, Jingang; Chu, Shushan; Chen, Jianjun; Chen, Yi; Xie, Zhengmiao

2014-06-01

The multiple effects of henna plant biomass as a source of carbon, electron donor, and redox mediator (RM) on the enhanced bio-reduction of Orange II (AO7) were investigated. The results indicated that the maximum AO7 reduction rate in the culture with henna powder was ∼6-fold that in the sludge control culture lacking henna. On the one hand, AO7 reduction can be advantageously enhanced by the release of available electron donors; on the other hand, the associated lawsone can act as a fixed RM and play a potential role in shuttling electrons from the released electron donors to the final electron acceptor, AO7. The soluble chemical oxygen demand (SCOD) during each experiment and the FTIR spectra suggested that the weakened AO7 reduction along with the retention of henna powder might not be attributed to the lack of fixed lawsone but rather to the insufficiency of electron donors. Copyright © 2014 Elsevier Ltd. All rights reserved.

ESR Experiments on a Single Donor Electron in Isotopically Enriched Silicon

NASA Astrophysics Data System (ADS)

Tracy, Lisa; Luhman, Dwight; Carr, Stephen; Borchardt, John; Bishop, Nathaniel; Ten Eyck, Gregory; Pluym, Tammy; Wendt, Joel; Witzel, Wayne; Blume-Kohout, Robin; Nielsen, Erik; Lilly, Michael; Carroll, Malcolm

In this talk we will discuss electron spin resonance experiments in single donor silicon qubit devices fabricated at Sandia National Labs. A self-aligned device structure consisting of a polysilicon gate SET located adjacent to the donor is used for donor electron spin readout. Using a cryogenic HEMT amplifier next to the silicon device, we demonstrate spin readout at 100 kHz bandwidth and Rabi oscillations with 0.96 visibility. Electron spin resonance measurements on these devices show a linewidth of 30 kHz and coherence times T2* = 10 us and T2 = 0.3 ms. We also discuss estimates of the fidelity of our donor electron spin qubit measurements using gate set tomography. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. DOE Office of Basic Energy Sciences user facility. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the U. S. Department of Energy under Contract No. DE-AC04-94AL85000. ESR Experiments on a Single Donor Electron in Isotopically Enriched Silicon.

Solvent as electron donor: Donor/acceptor electronic coupling is a dynamical variable

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

Castner, E.W. Jr.; Kennedy, D.; Cave, R.J.

2000-04-06

The authors combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken-Hush (GMH) theory in the study of electron-transfer reactions and electron donor-acceptor interactions. The study focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories: six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)-coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular dynamicsmore » trajectories, semiempirical quantum mechanical calculations (of the relevant adiabatic electronic states), and GMH theory to the C152/DMA photoreaction, the authors calculate the electron donor/acceptor interaction parameter H{sub DA} at various time frames, H{sub DA} is strongly modulated by both inner-sphere and outer-sphere nuclear dynamics, leading us to conclude that H{sub DA} must be considered as a dynamical variable.« less

Oxidation of humic substances supports denitrification reactions in agricultural soils.

NASA Astrophysics Data System (ADS)

van Trump, J. I.; Coates, J. D.

2007-12-01

Humic substances (HS) are a ubiquitous, recalcitrant, and diverse class of compounds arising from degradation and condensation of plant and microbial biopolymers. Many bacteria oxidize hydroquinones within humic substances to their quinone analogs, providing electrons for respiratory processes such as nitrate reduction. Microbial hydroquinone oxidation contributes to the redox state of HS and supports denitrification, which may be of import to agricultural soils where nitrate retention is critical and HS are prevalent. Most probable number counts were performed on soils collected from a Nebraska farm, with the model humic hydroquinone 2,6- anthrahydroquinone disulfonate (AHDS) serving as an electron donor and nitrate as the electron acceptor. Results indicated that AHDS oxidizing, nitrate reducing bacteria were present in soils from bluegrass fields (104 cells/g) and aspen groves (106 cells/g), as well as in plots of corn (106 cells/g), and soybean treated (106 cells/g) and un-treated (105 cells/g) with pig slurry. These results demonstrate that microorganisms participating in the proposed metabolism are prevalent within agricultural soils. Upflow glass columns were constructed, containing a support matrix of glass beads amended with 10% w/w soil from the corn plot previously mentioned. All columns were subjected to a continual flow of phosphate-buffered water amended with sodium nitrate. Above the point source for nitrate injection, phosphate-buffered water containing electron donor treatments were continually injected. The impacts of electron donor treatments (no donor, oxidized HS, reduced HS, and acetate) on denitrification and other geochemical parameters were observed. Column studies were able to resolve effects of electron donor treatment both spatially as a function of distance from the injection point source, and temporally, as a function of time of donor treatment. Four sample ports in each column were routinely analyzed for concentrations of nitrate, nitrite, Fe(II), and humic-born hydroquinones. All data were analyzed with respect to dilution factors obtained through analysis of a conservative bromide tracer present in electron donor medium. Addition of oxidized HS, reduced HS, and acetate all resulted in significant loss of nitrate from the columns. Significant nitrite accumulation was not observed. Of all the electron donor treatments, reduced HS, enriched for hydroquinone-containing functional moieties, supported the greatest degree of denitrification. The participation of excess hydroquinones in denitrification accounted for approximately 104% of the difference in nitrate reduction between reduced and oxidized HS treatments. This electron balance allowed for assignment of respiratory activity due to hydroquinone oxidation, rather than degradation of humic substances or associated electron-donating compounds. These results suggest that denitrification reactions catalyzed by microbial oxidation of reduced HS may be prevalent in agricultural soils. Likewise, these results demonstrate for the first time that respiratory behavior due to hydroquinone oxidation, as well as impact upon local geochemistry, can be analyzed in complex flow-through model systems.

Microbial electrochemical energy storage and recovery in a combined electrotrophic and electrogenic biofilm

USDA-ARS?s Scientific Manuscript database

Electroactive biofilms, used as biocatalysts in bioelectrochemical systems (BESs), are usually operated either as electrogenic (the electrode is the electron acceptor) or electrotrophic (the electrode is the electron donor). Here, we enriched a non-photosynthetic bifunctional electroactive biofilm c...

Interaction of photosystem I from Phaeodactylum tricornutum with plastocyanins as compared with its native cytochrome c6: Reunion with a lost donor.

PubMed

Bernal-Bayard, Pilar; Pallara, Chiara; Carmen Castell, M; Molina-Heredia, Fernando P; Fernández-Recio, Juan; Hervás, Manuel; Navarro, José A

2015-12-01

In the Phaeodactylum tricornutum alga, as in most diatoms, cytochrome c6 is the only electron donor to photosystem I, and thus they lack plastocyanin as an alternative electron carrier. We have investigated, by using laser-flash absorption spectroscopy, the electron transfer to Phaeodactylum photosystem I from plastocyanins from cyanobacteria, green algae and plants, as compared with its own cytochrome c6. Diatom photosystem I is able to effectively react with eukaryotic acidic plastocyanins, although with less efficiency than with Phaeodactylum cytochrome c6. This efficiency, however, increases in some green alga plastocyanin mutants mimicking the electrostatics of the interaction site on the diatom cytochrome. In addition, the structure of the transient electron transfer complex between cytochrome c6 and photosystem I from Phaeodactylum has been analyzed by computational docking and compared to that of green lineage and mixed systems. Taking together, the results explain why the Phaeodactylum system shows a lower efficiency than the green systems, both in the formation of the properly arranged [cytochrome c6-photosystem I] complex and in the electron transfer itself. Copyright © 2015 Elsevier B.V. All rights reserved.

Generalized Mulliken-Hush analysis of electronic coupling interactions in compressed pi-stacked porphyrin-bridge-quinone systems.

PubMed

Zheng, Jieru; Kang, Youn K; Therien, Michael J; Beratan, David N

2005-08-17

Donor-acceptor interactions were investigated in a series of unusually rigid, cofacially compressed pi-stacked porphyrin-bridge-quinone systems. The two-state generalized Mulliken-Hush (GMH) approach was used to compute the coupling matrix elements. The theoretical coupling values evaluated with the GMH method were obtained from configuration interaction calculations using the INDO/S method. The results of this analysis are consistent with the comparatively soft distance dependences observed for both the charge separation and charge recombination reactions. Theoretical studies of model structures indicate that the phenyl units dominate the mediation of the donor-acceptor coupling and that the relatively weak exponential decay of rate with distance arises from the compression of this pi-electron stack.

Where does the electron go? The nature of ortho/para and meta group directing in electrophilic aromatic substitution

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

Liu, Shubin, E-mail: shubin@email.unc.edu

Electrophilic aromatic substitution as one of the most fundamental chemical processes is affected by atoms or groups already attached to the aromatic ring. The groups that promote substitution at the ortho/para or meta positions are, respectively, called ortho/para and meta directing groups, which are often characterized by their capability to donate electrons to or withdraw electrons from the ring. Though resonance and inductive effects have been employed in textbooks to explain this phenomenon, no satisfactory quantitative interpretation is available in the literature. Here, based on the theoretical framework we recently established in density functional reactivity theory (DFRT), where electrophilicity andmore » nucleophilicity are simultaneously quantified by the Hirshfeld charge, the nature of ortho/para and meta group directing is systematically investigated for a total of 85 systems. We find that regioselectivity of electrophilic attacks is determined by the Hirshfeld charge distribution on the aromatic ring. Ortho/para directing groups have most negative charges on the ortho/para positions, while meta directing groups often possess the largest negative charge on the meta position. Our results do not support that ortho/para directing groups are electron donors and meta directing groups are electron acceptors. Most neutral species we studied here are electron withdrawal in nature. Anionic systems are always electron donors. There are also electron donors serving as meta directing groups. We predicted ortho/para and meta group directing behaviors for a list of groups whose regioselectivity is previously unknown. In addition, strong linear correlations between the Hirshfeld charge and the highest occupied molecular orbital have been observed, providing the first link between the frontier molecular orbital theory and DFRT.« less

Highly efficient exciplex organic light-emitting diodes incorporating a heptazine derivative as an electron acceptor.

PubMed

Li, Jie; Nomura, Hiroko; Miyazaki, Hiroshi; Adachi, Chihaya

2014-06-11

Highly efficient exciplex systems incorporating a heptazine derivative () as an electron acceptor and 1,3-di(9H-carbazol-9-yl)benzene () as an electron donor are developed. An organic light-emitting diode containing 8 wt% : as an emitting layer exhibits a maximum external quantum efficiency of 11.3%.

The significance of microbial processes in hydrogeology and geochemistry

USGS Publications Warehouse

Chapelle, F.H.

2000-01-01

Microbial processes affect the chemical composition of groundwater and the hydraulic properties of aquifers in both contaminated and pristine groundwater systems. The patterns of water-chemistry changes that occur depend upon the relative abundance of electron donors and electron acceptors. In many pristine aquifers, where microbial metabolism is limited by the availability of electron donors (usually organic matter), dissolved inorganic carbon (DIC) accumulates slowly along aquifer flow paths and available electron acceptors are consumed sequentially in the order dissolved oxygen > nitrate > Fe(III) > sulfate > CO2 (methanogenesis). In aquifers contaminated by anthropogenic contaminants, an excess of available organic carbon often exists, and microbial metabolism is limited by the availability of electron acceptors. In addition to changes in groundwater chemistry, the solid matrix of the aquifer is affected by microbial processes. The production of carbon dioxide and organic acids can lead to increased mineral solubility, which can lead to the development of secondary porosity and permeability. Conversely, microbial production of carbonate, ferrous iron, and sulfide can result in the precipitation of secondary calcite or pyrite cements that reduce primary porosity and permeability in groundwater systems.

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO 2 Interface in Quantum Dot-Sensitized Solar Cells

DOE PAGES

Xin, Xukai; Li, Bo; Jung, Jaehan; ...

2014-07-24

Quantum dot-sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next-generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO 2 acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. In order to understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO 2 substrate are simulated using a rigorous ab initio density functional method. Our method capitalizes onmore » localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO 2 occurring via the strong bonding between the conduction bands of QDs and TiO 2 is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO 2 acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO 2 systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO 2 acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.« less

Desferrioxamine as an electron donor. Inhibition of membranal lipid peroxidation initiated by H2O2-activated metmyoglobin and other peroxidizing systems.

PubMed

Kanner, J; Harel, S

1987-01-01

Desferrioxamine (DFO) involvement in several peroxidative systems was studied. These systems included: a) membranal lipid peroxidation initiated by H2O2-activated metmyoglobin (or methemoglobin); b) phenol-red oxidation by activated metmyoglobin or horseradish peroxidase (HRP): c) beta-carotene-linoleate couple oxidation stimulated by lipoxygenase or hemin. Desferrioxamine was found to inhibit all these systems but not ferrioxamine (FO). Phenol-red oxidation by H2O2-horseradish peroxidase was inhibited competitively with DFO. Kinetic studies using the spectra changes in the Soret region of metmyoglobin suggest a mechanism by which H2O2 reacts with the iron-heme to form an intermediate of oxy-ferryl myoglobin that subsequently reacts with DFO to return the activated compound to the resting state. These activities of DFO resemble the reaction of other electron donors.

Scanning Tunneling Microscopy Analysis of a Pentacene/Graphene/SiC(0001) system

NASA Astrophysics Data System (ADS)

Yost, Andrew; Suzer, Ozgun; Smerdon, Joseph; Chien, Teyu; Guest, Jeffrey

2014-03-01

A complete understanding of the structure of molecular assemblies, as well as an understanding of donor-acceptor interactions is crucial in the development of emergent molecular electronics technologies such as organic photovoltaics. The pentacene (C22H14) is a good electron donor in Pentacene-C60 system, which is a model system of an organic photovoltaic cell.. Here we present scanning tunneling microscopy studies of the pentacene(Pn) molecule on Graphene(G) that is epitaxially grown on SiC(0001). In addition to the morphologies reported in literature, several new structures of Pn on on G/SiC(0001) were observed with different periodicity and registry both in monolayer and bilayer coverages of molecules on the surface. Preliminary scanning tunneling spectroscopy of the molecular system is also discussed; well-isolated states and a large HOMO-LUMO gap indicate the Pn is weakly coupled to the grapheme and underlying substrate.

Algae as an electron donor promoting sulfate reduction for the bioremediation of acid rock drainage.

PubMed

Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A

2016-11-05

This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H2SO4 and Cu(2+). Sulfate, sulfide, Cu(2+) and pH were monitored throughout the experiment of 123d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7mg SO4(2-) d(-1)) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu(2+) removal were observed in the endogenous control. In algae amended-columns, Cu(2+) was precipitated with biogenic H2S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-qubit gates protected by adiabaticity and dynamical decoupling applicable to donor qubits in silicon

DOE PAGES

Witzel, Wayne; Montano, Ines; Muller, Richard P.; ...

2015-08-19

In this paper, we present a strategy for producing multiqubit gates that promise high fidelity with minimal tuning requirements. Our strategy combines gap protection from the adiabatic theorem with dynamical decoupling in a complementary manner. Energy-level transition errors are protected by adiabaticity and remaining phase errors are mitigated via dynamical decoupling. This is a powerful way to divide and conquer the various error channels. In order to accomplish this without violating a no-go theorem regarding black-box dynamically corrected gates [Phys. Rev. A 80, 032314 (2009)], we require a robust operating point (sweet spot) in control space where the qubits interactmore » with little sensitivity to noise. There are also energy gap requirements for effective adiabaticity. We apply our strategy to an architecture in Si with P donors where we assume we can shuttle electrons between different donors. Electron spins act as mobile ancillary qubits and P nuclear spins act as long-lived data qubits. Furthermore, this system can have a very robust operating point where the electron spin is bound to a donor in the quadratic Stark shift regime. High fidelity single qubit gates may be performed using well-established global magnetic resonance pulse sequences. Single electron-spin preparation and measurement has also been demonstrated. Thus, putting this all together, we present a robust universal gate set for quantum computation.« less

Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors.

PubMed

Sivakumar, V; Ponnamma, Deepalekshmi; Hussein, Yasser H A

2017-02-15

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQ T ) but not the triplets AQ T or AQS T . However in aqueous medium, AN quenches AQS T and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQ T or AQS T while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

PubMed

Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

2016-05-20

We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

Interfacial Molecular Packing Determines Exciton Dynamics in Molecular Heterostructures: The Case of Pentacene-Perfluoropentacene.

PubMed

Rinn, Andre; Breuer, Tobias; Wiegand, Julia; Beck, Michael; Hübner, Jens; Döring, Robin C; Oestreich, Michael; Heimbrodt, Wolfram; Witte, Gregor; Chatterjee, Sangam

2017-12-06

The great majority of electronic and optoelectronic devices depend on interfaces between p-type and n-type semiconductors. Finding matching donor-acceptor systems in molecular semiconductors remains a challenging endeavor because structurally compatible molecules may not necessarily be suitable with respect to their optical and electronic properties, and the large exciton binding energy in these materials may favor bound electron-hole pairs rather than free carriers or charge transfer at an interface. Regardless, interfacial charge-transfer exciton states are commonly considered as an intermediate step to achieve exciton dissociation. The formation efficiency and decay dynamics of such states will strongly depend on the molecular makeup of the interface, especially the relative alignment of donor and acceptor molecules. Structurally well-defined pentacene-perfluoropentacene heterostructures of different molecular orientations are virtually ideal model systems to study the interrelation between molecular packing motifs at the interface and their electronic properties. Comparing the emission dynamics of the heterosystems and the corresponding unitary films enables accurate assignment of every observable emission signal in the heterosystems. These heterosystems feature two characteristic interface-specific luminescence channels at around 1.4 and 1.5 eV that are not observed in the unitary samples. Their emission strength strongly depends on the molecular alignment of the respective donor and acceptor molecules, emphasizing the importance of structural control for device construction.

Photoinduced Charge Transfer and Electrochemical Properties of Triphenylamine Ih-Sc3N@C80 Donor-Acceptor Conjugates

PubMed Central

Pinzón, Julio R.; Gasca, Diana C.; Shankara, Gayathri. S; Bottari, Giovanni; Torres, Tomás; Guldi, Dirk M.; Echegoyen, Luis

2009-01-01

Two isomeric [5,6]-pyrrolidine-Ih-Sc3N@C80 electron donor acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C60 analogues, in order to determine i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, ii) the thermal stability towards the retro-cycloaddition reaction and iii) the effect of changing C60 for Ih-Sc3N@C80 as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C60 and Ih-Sc3N@C80 dyads. In addition to that, the N-substituted TPA-Ih-Sc3N@C80 dyad has much better thermal stability than the 2-subtituted one. Finally, the Ih-Sc3N@C80 dyads have considerably longer lived charge separated states than their C60 analogues, thus approving the advantage of using Ih-Sc3N@C80 instead of C60 as the acceptor for the construction of fullerene based donor acceptor conjugates. These findings are important for the design and future application of Ih-Sc3N@C80 dyads as materials for the construction of plastic organic solar cells. PMID:19445462

Phylogenetic analysis of TCE-dechlorinating consortia enriched on a variety of electron donors.

PubMed

Freeborn, Ryan A; West, Kimberlee A; Bhupathiraju, Vishvesh K; Chauhan, Sadhana; Rahm, Brian G; Richardson, Ruth E; Alvarez-Cohen, Lisa

2005-11-01

Two rapidly fermented electron donors, lactate and methanol, and two slowly fermented electron donors, propionate and butyrate, were selected for enrichment studies to evaluate the characteristics of anaerobic microbial consortia that reductively dechlorinate TCE to ethene. Each electron donor enrichment subculture demonstrated the ability to dechlorinate TCE to ethene through several serial transfers. Microbial community analyses based upon 16S rDNA, including terminal restriction fragment length polymorphism (T-RFLP) and clone library/sequencing, were performed to assess major changes in microbial community structure associated with electron donors capable of stimulating reductive dechlorination. Results demonstrated that five phylogenic subgroups or genera of bacteria were present in all consortia, including Dehalococcoides sp., low G+C Gram-positives (mostly Clostridium and Eubacterium sp.), Bacteroides sp., Citrobacter sp., and delta Proteobacteria (mostly Desulfovibrio sp.). Phylogenetic association indicates that only minor shifts in the microbial community structure occurred between the four alternate electron donor enrichments and the parent consortium. Inconsistent detection of Dehalococcoides spp. in clone libraries and T-RFLP of enrichment subcultures was resolved using quantitative polymerase chain reaction (Q-PCR). Q-PCR with primers specific to Dehalococcoides 16S rDNA resulted in positive detection of this species in all enrichments. Our results suggest that TCE-dechlorinating consortia can be stably maintained on a variety of electron donors and that quantities of Dehalococcoides cells detected with Dehalococcoides specific 16S rDNA primer/probe sets do not necessarily correlate well with solvent degradation rates.

Fine Splitting of Electron States in Silicon Nanocrystal with a Hydrogen-like Shallow Donor

PubMed Central

2007-01-01

Electron structure of a silicon quantum dot doped with a shallow hydrogen-like donor has been calculated for the electron states above the optical gap. Within the framework of the envelope-function approach we have calculated the fine splitting of the ground sixfold degenerate electron state as a function of the donor position inside the quantum dot. Also, dependence of the wave functions and energies on the dot size was obtained.

Ultrafast electron transfer in all-carbon-based SWCNT-C60 donor-acceptor nanoensembles connected by poly(phenylene-ethynylene) spacers

NASA Astrophysics Data System (ADS)

Barrejón, Myriam; Gobeze, Habtom B.; Gómez-Escalonilla, María J.; Fierro, José Luis G.; Zhang, Minfang; Yudasaka, Masako; Iijima, Sumio; D'Souza, Francis; Langa, Fernando

2016-08-01

Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices.Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices. Electronic supplementary information (ESI) available: Synthesis, TGA, FTIR, AFM and XPS data, UV-vis and transient absorption spectra (Fig. S1-S15 and Tables S1 and S2). See DOI: 10.1039/c6nr02829b

Modular Electron Donor Group Tuning Of Frontier Energy Levels In Diarylaminofluorenone Push-Pull Molecules

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

Homnick, Paul J.; Lahti, P. M.

2012-01-01

Push–pull organic molecules composed of electron donor diarylamines at the 2- and 2,7-positions of fluorenone exhibit intramolecular charge-transfer behaviour in static absorption and emission spectra. Electrochemical and spectral data combined in a modular electronic analysis model show how the donor HOMO and acceptor LUMO act as major determinants of the frontier molecular orbital energy levels.

Preferential inhibition of the plasma membrane NADH oxidase (NOX) activity by diphenyleneiodonium chloride with NADPH as donor

NASA Technical Reports Server (NTRS)

Morre, D. James

2002-01-01

The cell-surface NADH oxidase (NOX) protein of plant and animal cells will utilize both NADH and NADPH as reduced electron donors for activity. The two activities are distinguished by a differential inhibition by the redox inhibitor diphenyleneiodonium chloride (DPI). Using both plasma membranes and cells, activity with NADPH as donor was markedly inhibited by DPI at submicromolar concentrations, whereas with NADH as donor, DPI was much less effective or had no effect on the activity. The possibility of the inhibition being the result of two different enzymes was eliminated by the use of a recombinant NOX protein. The findings support the concept that NOX proteins serve as terminal oxidases for plasma membrane electron transport involving cytosolic reduced pyridine nucleotides as the natural electron donors and with molecular oxygen as the electron acceptor.

Excited state dynamics can be used to probe donor-acceptor distances for H-tunneling reactions catalyzed by flavoproteins.

PubMed

Hardman, Samantha J O; Pudney, Christopher R; Hay, Sam; Scrutton, Nigel S

2013-12-03

In enzyme systems where fast motions are thought to contribute to H-transfer efficiency, the distance between hydrogen donor and acceptor is a very important factor. Sub-ångstrom changes in donor-acceptor distance can have a large effect on the rate of reaction, so a sensitive probe of these changes is a vital tool in our understanding of enzyme function. In this study we use ultrafast transient absorption spectroscopy to investigate the photoinduced electron transfer rates, which are also very sensitive to small changes in distance, between coenzyme analog, NAD(P)H4, and the isoalloxazine center in the model flavoenzymes morphinone reductase (wild-type and selected variants) and pentaerythritol tetranitrate reductase (wild-type). It is shown that upon addition of coenzyme to the protein the rate of photoinduced electron transfer is increased. By comparing the magnitude of this increase with existing values for NAD(P)H4-FMN distances, based on charge-transfer complex absorbance and experimental kinetic isotope effect reaction data, we show that this method can be used as a sensitive probe of donor-acceptor distance in a range of enzyme systems. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Model of multistep electron transfer in a single-mode polar medium

NASA Astrophysics Data System (ADS)

Feskov, S. V.; Yudanov, V. V.

2017-09-01

A mathematical model of multistep photoinduced electron transfer (PET) in a polar medium with a single relaxation time (Debye solvent) is developed. The model includes the polarization nonequilibrity formed in the vicinity of the donor-acceptor molecular system at the initial steps of photoreaction and its influence on the subsequent steps of PET. It is established that the results from numerical simulation of transient luminescence spectra of photoexcited donor-acceptor complexes (DAC) conform to calculated data obtained on the basis of the familiar experimental technique used to measure the relaxation function of solvent polarization in the vicinity of DAC in the picosecond and subpicosecond ranges.

Photoinduced Electron Transfer from Various Aniline Derivatives to Graphene Quantum Dots.

PubMed

Ghosh, Tufan; Chatterjee, Swarupa; Prasad, Edamana

2015-12-10

The present study utilizes the luminescence nature of the graphene quantum dots (GQDs) to analyze the mechanistic aspects of the photoinduced electron transfer (PET) processes between GQDs and aniline derivatives. A systematic investigation of PET from various aniline derivatives to GQDs has been presented. Solution-processable GQDs have been synthesized from graphene oxide (GO) at 200 °C. The as-synthesized GQDs exhibit a strong green luminescence at 510 nm, upon photoexcitation at 440 nm. Various aniline derivatives (aniline, N-methylaniline, N,N'-dimethylaniline, N-ethylaniline, N,N'-diethylaniline, and N,N'-diphenylaniline) have been utilized as electron donors to probe the PET process. Results from UV-visible absorption and steady-state and time-resolve luminescence spectroscopy suggest that the GQDs interact with the aniline derivatives in the excited state, which results in a significant luminescence quenching of the GQDs. The bimolecular rate constants of the dynamic quenching have been deduced for various donor-acceptor systems, and the values are in the range of (1.06-2.68) × 10(9) M(-1) s(-1). The negative values of the free energy change of the electron transfer process suggest that PET from aniline derivatives to GQDs is feasible and could be responsible for the luminescence quenching. The PET has been confirmed by detecting radical cations for certain aniline derivatives, using a nanosecond laser flash photolysis setup. The present study shows that among the various types of graphene systems, GQDs are better candidates for understanding the mechanism of PET in graphene-based donor-acceptor systems.

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

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

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

Comparison of exciplex generation under optical and X-ray excitation

NASA Astrophysics Data System (ADS)

Kipriyanov, A. A.; Melnikov, A. R.; Stass, D. V.; Doktorov, A. B.

2017-09-01

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Comparison of exciplex generation under optical and X-ray excitation.

PubMed

Kipriyanov, A A; Melnikov, A R; Stass, D V; Doktorov, A B

2017-09-07

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Autotrophic antimonate bio-reduction using hydrogen as the electron donor.

PubMed

Lai, Chun-Yu; Wen, Li-Lian; Zhang, Yin; Luo, Shan-Shan; Wang, Qing-Ying; Luo, Yi-Hao; Chen, Ran; Yang, Xiaoe; Rittmann, Bruce E; Zhao, He-Ping

2016-01-01

Antimony (Sb), a toxic metalloid, is soluble as antimonate (Sb(V)). While bio-reduction of Sb(V) is an effective Sb-removal approach, its bio-reduction has been coupled to oxidation of only organic electron donors. In this study, we demonstrate, for the first time, the feasibility of autotrophic microbial Sb(V) reduction using hydrogen gas (H2) as the electron donor without extra organic carbon source. SEM and EDS analysis confirmed the production of the mineral precipitate Sb2O3. When H2 was utilized as the electron donor, the consortium was able to fully reduce 650 μM of Sb(V) to Sb(III) in 10 days, a rate comparable to the culture using lactate as the electron donor. The H2-fed culture directed a much larger fraction of it donor electrons to Sb(V) reduction than did the lactate-fed culture. While 98% of the electrons from H2 were used to reduce Sb(V) by the H2-fed culture, only 12% of the electrons from lactate was used to reduce Sb(V) by the lactate-fed culture. The rest of the electrons from lactate went to acetate and propionate through fermentation, to methane through methanogenesis, and to biomass synthesis. High-throughput sequencing confirmed that the microbial community for the lactate-fed culture was much more diverse than that for the H2-fed culture, which was dominated by a short rod-shaped phylotype of Rhizobium (α-Protobacteria) that may have been active in Sb(V) reduction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular Engineering of UV/Vis Light-Emitting Diode (LED)-Sensitive Donor-π-Acceptor-Type Sulfonium Salt Photoacid Generators: Design, Synthesis, and Study of Photochemical and Photophysical Properties.

PubMed

Wu, Xingyu; Jin, Ming; Xie, Jianchao; Malval, Jean-Pierre; Wan, Decheng

2017-11-07

A series of donor-π-acceptor-type sulfonium salt photoacid generators (PAGs) were designed and synthesized by systematically changing electron-donating groups, π-conjugated systems, electron-withdrawing groups, and the number of branches through molecular engineering. These PAGs can effectively decompose under UV/Vis irradiation from a light-emitting diode (LED) light source because of the matching absorption and emitting spectra of the LEDs. The absorption and acid-generation properties of these sulfonium salts were elucidated by UV/Vis spectroscopy and so forth. Results indicated that the PAG performance benefited from the introduction of strong electron-donating groups, specific π-conjugated structures, certain electron-withdrawing groups, or two-branched structures. Most sulfonium salts showed potential as photoinitiators under irradiation by a wide variety of UV and visible LEDs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shewanella oneidensis in a lactate-fed pure-culture and a glucose-fed co-culture with Lactococcus lactis with an electrode as electron acceptor

USDA-ARS?s Scientific Manuscript database

Bioelectrochemical systems (BESs) employing mixed microbial communities as biocatalysts are gaining importance as potential renewable energy, bioremediation, or biosensing devices. While we are beginning to understand how individual microbial species interact with an electrode as electron donor, li...

Microbial utilization of electrically reduced neutral red as the sole electron donor for growth and metabolite production

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

Park, D.H.; Laivenieks, M.; Guettler, M.V.

1999-07-01

Electrically reduced neutral red (NR) served as the sole source of reducing power for growth and metabolism of pure and mixed cultures of H[sub 2]-consuming bacteria in a novel electrochemical bioreactor system. NR was continuously reduced by the cathodic potential ([minus]1.5 V) generated from an electric current (0.3 to 1.0 mA), and it was subsequently oxidized by Actinobacillus succinogenes or by mixed methanogenic cultures. The A. succinogenes mutant strain FZ-6 did not grow on fumarate alone unless electrically reduced NR or hydrogen was present as the electron donor for succinate production. The mutant strain, unlike the wild type, lacked pyruvatemore » formate lyase and formate dehydrogenase. Electrically reduced NR also replaced hydrogen as the sole electron donor source for growth and production of methane from CO[sub 2]. These results show that both pure and mixed cultures can function as electrochemical devices when electrically generated reducing power can be used to drive metabolism. The potential utility of utilizing electrical reducing power in enhancing industrial fermentations or biotransformation processes is discussed.« less

Self Organization in Compensated Semiconductors

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2004-03-01

In partially compensated semiconductor (PCS) Fermi level is pinned to donor sub-band. Due to positional randomness and almost isoenergetic hoppings, donor-spanned electronic subsystem in PCS forms fluid-like highly mobile collective state. This makes PCS playground for pattern formation, self-organization, complexity emergence, electronic neural networks, and perhaps even for origins of life, bioevolution and consciousness. Through effects of impact and/or Auger ionization of donor sites, whole PCS may collapse (spinodal decomposition) into microblocks potentially capable of replication and protobiological activity (DNA analogue). Electronic screening effects may act in RNA fashion by introducing additional length scale(s) to system. Spontaneous quantum computing on charged/neutral sites becomes potential generator of informationally loaded microstructures akin to "Carl Sagan Effect" (hidden messages in Pi in his "Contact") or informational self-organization of "Library of Babel" of J.L. Borges. Even general relativity effects at Planck scale (R.Penrose) may affect the dynamics through (e.g.) isotopic variations of atomic mass and local density (A.A.Berezin, 1992). Thus, PCS can serve as toy model (experimental and computational) at interface of physics and life sciences.

Spin-orbit coupling induced two-electron relaxation in silicon donor pairs

NASA Astrophysics Data System (ADS)

Song, Yang; Das Sarma, S.

2017-09-01

We unravel theoretically a key intrinsic relaxation mechanism among the low-lying singlet and triplet donor-pair states in silicon, an important element in the fast-developing field of spintronics and quantum computation. Despite the perceived weak spin-orbit coupling (SOC) in Si, we find that our discovered relaxation mechanism, combined with the electron-phonon and interdonor interactions, drives the transitions in the two-electron states over a large range of donor coupling regimes. The scaling of the relaxation rate with interdonor exchange interaction J goes from J5 to J4 at the low to high temperature limits. Our analytical study draws on the symmetry analysis over combined band, donor envelope, and valley configurations. It uncovers naturally the dependence on the donor-alignment direction and triplet spin orientation, and especially on the dominant SOC source from donor impurities. While a magnetic field is not necessary for this relaxation, unlike in the single-donor spin relaxation, we discuss the crossover behavior with increasing Zeeman energy in order to facilitate comparison with experiments.

Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

DOEpatents

Liepins, R.; Aldissi, M.

1984-07-27

Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

DOEpatents

Liepins, Raimond; Aldissi, Mahmoud

1988-01-01

Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

Spin noise spectroscopy of ZnO

NASA Astrophysics Data System (ADS)

Horn, H.; Berski, F.; Balocchi, A.; Marie, X.; Mansur-Al-Suleiman, M.; Bakin, A.; Waag, A.; Hübner, J.; Oestreich, M.

2013-12-01

We investigate the thermal equilibrium dynamics of electron spins bound to donors in nanoporous ZnO by optical spin noise spectroscopy. The spin noise spectra reveal two noise contributions: A weak spin noise signal from undisturbed localized donor electrons with a dephasing time of 24 ns due to hyperfine interaction and a strong spin noise signal with a spin dephasing time of 5 ns which we attribute to localized donor electrons which interact with lattice defects.

Carbon Monoxide as an Electron Donor for the Biological Reduction of Sulphate

PubMed Central

Parshina, Sofiya N.; Sipma, Jan; Henstra, Anne Meint; Stams, Alfons J. M.

2010-01-01

Several strains of Gram-negative and Gram-positive sulphate-reducing bacteria (SRB) are able to use carbon monoxide (CO) as a carbon source and electron donor for biological sulphate reduction. These strains exhibit variable resistance to CO toxicity. The most resistant SRB can grow and use CO as an electron donor at concentrations up to 100%, whereas others are already severely inhibited at CO concentrations as low as 1-2%. Here, the utilization, inhibition characteristics, and enzymology of CO metabolism as well as the current state of genomics of CO-oxidizing SRB are reviewed. Carboxydotrophic sulphate-reducing bacteria can be applied for biological sulphate reduction with synthesis gas (a mixture of hydrogen and carbon monoxide) as an electron donor. PMID:20628586

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

A biofilm microreactor system for simultaneous electrochemical and nuclear magnetic resonance techniques

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

Renslow, Ryan S.; Babauta, Jerome T.; Majors, Paul D.

2014-03-01

In order to fully understand electrochemically active biofilms and the limitations to their scale-up in industrial biofilm reactors, a complete picture of the microenvironments inside the biofilm is needed. Nuclear magnetic resonance (NMR) techniques are ideally suited for the study of biofilms and for probing their microenvironments because these techniques allow for non-invasive interrogation and in situ monitoring with high resolution. By combining NMR with simultaneous electrochemical techniques, it is possible to sustain and study live electrochemically active biofilms. Here, we introduce a novel biofilm microreactor system that allows for simultaneous electrochemical and NMR techniques (EC-NMR) at the microscale. Microreactorsmore » were designed with custom radiofrequency resonator coils, which allowed for NMR measurements of biofilms growing on polarized gold electrodes. For an example application of this system, we grew Geobacter sulfurreducens biofilms. NMR was used to investigate growth media flow velocities, which were compared to simulated laminar flow, and electron donor concentrations inside the biofilms. We use Monte Carlo error analysis to estimate standard deviations of the electron donor concentration measurements within the biofilm. The EC-NMR biofilm microreactor system can ultimately be used to correlate extracellular electron transfer rates with metabolic reactions and explore extracellular electron transfer mechanisms.« less

Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection from a PbSe quantum dot into the TiO2 surface.

PubMed

Long, Run; Prezhdo, Oleg V

2011-11-30

Following recent experiments [Science 2010, 328, 1543; PNAS 2011, 108, 965], we report an ab initio nonadiabatic molecular dynamics (NAMD) simulation of the ultrafast photoinduced electron transfer (ET) from a PbSe quantum dot (QD) into the rutile TiO(2) (110) surface. The system forms the basis for QD-sensitized semiconductor solar cells and demonstrates that ultrafast interfacial ET is instrumental for achieving high efficiencies in solar-to-electrical energy conversion. The simulation supports the observation that the ET successfully competes with energy losses due to electron-phonon relaxation. The ET proceeds by the adiabatic mechanism because of strong donor-acceptor coupling. High frequency polar vibrations of both QD and TiO(2) promote the ET, since these modes can rapidly influence the donor-acceptor state energies and coupling. Low frequency vibrations generate a distribution of initial conditions for ET, which shows a broad variety of scenarios at the single-molecule level. Compared to the molecule-TiO(2) interfaces, the QD-TiO(2) system exhibits pronounced differences that arise due to the larger size and higher rigidity of QDs relative to molecules. Both donor and acceptor states are more delocalized in the QD system, and the ET is promoted by optical phonons, which have relatively low frequencies in the QD materials composed of heavy elements. In contrast, in molecular systems, optical phonons are not thermally accessible under ambient conditions. Meanwhile, TiO(2) acceptor states resemble surface impurities due to the local influence of molecular chromophores. At the same time, the photoinduced ET at both QD-TiO(2) and molecule-TiO(2) interfaces is ultrafast and occurs by the adiabatic mechanism, as a result of strong donor-acceptor coupling. The reported state-of-the-art simulation generates a detailed time-domain atomistic description of the interfacial ET process that is fundamental to a wide variety of applications.

The C-type Arabidopsis thioredoxin reductase ANTR-C acts as an electron donor to 2-Cys peroxiredoxins in chloroplasts

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

Moon, Jeong Chan; Jang, Ho Hee; Chae, Ho Byoung

2006-09-22

2-Cys peroxiredoxins (Prxs) play important roles in the antioxidative defense systems of plant chloroplasts. In order to determine the interaction partner for these proteins in Arabidopsis, we used a yeast two-hybrid screening procedure with a C175S-mutant of Arabidopsis 2-Cys Prx-A as bait. A cDNA encoding an NADPH-dependent thioredoxin reductase (NTR) isotype C was identified and designated ANTR-C. We demonstrated that this protein effected efficient transfer of electrons from NADPH to the 2-Cys Prxs of chloroplasts. Interaction between 2-Cys Prx-A and ANTR-C was confirmed by a pull-down experiment. ANTR-C contained N-terminal TR and C-terminal Trx domains. It exhibited both TR andmore » Trx activities and co-localized with 2-Cys Prx-A in chloroplasts. These results suggest that ANTR-C functions as an electron donor for plastidial 2-Cys Prxs and represents the NADPH-dependent TR/Trx system in chloroplasts.« less

Improving Effectiveness of Bioremediation at DNAPL Source Zone Sites by Applying Partitioning Electron Donors (PEDs)

DTIC Science & Technology

2014-05-01

as trichloroethene (TCE) and tetrachloroethene (PCE). EISB typically relies on the addition of electron donor formulations to enhance the rate of... value (NPV) cost when applied using passive (i.e., biostimulation) methods. Hence, the selection of electron donors has a major implication on EISB...Engineering Service Center NAVFACSW NAVFAC Southwest nBA n-Butyl acetate nBuOH n-Butanol nHEX n-Hexanol NPV net present value O&M operation and

Mechanistic details for cobalt catalyzed photochemical hydrogen production in aqueous solution: Efficiencies of the photochemical and non-photochemical steps

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

Shan, Bing; Baine, Teera; Ma, Xuan Anh N.

2013-04-17

The use of sunlight to drive chemical reactions that lead to the reduction of water to produce hydrogen is a potential avenue of solar energy utilization. There are many individual steps that take place in this process. This paper reports the investigation of a particular system that involves light absorbing molecules, electron donating agents and a catalyst for water reduction to hydrogen. We evaluated the efficiency of the light induced formation of a strong electron donor, the use of this donor to reduce the catalyst and finally the efficiency of the catalyst to produce hydrogen from water. From this, themore » sources of loss of efficiency could be clearly identified and used in the design of better systems to produce hydrogen from water.« less

Artificial photosynthesis using chlorophyll based carotenoid quinone triads: A brief synopsis of research progress as of 31 December 1986

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

Gust, D.; Moore, T.A.

1986-12-31

The design, synthesis and study of a series of carotenoid-chlorophyll-quinone triad molecules which mimic some of the basic photochemistry and photophysics of natural photosynthesis is sought. The first members of this series have now been prepared, and have been found to mimic photosynthetic charge separation, carotenoid antenna function, and carotenoid photoprotection from singlet oxygen damage. Although the triad molecules mimic the general principle of multistep electron transfer which is found in natural photosynthesis, the details of photosynthetic electron transfer differ in the triads, in that the first electron transfer step involves electron donation from the excited state donor, followed bymore » reduction of the resulting donor radical cation by the carotenoid. In photosynthesis, the electron is moved through several acceptors before the chlorophyll radical cation is reduced. Therefore, our recent work has concentrated on the design and synthesis of new model systems which better mimic certain aspects of natural photosynthesis.« less

Spin Measurements of an Electron Bound to a Single Phosphorous Donor in Silicon

NASA Astrophysics Data System (ADS)

Luhman, D. R.; Nguyen, K.; Tracy, L. A.; Carr, S. M.; Borchardt, J.; Bishop, N. C.; Ten Eyck, G. A.; Pluym, T.; Wendt, J.; Carroll, M. S.; Lilly, M. P.

2014-03-01

The spin of an electron bound to a single donor implanted in silicon is potentially useful for quantum information processing. We report on our efforts to measure and manipulate the spin of an electron bound to a single P donor in silicon. A low number of P donors are implanted using a self-aligned process into a silicon substrate in close proximity to a single-electron-transistor (SET) defined by lithographically patterned polysilicon gates. The SET is used to sense the occupancy of the electron on the donor and for spin read-out. An adjacent transmission line allows the application of microwave pulses to rotate the spin of the electron. We will present data from various experiments designed to exploit these capabilities. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. DOE Office of Basic Energy Sciences user facility. The work was supported by Sandia National Laboratories Directed Research and Development Program. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the U. S. Department of Energy under Contract No. DE-AC04-94AL85000.

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

NASA Technical Reports Server (NTRS)

Fischer, U.

1985-01-01

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

Electron donor concentrations in sediments and sediment properties at the agricultural chemicals team research site near New Providence, Iowa, 2006-07

USGS Publications Warehouse

Maharjan, Bijesh; Korom, Scott F.; Smith, Erik A.

2013-01-01

The concentrations of electron donors in aquifer sediments are important to the understanding of the fate and transport of redox-sensitive constituents in groundwater, such as nitrate. For a study by the U.S. Geological Survey National Water-Quality Assessment Program, 50 sediment samples were collected from below the water table from 11 boreholes at the U.S. Geological Survey Agricultural Chemicals Team research site near New Providence, Iowa, during 2006-07. All samples were analyzed for gravel, sand (coarse, medium, and fine), silt, clay, Munsell soil color, inorganic carbon content, and for the following electron donors: organic carbon, ferrous iron, and inorganic sulfide. A subset of 14 sediment samples also was analyzed for organic sulfur, but all of these samples had concentrations less than the method detection limit; therefore, the presence of this potential electron donor was not considered further. X-ray diffraction analyses provided important semi-quantitative information of well-crystallized dominant minerals within the sediments that might be contributing electron donors.

Motivations for Giving of Alumni Donors, Lapsed Donors and Non-Donors: Implications for Christian Higher Education

ERIC Educational Resources Information Center

Rugano, Emilio Kariuki

2011-01-01

This descriptive and causal comparative study sought to identify motivations for alumni donor acquisition and retention in Christian institutions of higher learning. To meet this objective, motivations for alumni donors, lapsed donors, and non-donors were analyzed and compared. Data was collected through an electronic survey of a stratified sample…

Optical coefficients in a semiconductor quantum ring: Electric field and donor impurity effects

NASA Astrophysics Data System (ADS)

Duque, C. M.; Acosta, Ruben E.; Morales, A. L.; Mora-Ramos, M. E.; Restrepo, R. L.; Ojeda, J. H.; Kasapoglu, E.; Duque, C. A.

2016-10-01

The electron states in a two-dimensional quantum dot ring are calculated in the presence of a donor impurity atom under the effective mass and parabolic band approximations. The effect of an externally applied electric field is also taken into account. The wavefunctions are obtained via the exact diagonalization of the problem Hamiltonian using a 2D expansion within the adiabatic approximation. The impurity-related optical response is analyzed via the optical absorption, relative refractive index change and the second harmonics generation. The dependencies of the electron states and these optical coefficients with the changes in the configuration of the quantum ring system are discussed in detail.

Photosensitized H2 Production Using a Zinc Porphyrin-Substituted Protein, Platinum Nanoparticles, and Ascorbate with No Electron Relay: Participation of Good's Buffers.

PubMed

Clark, Emily R; Kurtz, Donald M

2017-04-17

Development of efficient light-driven splitting of water, 2H 2 O → 2H 2 + O 2 , often attempts to optimize photosensitization of the reductive and oxidative half-reactions individually. Numerous homogeneous and heterogeneous systems have been developed for photochemical stimulation of the reductive half reaction, 2H + + 2e - → H 2 . These systems generally consist of various combinations of a H + reduction catalyst, a photosensitizer (PS), and a "sacrificial" electron donor. Zinc(II)-porphyrins (ZnPs) have frequently been used as PSs for H 2 generation, but they are subject to various self-quenching processes in aqueous solutions. Colloidal platinum in nanoparticle form (Pt NP) is a classical H + reduction catalyst using ZnP photosensitizers, but efficient photosensitized H 2 generation requires an electron relay molecule between ZnP and Pt NP. The present report describes an aqueous system for visible (white) light-sensitized generation of H 2 using a protein-embedded Zn(II)-protoporphyrin IX as PS and Pt NP as H + reduction catalyst without an added electron relay. This system operated efficiently in piperazino- and morpholino-alkylsulfonic acid (Good's buffers), which served as sacrificial electron donors. The system also required ascorbate at relatively modest concentrations, which stabilized the Zn(II)-protoporphyrin IX against photodegradation. In the absence of an electron relay molecule, the photosensitized H 2 generation must involve formation of at least a transient complex between a protein-embedded Zn(II)-protoporphyrin IX species and Pt NP.

Chemical and quantum simulation of electron transfer through a polypeptide

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

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

1999-08-26

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

Organic photosensitizers with a heteroleptic dual donor for dye-sensitized solar cells.

PubMed

Kim, Joo Young; Kim, Young Sik

2012-04-01

Using DFT and TDDFT calculations, we investigated the substitution effect in the electronic and optical properties of dye sensitizers with a dual donor composed of triphenylamine and/or indoline moieties. Due to replacement with the dual donor moieties, the HOMO levels were split into HOMO and HOMO - 1 levels, and the bandgaps between the HOMO and LUMO levels decreased, leading to the creation of bathochromically extended absorption spectra. Nearly degenerated splitting of the HOMO levels resulted from the similarity of the electronic structure between the HOMO and the HOMO - 1 levels, delocalized over both dual-donor moieties, when replacing the dual donors. It was shown that the additional electron-donating group creates an additional absorption band and causes a cascading two-electron process aiding the charge separation process. Owing to a more panchromatic attribute, easier energy transfer and feasible retardation of the recombination between the injected electrons and the electrolyte, it is expected that dyeTI will show better performance than the other dyes (dyeT dyeTT and dyeIT) as denoted here in terms of the conversion efficiency of dye-sensitized solar cells (DSSCs). This work presents the probable benefits of dye sensitizers with dual-donor moieties and provides insight into the development of more efficient dye sensitizers for DSSCs through modification of the Frontier molecular orbitals.

High-field Overhauser dynamic nuclear polarization in silicon below the metal-insulator transition.

PubMed

Dementyev, Anatoly E; Cory, David G; Ramanathan, Chandrasekhar

2011-04-21

Single crystal silicon is an excellent system to explore dynamic nuclear polarization (DNP), as it exhibits a continuum of properties from metallic to insulating as a function of doping concentration and temperature. At low doping concentrations DNP has been observed to occur via the solid effect, while at very high-doping concentrations an Overhauser mechanism is responsible. Here we report the hyperpolarization of (29)Si in n-doped silicon crystals, with doping concentrations in the range of (1-3) × 10(17) cm(-3). In this regime exchange interactions between donors become extremely important. The sign of the enhancement in our experiments and its frequency dependence suggest that the (29)Si spins are directly polarized by donor electrons via an Overhauser mechanism within exchange-coupled donor clusters. The exchange interaction between donors only needs to be larger than the silicon hyperfine interaction (typically much smaller than the donor hyperfine coupling) to enable this Overhauser mechanism. Nuclear polarization enhancement is observed for a range of donor clusters in which the exchange energy is comparable to the donor hyperfine interaction. The DNP dynamics are characterized by a single exponential time constant that depends on the microwave power, indicating that the Overhauser mechanism is a rate-limiting step. Since only about 2% of the silicon nuclei are located within 1 Bohr radius of the donor electron, nuclear spin diffusion is important in transferring the polarization to all the spins. However, the spin-diffusion time is much shorter than the Overhauser time due to the relatively weak silicon hyperfine coupling strength. In a 2.35 T magnetic field at 1.1 K, we observed a DNP enhancement of 244 ± 84 resulting in a silicon polarization of 10.4 ± 3.4% following 2 h of microwave irradiation.

Electron donor preference of a reductive dechlorinating consortium

USGS Publications Warehouse

Lorah, M.M.; Majcher, E.; Jones, E.; Driedger, G.; Dworatzek, S.; Graves, D.

2005-01-01

A wetland sediment-derived microbial consortium was developed by the USGS and propagated in vitro to large quantities by SiREM Laboratory for use in bioaugmentation applications. The consortium had the capacity to completely dechlorinate 1,1,2,2-tetrachloroethene, tetrachloroethylene, trichloroethylene, 1,1,2-trichloroethane, cis- and trans-1,2-dichoroethylene, 1.1-dichloroethylene, 1,2-dichloroethane, vinyl chloride, carbon tetrachloride and chloroform. A suite of electron donors with characteristics useful for bioaugmentation applications was tested. The electron donors included lactate (the donor used during WBC-2 development), ethanol, chitin (Chitorem???), hydrogen releasing compound (HRC???), emulsified vegetable oil (Newman Zone???), and hydrogen gas. Ethanol, lactate, and chitin were particularly effective with respect to stimulating, supporting, and sustaining reductive dechlorination of the broad suite of chemicals that WBC-2 biodegraded. Chitorem??? was the most effective "slow release" electron donor tested. This is an abstract of a paper presented at the Proceedings of the 8th International In Situ and On-Site Bioremediation Symposium (Baltimore, MD 6/6-9/2005).

Biophotolysis systems for hydrogen production

NASA Astrophysics Data System (ADS)

Rao, K. K.; Adams, M. W. W.; Morris, P.; Hall, D. O.; Gisby, P. E.

Model systems containing natural and sythetic catalysts were constructed for the production of H2 from water using visible solar radiation as the energy source. Chloroplast membranes were used for light absorption and photodecomposition of water, ferredoxin, flavodoxin, cytochrome, viologen dyes, 'Jeevanu' particles or synthetic clusters containing Fe-Mo-S centers were used as electron transfer catalysts, and hydrogenase or PtO2 served as the proton activator. We have also investigated the use of aqueous systems with proflavine as the light activator and artificial electron donors for subsequent production of H2 when coupled to electron mediators and hydrogenase (or Pt). The characteristics, relative merits and defects of these systems are discussed.

A surface code quantum computer in silicon

PubMed Central

Hill, Charles D.; Peretz, Eldad; Hile, Samuel J.; House, Matthew G.; Fuechsle, Martin; Rogge, Sven; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.

2015-01-01

The exceptionally long quantum coherence times of phosphorus donor nuclear spin qubits in silicon, coupled with the proven scalability of silicon-based nano-electronics, make them attractive candidates for large-scale quantum computing. However, the high threshold of topological quantum error correction can only be captured in a two-dimensional array of qubits operating synchronously and in parallel—posing formidable fabrication and control challenges. We present an architecture that addresses these problems through a novel shared-control paradigm that is particularly suited to the natural uniformity of the phosphorus donor nuclear spin qubit states and electronic confinement. The architecture comprises a two-dimensional lattice of donor qubits sandwiched between two vertically separated control layers forming a mutually perpendicular crisscross gate array. Shared-control lines facilitate loading/unloading of single electrons to specific donors, thereby activating multiple qubits in parallel across the array on which the required operations for surface code quantum error correction are carried out by global spin control. The complexities of independent qubit control, wave function engineering, and ad hoc quantum interconnects are explicitly avoided. With many of the basic elements of fabrication and control based on demonstrated techniques and with simulated quantum operation below the surface code error threshold, the architecture represents a new pathway for large-scale quantum information processing in silicon and potentially in other qubit systems where uniformity can be exploited. PMID:26601310

A surface code quantum computer in silicon.

PubMed

Hill, Charles D; Peretz, Eldad; Hile, Samuel J; House, Matthew G; Fuechsle, Martin; Rogge, Sven; Simmons, Michelle Y; Hollenberg, Lloyd C L

2015-10-01

The exceptionally long quantum coherence times of phosphorus donor nuclear spin qubits in silicon, coupled with the proven scalability of silicon-based nano-electronics, make them attractive candidates for large-scale quantum computing. However, the high threshold of topological quantum error correction can only be captured in a two-dimensional array of qubits operating synchronously and in parallel-posing formidable fabrication and control challenges. We present an architecture that addresses these problems through a novel shared-control paradigm that is particularly suited to the natural uniformity of the phosphorus donor nuclear spin qubit states and electronic confinement. The architecture comprises a two-dimensional lattice of donor qubits sandwiched between two vertically separated control layers forming a mutually perpendicular crisscross gate array. Shared-control lines facilitate loading/unloading of single electrons to specific donors, thereby activating multiple qubits in parallel across the array on which the required operations for surface code quantum error correction are carried out by global spin control. The complexities of independent qubit control, wave function engineering, and ad hoc quantum interconnects are explicitly avoided. With many of the basic elements of fabrication and control based on demonstrated techniques and with simulated quantum operation below the surface code error threshold, the architecture represents a new pathway for large-scale quantum information processing in silicon and potentially in other qubit systems where uniformity can be exploited.

MODE OF FISSION OF BENZENE NUCLEUS IN THE MICRO-ORGANISMS AND REGULATION OF CELL GROWTH AND DIVISION BY BENZENE DERIVATIVES.

DTIC Science & Technology

as an amino donor in this microbial system. The conversion D-tryptophan to L-tryptophan in a cell-free system can be demonstrated when an electron acceptor, such as phenazine methosulfate, is present. (Author)

On chirality transfer in electron donor-acceptor complexes. A prediction for the sulfinimine···BF3 system.

PubMed

Rode, Joanna E; Dobrowolski, Jan Cz

2012-01-01

Stabilization energies of the electron donor-acceptor sulfinimine···BF(3) complexes calculated at either the B3LYP/aug-cc-pVTZ or the MP2/aug-cc-pVTZ level do not allow to judge, whether the N- or O-atom in sulfinimine is stronger electron-donor to BF(3) . The problem seems to be solvable because chirality transfer phenomenon between chiral sulfinimine and achiral BF(3) is expected to be vibrational circular dichroism (VCD) active. Moreover, the bands associated with the achiral BF(3) molecule are predicted to be the most intense in the entire spectrum. However, the VCD band robustness analyses show that most of the chirality transfer modes of BF(3) are unreliable. Conversely, variation of VCD intensity with change of intermolecular distance, angle, and selected dihedrals between the complex partners shows that to establish the robustness of chirality transfer mode. It is also necessary to determine the influence of the potential energy surface (PES) shape on the VCD intensity. At the moment, there is still no universal criterion for the chirality transfer mode robustness and the conclusions formulated based on one system cannot be directly transferred even to a quite similar one. However, it is certain that more attention should be focused on relation of PES shape and the VCD mode robustness problem. Copyright © 2011 Wiley Periodicals, Inc.

Flowpath independent monitoring of reductive dechlorination potential in a fractured rock aquifer

USGS Publications Warehouse

Bradley, P.M.; Lacombe, P.J.; Imbrigiotta, T.E.; Chapelle, F.H.; Goode, D.J.

2009-01-01

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2- 14C] cis-DCE microcosm experiments. Microcosms were prepared with depth-specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of 14C-labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems. ?? 2009 National Ground Water Association.

Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model.

PubMed

Xu, Peng; Zhang, Cai-Rong; Wang, Wei; Gong, Ji-Jun; Liu, Zi-Jiang; Chen, Hong-Shan

2018-04-10

The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT), local excitations, and triplet excited states, several ab initio and density functional theory (DFT) methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE) complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT) with the Tamm-Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed.

Optoelectronics of organic nanofibers formed by co-assembly of porphyrin and perylenediimide.

PubMed

Li, Yuangang; Wang, Weina; Leow, Wan Ru; Zhu, Bowen; Meng, Fanben; Zheng, Liyan; Zhu, Jia; Chen, Xiaodong

2014-07-23

Organic nanofibers are formed by simple ionic co-assembly of positively charged porphyrin (electron donor) and negatively charged perylenediimide (electron acceptor) derivatives in aqueous solution. Two kinds of electron transfer routes between electron donor and electron acceptor under light excitation in nanofibers are confirmed by DFT calculations and experimental data. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular complexes of some anthraquinone anti-cancer drugs: experimental and computational study

NASA Astrophysics Data System (ADS)

El-Gogary, Tarek M.

2003-03-01

It is known that anti-cancer drugs target DNA in the cell. The mechanism of interaction of anti-cancer drugs with DNA is not fully understood. It is thought that the forces of interaction have some contribution from charge-transfer (CT) binding. The ability of some anthraquinones (AQs) anti-cancer drugs to form CT complexes with well-known electron donor molecules was investigated by NMR. The NMR spectroscopy has indicated the formation of CT complexes between 1,4-bis{[2-(dimethylamino) ethyl]amino}-5,8-dihydroxyanthracene-9,10-dione, (AQ4), and its des-hydroxylated equivalent 1,4-bis{[2-(dimethylamino) ethyl]amino}anthracene-9,10-dione, (AQ4H), as electron acceptors and pyrene (PY) and hexamethylbenzene (HMB) as electron donors. Association constants of the formed CT complexes were determined from the NMR data. AQ4 showed weaker electron accepting power than AQ4H, which could be easily explained on the basis of the electron donating nature of the two-hydroxyl groups. AQ4 and AQ4H have higher stability constant with PY than with HMB. This reflects the weaker interaction of the AQs with the latter, which is a direct effect of the six bulky methyl groups. Electronic absorption spectroscopy of the studied system was performed in chloroform and showed the absence of new absorption bands. The extent of interaction between AQs and donors has been computed using molecular mechanics and quantum mechanics. The computed values were compared with the experimental results of association constants.

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

NASA Astrophysics Data System (ADS)

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

2006-05-01

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

Scanning Electron Microscopy Findings of Machine Perfused Liver Graft After Warm Ischemia Between Hypothermic and Rewarming Machine Perfusion in Pigs.

PubMed

Meng, L; Matsuno, N; Watanabe, K; Furukori, M; Obara, H; Bochimoto, H; Watanabe, T; Fukukawa, H

2016-09-01

The shortage of organ donors is a universal problem. Use of grafts from donors after cardiac death would greatly contribute to the expansion of the donor organ pool. The two major methods of preservation are cold storage and machine perfusion (MP) preservation, and each has its own advantages. Several studies have reported the relative merits of MP for the preservation for grafts from donors after cardiac death. In this study, we used scanning electron microscopy (SEM) to assess the damage to the liver between hypothermic and rewarming preservation conditions. Porcine livers were perfused with a newly developed MP system. The livers were perfused for 4 hours with a modified University of Wisconsin solution-gluconate solution. In group 1, grafts were preserved with warm ischemic time for 60 minutes and hypothermic machine perfusion (HMP) for 4 hours. In group 2, grafts were preserved with warn ischemic time for 60 minutes and had rewarming up to 22°C by MP (RMP) for 4 hours. A significant enlargement of the mitochondria were observed in both the HMP and RMP groups under higher magnification, Additionally, vacuoles appeared occasionally in hepatocytes in the RMP for 4 hours group, but not in the HMP for 4 hours group. An analysis by scanning electron microscope appears to be useful to evaluate the levels of damage of hepatocytes compared with transmission electron microscopy, and further study is needed to analyze the significance of the appearance of swelling of mitochondria and vacuolization during preservation. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Carbon fixation in sediments of Sino-Pacific seas-differential contributions of bacterial and archaeal domains

NASA Astrophysics Data System (ADS)

Das, Anindita; Cao, Wenrui; Zhang, Hongjie; Saren, Gaowa; Jiang, Mingyu; Yu, Xinke

2017-11-01

Oceanic stretches experiencing perpetual darkness and extreme limitation of utilizable organic matter often rely on chemosynthetic carbon (C)-fixation. However, C-fixation is not limited to carbon-deplete environments alone but might also occur in varying degrees in carbon-replete locales depending on the nature and concentration of utilizable carbon, electron donors and acceptors. Quantification of microbial C-fixation and relative contribution of domains bacteria and archaea are therefore crucial. The present experiment estimates the differential rates of C-fixation by archaea and bacteria along with the effects of different electron donors. Four Sino-Pacific marine sediments from Bashi strait (Western Pacific Warm Pool), East China Sea, South China Sea and Okinawa Trough were examined. Total microbial C-uptake was estimated by doping of aqueous NaH14CO3. Total bacterial C-uptake was measured by blocking archaeal metabolism using inhibitor GC7. Archaeal contribution was estimated by subtracting total bacterial from total microbial C-uptake. Effect of electron donor addition was analyzed by spiking with ammonium, sulfide, and reduced metals. Results suggested that C-fixation in marine sediments was not the function of archaea alone, which was in contrast to results from several recent publications. C-fixing bacteria are also equally active. Often in spite of great effort of one domain to fix carbon, the system does not become net C-fixing due to equal and opposite C-releasing activity of the other domain. Thus a C-releasing bacterial or archaeal community can become C-fixing with the change of nature and concentration of electron donors.

Bundle-sheath thylakoids from NADP-malic enzyme-type C4 plants require an exogenous electron donor for enzyme light activation.

PubMed

Lavergne, D; Droux, M; Jacquot, J P; Miginiac-Maslow, M; Champigny, M L; Gadal, P

1985-10-01

Light activation of either NADP-malate dehydrogenase (EC 1.1.1.82) or fructose-1,6-bisphosphate phosphatase (EC 3.1.3.11) was assayed in a reconstituted chloroplastic, system comprising the isolated proteins of the ferredoxin-thioredoxin light-activation system and thylakoids from either mesophyll or bundle-sheath tissues of different C4 plants. While C4-plant thylakoids functionned almost equally well with C3-or C4-plant proteins, the photosyntem-II-deficient bundle-sheath thylakoids from the NADP-malic enzyme type, were unable to perform enzyme photoactivation unless supplemented with an electron donor to photosystem I. Bundle-sheath thylakoids isolated from plants showing no photosystem-II deficiency did not require such an addition. The results are discussed with respect to a possible requirement for a physiological reductant of ferredoxin for enzyme light activation in bundle-sheath, tissues.

Enhanced CAH dechlorination in a low permeability, variably-saturated medium

USGS Publications Warehouse

Martin, J.P.; Sorenson, K.S.; Peterson, L.N.; Brennan, R.A.; Werth, C.J.; Sanford, R.A.; Bures, G.H.; Taylor, C.J.; ,

2002-01-01

An innovative pilot-scale field test was performed to enhance the anaerobic reductive dechlorination (ARD) of chlorinated aliphatic hydrocarbons (CAHs) in a low permeability, variably-saturated formation. The selected technology combines the use of a hydraulic fracturing (fracking) technique with enhanced bioremediation through the creation of highly-permeable sand- and electron donor-filled fractures in the low permeability matrix. Chitin was selected as the electron donor because of its unique properties as a polymeric organic material and based on the results of lab studies that indicated its ability to support ARD. The distribution and impact of chitin- and sand-filled fractures to the system was evaluated using hydrologic, geophysical, and geochemical parameters. The results indicate that, where distributed, chitin favorably impacted redox conditions and supported enhanced ARD of CAHs. These results indicate that this technology may be a viable and cost-effective approach for remediation of low-permeability, variably saturated systems.

Organic solid state switches incorporating porphyrin compounds and method for producing organic solid state optical switches

DOEpatents

Wasielewski, Michael R.; Gaines, George L.; Niemczyk, Mark P.; Johnson, Douglas G.; Gosztola, David J.; O'Neil, Michael P.

1996-01-01

A light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, said donors selected from porphyrins and other compounds, and a method for making said compound.

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

PubMed

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

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.

Energy transfer enhancement by oxygen perturbation of spin-forbidden electronic transitions in aromatic systems

NASA Astrophysics Data System (ADS)

Monguzzi, A.; Tubino, R.; Salamone, M. M.; Meinardi, F.

2010-09-01

Triplet-triplet energy transfer in multicomponent organic systems is usually entirely ascribed to a Dexter-type mechanism involving only short-range donor/acceptor interactions. We demonstrate that the presence of molecular oxygen introduces a perturbation to the electronic structure of one of the involved moieties which can induce a large increase in the spin-forbidden transition oscillator strength so that the otherwise negligible Förster contribution dominates the overall energy transfer rate.

Electronic structure and charge transfer excited states of endohedral fullerene containing electron donoracceptor complexes utilized in organic photovoltaics

NASA Astrophysics Data System (ADS)

Amerikheirabadi, Fatemeh

Organic Donor-Acceptor complexes form the main component of the organic photovoltaic devices (OPVs). The open circuit voltage of OPVs is directly related to the charge transfer excited state energies of these complexes. Currently a large number of different molecular complexes are being tested for their efficiency in photovoltaic devices. In this work, density functional theory as implemented in the NRLMOL code is used to investigate the electronic structure and related properties of these donor-acceptor complexes. The charge transfer excitation energies are calculated using the perturbative delta self-consistent field method recently developed in our group as the standard time dependent density functional approaches fail to accurately provide them. The model photovoltaics systems analyzed are as follows: Sc3N C 80--ZnTPP, Y3 N C80-- ZnTPP and Sc3 N C80-- ZnPc. In addition, a thorough analysis of the isolated donor and acceptor molecules is also provided. The studied acceptors are chosen from a class of fullerenes named trimetallic nitride endohedral fullerenes. These molecules have shown to possess advantages as acceptors such as long lifetimes of the charge-separated states.

THz emission of donor and acceptor doped GaAs/AlGaAs quantum well structures with inserted thin AlAs monolayer

NASA Astrophysics Data System (ADS)

van Dommelen, Paphavee; Daengngam, Chalongrat; Kalasuwan, Pruet

2018-04-01

In this paper, we explore THz range optical intersubband transition energies in a donor doped quantum well of a GaAs/AlGaAs system as a function of the insertion position of an AlAs monolayer in the GaAs quantum well. In simulated models, the optical transition energies between electron subband levels 1 and 2 were higher in the doped structure than in the undoped structure. This may be because the envelope wave function of the second electron subband strongly overlapped the envelope wave function of the first electron subband and influenced the optical intersubband transition between the two levels in the THz range. At different levels of bias voltage at the Schottky barrier on the donor doped structure, the electric field in the growth direction of the structure linearly increased the further away the AlAs monolayer was placed from the reference position. We also simulated the optical transition energies between acceptor energy levels of the acceptor doped structure as a function of the insertion position of the AlAs monolayer. The acceptor doped structure induced THz range emission whereas the undoped structure induced mid-IR emission.

Effects of heteroatom substitution in conjugated heterocyclic compounds on photovoltaic performance: from sulfur to tellurium.

PubMed

Park, Y S; Kale, T S; Nam, C-Y; Choi, D; Grubbs, R B

2014-07-28

We report a general strategy for fine-tuning the bandgap of donor-acceptor-donor based organic molecules by modulating the electron-donating ability of the donor moiety by changing the benzochalcogenophene donor groups from benzothiophenes to benzoselenophenes to benzotellurophenes. These molecules show red-shifts in absorption and external quantum efficiency maxima from sulfur to selenium to tellurium. In bulk heterojunction solar cell devices, the benzoselenophene derivative shows a power conversion efficiency as high as 5.8% with PC61BM as the electron acceptor.

Microbial community structure elucidates performance of Glyceria maxima plant microbial fuel cell.

PubMed

Timmers, Ruud A; Rothballer, Michael; Strik, David P B T B; Engel, Marion; Schulz, Stephan; Schloter, Michael; Hartmann, Anton; Hamelers, Bert; Buisman, Cees

2012-04-01

The plant microbial fuel cell (PMFC) is a technology in which living plant roots provide electron donor, via rhizodeposition, to a mixed microbial community to generate electricity in a microbial fuel cell. Analysis and localisation of the microbial community is necessary for gaining insight into the competition for electron donor in a PMFC. This paper characterises the anode-rhizosphere bacterial community of a Glyceria maxima (reed mannagrass) PMFC. Electrochemically active bacteria (EAB) were located on the root surfaces, but they were more abundant colonising the graphite granular electrode. Anaerobic cellulolytic bacteria dominated the area where most of the EAB were found, indicating that the current was probably generated via the hydrolysis of cellulose. Due to the presence of oxygen and nitrate, short-chain fatty acid-utilising denitrifiers were the major competitors for the electron donor. Acetate-utilising methanogens played a minor role in the competition for electron donor, probably due to the availability of graphite granules as electron acceptors.

Modeling donor/acceptor interactions: Combined roles of theory and computation

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

Newton, M.D.

2000-03-05

An extended superexchange model for electron transfer (ET) matrix elements (H{sub DA}) has been formulated as a superposition of McConnell-type pathways and implemented by combined use of configuration interaction wave functions (obtained using the INDO/s model of Zerner and co-workers) and the generalized Muliken-Hush formulation of charge-localized diabatic states. Applications are made for et (and hold transfer) in several donor/bridge/acceptor radical anion (and cation) systems, (DBA){sup {+-}}, allowing detailed comparison with experimental H{sub DA} estimates. For the case of oligo phenylene ethynylene (OPE) bridges, the role of {pi} and {sigma} electronic manifolds for different distributions of phenylene torsion angles ismore » analyzed in detail.« less

Resonant tunneling spectroscopy of valley eigenstates on a donor-quantum dot coupled system

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

Kobayashi, T., E-mail: t.kobayashi@unsw.edu.au; Heijden, J. van der; House, M. G.

We report on electronic transport measurements through a silicon double quantum dot consisting of a donor and a quantum dot. Transport spectra show resonant tunneling peaks involving different valley states, which illustrate the valley splitting in a quantum dot on a Si/SiO{sub 2} interface. The detailed gate bias dependence of double dot transport allows a first direct observation of the valley splitting in the quantum dot, which is controllable between 160 and 240 μeV with an electric field dependence 1.2 ± 0.2 meV/(MV/m). A large valley splitting is an essential requirement for implementing a physical electron spin qubit in a silicon quantum dot.

Electron Donors Supporting Growth and Electroactivity of Geobacter sulfurreducens Anode Biofilms

PubMed Central

Speers, Allison M.

2012-01-01

Geobacter bacteria efficiently oxidize acetate into electricity in bioelectrochemical systems, yet the range of fermentation products that support the growth of anode biofilms and electricity production has not been thoroughly investigated. Here, we show that Geobacter sulfurreducens oxidized formate and lactate with electrodes and Fe(III) as terminal electron acceptors, though with reduced efficiency compared to acetate. The structure of the formate and lactate biofilms increased in roughness, and the substratum coverage decreased, to alleviate the metabolic constraints derived from the assimilation of carbon from the substrates. Low levels of acetate promoted formate carbon assimilation and biofilm growth and increased the system's performance to levels comparable to those with acetate only. Lactate carbon assimilation also limited biofilm growth and led to the partial oxidization of lactate to acetate. However, lactate was fully oxidized in the presence of fumarate, which redirected carbon fluxes into the tricarboxylic acid (TCA) cycle, and by acetate-grown biofilms. These results expand the known ranges of electron donors for Geobacter-driven fuel cells and identify microbial constraints that can be targeted to develop better-performing strains and increase the performance of bioelectrochemical systems. PMID:22101036

Atropisomerization of di-para-substituted propyl-bridged biphenyl cyclophanes.

PubMed

Rotzler, Jürgen; Gsellinger, Heiko; Bihlmeier, Angela; Gantenbein, Markus; Vonlanthen, David; Häussinger, Daniel; Klopper, Wim; Mayor, Marcel

2013-01-07

The influence of electron donors and electron acceptors of variable strength in the 4 and 4' position of 2 and 2' propyl-bridged axial chiral biphenyl cyclophanes on their atropisomerization process was studied. Estimated free energies ΔG(‡)(T) of the rotation around the central biphenyl bond which were obtained from (1)H-NMR coalescence measurements were correlated to the Hammett parameters σ(p) as a measure for electron donor and acceptor strength. It is demonstrated that the resulting nice linear correlation is mainly based on the influence of the different substituents on the π-system of the biphenyl cyclophanes. By lineshape analysis the rate constants were calculated and by the use of the Eyring equation the enthalpic and entropic contributions were evaluated. Density functional theory calculations show a planar transition state of the isomerization process and the calculated energy barriers based on this reaction mechanism are in good agreement with the experimentally obtained free energies.

Statistical exchange-coupling errors and the practicality of scalable silicon donor qubits

NASA Astrophysics Data System (ADS)

Song, Yang; Das Sarma, S.

2016-12-01

Recent experimental efforts have led to considerable interest in donor-based localized electron spins in Si as viable qubits for a scalable silicon quantum computer. With the use of isotopically purified 28Si and the realization of extremely long spin coherence time in single-donor electrons, the recent experimental focus is on two-coupled donors with the eventual goal of a scaled-up quantum circuit. Motivated by this development, we simulate the statistical distribution of the exchange coupling J between a pair of donors under realistic donor placement straggles, and quantify the errors relative to the intended J value. With J values in a broad range of donor-pair separation ( 5 <|R |<60 nm), we work out various cases systematically, for a target donor separation R0 along the [001], [110] and [111] Si crystallographic directions, with |R0|=10 ,20 or 30 nm and standard deviation σR=1 ,2 ,5 or 10 nm. Our extensive theoretical results demonstrate the great challenge for a prescribed J gate even with just a donor pair, a first step for any scalable Si-donor-based quantum computer.

Dexter energy transfer pathways.

PubMed

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

2016-07-19

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

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

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

Soudackov, Alexander; Hammes-Schiffer, Sharon

2015-11-17

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

Organic solid state switches incorporating porphyrin compounds and method for producing organic solid state optical switches

DOEpatents

Wasielewski, M.R.; Gaines, G.L.; Niemczyk, M.P.; Johnson, D.G.; Gosztola, D.J.; O`Neil, M.P.

1996-07-23

A light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, said donors selected from porphyrins and other compounds, and a method for making said compound are disclosed. 4 figs.

Non-conjugated, phenyl assisted coupling in through bond electron transfer in a perylenemonoimide-triphenylamine system.

PubMed

Bell, Toby D M; Stefan, Alina; Lemaur, Vincent; Bernhardt, Stefan; Müllen, Klaus; Cornil, Jérôme; Beljonne, David; Hofkens, Johan; Van der Auweraer, Mark; De Schryver, Frans C

2007-04-01

Two donor-bridge-acceptor compounds containing triphenylamine (TPA) donors and perylenemonoimide (PMI) acceptors have been studied by spectroscopic techniques and quantum chemical computation. Both systems have been observed to emit prompt and delayed fluorescence under certain conditions indicating that forward and reverse electron transfer (ET) processes can occur between the locally excited and the charge separated states. The experimental and computational results show that the TPA and PMI chromophores are better coupled by almost 50% in the meta isomers which undergo ET more readily than the para isomers. Quantum chemical calculations indicate that this unexpected situation is the result of a phenyl group on the side of the bridge being advantageously positioned in the meta isomers. This leads to more extensive delocalisation of the TPA HOMO into the bridge enhancing the total through bond electronic coupling between the TPA and PMI chromophores. The calculations also indicate a strong angle dependence of the total coupling in both isomers. The experimental results are discussed in the context of the high temperature limit of Marcus's theory of non-adiabatic ET.

Theoretical Discussion of Electron Transport Rate Constant at TCNQ / Ge and TiO2 System

NASA Astrophysics Data System (ADS)

Al-agealy, Hadi J. M.; Alshafaay, B.; Hassooni, Mohsin A.; Ashwiekh, Ahmed M.; Sadoon, Abbas K.; Majeed, Raad H.; Ghadhban, Rawnaq Q.; Mahdi, Shatha H.

2018-05-01

We have been studying and estimation the electronic transport constant at TCNQ / Ge and Tio2 interface by means of tunneling potential (TP), transport energy reorientation (TER), driving transition energy DTE and coupling coefficient constant. A simple quantum model for the transition processes was adapted to estimation and analysis depending on the quantum state for donor state |α D > and acceptor stated |α A > and assuming continuum levels of the system. Evaluation results were performed for the surfaces of Ge and Tio2 as best as for multilayer TCNQ. The results show an electronic transfer feature for electronic TCNQ density of states and a semiconductor behavior. The electronic rate constant result for both systems shows a good tool to election system in applied devices. All these results indicate the

Creating Two-Dimensional Electron Gas in Polar/Polar Perovskite Oxide Heterostructures: First-Principles Characterization of LaAlO3/A(+)B(5+)O3.

PubMed

Wang, Yaqin; Tang, Wu; Cheng, Jianli; Behtash, Maziar; Yang, Kesong

2016-06-01

By using first-principles electronic structure calculations, we explored the possibility of producing two-dimensional electron gas (2DEG) at the polar/polar (LaO)(+)/(BO2)(+) interface in the LaAlO3/A(+)B(5+)O3 (A = Na and K, B = Nb and Ta) heterostructures (HS). Unlike the prototype polar/nonpolar LaAlO3/SrTiO3 HS system where there exists a least film thickness of four LaAlO3 unit cells to have an insulator-to-metal transition, we found that the polar/polar LaAlO3/A(+)B(5+)O3 HS systems are intrinsically conducting at their interfaces without an insulator-to-metal transition. The interfacial charge carrier densities of these polar/polar HS systems are on the order of 10(14) cm(-2), much larger than that of the LaAlO3/SrTiO3 system. This is mainly attributed to two donor layers, i.e., (LaO)(+) and (BO2)(+) (B = Nb and Ta), in the polar/polar LaAlO3/A(+)B(5+)O3 systems, while only one (LaO)(+) donor layer in the polar/nonpolar LaAlO3/SrTiO3 system. In addition, it is expected that, due to less localized Nb 4d and Ta 5d orbitals with respect to Ti 3d orbitals, these LaAlO3/A(+)B(5+)O3 HS systems can exhibit potentially higher electron mobility because of their smaller electron effective mass than that in the LaAlO3/SrTiO3 system. Our results demonstrate that the electronic reconstruction at the polar/polar interface could be an alternative way to produce superior 2DEG in the perovskite-oxide-based HS systems.

Bistable mixed-valence molecular architectures for bit storage

NASA Astrophysics Data System (ADS)

Guihery, Nathalie; Durand, Gérard; Lepetit, Marie-Bernadette

1994-05-01

The work examines the possible realization of bit storage at the molecular scale using mixed valence compounds i.e. the existence of two stable and degenerate forms associated with the 0 and 1 positions of the bit. The proposed systems are constituted of two donors (D) and acceptor (A), or one donor and two acceptors, juxtaposed in DAD or ADA architectures. Our proposals take advantage of the possibility of donor—acceptor complexes to exhibit either complete or partial charge transfer. The first system we propose has an essentially neutral ground state. However, the potential energy surface (PES) presents two degenerated minima associated with a partial charge transfer between the donor and one of the two acceptor molecules (A δ-D δ+1 A and AD δ+ A δ-). Systems presenting a complete charge transfer give rise to two stable, weakly coupled, and degenerate ionic electronic states, A - A + A and AD + A - for an ADA architecture and D + A -D and DA -D + for a DAD In these cases, the two forms differ by both their intramolecular geometries and the relative positions of their constituents. It seems rather difficult to conceive such bistable molecular systems using closed-shell molecules, while a donor radical and a closed-shell acceptor or an acceptor radical and closed-shell donor can generate very stable ionic states. It is assumed that the relative positions of the donor and acceptor molecules can be fixed using chemical bridges constituted of rigid or flexible ligands. The writing and reading processes are discussed for each system as well as the information stability when a large number of bits are juxtaposed on a surface.

Evidence for multiple hydrogen-ion donor systems in rain

Treesearch

Sagar V. Krupa; M. R., Jr. Coscio; F. A. Wood

1976-01-01

An integrated analytical system consisting of combined scanning electron microscopy and x-ray analysis, atomic absorption, colorimetry and coulometry was used to study rain water chemistry. The coulometry facilitated the determination in molarities of strong and non-volatile and volatile weak acids. The pH of individual rains in St. Paul - Minneapolis, Minnesota ranged...

Metal-phosphate binders

DOEpatents

Howe, Beth Ann [Lewistown, IL; Chaps-Cabrera, Jesus Guadalupe [Coahuila, MX

2009-05-12

A metal-phosphate binder is provided. The binder may include an aqueous phosphoric acid solution, a metal-cation donor including a metal other than aluminum, an aluminum-cation donor, and a non-carbohydrate electron donor.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

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

PubMed

Hirakawa, Kazutaka; Taguchi, Makoto; Okazaki, Shigetoshi

2015-10-15

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

Calculation of rates of exciton dissociation into hot charge-transfer states in model organic photovoltaic interfaces

NASA Astrophysics Data System (ADS)

Vázquez, Héctor; Troisi, Alessandro

2013-11-01

We investigate the process of exciton dissociation in ordered and disordered model donor/acceptor systems and describe a method to calculate exciton dissociation rates. We consider a one-dimensional system with Frenkel states in the donor material and states where charge transfer has taken place between donor and acceptor. We introduce a Green's function approach to calculate the generation rates of charge-transfer states. For disorder in the Frenkel states we find a clear exponential dependence of charge dissociation rates with exciton-interface distance, with a distance decay constant β that increases linearly with the amount of disorder. Disorder in the parameters that describe (final) charge-transfer states has little effect on the rates. Exciton dissociation invariably leads to partially separated charges. In all cases final states are “hot” charge-transfer states, with electron and hole located far from the interface.

CGS-MSFSS Project report

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

Harvey-Collard, Patrick

2015-10-27

From January 2015 to July 2015, I was doing research at Sandia National Laboratories in Albuquerque, United States. My work there consisted of performing experimental measurements using Sandia’s unique silicon quantum computing platform. The project is about coupling donor spin quantum bits, or qubits, to quantum dots in a silicon nanostructure based on conventional microchip technology. During the project, I devised a new quantum state readout mechanism that allow better, longer lived measurement signals. The measurement (or readout) mechanism is key to any qubit architecture. Next, I was able to demonstrate a quantum manipulation of the two-electron spin states ofmore » the coupled donor and quantum dot system. This constitutes a breakthrough for donor spin qubits in silicon because it could enable larger systems consisting of many qubits. This project will lead to publications in scientific journals, presentations in international conferences, and generates exciting new opportunities for manipulating nature at the nanoscale.« less

Simultaneous removal of perchlorate and energetic compounds in munitions wastewater by zero-valent iron and perchlorate-respiring bacteria.

PubMed

Ahn, Se Chang; Hubbard, Brian; Cha, Daniel K; Kim, Byung J

2014-01-01

Ammonium perchlorate is one of the main constituents in Army's insensitive melt-pour explosive, PAX-21 in addition to RDX and 2,4-dinitroanisole (DNAN). The objective of this study is to develop an innovative treatment process to remove both perchlorate and energetic compounds simultaneously from PAX-21 production wastewater. It was hypothesized that the pretreatment of PAX-21 wastewater with zero-valent iron (ZVI) would convert energetic compounds to products that are more amenable for biological oxidation and that these products serve as electron donors for perchlorate-reducing bacteria. Results of batch ZVI reduction experiments showed that DNAN was completely reduced to 2,4-diaminoanisole and RDX was completely reduced to formaldehyde. Anaerobic batch biodegradation experiments showed that perchlorate (30 mg L(-1)) in ZVI-treated PAX-21 wastewater was decreased to an undetectable level after 5 days. Batch biodegradation experiments also confirmed that formaldehyde in ZVI-treated wastewater was the primary electron donor for perchlorate-respiring bacteria. The integrated iron-anaerobic bioreactor system was effective in completely removing energetic compounds and perchlorate from the PAX-21 wastewater without adding an exogenous electron donor. This study demonstrated that ZVI pretreatment not only removed energetic compounds, but also transformed energetic compounds to products that can serve as the source of electrons for perchlorate-respiring bacteria.

Supramolecular networks with electron transfer in two dimensions

DOEpatents

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

2016-09-13

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

Polaronic effects on the off-center donor impurity in AlAs/GaAs/SiO2 spherical core/shell quantum dots

NASA Astrophysics Data System (ADS)

El Haouari, M.; Feddi, E.; Dujardin, F.; Restrepo, R. L.; Mora-Ramos, M. E.; Duque, C. A.

2017-11-01

The ground state of a conduction electron coupled to an off-center impurity donor in a AlAS/GaAs spherical core/shell quantum dot is investigated theoretically. The image-charge effect and the influence of the electron-polar-LO-phonon interaction are considered. The electron-impurity binding energy is calculated via a variational procedure and is reported both as a function of the shell width and of the radial position of the donor atom. The polaronic effects on this quantity are particularly discussed.

Improvement of photovoltaic performance by substituent effect of donor and acceptor structure of TPA-based dye-sensitized solar cells.

PubMed

Inostroza, Natalia; Mendizabal, Fernando; Arratia-Pérez, Ramiro; Orellana, Carlos; Linares-Flores, Cristian

2016-01-01

We report a computational study of a series of organic dyes built with triphenylamine (TPA) as an electron donor group. We designed a set of six dyes called (TPA-n, where n = 0-5). In order to enhance the electron-injection process, the electron-donor effect of some specific substituent was studied. Thus, we gave insights into the rational design of organic TPA-based chromophores for use in dye-sensitized solar cells (DSSCs). In addition, we report the HOMO, LUMO, the calculated excited state oxidized potential E(dye*)(eV) and the free energy change for electron-injection ΔGinject(eV), and the UV-visible absorption bands for TPA-n dyes by a time-dependent density functional theory (TDDFT) procedure at the B3LYP and CAM-B3LYP levels with solvent effect. The results demonstrate that the introduction of the electron-acceptor groups produces an intramolecular charge transfer showing a shift of the absorption wavelengths of TPA-n under studies. Graphical Abstract Several organic dyes TPA-n with different donors and acceptors are modeled. A strong conjugation acrros the donor and anchoring groips (TPA-n) bas been studied. Candidate TPA-3 shows a promising results.

Accelerating Quinoline Biodegradation and Oxidation with Endogenous Electron Donors.

PubMed

Bai, Qi; Yang, Lihui; Li, Rongjie; Chen, Bin; Zhang, Lili; Zhang, Yongming; Rittmann, Bruce E

2015-10-06

Quinoline, a recalcitrant heterocyclic compound, is biodegraded by a series of reactions that begin with mono-oxygenations, which require an intracellular electron donor. Photolysis of quinoline can generate readily biodegradable products, such as oxalate, whose bio-oxidation can generate endogenous electron donors that ought to accelerate quinoline biodegradation and, ultimately, mineralization. To test this hypothesis, we compared three protocols for the biodegradation of quinoline: direct biodegradation (B), biodegradation after photolysis of 1 h (P1h+B) or 2 h (P2h+B), and biodegradation by adding oxalate commensurate to the amount generated from photolysis of 1 h (O1+B) or 2 h (O2+B). The experimental results show that P1h+B and P2h+B accelerated quinoline biodegradation by 19% and 50%, respectively, compared to B. Protocols O1+B and O2+B also gave 19% and 50% increases, respectively. During quinoline biodegradation, its first intermediate, 2-hydroxyquinoline, accumulated gradually in parallel to quinoline loss but declined once quinoline was depleted. Mono-oxygenation of 2-hydroxyquinoline competed with mono-oxygenation of quinoline, but the inhibition was relieved when extra electrons donors were added from oxalate, whether formed by UV photolysis or added exogenously. Rapid oxalate oxidation stimulated both mono-oxygenations, which accelerated the overall quinoline oxidation that provided the bulk of the electron donor.

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

NASA Astrophysics Data System (ADS)

Seibt, Joachim; Mančal, Tomáš

2017-05-01

We derive equations of motion for the reduced density matrix of a molecular system which undergoes energy transfer dynamics competing with fast internal conversion channels. Environmental degrees of freedom of such a system have no time to relax to quasi-equilibrium in the electronic excited state of the donor molecule, and thus the conditions of validity of Förster and Modified Redfield theories in their standard formulations do not apply. We derive non-equilibrium versions of the two well-known rate theories and apply them to the case of carotenoid-chlorophyll energy transfer. Although our reduced density matrix approach does not account for the formation of vibronic excitons, it still confirms the important role of the donor ground-state vibrational states in establishing the resonance energy transfer conditions. We show that it is essential to work with a theory valid in a strong system-bath interaction regime to obtain correct dependence of the rates on donor-acceptor energy gap.

Competition for electrons between mono-oxygenations of pyridine and 2-hydroxypyridine.

PubMed

Yang, Chao; Tang, Yingxia; Xu, Hua; Yan, Ning; Li, Naiyu; Zhang, Yongming; Rittmann, Bruce E

2018-05-21

Pyridine and its heterocyclic derivatives are widely encountered in industrial wastewaters, and they are relatively recalcitrant to biodegradation. Pyridine biodegradation is initiated by two mono-oxygenation reactions that compete for intracellular electron donor (2H). In our experiments, UV photolysis of pyridine generated succinate, whose oxidation augmented the intracellular electron donor and accelerated pyridine biodegradation and mineralization. The first mono-oxygenation reaction always was faster than the second one, because electrons provided by intracellular electron donors were preferentially utilized by the first mono-oxygenase; this was true even when the concentration of 2HP was greater than the concentration of pyridine. In addition, the first mono-oxygenation had faster kinetics because it had higher affinity for its substrate (pyridine), along with less substrate self-inhibition.

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

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

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

DOE PAGES

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel; ...

2018-04-13

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics [On the Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics

DOE PAGES

Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang; ...

2017-02-22

Here, we report a novel method to determine the amount of pure, aggregated phase of donor and acceptor in organic photovoltaic (OPV) bulk heterojunctions. By determination of the diffraction intensity per unit volume for both donor and acceptor, the volume content of pure, aggregated donor and acceptor in the blend can be determined. We find that for the small molecule X2:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) system, in contrast to most polymer systems, all the PCBM is aggregated, indicating there is negligible miscibility of PCBM with X2. This provides an explanation why the performance of OPV devices of X2:PCBM are highmore » over a large range of PCBM concentrations. This is in contrast to many other OPV blends, where PCBM forms a mixed phase with the donor and does not provide sufficient transport for electrons when the PCBM concentration is low. This study demonstrates that a mixed phase is not necessarily a requirement for good OPV device performance.« less

Location and Electronic Nature of Phosphorus in the Si Nanocrystal − SiO2 System

PubMed Central

König, Dirk; Gutsch, Sebastian; Gnaser, Hubert; Wahl, Michael; Kopnarski, Michael; Göttlicher, Jörg; Steininger, Ralph; Zacharias, Margit; Hiller, Daniel

2015-01-01

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P. PMID:25997696

Fullerene derivatives as electron donor for organic photovoltaic cells

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

Zhuang, Taojun; Wang, Xiao-Feng, E-mail: xf-wang@yz.yamagata-u.ac.jp, E-mail: ziruo@yz.yamagata-u.ac.jp; Sano, Takeshi

2013-11-11

We demonstrated the performance of unconventional, all-fullerene-based, planar heterojunction (PHJ) organic photovoltaic (OPV) cells using fullerene derivatives indene-C{sub 60} bisadduct (ICBA) and phenyl C{sub 61}-butyric acid methyl ester as the electron donors with fullerene C{sub 70} as the electron acceptor. Two different charge generation processes, including charge generation in the fullerene bulk and exciton dissociation at the donor-acceptor interface, have been found to exist in such all-fullerene-based PHJ cells and the contribution to the total photocurrent from each process is strongly dependent on the thickness of fullerene donor. The optimized 5 nm ICBA/40 nm C{sub 70} PHJ cell gives clear external quantummore » efficiency responses for the long-wavelength photons corresponding to the dissociation of strongly bound Frenkel excitons, which is hardly observed in fullerene-based single layer reference devices. This approach using fullerene as a donor material provides further possibilities for developing high performance OPV cells.« less

Donor states in inverse opals

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

Mahan, G. D.

We calculate the binding energy of an electron bound to a donor in a semiconductor inverse opal. Inverse opals have two kinds of cavities, which we call octahedral and tetrahedral, according to their group symmetry. We put the donor in the center of each of these two cavities and obtain the binding energy. The binding energies become very large when the inverse opal is made from templates with small spheres. For spheres less than 50 nm in diameter, the donor binding can increase to several times its unconfined value. Then electrons become tightly bound to the donor and are unlikelymore » to be thermally activated to the semiconductor conduction band. This conclusion suggests that inverse opals will be poor conductors.« less

Supramolecular aromaticity

NASA Astrophysics Data System (ADS)

Karabıyık, Hande; Sevinçek, Resul; Karabıyık, Hasan

2014-05-01

We report experimental and theoretical evidences for supramolecular aromaticity as a new concept to be widely used in researches about molecular crystals. CSD survey regarding frequently encountered resonance-assisted H-bonds (RAHBs) in formic acid, formamide, formimidamide, formic acid-formamide, and formamide-formimidamide dimers shows that supramolecular quasirings formed by RAHBs have remarkable electronic delocalization within themselves, which is reminiscent of aromaticity at supramolecular level. This study criticizes and reevaluates the validity of conventional judgment which states that ring systems formed by intermolecular H-bonds cannot be aromatic. Thus, the term aromaticity can be extended to supramolecular systems formed by RAHBs. Supramolecular aromaticity has a multi-fold nature involving both σ- and π-delocalization, and σ-delocalization through RAHBs takes on a task of compensating σ-deficiency within quasirings. Atomic composition in donor-acceptor set of the dimers is descriptive for supramolecular aromaticity. We revised bond-valence parameters for RAHBs and they suggest that hypervalent character of H atoms is more pronounced than their hypovalent character in RAHBs. The σ-delocalized bonding within H-bonded quasirings necessitates hypervalent character of H atoms. Quantum chemical calculations based on adiabatic Hydrogen Atom Transfer (HAT) between the monomers reveal that topological parameters at ring critical points (RCPs) of the quasirings correlate well with Shannon's entropic aromaticity index. The presence of additional LP orbital on O atoms implying more diffused LP-orbitals in donor-acceptor set leads to the formation of resonance-disabling states reducing supramolecular aromaticity of a quasiring and energetic cost of the electron transfer between the monomers. There is a nonignorable electron transfer between the monomers even in the cases where H atoms are close to donor or acceptor atom. NBO analyses have revealed that formally vacant LP* orbitals on H-atoms in TS geometries mediate intermolecular electron transfer as a result of the hyperconjugative stereoelectronic interactions.

Electron transfer complex between nitrous oxide reductase and cytochrome c552 from Pseudomonas nautica: kinetic, nuclear magnetic resonance, and docking studies.

PubMed

Dell'acqua, Simone; Pauleta, Sofia R; Monzani, Enrico; Pereira, Alice S; Casella, Luigi; Moura, José J G; Moura, Isabel

2008-10-14

The multicopper enzyme nitrous oxide reductase (N 2OR) catalyzes the final step of denitrification, the two-electron reduction of N 2O to N 2. This enzyme is a functional homodimer containing two different multicopper sites: CuA and CuZ. CuA is a binuclear copper site that transfers electrons to the tetranuclear copper sulfide CuZ, the catalytic site. In this study, Pseudomonas nautica cytochrome c 552 was identified as the physiological electron donor. The kinetic data show differences when physiological and artificial electron donors are compared [cytochrome vs methylviologen (MV)]. In the presence of cytochrome c 552, the reaction rate is dependent on the ET reaction and independent of the N 2O concentration. With MV, electron donation is faster than substrate reduction. From the study of cytochrome c 552 concentration dependence, we estimate the following kinetic parameters: K m c 552 = 50.2 +/- 9.0 muM and V max c 552 = 1.8 +/- 0.6 units/mg. The N 2O concentration dependence indicates a K mN 2 O of 14.0 +/- 2.9 muM using MV as the electron donor. The pH effect on the kinetic parameters is different when MV or cytochrome c 552 is used as the electron donor (p K a = 6.6 or 8.3, respectively). The kinetic study also revealed the hydrophobic nature of the interaction, and direct electron transfer studies showed that CuA is the center that receives electrons from the physiological electron donor. The formation of the electron transfer complex was observed by (1)H NMR protein-protein titrations and was modeled with a molecular docking program (BiGGER). The proposed docked complexes corroborated the ET studies giving a large number of solutions in which cytochrome c 552 is placed near a hydrophobic patch located around the CuA center.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Carrier concentration dependence of donor activation energy in n-type GaN epilayers grown on Si (1 1 1) by plasma-assisted MBE

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

Kumar, Mahesh; Central Research Laboratory, Bharat Electronics, Bangalore 560 013; Bhat, Thirumaleshwara N.

Highlights: ► The n-type GaN layers were grown by plasma-assisted molecular beam epitaxy. ► The optical characteristics of a donor level in Si-doped GaN were studied. ► Activation energy of a Si-related donor was estimated from temperature dependent PL measurements. ► PL peak positions, FWHM of PL and activation energies are found to be proportional to the cube root of carrier density. ► The involvement of donor levels is supported by the temperature-dependent electron concentration measurements. -- Abstract: The n-type GaN layers were grown by plasma-assisted MBE and either intentionally doped with Si or unintentionally doped. The optical characteristics ofmore » a donor level in Si-doped, GaN were studied in terms of photoluminescence (PL) spectroscopy as a function of electron concentration. Temperature dependent PL measurements allowed us to estimate the activation energy of a Si-related donor from temperature-induced decay of PL intensity. PL peak positions, full width at half maximum of PL and activation energies are found to be proportional to the cube root of carrier density. The involvement of donor levels is supported by the temperature-dependent electron concentration measurements.« less

Donor-acceptor-donor thienyl/bithienyl-benzothiadiazole/quinoxaline model oligomers: experimental and theoretical studies.

PubMed

Pina, João; de Melo, J Seixas; Breusov, D; Scherf, Ullrich

2013-09-28

A comprehensive spectral and photophysical investigation of four donor-acceptor-donor (DAD) oligomers consisting of electron-deficient 2,1,3-benzothiadiazole or quinoxaline moieties linked to electron-rich thienyl or bithienyl units has been undertaken. Additionally, a bis(dithienyl) substituted naphthalene was also investigated. The D-A-D nature of these oligomers resulted in the presence of an intramolecular charge transfer (ICT) state, which was further substantiated by solvatochromism studies (analysis with the Lippert-Mataga formalism). Hereby, significant differences have been obtained for the fluorescence quantum yields of the oligomers in the non-polar solvent methylcyclohexane vs. the polar ethanol. The study was further complemented with the determination of the optimized ground-state molecular geometries for the oligomers together with the prediction of the lowest vertical one-electron excitation energy and the relevant molecular orbital contours using DFT calculations. The electronic transitions show a clear HOMO to LUMO charge-transfer character. In contrast to the thiophene oligomers (the oligothiophenes with n = 1-7), where the intersystem crossing (ISC) yield decreases with n, the studied DAD oligomers were found to show an increase in the ISC efficiency with the number of (donor) thienyl units.

Transmembrane electric potential difference in the protein-pigment complex of photosystem 2.

PubMed

Mamedov, M D; Kurashov, V N; Petrova, I O; Semenov, A Yu

2012-09-01

The protein-pigment complex of photosystem 2 (PS2) localized in the thylakoid membranes of higher plants, algae, and cyanobacteria is the main source of oxygen on Earth. The light-induced functioning of PS2 is directly linked to electron and proton transfer across the membrane, which results in the formation of transmembrane electric potential difference (ΔΨ). The major contribution to ΔΨ of the PS2 reaction center is due to charge separation between the primary chlorophyll donor P(680) and the quinone acceptor Q(A), accompanied by re-reduction of P(680)(+) by the redox-active tyrosine residue Y(Z). The processes associated with the uptake and release of protons on the acceptor and donor sides of the enzyme, respectively, are also coupled with ΔΨ generation. The objective of this work was to describe the mechanisms of ΔΨ generation associated with the S-state transitions of the water-oxidizing complex in intact PS2 complex and in PS2 preparation depleted of Mn(4)Ca cluster in the presence of artificial electron donors. The findings elucidate the mechanisms of electrogenic reactions on the PS2 donor side and may be a basis for development of an effective solar energy conversion system.

Organic Donor-Acceptor Complexes as Novel Organic Semiconductors.

PubMed

Zhang, Jing; Xu, Wei; Sheng, Peng; Zhao, Guangyao; Zhu, Daoben

2017-07-18

Organic donor-acceptor (DA) complexes have attracted wide attention in recent decades, resulting in the rapid development of organic binary system electronics. The design and synthesis of organic DA complexes with a variety of component structures have mainly focused on metallicity (or even superconductivity), emission, or ferroelectricity studies. Further efforts have been made in high-performance electronic investigations. The chemical versatility of organic semiconductors provides DA complexes with a great number of possibilities for semiconducting applications. Organic DA complexes extend the semiconductor family and promote charge separation and transport in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). In OFETs, the organic complex serves as an active layer across extraordinary charge pathways, ensuring the efficient transport of induced charges. Although an increasing number of organic semiconductors have been reported to exhibit good p- or n-type properties (mobilities higher than 1 or even 10 cm 2 V -1 s -1 ), critical scientific challenges remain in utilizing the advantages of existing semiconductor materials for more and wider applications while maintaining less complicated synthetic or device fabrication processes. DA complex materials have revealed new insight: their unique molecular packing and structure-property relationships. The combination of donors and acceptors could offer practical advantages compared with their unimolecular materials. First, growing crystals of DA complexes with densely packed structures will reduce impurities and traps from the self-assembly process. Second, complexes based on the original structural components could form superior mixture stacking, which can facilitate charge transport depending on the driving force in the coassembly process. Third, the effective use of organic semiconductors can lead to tunable band structures, allowing the operation mode (p- or n-type) of the transistor to be systematically controlled by changing the components. Finally, theoretical calculations based on cocrystals with unique stacking could widen our understanding of structure-property relationships and in turn help us design high-performance semiconductors based on DA complexes. In this Account, we focus on discussing organic DA complexes as a new class of semiconducting materials, including their design, growth methods, packing modes, charge-transport properties, and structure-property relationships. We have also fabricated and investigated devices based on these binary crystals. This interdisciplinary work combines techniques from the fields of self-assembly, crystallography, condensed-matter physics, and theoretical chemistry. Researchers have designed new complex systems, including donor and acceptor compounds that self-assemble in feasible ways into highly ordered cocrystals. We demonstrate that using this crystallization method can easily realize ambipolar or unipolar transport. To further improve device performance, we propose several design strategies, such as using new kinds of donors and acceptors, modulating the energy alignment of the donor (ionization potential, IP) and acceptor (electron affinity, EA) components, and extending the π-conjugated backbones. In addition, we have found that when we use molecular "doping" (2:1 cocrystallization), the charge-transport nature of organic semiconductors can be switched from hole-transport-dominated to electron-transport-dominated. We expect that the formation of cocrystals through the complexation of organic donor and acceptor species will serve as a new strategy to develop semiconductors for organic electronics with superior performances over their corresponding individual components.

Effect of Electron Donor and Solution Chemistry on Products of Dissimilatory Reduction of Technetium by Shewanella putrefaciens

PubMed Central

Wildung, R. E.; Gorby, Y. A.; Krupka, K. M.; Hess, N. J.; Li, S. W.; Plymale, A. E.; McKinley, J. P.; Fredrickson, J. K.

2000-01-01

To help provide a fundamental basis for use of microbial dissimilatory reduction processes in separating or immobilizing 99Tc in waste or groundwaters, the effects of electron donor and the presence of the bicarbonate ion on the rate and extent of pertechnetate ion [Tc(VII)O4−] enzymatic reduction by the subsurface metal-reducing bacterium Shewanella putrefaciens CN32 were determined, and the forms of aqueous and solid-phase reduction products were evaluated through a combination of high-resolution transmission electron microscopy, X-ray absorption spectroscopy, and thermodynamic calculations. When H2 served as the electron donor, dissolved Tc(VII) was rapidly reduced to amorphous Tc(IV) hydrous oxide, which was largely associated with the cell in unbuffered 0.85% NaCl and with extracellular particulates (0.2 to 0.001 μm) in bicarbonate buffer. Cell-associated Tc was present principally in the periplasm and outside the outer membrane. The reduction rate was much lower when lactate was the electron donor, with extracellular Tc(IV) hydrous oxide the dominant solid-phase reduction product, but in bicarbonate systems much less Tc(IV) was associated directly with the cell and solid-phase Tc(IV) carbonate may have been present. In the presence of carbonate, soluble (<0.001 μm) electronegative, Tc(IV) carbonate complexes were also formed that exceeded Tc(VII)O4− in electrophoretic mobility. Thermodynamic calculations indicate that the dominant reduced Tc species identified in the experiments would be stable over a range of Eh and pH conditions typical of natural waters. Thus, carbonate complexes may represent an important pathway for Tc transport in anaerobic subsurface environments, where it has generally been assumed that Tc mobility is controlled by low-solubility Tc(IV) hydrous oxide and adsorptive, aqueous Tc(IV) hydrolysis products. PMID:10831424

Two-electron states of a group-V donor in silicon from atomistic full configuration interactions

NASA Astrophysics Data System (ADS)

Tankasala, Archana; Salfi, Joseph; Bocquel, Juanita; Voisin, Benoit; Usman, Muhammad; Klimeck, Gerhard; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.; Rogge, Sven; Rahman, Rajib

2018-05-01

Two-electron states bound to donors in silicon are important for both two-qubit gates and spin readout. We present a full configuration interaction technique in the atomistic tight-binding basis to capture multielectron exchange and correlation effects taking into account the full band structure of silicon and the atomic-scale granularity of a nanoscale device. Excited s -like states of A1 symmetry are found to strongly influence the charging energy of a negative donor center. We apply the technique on subsurface dopants subjected to gate electric fields and show that bound triplet states appear in the spectrum as a result of decreased charging energy. The exchange energy, obtained for the two-electron states in various confinement regimes, may enable engineering electrical control of spins in donor-dot hybrid qubits.

An additional simple denitrification bioreactor using packed gel envelopes applicable to industrial wastewater treatment.

PubMed

Morita, Masahiko; Uemoto, Hiroaki; Watanabe, Atsushi

2007-08-15

A simple denitrification bioreactor for nitrate-containing wastewater without organic compounds was developed. This bioreactor consisted of packed gel envelopes in a single tank. Each envelope comprised two plates of gels containing Paracoccus denitrificans cells with an internal space between the plates. As an electron donor for denitrification, ethanol was injected into the internal space and not directly into the wastewater. P. denitrificans cells in the gel reduced nitrate to nitrogen gas by using the injected ethanol. Nitrate-containing desulfurization wastewater derived from a coal-fired thermal power plant was continuously treated with 20 packed gel envelopes (size, 1,000 x 900 x 12 mm; surface area, 1.44 m(2)) in a reactor tank (volume 1.5 m(3)). When the total nitrogen concentration in the inflow was around 150 mg-N x L(-1), the envelopes removed approximately 60-80% of the total nitrogen, and the maximum nitrogen removal rate was 5.0 g-N x day(-1) per square meter of the gel surface. This value corresponded to the volumetric nitrogen removal performance of 0.109 kg-N x m(-3) x day(-1). In each envelope, a high utilization efficiency of the electron donor was attained, although more than the double amount of the electron donor was empirically injected in the present activated sludge system to achieve denitrification when compared with the theoretical value. The bioreactor using the envelopes would be extremely effective as an additional denitrification system because these envelopes can be easily installed in the vacant spaces of preinstalled water treatment systems, without requiring additional facilities for removing surplus ethanol and sludge. (c) 2007 Wiley Periodicals, Inc.

High-Fidelity Rapid Initialization and Read-Out of an Electron Spin via the Single Donor D(-) Charge State.

PubMed

Watson, T F; Weber, B; House, M G; Büch, H; Simmons, M Y

2015-10-16

We demonstrate high-fidelity electron spin read-out of a precision placed single donor in silicon via spin selective tunneling to either the D(+) or D(-) charge state of the donor. By performing read-out at the stable two electron D(0)↔D(-) charge transition we can increase the tunnel rates to a nearby single electron transistor charge sensor by nearly 2 orders of magnitude, allowing faster qubit read-out (1 ms) with minimum loss in read-out fidelity (98.4%) compared to read-out at the D(+)↔D(0) transition (99.6%). Furthermore, we show that read-out via the D(-) charge state can be used to rapidly initialize the electron spin qubit in its ground state with a fidelity of F(I)=99.8%.

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

NASA Astrophysics Data System (ADS)

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

1999-06-01

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

Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1989-01-01

The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

Extended Hubbard model for mesoscopic transport in donor arrays in silicon

NASA Astrophysics Data System (ADS)

Le, Nguyen H.; Fisher, Andrew J.; Ginossar, Eran

2017-12-01

Arrays of dopants in silicon are promising platforms for the quantum simulation of the Fermi-Hubbard model. We show that the simplest model with only on-site interaction is insufficient to describe the physics of an array of phosphorous donors in silicon due to the strong intersite interaction in the system. We also study the resonant tunneling transport in the array at low temperature as a mean of probing the features of the Hubbard physics, such as the Hubbard bands and the Mott gap. Two mechanisms of localization which suppresses transport in the array are investigated: The first arises from the electron-ion core attraction and is significant at low filling; the second is due to the sharp oscillation in the tunnel coupling caused by the intervalley interference of the donor electron's wave function. This disorder in the tunnel coupling leads to a steep exponential decay of conductance with channel length in one-dimensional arrays, but its effect is less prominent in two-dimensional ones. Hence, it is possible to observe resonant tunneling transport in a relatively large array in two dimensions.

Proton transfer along water bridges in biological systems with density-functional tight-binding

NASA Astrophysics Data System (ADS)

Reiss, Krystle; Wise, Abigail; Mazzuca, James

2015-03-01

When examining the dynamics of charge transfer in high dimensional enzymatic systems, the cost of quantum mechanical treatment of electrons increases exponentially with the size of the system. As a semi-empirical method, density-functional tight-binding aids in shortening these calculation times, but can be inaccurate in the regime where bonds are being formed and broken. To address these inaccuracies with respect to proton transfer in an enzymatic system, DFTB is being used to calculate small model systems containing only a single amino acid residue donor, represented by an imidazole molecule, and a water acceptor. When DFTB calculations are compared to B3LYP geometry calculations of the donor molecule, we observe a bond angle error on the order of 1.2 degrees and a bond length error on the order of 0.011 Å. As we move forward with small donor-acceptor systems, comparisons between DFTB and B3LYP energy profiles will provide a better clue as to what extent improvements need to be made. To improve the accuracy of the DFTB calculations, the internuclear repulsion term may be altered. This would result in energy profiles that closely resemble those produced by higher-level theory. Alma College Provost's Office.

Current oscillations in semi-insulating GaAs associated with field-enhanced capture of electrons by the major deep donor EL2

NASA Technical Reports Server (NTRS)

Kaminska, M.; Parsey, J. M.; Lagowski, J.; Gatos, H. C.

1982-01-01

Current oscillations thermally activated by the release of electrons from deep levels in undoped semiinsulating GaAs were observed for the first time. They were attributed to electric field-enhanced capture of electrons by the dominant deep donor EL2 (antisite AsGa defect). This enhanced capture is due to the configurational energy barrier of EL2, which is readily penetrated by hot electrons.

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

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

Wu, Boning; Liang, Min; Zmich, Nicole

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

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

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

2018-01-29

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

42 CFR 486.330 - Condition: Information management.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 5 2010-10-01 2010-10-01 false Condition: Information management. 486.330 Section...: Information management. An OPO must establish and use an electronic information management system to maintain the required medical, social and identifying information for every donor and transplant recipient and...

42 CFR 486.330 - Condition: Information management.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 42 Public Health 5 2012-10-01 2012-10-01 false Condition: Information management. 486.330 Section...: Information management. An OPO must establish and use an electronic information management system to maintain the required medical, social and identifying information for every donor and transplant beneficiary...

42 CFR 486.330 - Condition: Information management.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 42 Public Health 5 2013-10-01 2013-10-01 false Condition: Information management. 486.330 Section...: Information management. An OPO must establish and use an electronic information management system to maintain the required medical, social and identifying information for every donor and transplant beneficiary...

42 CFR 486.330 - Condition: Information management.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 5 2011-10-01 2011-10-01 false Condition: Information management. 486.330 Section...: Information management. An OPO must establish and use an electronic information management system to maintain the required medical, social and identifying information for every donor and transplant recipient and...

42 CFR 486.330 - Condition: Information management.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 42 Public Health 5 2014-10-01 2014-10-01 false Condition: Information management. 486.330 Section...: Information management. An OPO must establish and use an electronic information management system to maintain the required medical, social and identifying information for every donor and transplant beneficiary...

PCE dechlorination by non-Dehalococcoides in a microbial electrochemical system.

PubMed

Yu, Jaecheul; Park, Younghyun; Nguyen, Van Khanh; Lee, Taeho

2016-08-01

The bioremediation of tetrachloroethene (perchloroethene; PCE) contaminated sites generally requires a supply of some fermentable organic substrates as an electron donor. On the other hand, organic substrates can induce the massive growth of microorganisms around the injection wells, which can foul the contaminated subsurface environment. In this study, PCE dechlorination to ethene was performed in a microbial electrochemical system (MES) using the electrode (a cathode polarized at -500 mV vs. standard hydrogen electrode) as the electron donor. Denaturing gel gradient electrophoresis and pyrosequencing revealed a variety of non-Dehalococcoides bacteria dominant in MES, such as Acinetobacter sp. (25.7 % for AS1 in suspension of M3), Rhodopseudomonas sp. (10.5 % for AE1 and 10.1 % for AE2 in anodic biofilm of M3), Pseudomonas aeruginosa (22.4 % for BS1 in suspension of M4), and Enterobacter sp. (21.7 % for BE1 in anodic biofilm of M4) which are capable of electron transfer, hydrogen production and dechlorination. The Dehalococcoides group, however, was not detected in this system. Therefore, these results suggest that a range of bacterial species outside the Dehalococcoides can play an important role in the microbial electrochemical dechlorination process, which may lead to innovative bioremediation technology.

Luminescent substituted fluoranthenes - synthesis, structure, electrochemical and optical properties.

PubMed

Slodek, Aneta; Maroń, Anna; Pająk, Michał; Matussek, Marek; Grudzka-Flak, Iwona; Małecki, Jan Grzegorz; Świtlicka, Anna; Krompiec, Stanisław; Danikiewicz, Witold; Grela, Małgorzata; Gryca, Izabela; Penkala, Mateusz

2018-04-16

Six novel fluoranthene derivatives, three terminally substituted and three bis(fluoranthenes) with fluorene, bithiophene and carbazole spacers were obtained via [2+2+2] cycloaddition and thoroughly characterized. Based on the conducted studies, the obtained derivatives can be classified as D-A (donor-acceptor) and A-D-A (acceptor-donor-acceptor) systems, where fluoranthene unit acts as an electron-withdrawing unit. The optical results revealed that novel fluoranthene derivatives absorb light in the range of 236-417 nm originating from ππ* transition within the conjugated system. The compounds exhibit fluorescence ranging from deep blue to green originating mainly from intramolecular charge transfer (ICT) states. The high Stoke shifts, high quantum yield in solution (φ= 0.22-0.57) and in the solid state (φ= 0.18-0.44) have been observed for fluoranthene derivatives. All derivatives possess multi-step oxidations at low potentials. The electronic structure of presented compounds is additionally supported by TD-DFT computations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge-transfer contributions to the excitonic coupling matrix element in BODIPY-based energy transfer cassettes

NASA Astrophysics Data System (ADS)

Spiegel, J. Dominik; Lyskov, Igor; Kleinschmidt, Martin; Marian, Christel M.

2017-01-01

BODIPY-based dyads serve as model systems for the investigation of excitation energy transfer (EET). Through-space EET is brought about by direct and exchange interactions between the transition densities of donor and acceptor localized states. The presence of a molecular linker gives rise to additional charge transfer (CT) contributions. Here, we present a novel approach for the calculation of the excitonic coupling matrix element (ECME) including CT contributions which is based on supermolecular one-electron transition density matrices (STD). The validity of the approach is assessed for a model system of two π -stacked ethylene molecules at varying intermolecular separation. Wave functions and electronic excitation energies of five EET cassettes comprising anthracene as exciton donor and BODIPY as exciton acceptor are obtained by the redesigned combined density functional theory and multireference configuration interaction (DFT/MRCI-R) method. CT contributions to the ECME are shown to be important in the covalently linked EET cassettes.

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

PubMed

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

2018-01-11

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

Pertinent parameters in photo-generation of electrons: Comparative study of anatase-based nano-TiO2 suspensions.

PubMed

Martel, D; Guerra, A; Turek, P; Weiss, J; Vileno, B

2016-04-01

In the field of solar fuel cells, the development of efficient photo-converting semiconductors remains a major challenge. A rational analysis of experimental photocatalytic results obtained with material in colloïdal suspensions is needed to access fundamental knowledge required to improve the design and properties of new materials. In this study, a simple system electron donor/nano-TiO2 is considered and examined via spin scavenging electron paramagnetic resonance as well as a panel of analytical techniques (composition, optical spectroscopy and dynamic light scattering) for selected type of nano-TiO2. Independent variables (pH, electron donor concentration and TiO2 amount) have been varied and interdependent variables (aggregate size, aggregate surface vs. volume and acid/base groups distribution) are discussed. This work shows that reliable understanding involves thoughtful combination of interdependent parameters, whereas the specific surface area seems not a pertinent parameter. The conclusion emphasizes the difficulty to identify the key features of the mechanisms governing photocatalytic properties in nano-TiO2. Copyright © 2016 Elsevier Inc. All rights reserved.

78 FR 46954 - Agency Information Collection Activities; Proposed Collection; Comment Request; Draft Guidance...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-02

... either electronic or written comments on the collection of information by October 1, 2013. ADDRESSES: Submit electronic comments on the collection of information to http://www.regulations.gov . Submit... detecting antibodies to T. cruzi in plasma and serum samples from individual human donors, including donors...

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems.

PubMed

Teuscher, Joël; Brauer, Jan C; Stepanov, Andrey; Solano, Alicia; Boziki, Ariadni; Chergui, Majed; Wolf, Jean-Pierre; Rothlisberger, Ursula; Banerji, Natalie; Moser, Jacques-E

2017-11-01

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research "Molecular Ultrafast Science and Technology," a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here.

Donor defects and small polarons on the TiO2(110) surface

NASA Astrophysics Data System (ADS)

Moses, P. G.; Janotti, A.; Franchini, C.; Kresse, G.; Van de Walle, C. G.

2016-05-01

The role of defects in the chemical activity of the rutile TiO2(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend to localize in the form of small polarons, which are the factual cause of the deep states ˜1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO2 and related oxides.

Two-photon or higher-order absorbing optical materials and methods of use

NASA Technical Reports Server (NTRS)

Marder, Seth (Inventor); Perry, Joseph (Inventor)

2012-01-01

Compositions capable of simultaneous two-photon absorption and higher order absorptivities are provided. Compounds having a donor-pi-donor or acceptor-pi-acceptor structure are of particular interest, where the donor is an electron donating group, acceptor is an electron accepting group, and pi is a pi bridge linking the donor and/or acceptor groups. The pi bridge may additionally be substituted with electron donating or withdrawing groups to alter the absorptive wavelength of the structure. Also disclosed are methods of generating an excited state of such compounds through optical stimulation with light using simultaneous absorption of photons of energies individually insufficient to achieve an excited state of the compound, but capable of doing so upon simultaneous absorption of two or more such photons. Applications employing such methods are also provided, including controlled polymerization achieved through focusing of the light source(s) used.

Organic photovoltaic devices comprising solution-processed substituted metal-phthalocyanines and exhibiting near-IR photo-sensitivity

DOEpatents

McGrath, Dominic V.; Mayukh, Mayank; Placencia, Diogenes; Armstrong, Neal R.

2016-11-29

Organic photovoltaic (OPV) devices are disclosed. An exemplary device has first and second electrodes and an organic, photovoltaically active zone located between the first and second electrodes. The photovoltaically active zone includes an organic electron-donor material and an organic electron-acceptor material. The electron-donor material includes one or more trivalent- or tetravalent-metal phthalocyanines with alkylchalcogenide ring substituents, and is soluble in at least one organic solvent. This solubility facilitates liquid-processability of the donor material, including formation of thin-films, on an unlimited scale to form planar and bulk heterojunctions in organic OPVs. These donor materials are photovoltaically active in both visible and near-IR wavelengths of light, enabling more of the solar spectrum, for example, to be applied to producing electricity. Also disclosed are methods for producing the metalated phthalocyanines and actual devices.

Spectrophotometric and spectroscopic studies of charge transfer complexes of p-toluidine as an electron donor with picric acid as an electron acceptor in different solvents

NASA Astrophysics Data System (ADS)

Singh, Neeti; Khan, Ishaat M.; Ahmad, Afaq

2010-04-01

The charge transfer complexes of the donor p-toluidine with π-acceptor picric acid have been studied spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ Go), oscillator strength ( f), transition dipole moment ( μEN), resonance energy ( RN) and ionization potential ( ID). The results indicate that the formation constant ( KCT) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used.

A simplified methylcoenzyme M methylreductase assay with artificial electron donors and different preparations of component C from Methanobacterium thermoautotrophicum delta H.

PubMed Central

Hartzell, P L; Escalante-Semerena, J C; Bobik, T A; Wolfe, R S

1988-01-01

Different preparations of the methylreductase were tested in a simplified methylcoenzyme M methylreductase assay with artificial electron donors under a nitrogen atmosphere. ATP and Mg2+ stimulated the reaction. Tris(2,2'-bipyridine)ruthenium (II), chromous chloride, chromous acetate, titanium III citrate, 2,8-diaminoacridine, formamidinesulfinic acid, cob(I)alamin (B12s), and dithiothreitol were tested as electron donors; the most effective donor was titanium III citrate. Methylreductase (component C) was prepared by 80% ammonium sulfate precipitation, 70% ammonium sulfate precipitation, phenyl-Sepharose chromatography, Mono Q column chromatography, DEAE-cellulose column chromatography, or tetrahydromethanopterin affinity column chromatography. Methylreductase preparations which were able to catalyze methanogenesis in the simplified reaction mixture contained contaminating proteins. Homogeneous component C obtained from a tetrahydromethanopterin affinity column was not active in the simplified assay but was active in a methylreductase assay that contained additional protein components. Images PMID:3372480

Insights Gained from the Dehalococcoides ethenogenes Strain 195’s Transcriptome Responding to a Wide Range of Respiration Rates and Substrate Types

DTIC Science & Technology

2012-04-01

fermented yeast , pure hydrogen, or endogenous biomass decay). When similarly respiring (~120 ?eeq PCE/(L-hr)) batch and PSS cultures were contrasted, the...electron equivalence (eeq) basis), and electron donor type (butyrate, lactate, yeast extract, fermented yeast , pure hydrogen, or endogenous biomass...acceptor ratios (0.7 to 17 on an electron equivalence (eeq) basis), and 12 electron donor type (butyrate, lactate, yeast extract, fermented yeast , pure

Stepwise Bay Annulation of Indigo for the Synthesis of Desymmetrized Electron Acceptors and Donor–Acceptor Constructs

DOE PAGES

Kolaczkowski, Matthew A.; He, Bo; Liu, Yi

2016-10-10

In this work, a selective stepwise annulation of indigo has been demonstrated as a means of providing both monoannulated and differentially double-annulated indigo derivatives. Disparate substitution of the electron accepting bay-annulated indigo system allows for fine control over both the electronic properties as well as donor-acceptor structural architectures. Optical and electronic properties were characterized computationally as well as through UV-vis absorption spectroscopy and cyclic voltammetry. Finally, this straightforward method provides a modular approach for the design of indigo-based materials with tailored optoelectronic properties.

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

PubMed

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

2018-03-28

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

Low potential manganese ions as efficient electron donors in native anoxygenic bacteria.

PubMed

Deshmukh, Sasmit S; Protheroe, Charles; Ivanescu, Matei-Alexandru; Lag, Sarah; Kálmán, László

2018-04-01

Systematic control over molecular driving forces is essential for understanding the natural electron transfer processes as well as for improving the efficiency of the artificial mimics of energy converting enzymes. Oxygen producing photosynthesis uniquely employs manganese ions as rapid electron donors. Introducing this attribute to anoxygenic photosynthesis may identify evolutionary intermediates and provide insights to the energetics of biological water oxidation. This work presents effective environmental methods that substantially and simultaneously tune the redox potentials of manganese ions and the cofactors of a photosynthetic enzyme from native anoxygenic bacteria without the necessity of genetic modification or synthesis. A spontaneous coordination with bis-tris propane lowered the redox potential of the manganese (II) to manganese (III) transition to an unusually low value (~400 mV) at pH 9.4 and allowed its binding to the bacterial reaction center. Binding to a novel buried binding site elevated the redox potential of the primary electron donor, a dimer of bacteriochlorophylls, by up to 92 mV also at pH 9.4 and facilitated the electron transfer that is able to compete with the wasteful charge recombination. These events impaired the function of the natural electron donor and made BTP-coordinated manganese a viable model for an evolutionary alternative. Copyright © 2018 Elsevier B.V. All rights reserved.

Donor states in a semimagnetic Cd1 -xinMnxin Te /Cd1 -xoutMnxout Te Double Quantum Well

NASA Astrophysics Data System (ADS)

Kalpana, Panneer Selvam; Nithiananthi, Perumal; Jayakumar, Kalyanasundaram

2017-02-01

The theoretical investigation has been carried out on the binding energy of donor associated with the electrons confined in a Cd1 -xinMnxin Te /Cd1 -xoutMnxout Te Double Quantum Well (DQW) as a function of central barrier width for various well dimensions and impurity locations in the barrier and the well. The magnetic field can act as a tool to continuously change the interwell coupling inside this DQW systems and its effect on donor binding has also been studied. Moreover, the polaronic corrections, which is due to the strong exchange interaction between the magnetic moment of Mn2+ ion and the spin of the confined carrier, to the binding energy of the hydrogenic donor impurity has also been estimated with and without the application of magnetic field. The binding energy of the donor impurity is determined by solving the Schrodinger equation variationally in the effective mass approximation and the effect due to Bound Magnetic Polaron (BMP) is included using mean field theory with the modified Brillouin function. The results are reported and discussed.

Fabrication of ordered bulk heterojunction organic photovoltaic cells using nanopatterning and electrohydrodynamic spray deposition methods.

PubMed

Park, Sung-Eun; Kim, Sehwan; Kim, Kangmin; Joe, Hang-Eun; Jung, Buyoung; Kim, Eunkyoung; Kim, Woochul; Min, Byung-Kwon; Hwang, Jungho

2012-12-21

Organic photovoltaic cells with an ordered heterojunction (OHJ) active layer are expected to show increased performance. In the study described here, OHJ cells were fabricated using a combination of nanoimprinting and electrohydrodynamic (EHD) spray deposition methods. After an electron donor material was nanoimprinted with a PDMS stamp (valley width: 230 nm, period: 590 nm) duplicated from a Si nanomold, an electron acceptor material was deposited onto the nanoimprinted donor layer using an EHD spray deposition method. The donor-acceptor interface layer was observed by obtaining cross-sectional images with a focused ion beam (FIB) microscope. The photocurrent generation performance of the OHJ cells was evaluated with the current density-voltage curve under air mass (AM) 1.5 conditions. It was found that the surface morphology of the electron acceptor layer affected the current and voltage outputs of the photovoltaic cells. When an electron acceptor layer with a smooth thin (250 nm above the valley of the electron donor layer) surface morphology was obtained, power conversion efficiency was as high as 0.55%. The electrohydrodynamic spray deposition method used to produce OHJ photovoltaic cells provides a means for the adoption of large area, high throughput processes.

Synthesis of a zinc(II) complex with hexadentate N4S2 donor thioether ligand: X-ray structure, DNA binding study and DFT computation

NASA Astrophysics Data System (ADS)

Mondal, Apurba Sau; Jana, Mahendra Sekhar; Manna, Chandan Kumar; Naskar, Rahul; Mondal, Tapan Kumar

2018-07-01

A new zinc(II) complex, [Zn(L)](ClO4) with hexadentate N4S2 donor azo-thioether ligand (HL) was synthesized and characterized by several spectroscopic techniques. The structure was confirmed by single crystal X-ray analysis. The interaction of the complex with CT DNA was investigated by UV-vis method and binding constant is found to be 6.6 × 104 M-1. Competitive binding titration with ethidium bromide (EB) by fluorescence titration method reveals that the complex efficiently displaces EB from EB-DNA system and the Stern-Volmer dynamic quenching constant, Ksv is found to be 2.6 × 104 M-1. DFT and TDDFT calculations were carried out to interpret the electronic structure and electronic spectra of the complex.

Electronic states and optical properties of single donor in GaN conical quantum dot with spherical edge

NASA Astrophysics Data System (ADS)

El Aouami, A.; Feddi, E.; El-Yadri, M.; Aghoutane, N.; Dujardin, F.; Duque, C. A.; Phuc, Huynh Vinh

2018-02-01

In this paper we present a theoretical investigation of quantum confinement effects on the electron and single donor states in GaN conical quantum dot with spherical edge. In the framework of the effective mass approximation, the Schrödinger equations of electron and donor have been solved analytically in an infinite potential barrier model. Our calculations show that the energies of electron and donor impurity are affected by the two characteristic parameters of the structure which are the angle Ω and the radial dimension R. We show that, despite the fact that the reduction of the two parameters Ω and R leads to the same confinement effects, the energy remains very sensitive to the variation of the radial part than the variation of the angular part. The analysis of the photoionization cross-section corresponding to optical transitions between the conduction band and the first donor energy level shows clearly that the reduction of the radius R causes a shift in resonance peaks towards the high energies. On the other hand, the optical transitions between 1 s - 1 p , 1 p - 1 d and 1 p - 2 s show that the increment of the conical aperture Ω (or reduction of R) implies a displacement of the excitation energy to higher energies.

Lack of a peroxiredoxin suppresses the lethality of cells devoid of electron donors by channelling electrons to oxidized ribonucleotide reductase.

PubMed

Boronat, Susanna; Domènech, Alba; Carmona, Mercè; García-Santamarina, Sarela; Bañó, M Carmen; Ayté, José; Hidalgo, Elena

2017-06-01

The thioredoxin and glutaredoxin pathways are responsible of recycling several enzymes which undergo intramolecular disulfide bond formation as part of their catalytic cycles such as the peroxide scavengers peroxiredoxins or the enzyme ribonucleotide reductase (RNR). RNR, the rate-limiting enzyme of deoxyribonucleotide synthesis, is an essential enzyme relying on these electron flow cascades for recycling. RNR is tightly regulated in a cell cycle-dependent manner at different levels, but little is known about the participation of electron donors in such regulation. Here, we show that cytosolic thioredoxins Trx1 and Trx3 are the primary electron donors for RNR in fission yeast. Unexpectedly, trx1 transcript and Trx1 protein levels are up-regulated in a G1-to-S phase-dependent manner, indicating that the supply of electron donors is also cell cycle-regulated. Indeed, genetic depletion of thioredoxins triggers a DNA replication checkpoint ruled by Rad3 and Cds1, with the final goal of up-regulating transcription of S phase genes and constitutive RNR synthesis. Regarding the thioredoxin and glutaredoxin cascades, one combination of gene deletions is synthetic lethal in fission yeast: cells lacking both thioredoxin reductase and cytosolic dithiol glutaredoxin. We have isolated a suppressor of this lethal phenotype: a mutation at the Tpx1-coding gene, leading to a frame shift and a loss-of-function of Tpx1, the main client of electron donors. We propose that in a mutant strain compromised in reducing equivalents, the absence of an abundant and competitive substrate such as the peroxiredoxin Tpx1 has been selected as a lethality suppressor to favor RNR function at the expense of the non-essential peroxide scavenging function, to allow DNA synthesis and cell growth.

Electron Donor-Acceptor Nature of the Ethanol-CO2 Dimer

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Martin-Drumel, Marie-Aline; McCarthy, Michael A.

2017-08-01

Supercritical CO2 is an appealing nontoxic, environmentally friendly solvent for the industrial extraction of many classes of compounds, from caffeine to natural product drug precursors to petrochemical impurities. Apolar in isolation, the ability of supercritical CO2 to dissolve polar species has been empirically shown to be greatly enhanced by the addition of a small molar percentage of a polar cosolvent, often ethanol. Computational work predicts that the isolated ethanol-CO2 complex can exist either in an electron-donor configuration or through a hydrogen-bonding one; yet, neither has been previously experimentally observed. Here, we demonstrate by rotational spectroscopy that the isolated, gas-phase ethanol-CO2 dimer is an electron donor-acceptor complex.

Effects of Alkylthio and Alkoxy Side Chains in Polymer Donor Materials for Organic Solar Cells.

PubMed

Cui, Chaohua; Wong, Wai-Yeung

2016-02-01

Side chains play a considerable role not only in improving the solubility of polymers for solution-processed device fabrication, but also in affecting the molecular packing, electron affinity and thus the device performance. In particular, electron-donating side chains show unique properties when employed to tune the electronic character of conjugated polymers in many cases. Therefore, rational electron-donating side chain engineering can improve the photovoltaic properties of the resulting polymer donors to some extent. Here, a survey of some representative examples which use electron-donating alkylthio and alkoxy side chains in conjugated organic polymers for polymer solar cell applications will be presented. It is envisioned that an analysis of the effect of such electron-donating side chains in polymer donors would contribute to a better understanding of this kind of side chain behavior in solution-processed conjugated organic polymers for polymer solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chromium Isotope Behaviour During Aerobic Microbial Reduction Activities

NASA Astrophysics Data System (ADS)

Zhang, Q.; Amor, K.; Porcelli, D.; Thompson, I.

2014-12-01

Microbial activity is a very important, and possibly even the dominant, reduction mechanism for many metals in natural water systems. Isotope fractionations during microbial metal reduction can reflect one major mechanism in metal cycling in the environment, and isotopic signatures can be used to identify and quantify reduction processes during biogeochemical cycling in the present environment as well as in the past. There are many Cr (VI)-reducing bacteria that have been discovered and isolated from the environment, and Cr isotopes were found to be fractionated during microbial reduction processes. In this study, Cr reduction experiments have been undertaken to determine the conditions under which Cr is reduced and the corresponding isotope signals that are generated. The experiments have been done with a facultative bacteria Pseudomonas fluorescens LB 300, and several parameters that have potential impact on reduction mechanisms have been investigated. Electron donors are important for bacteria growth and metabolism. One factor that can control the rate of Cr reduction is the nature of the electron donor. The results show that using citrate as an electron donor can stimulate bacteria reduction activity to a large extent; the reduction rate is much higher (15.10 mgˑL-1hour-1) compared with experiments using glucose (6.65 mgˑL-1ˑhour-1), acetate (4.88 mgˑL-1hour-1) or propionate (4.85 mgˑL-1hour-1) as electron donors. Groups with higher electron donor concentrations have higher reduction rates. Chromium is toxic, and when increasing Cr concentrations in the medium, the bacteria reduction rate is also higher, which reflects bacteria adapting to the toxic environment. In the natural environment, under different pH conditions, bacteria may metabolise in different ways. In our experiments with pH, bacteria performed better in reducing Cr (VI) when pH = 8, and there are no significant differences between groups with pH = 4 or pH = 6. To investigate this further, Cr isotope determinations will be presented, which are essential in better understanding bacterial reducing activities under different environmental conditions and can also provide important background information for interpreting Cr isotope fractionations in natural environment, and using Cr isotopes to identify reduction by microbial activity.

Metal-organic frameworks for adsorption and separation of noble gases

DOEpatents

Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

2017-05-30

A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

Dexter energy transfer pathways

PubMed Central

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

2016-01-01

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

Intramolecular singlet-singlet energy transfer in antenna-substituted azoalkanes.

PubMed

Pischel, Uwe; Huang, Fang; Nau, Werner M

2004-03-01

Two novel azoalkane bichromophores and related model compounds have been synthesised and photophysically characterised. Dimethylphenylsiloxy (DPSO) or dimethylnaphthylsiloxy (DNSO) serve as aromatic donor groups (antenna) and the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as the acceptor. The UV spectral window of DBO (250-300 nm) allows selective excitation of the donor. Intramolecular singlet-singlet energy transfer to DBO is highly efficient and proceeds with quantum yields of 0.76 with DPSO and 0.99 with DNSO. The photophysical and spectral properties of the bichromophoric systems suggest that energy transfer occurs through diffusional approach of the donor and acceptor within a van der Waals contact at which the exchange mechanism is presumed to dominate. Furthermore, akin to the behaviour of electron-transfer systems in the Marcus inverted region, a rate of energy transfer 2.5 times slower was observed for the system with the more favourable energetics, i.e. singlet-singlet energy transfer from DPSO proceeded slower than from DNSO, although the process is more exergonic for DPSO (-142 kJ mol(-1) for DPSO versus-67 kJ mol(-1) for DNSO).

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, R.; Calvin, M.

1984-01-24

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

Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives.

PubMed

Kurowska, Aleksandra; Zassowski, Pawel; Kostyuchenko, Anastasia S; Zheleznova, Tatyana Yu; Andryukhova, Kseniya V; Fisyuk, Alexander S; Pron, Adam; Domagala, Wojciech

2017-11-15

A structure-property study across a series of donor-acceptor-donor structures composed of mono- and bi-(1,3,4-oxadiazole) units symmetrically substituted with alkyl functionalized bi-, ter- and quaterthiophene segments is presented. Synthetically tailoring the ratio of electron-withdrawing 1,3,4-oxadiazole to electron-releasing thiophene units and their alkyl grafting pattern permitted us to scrutinize the impact of these structural factors on the redox, absorptive and emissive properties of these push-pull molecules. Contrasting trends of redox potentials were observed, with the oxidation potential closely following the donor-to-acceptor ratio, whereas the reduction potential being tuned independently by either the number of acceptor units or the conjugation length of the donor-acceptor system. Increasing the thiophene unit contribution delivered a shift from blue to green luminescence, while the structural rigidity afforded by intramolecular non-covalent interactions between 1,3,4-oxadiazole and the thiophene moieties has been identified as the prime factor determining the emission efficiency of these molecules. All six structures investigated electro-polymerize easily, yielding electroactive and electrochromic polymers. The polymer doping process is largely influenced by the length of the oligothiophene repeating unit and the alkyl chain grafting density. Polymers with relatively short oligothiophene segments are able to support polarons and polaron-pairs, whereas those with segments longer than six thiophene units could also stabilize diamagnetic charge carries - bipolarons. Increasing the alkyl chain grafting density improved the reversibility and broadened the working potential window of the p-doping process. Stable radical anions have also been investigated, bringing detailed information about the conjugation pattern of these electron-surplus species. This study delivers interesting clues towards the conscious structural design of bespoke frontier energy level oligothiophene functional materials and their polymers by incorporating a structurally matching 1,3,4-oxadiazole unit.

Identification of rhenium donors and sulfur vacancy acceptors in layered MoS{sub 2} bulk samples

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

Brandão, F. D., E-mail: fdbrand@fisica.ufmg.br; Ribeiro, G. M.; Vaz, P. H.

2016-06-21

MoS{sub 2} monolayers, a two-dimensional (2D) direct semiconductor material with an energy gap of 1.9 eV, offer many opportunities to be explored in different electronic devices. Defects often play dominant roles in the electronic and optical properties of semiconductor devices. However, little experimental information about intrinsic and extrinsic defects or impurities is available for this 2D system, and even for macroscopic 3D samples for which MoS{sub 2} shows an indirect bandgap of 1.3 eV. In this work, we evaluate the nature of impurities with unpaired spins using electron paramagnetic resonance (EPR) in different geological macroscopic samples. Regarding the fact that monolayers aremore » mostly obtained from natural crystals, we expect that the majority of impurities found in macroscopic samples are also randomly present in MoS{sub 2} monolayers. By EPR at low temperatures, rhenium donors and sulfur vacancy acceptors are identified as the main impurities in bulk MoS{sub 2} with a corresponding donor concentration of about 10{sup 8–12} defects/cm{sup 2} for MoS{sub 2} monolayer. Electrical transport experiments as a function of temperature are in good agreement with the EPR results, revealing a shallow donor state with an ionization energy of 89 meV and a concentration of 7 × 10{sup 15 }cm{sup −3}, which we attribute to rhenium, as well as a second deeper donor state with ionization energy of 241 meV with high concentration of 2 × 10{sup 19 }cm{sup −3} and net acceptor concentration of 5 × 10{sup 18 }cm{sup −3} related to sulfur vacancies.« less

Antiferromagnetic d-Electron Exchange via a Spin-Singlet π-Electron Ground State in an Organic Conductor

NASA Astrophysics Data System (ADS)

Tokumoto, T.; Brooks, J. S.; Oshima, Y.; Choi, E. S.; Brunel, L. C.; Akutsu, H.; Kaihatsu, T.; Yamada, J.; van Tol, J.

2008-04-01

Electron spin resonance reveals the spin behavior of conduction (π) and localized (d) electrons in β-(BDA-TTP)2MCl4 (M=Fe, Ga). Both the Ga3+(S=0) and Fe3+(S=5/2) compounds exhibit a metal-insulator transition at 113 K with the simultaneous formation of a spin-singlet ground state in the π electron system of the donor molecules. The behavior is consistent with charge ordering in β-(BDA-TTP)2MCl4 at the metal-insulator transition. At 5 K, the Fe3+ compound orders antiferromagnetically, even though the π electrons, which normally would facilitate magnetic exchange, are localized nonmagnetic singlets.

The Age-Related Macular Degeneration Complex: Linking Epidemiology and Histopathology Using the Minnesota Grading System (The Inaugural Frederick C. Blodi Lecture).

PubMed

Olsen, Timothy W; Bottini, Alexander R; Mendoza, Pia; Grossniklausk, Hans E

2015-09-01

To describe the histopathologic findings of the four stages of age-related macular degeneration (AMD) as defined by the Age-Related Eye Disease Study (AREDS) using the Minnesota grading system (MGS). There are no animal models for AMD. Eye banks enable access to human tissue with AMD. The level of AMD (grades 1 through 4) as defined by AREDS is determined ex vivo using the MGS. The AREDS has the largest collection to date of prospectively gathered data on the natural history of AMD. Since the MGS uses the same clinical criteria as AREDS, the addition of histopathologic findings of graded tissue confirms important pathophysiology at each stage of AMD. Four eye bank eyes were graded according to the MGS. Only the right eyes were dissected for phenotype grading. The fellow (left) eyes were fixed for histopathologic study. The eyes were serially sectioned (7 μm) through the macula. Individual slides were examined, and a two-dimensional reconstruction of the topography of the macula was created for each donor. Selected, unstained slides were used for immunohistochemical staining. In one donor, portions of tissue were obtained for transmission electron microscopic (TEM) processing. Donor 1 had a rare hard, nodular druse (MGS1). Donor 2 had intermediate confluent drusen (MGS2). Donor 3 had numerous intermediate drusen (MGS3) in the right eye. Histopathology of the fellow left showed basal laminar deposits (BLamD), soft drusen, and an area of occult choroidal neovascularization underlying the retinal pigment epithelium (RPE) with endothelial cells (CD31-positive). Donor 4 also had MGS 3 along with reticular pseudodrusen (RPD). Histologic and TEM examination demonstrated diffuse BLamD, thickening of Bruch's membrane, hard drusen, and focal nodules underlying the RPE that corresponded to the RPD. EM examination demonstrated both BLamD and electron-dense material located just external to the elastic layer of Bruch's membrane. Eye bank eyes graded using the MGS serve as an important link to the phenotypic and epidemiologic data from the AREDS. Thus, the MGS serves as a system to study the histopathology at each stage of AMD to better understand the relevant pathophysiologic changes in disease progression.

The Age-Related Macular Degeneration Complex: Linking Epidemiology and Histopathology Using the Minnesota Grading System (The Inaugural Frederick C. Blodi Lecture)

PubMed Central

Olsen, Timothy W.; Bottini, Alexander R.; Mendoza, Pia; Grossniklausk, Hans E.

2015-01-01

Purpose To describe the histopathologic findings of the four stages of age-related macular degeneration (AMD) as defined by the Age-Related Eye Disease Study (AREDS) using the Minnesota grading system (MGS). Clinical Relevance There are no animal models for AMD. Eye banks enable access to human tissue with AMD. The level of AMD (grades 1 through 4) as defined by AREDS is determined ex vivo using the MGS. The AREDS has the largest collection to date of prospectively gathered data on the natural history of AMD. Since the MGS uses the same clinical criteria as AREDS, the addition of histopathologic findings of graded tissue confirms important pathophysiology at each stage of AMD. Methods Four eye bank eyes were graded according to the MGS. Only the right eyes were dissected for phenotype grading. The fellow (left) eyes were fixed for histopathologic study. The eyes were serially sectioned (7 μm) through the macula. Individual slides were examined, and a two-dimensional reconstruction of the topography of the macula was created for each donor. Selected, unstained slides were used for immunohistochemical staining. In one donor, portions of tissue were obtained for transmission electron microscopic (TEM) processing. Results Donor 1 had a rare hard, nodular druse (MGS1). Donor 2 had intermediate confluent drusen (MGS2). Donor 3 had numerous intermediate drusen (MGS3) in the right eye. Histopathology of the fellow left showed basal laminar deposits (BLamD), soft drusen, and an area of occult choroidal neovascularization underlying the retinal pigment epithelium (RPE) with endothelial cells (CD31-positive). Donor 4 also had MGS 3 along with reticular pseudodrusen (RPD). Histologic and TEM examination demonstrated diffuse BLamD, thickening of Bruch’s membrane, hard drusen, and focal nodules underlying the RPE that corresponded to the RPD. EM examination demonstrated both BLamD and electron-dense material located just external to the elastic layer of Bruch’s membrane. Conclusion Eye bank eyes graded using the MGS serve as an important link to the phenotypic and epidemiologic data from the AREDS. Thus, the MGS serves as a system to study the histopathology at each stage of AMD to better understand the relevant pathophysiologic changes in disease progression. PMID:27895380

OXIDATION OF BIPHENYL BY A MULTICOMPONENT ENZYME SYSTEM FROM PSEUDOMONAS SP. STRAIN LB400

EPA Science Inventory

Pseudomonas sp. strain LB400 grows on biphenyl as the sole carbon and energy source. This organism also cooxidizes several chlorinated biphenyl congeners. Biphenyl dioxygenase activity in cell extract required addition of NAD(P)H as an electron donor for the conversion of bipheny...

Design principle for efficient charge separation at the donor-acceptor interface for high performance organic solar cell device

NASA Astrophysics Data System (ADS)

Nie, Wanyi; Gupta, Gautam; Crone, Brian; Wang, Hsing-Lin; Mohite, Aditya; MPA-11 Material synthesis and integrated device Team; MPA-chemistry Team

2014-03-01

The performance of donor (D) /acceptor (A) structure based organic electronic devices, such as solar cell, light emitting devices etc., relays on the charge transfer process at the interface dramatically. In organic solar cell, the photo-induced electron-hole pair is tightly bonded and will form a charge transfer (CT) state at the D/A interface after dissociation. There is a large chance for them to recombine through CT state and thus is a major loss that limit the overall performance. Here, we report three different strategies that allow us to completely suppress the exciplex (or charge transfer state) recombination between any D/A system. We observe that the photocurrent increases by 300% and the power conversion efficiency increases by 4-5 times simply by inserting a spacer layer in the form of an a) insulator b) Oliogomer or using a c) heavy atom at the donor-acceptor interface in a P3HT/C60 bilayer device. By using those different functional mono layers, we successfully suppressed the exciplex recombination in evidence of increased photocurrent and open circuit voltage. Moreover, these strategies are applicable universally to any donor-acceptor interface. And we demonstrated such strategies in a bulk-heterojunction device which improved the power conversion efficiency from 3.5% up to 4.6%.

[Potential Carbon Fixation Capability of Non-photosynthetic Microbial Community at Different Depth of the South China Sea and Its Response to Different Electron Donors].

PubMed

Fang, Feng; Wang, Lei; Xi, Xue-fei; Hu, Jia-jun; Fu, Xiao-hua; Lu, Bing; Xu, Dian-sheng

2015-05-01

The seawater samples collected from many different areas with different depth in the South China Sea were cultivated using different electron donors respectively. And the variation in the potential carbon fixation capability ( PCFC ) of non-photosynthetic microbial community (NPMC) in seawater with different depth was determined after a cycle of cultivation through the statistic analysis. In addition, the cause for the variation was clarified through analyzing key gene abundance regarding CO2 fixation and characteristics of seawater with different depth. The result showed that the PCFCs of NPMC in seawater with different depth were generally low and had no significant difference when using NaNO2 as the electron donor. The PCFC of NPMC in surface seawater was higher than that in deep seawater when using H2 as the electron donor, on the contrary, the PCFC of NPMC in deep seawater was higher than that in surface seawater when using Na2S2O3 as the electron donor. The abundance of the main CO2 fixation gene cbbL in surface seawater was higher than that in deep seawater while the cbbM gene abundance in deep seawater was higher than that in surface seawater. Most hydrogen-oxidizing bacteria had the cbbL gene, and most sulfur bacteria had the cbbM gene. The tendency of seawater cbbL/cbbM gene abundance with the change of depth revealed that there were different kinds of bacteria accounting for the majority in NPMC fixing CO2 at different depth of ocean, which led to different response of PCFC of NPMC at different depth of the sea to different electron donors. The distributions of dissolved oxygen and inorganic carbon concentration with the change of the depth of the sea might be an important reason leading to the difference of NPMC structure and even the difference of PCFC at different depth of the sea.

The donor star of the X-ray pulsar X1908+075

NASA Astrophysics Data System (ADS)

Martínez-Núñez, S.; Sander, A.; Gímenez-García, A.; Gónzalez-Galán, A.; Torrejón, J. M.; Gónzalez-Fernández, C.; Hamann, W.-R.

2015-06-01

High-mass X-ray binaries consist of a massive donor star and a compact object. While several of those systems have been well studied in X-rays, little is known for most of the donor stars as they are often heavily obscured in the optical and ultraviolet regime. There is an opportunity to observe them at infrared wavelengths, however. The goal of this study is to obtain the stellar and wind parameters of the donor star in the X1908+075 high-mass X-ray binary system with a stellar atmosphere model to check whether previous studies from X-ray observations and spectral morphology lead to a sufficient description of the donor star. We obtained H- and K-band spectra of X1908+075 and analysed them with the Potsdam Wolf-Rayet (PoWR) model atmosphere code. For the first time, we calculated a stellar atmosphere model for the donor star, whose main parameters are: Mspec = 15 ± 6 M⊙, T∗ = 23-3+6 kK, log geff = 3.0 ± 0.2 and log L/L⊙ = 4.81 ± 0.25. The obtained parameters point towards an early B-type (B0-B3) star, probably in a supergiant phase. Moreover we determined a more accurate distance to the system of 4.85 ± 0.50 kpc than the previously reported value. Based on observations made with the William Herschel Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofísica de Canarias.Appendix A is available in electronic form at http://www.aanda.org

Radio frequency reflectometry and charge sensing of a precision placed donor in silicon

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

Hile, Samuel J., E-mail: samhile@gmail.com; House, Matthew G.; Peretz, Eldad

2015-08-31

We compare charge transitions on a deterministic single P donor in silicon using radio frequency reflectometry measurements with a tunnel coupled reservoir and DC charge sensing using a capacitively coupled single electron transistor (SET). By measuring the conductance through the SET and comparing this with the phase shift of the reflected radio frequency (RF) excitation from the reservoir, we can discriminate between charge transfer within the SET channel and tunneling between the donor and reservoir. The RF measurement allows observation of donor electron transitions at every charge degeneracy point in contrast to the SET conductance signal where charge transitions aremore » only observed at triple points. The tunnel coupled reservoir has the advantage of a large effective lever arm (∼35%), allowing us to independently extract a neutral donor charging energy ∼62 ± 17 meV. These results demonstrate that we can replace three terminal transistors by a single terminal dispersive reservoir, promising for high bandwidth scalable donor control and readout.« less

Surface code architecture for donors and dots in silicon with imprecise and nonuniform qubit couplings

DOE PAGES

Pica, G.; Lovett, B. W.; Bhatt, R. N.; ...

2016-01-14

A scaled quantum computer with donor spins in silicon would benefit from a viable semiconductor framework and a strong inherent decoupling of the qubits from the noisy environment. Coupling neighboring spins via the natural exchange interaction according to current designs requires gate control structures with extremely small length scales. In this work, we present a silicon architecture where bismuth donors with long coherence times are coupled to electrons that can shuttle between adjacent quantum dots, thus relaxing the pitch requirements and allowing space between donors for classical control devices. An adiabatic SWAP operation within each donor/dot pair solves the scalabilitymore » issues intrinsic to exchange-based two-qubit gates, as it does not rely on subnanometer precision in donor placement and is robust against noise in the control fields. In conclusion, we use this SWAP together with well established global microwave Rabi pulses and parallel electron shuttling to construct a surface code that needs minimal, feasible local control.« less

Creating Graphitic Carbon Nitride Based Donor-π-Acceptor-π-Donor Structured Catalysts for Highly Photocatalytic Hydrogen Evolution.

PubMed

Li, Kui; Zhang, Wei-De

2018-03-01

Conjugated polymers with tailored donor-acceptor units have recently attracted considerable attention in organic photovoltaic devices due to the controlled optical bandgap and retained favorable separation of charge carriers. Inspired by these advantages, an effective strategy is presented to solve the main obstructions of graphitic carbon nitride (g-C 3 N 4 ) photocatalyst for solar energy conversion, that is, inefficient visible light response and insufficient separation of photogenerated electrons and holes. Donor-π-acceptor-π-donor polymers are prepared by incorporating 4,4'-(benzoc 1,2,5 thiadiazole-4,7-diyl) dianiline (BD) into the g-C 3 N 4 framework (UCN-BD). Benefiting from the visible light band tail caused by the extended π conjugation, UCN-BD possesses expanded visible light absorption range. More importantly, the BD monomer also acts as an electron acceptor, which endows UCN-BD with a high degree of intramolecular charge transfer. With this unique molecular structure, the optimized UCN-BD sample exhibits a superior performance for photocatalytic hydrogen evolution upon visible light illumination (3428 µmol h -1 g -1 ), which is nearly six times of that of the pristine g-C 3 N 4 . In addition, the photocatalytic property remains stable for six cycles in 3 d. This work provides an insight into the synthesis of g-C 3 N 4 -based D-π-A-π-D systems with highly visible light response and long lifetime of intramolecular charge carriers for solar fuel production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge-transfer excitons at organic semiconductor surfaces and interfaces.

PubMed

Zhu, X-Y; Yang, Q; Muntwiler, M

2009-11-17

When a material of low dielectric constant is excited electronically from the absorption of a photon, the Coulomb attraction between the excited electron and the hole gives rise to an atomic H-like quasi-particle called an exciton. The bound electron-hole pair also forms across a material interface, such as the donor/acceptor interface in an organic heterojunction solar cell; the result is a charge-transfer (CT) exciton. On the basis of typical dielectric constants of organic semiconductors and the sizes of conjugated molecules, one can estimate that the binding energy of a CT exciton across a donor/acceptor interface is 1 order of magnitude greater than k(B)T at room temperature (k(B) is the Boltzmann constant and T is the temperature). How can the electron-hole pair escape this Coulomb trap in a successful photovoltaic device? To answer this question, we use a crystalline pentacene thin film as a model system and the ubiquitous image band on the surface as the electron acceptor. We observe, in time-resolved two-photon photoemission, a series of CT excitons with binding energies < or = 0.5 eV below the image band minimum. These CT excitons are essential solutions to the atomic H-like Schrodinger equation with cylindrical symmetry. They are characterized by principal and angular momentum quantum numbers. The binding energy of the lowest lying CT exciton with 1s character is more than 1 order of magnitude higher than k(B)T at room temperature. The CT(1s) exciton is essentially the so-called exciplex and has a very low probability of dissociation. We conclude that hot CT exciton states must be involved in charge separation in organic heterojunction solar cells because (1) in comparison to CT(1s), hot CT excitons are more weakly bound by the Coulomb potential and more easily dissociated, (2) density-of-states of these hot excitons increase with energy in the Coulomb potential, and (3) electronic coupling from a donor exciton to a hot CT exciton across the D/A interface can be higher than that to CT(1s) as expected from energy resonance arguments. We suggest a design principle in organic heterojunction solar cells: there must be strong electronic coupling between molecular excitons in the donor and hot CT excitons across the D/A interface.

Synthesis and photophysical properties of new catenated electron donor-acceptor materials with magnesium and free base porphyrins as donors and C60 as the acceptor

NASA Astrophysics Data System (ADS)

Kirner, Sabrina V.; Guldi, Dirk M.; Megiatto, Jackson D., Jr.; Schuster, David I.

2014-12-01

A new series of nanoscale electron donor-acceptor systems with [2]catenane architectures has been synthesized, incorporating magnesium porphyrin (MgP) or free base porphyrin (H2P) as electron donor and C60 as electron acceptor, surrounding a central tetrahedral Cu(i)-1,10-phenanthroline (phen) complex. Model catenated compounds incorporating only one or none of these photoactive moieties were also prepared. The synthesis involved the use of Sauvage's metal template protocol in combination with the 1,3-dipolar cycloaddition of azides and alkynes (``click chemistry''), as in other recent reports from our laboratories. Ground state electron interactions between the individual constituents was probed using electrochemistry and UV-vis absorption spectroscopy, while events occurring following photoexcitation in tetrahydrofuran (under both aerobic and anaerobic conditions) at various wavelengths were followed by means of time-resolved transient absorption and emission spectroscopies on the femtosecond and nanosecond time scales, respectively, complemented by measurements of quantum yields for generation of singlet oxygen. From similar studies with model catenates containing one or neither of the chromophores, the events following photoexcitation could be elucidated. The results were compared with those previously reported for analogous catenates based on zinc porphyrin (ZnP). It was determined that a series of energy transfer (EnT) and electron transfer (ET) processes take place in the present catenates, ultimately generating long-distance charge separated (CS) states involving oxidized porphyrin and reduced C60 moieties, with lifetimes ranging from 400 to 1060 nanoseconds. Shorter lived short-distance CS states possessing oxidized copper complexes and reduced C60, with lifetimes ranging from 15 to 60 ns, were formed en route to the long-distance CS states. The dynamics of the ET processes were analyzed in terms of their thermodynamic driving forces. It was clear that intramolecular back ET was occurring in the inverted region of the Marcus parabola correlating rates and driving forces for electron transfer processes. In addition, evidence for triplet excited states as a product of either incomplete ET or back ET was found. The differences in behavior of the three catenates upon photoexcitation are analyzed in terms of the energy levels of the various intermediate states and the driving forces for EnT and ET processes.

Donor-bridge-acceptor energetics determine the distance dependence of electron tunneling in DNA

NASA Astrophysics Data System (ADS)

Lewis, Frederick D.; Liu, Jianqin; Weigel, Wilfried; Rettig, Wolfgang; Kurnikov, Igor V.; Beratan, David N.

2002-10-01

Electron transfer (ET) processes in DNA are of current interest because of their involvement in oxidative strand cleavage reactions and their relevance to the development of molecular electronics. Two mechanisms have been identified for ET in DNA, a single-step tunneling process and a multistep charge-hopping process. The dynamics of tunneling reactions depend on both the distance between the electron donor and acceptor and the nature of the molecular bridge separating the donor and acceptor. In the case of protein and alkane bridges, the distance dependence is not strongly dependent on the properties of the donor and acceptor. In contrast, we show here that the distance decay of DNA ET rates varies markedly with the energetics of the donor and acceptor relative to the bridge. Specifically, we find that an increase in the energy of the bridge states by 0.25 eV (1 eV = 1.602 × 1019 J) relative to the donor and acceptor energies for photochemical oxidation of nucleotides, without changing the reaction free energy, results in an increase in the characteristic exponential distance decay constant for the ET rates from 0.71 to 1.1 Å1. These results show that, in the small tunneling energy gap regime of DNA ET, the distance dependence is not universal; it varies strongly with the tunneling energy gap. These DNA ET reactions fill a "missing link" or transition regime between the large barrier (rapidly decaying) tunneling regime and the (slowly decaying) hopping regime in the general theory of bridge-mediated ET processes.

IR and TPD studies of the interaction of alkenes with Cu + sites in CuNaY and CuNaX zeolites of various Cu content. The heterogeneity of Cu + sites

NASA Astrophysics Data System (ADS)

Datka, J.; Kukulska-Zajaç, E.; Kozyra, P.

2006-08-01

Cu + ions in zeolites activate organic molecules containing π electrons by π back donation, which results in a distinct weakening of multiple bonds. In this study, we followed the activation of alkenes (ethene and propene) by Cu + ions in CuY and CuX zeolites of various Cu content. We also studied the strength of bonding of alkenes to Cu + ions. IR studies have shown that there are two kinds of Cu + sites of various electron donor properties. We suppose that they could be attributed to the presence of Cu + ions of various number of oxygen atoms surrounding the cation. IR studies have shown that Cu ions introduced into Y and X zeolites in the first-order (at low Cu content) form Cu + ions of stronger electron donor properties (i.e. activate alkenes to larger extend) than Cu ions introduced in the next order (at higher Cu content). IR and TPD studies of alkenes desorption evidenced that Cu + ions of stronger electron donor properties bond alkenes stronger than less electron donor ones. It suggests that π back donation has more important contribution to the strength of bonding alkenes to cation than π donation.

Resonance Raman study of a two-chromophore system. The 2:1 complex of hexamethylbenzene with tetracyanoethylene

NASA Astrophysics Data System (ADS)

Mark Britt, B.; McHale, Jeanne L.

1997-05-01

Raman excitation profiles are presented for the 2:1 electron donor-acceptor (EDA) complex of hexamethylbenzene (HMB) and tetracyanoethylene (TCNE) in cyclohexane. Though the absorption and Raman spectra of the 1:1 and 2:1 complexes are similar, distinct differences are found in the Raman excitation profiles (REPs) of vibrational modes common to both systems. REPs of the 2:1 complex show intensity cancellation that is taken as evidence for interference of two charge-transfer excited states. The implications of the observed spectra concerning excited state electron delocalization are considered.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, Roland; Calvin, Melvin

1984-01-01

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

Tracking Hole Transport in DNA Hairpins Using a Phenylethynylguanine Nucleobase.

PubMed

Brown, Kristen E; Singh, Arunoday P N; Wu, Yi-Lin; Mishra, Ashutosh Kumar; Zhou, Jiawang; Lewis, Frederick D; Young, Ryan M; Wasielewski, Michael R

2017-08-30

The hole transport dynamics of DNA hairpins possessing a stilbene electron acceptor and donor along with a modified guanine (G) nucleobase, specifically 8-(4'-phenylethynyl)deoxyguanosine, or EG, have been investigated. The nearly indistinguishable oxidation potentials of EG and G and unique spectroscopic characteristics of EG +• make it well-suited for directly observing transient hole occupation during charge transport between a stilbene electron donor and acceptor. In contrast to the cation radical G +• , EG +• possesses a strong absorption near 460 nm and has a distinct Raman-active ethynyl stretch. Both spectroscopic characteristics are easily distinguished from those of the stilbene donor/acceptor radical ion chromophores. Employing EG, we observe its role as a shallow hole trap, or as an intermediate hole transport site when a deeper trap state is present. Using a combination of ultrafast absorption and stimulated Raman spectroscopies, the hole-transport dynamics are observed to be similar in systems having EG vs G bases, with small perturbations to the charge transport rates and yields. These results show EG can be deployed at specified locations throughout the sequence to report on hole occupancy, thereby enabling detailed monitoring of the hole transport dynamics with base-site specificity.

Kinetics of sulfate and hydrogen uptake by the thermophilic sulfate-reducing bacteria Thermodesulfobacterium sp. strain JSP and Thermodesulfovibrio sp. strain R1Ha3

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

Sonne-Hansen, J.; Ahring, B.K.; Westermann, P.

1999-03-01

Dissimilatory sulfate reduction and methanogenesis are the main terminal processes in the anaerobic food chain. Both the sulfate-reducing bacteria (SRB) and the methane-producing archaea (MPA) use acetate and hydrogen as substrates and, therefore, compete for common electron donors in sulfate-containing natural environments. Due to a higher affinity for the electron donors acetate and hydrogen, SRB outcompete MPA for these compounds whenever sulfate is present in sufficient concentrations. Half-saturation constants (K{sub m}), maximum uptake rates (V{sub max}), and threshold concentrations for sulfate and hydrogen were determined for two thermophilic sulfate-reducing bacteria (SRB) in an incubation system without headspace. K{sub m} valuesmore » determined for the thermophilic SRB were similar to the constants described for mesophilic SRB isolated from environments with low sulfate concentrations.« less

Inhomogeneous nuclear spin polarization induced by helicity-modulated optical excitation of fluorine-bound electron spins in ZnSe

NASA Astrophysics Data System (ADS)

Heisterkamp, F.; Greilich, A.; Zhukov, E. A.; Kirstein, E.; Kazimierczuk, T.; Korenev, V. L.; Yugova, I. A.; Yakovlev, D. R.; Pawlis, A.; Bayer, M.

2015-12-01

Optically induced nuclear spin polarization in a fluorine-doped ZnSe epilayer is studied by time-resolved Kerr rotation using resonant excitation of donor-bound excitons. Excitation with helicity-modulated laser pulses results in a transverse nuclear spin polarization, which is detected as a change of the Larmor precession frequency of the donor-bound electron spins. The frequency shift in dependence on the transverse magnetic field exhibits a pronounced dispersion-like shape with resonances at the fields of nuclear magnetic resonance of the constituent zinc and selenium isotopes. It is studied as a function of external parameters, particularly of constant and radio frequency external magnetic fields. The width of the resonance and its shape indicate a strong spatial inhomogeneity of the nuclear spin polarization in the vicinity of a fluorine donor. A mechanism of optically induced nuclear spin polarization is suggested based on the concept of resonant nuclear spin cooling driven by the inhomogeneous Knight field of the donor-bound electron.

Radio frequency measurements of tunnel couplings and singlet–triplet spin states in Si:P quantum dots

PubMed Central

House, M. G.; Kobayashi, T.; Weber, B.; Hile, S. J.; Watson, T. F.; van der Heijden, J.; Rogge, S.; Simmons, M. Y.

2015-01-01

Spin states of the electrons and nuclei of phosphorus donors in silicon are strong candidates for quantum information processing applications given their excellent coherence times. Designing a scalable donor-based quantum computer will require both knowledge of the relationship between device geometry and electron tunnel couplings, and a spin readout strategy that uses minimal physical space in the device. Here we use radio frequency reflectometry to measure singlet–triplet states of a few-donor Si:P double quantum dot and demonstrate that the exchange energy can be tuned by at least two orders of magnitude, from 20 μeV to 8 meV. We measure dot–lead tunnel rates by analysis of the reflected signal and show that they change from 100 MHz to 22 GHz as the number of electrons on a quantum dot is increased from 1 to 4. These techniques present an approach for characterizing, operating and engineering scalable qubit devices based on donors in silicon. PMID:26548556

Charge transfer complex studies between some non-steroidal anti-inflammatory drugs and π-electron acceptors

NASA Astrophysics Data System (ADS)

Duymus, Hulya; Arslan, Mustafa; Kucukislamoglu, Mustafa; Zengin, Mustafa

2006-12-01

Charge transfer (CT) complexes of some non-steroidal anti-inflammatory drugs, naproxen and etodolac which are electron donors with some π-acceptors, such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL), have been investigated spectrophotometrically in chloroform at 21 °C. The coloured products are measured spectrophotometrically at different wavelength depending on the electronic transition between donors and acceptors. Beer's law is obeyed and colours were produced in non-aqueous media. All complexes were stable at least 2 h except for etodolac with DDQ stable for 5 min. The equilibrium constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters Δ H, Δ S, Δ G° were calculated by Van't Hoff equation. Stochiometries of the complexes formed between donors and acceptors were defined by the Job's method of the continuous variation and found in 1:1 complexation with donor and acceptor at the maximum absorption bands in all cases.

Donor defects and small polarons on the TiO{sub 2}(110) surface

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

Moses, P. G.; Janotti, A., E-mail: janotti@udel.edu; Van de Walle, C. G.

2016-05-14

The role of defects in the chemical activity of the rutile TiO{sub 2}(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend tomore » localize in the form of small polarons, which are the factual cause of the deep states ∼1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO{sub 2} and related oxides.« less

Spectrophotometric and spectroscopic studies of charge transfer complexes of p-toluidine as an electron donor with picric acid as an electron acceptor in different solvents.

PubMed

Singh, Neeti; Khan, Ishaat M; Ahmad, Afaq

2010-04-01

The charge transfer complexes of the donor p-toluidine with pi-acceptor picric acid have been studied spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (K(CT)), molar extinction coefficient (epsilon(CT)), standard free energy (DeltaG(o)), oscillator strength (f), transition dipole moment (mu(EN)), resonance energy (R(N)) and ionization potential (I(D)). The results indicate that the formation constant (K(CT)) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used. Copyright 2010 Elsevier B.V. All rights reserved.

Comparison of lactate, formate, and propionate as hydrogen donors for the reductive dehalogenation of trichloroethene in a continuous-flow column.

PubMed

Azizian, Mohammad F; Marshall, Ian P G; Behrens, Sebastian; Spormann, Alfred M; Semprini, Lewis

2010-04-01

A continuous-flow column study was conducted to analyze the reductive dehalogenation of trichloroethene (TCE) with aquifer material with high content of iron oxides. The column was bioaugmented with the Point Mugu (PM) culture, which is a mixed microbial enrichment culture capable of completely transforming TCE to ethene (ETH). We determined whether lactate, formate, or propionate fermentation resulted in more effective dehalogenation. Reductive dehalogenation, fermentation, and sulfate, Fe(III), and Mn(IV) reduction were all exhibited within the column. Different steady-states of dehalogenation were achieved based on the concentration of substrates added, with effective transformation to ETH obtained when ample electron donor equivalents were provided. Most of the metabolic reducing equivalents were channeled to sulfate, Fe(III), and Mn(IV) reduction. When similar electron reducing equivalents were added, the most effective dehalogenation was achieved with formate, with 14% of the electron equivalents going towards dehalogenation reactions, compared to 6.5% for lactate and 9.6% for propionate. Effective dehalogenation was maintained over 1000 days of column operation. Over 90% of electron equivalents added could be accounted for by the different electron accepting processes in the column, with 50% associated with soluble and precipitated Fe(II) and Mn(II). Bulk Fe(III) and Mn(IV) reduction was rather associated with lactate and propionate addition than formate addition. Sulfate reduction was a competing electron acceptor reaction with all three electron donors. DNA was extracted from solid coupon samples obtained during the course of the experiment and analyzed using 16S rRNA gene clone libraries and quantitative PCR. Lactate and propionate addition resulted in a significant increase in Geobacter, Spirochaetes, and Desulfitobacterium phylotypes relative to "Dehalococcoides" when compared to formate addition. Results from the molecular biological analyses support chemical observations that a greater percentage of the electron donor addition was channeled to Fe(III) reduction when lactate and propionate were added compared to formate, and formate was more effective than lactate in supporting dehalogenation. The results demonstrate the importance of electron donor selection and competing electron acceptor reactions when implementing reductive dehalogenation remediation technologies. Published by Elsevier B.V.

Comparison of lactate, formate, and propionate as hydrogen donors for the reductive dehalogenation of trichloroethene in a continuous-flow column

NASA Astrophysics Data System (ADS)

Azizian, Mohammad F.; Marshall, Ian P. G.; Behrens, Sebastian; Spormann, Alfred M.; Semprini, Lewis

2010-04-01

A continuous-flow column study was conducted to analyze the reductive dehalogenation of trichloroethene (TCE) with aquifer material with high content of iron oxides. The column was bioaugmented with the Point Mugu (PM) culture, which is a mixed microbial enrichment culture capable of completely transforming TCE to ethene (ETH). We determined whether lactate, formate, or propionate fermentation resulted in more effective dehalogenation. Reductive dehalogenation, fermentation, and sulfate, Fe(III), and Mn(IV) reduction were all exhibited within the column. Different steady-states of dehalogenation were achieved based on the concentration of substrates added, with effective transformation to ETH obtained when ample electron donor equivalents were provided. Most of the metabolic reducing equivalents were channeled to sulfate, Fe(III), and Mn(IV) reduction. When similar electron reducing equivalents were added, the most effective dehalogenation was achieved with formate, with 14% of the electron equivalents going towards dehalogenation reactions, compared to 6.5% for lactate and 9.6% for propionate. Effective dehalogenation was maintained over 1000 days of column operation. Over 90% of electron equivalents added could be accounted for by the different electron accepting processes in the column, with 50% associated with soluble and precipitated Fe(II) and Mn(II). Bulk Fe(III) and Mn(IV) reduction was rather associated with lactate and propionate addition than formate addition. Sulfate reduction was a competing electron acceptor reaction with all three electron donors. DNA was extracted from solid coupon samples obtained during the course of the experiment and analyzed using 16S rRNA gene clone libraries and quantitative PCR. Lactate and propionate addition resulted in a significant increase in Geobacter, Spirochaetes, and Desulfitobacterium phylotypes relative to " Dehalococcoides" when compared to formate addition. Results from the molecular biological analyses support chemical observations that a greater percentage of the electron donor addition was channeled to Fe(III) reduction when lactate and propionate were added compared to formate, and formate was more effective than lactate in supporting dehalogenation. The results demonstrate the importance of electron donor selection and competing electron acceptor reactions when implementing reductive dehalogenation remediation technologies.

Enhanced dimethyl phthalate biodegradation by accelerating phthalic acid di-oxygenation.

PubMed

Tang, Yingxia; Zhang, Yongming; Jiang, Ling; Yang, Chao; Rittmann, Bruce E

2017-12-01

The aerobic biodegradation of dimethyl phthalate (DMP) is initiated with two hydrolysis reactions that generate an intermediate, phthalic acid (PA), that is further biodegraded through a two-step di-oxygenation reaction. DMP biodegradation is inhibited when PA accumulates, but DMP's biodegradation can be enhanced by adding an exogenous electron donor. We evaluated the effect of adding succinate, acetate, or formate as an exogenous electron donor. PA removal rates were increased by 15 and 30% for initial PA concentrations of 0.3 and 0.6 mM when 0.15 and 0.30 mM succinate, respectively, were added as exogenous electron donor. The same electron-equivalent additions of acetate and formate had the same acceleration impacts on PA removal. Consequently, the DMP-removal rate, even PA coexisting with DMP simultaneously, was accelerated by 37% by simultaneous addition of 0.3 mM succinate. Thus, lowering the accumulation of PA by addition of an electron increased the rate of DMP biodegradation.

High-Efficiency Nonfullerene Polymer Solar Cell Enabling by Integration of Film-Morphology Optimization, Donor Selection, and Interfacial Engineering.

PubMed

Zhang, Xin; Li, Weiping; Yao, Jiannian; Zhan, Chuanlang

2016-06-22

Carrier mobility is a vital factor determining the electrical performance of organic solar cells. In this paper we report that a high-efficiency nonfullerene organic solar cell (NF-OSC) with a power conversion efficiency of 6.94 ± 0.27% was obtained by optimizing the hole and electron transportations via following judicious selection of polymer donor and engineering of film-morphology and cathode interlayers: (1) a combination of solvent annealing and solvent vapor annealing optimizes the film morphology and hence both hole and electron mobilities, leading to a trade-off of fill factor and short-circuit current density (Jsc); (2) the judicious selection of polymer donor affords a higher hole and electron mobility, giving a higher Jsc; and (3) engineering the cathode interlayer affords a higher electron mobility, which leads to a significant increase in electrical current generation and ultimately the power conversion efficiency (PCE).

Enhanced Efficiency in Fullerene-Free Polymer Solar Cell by Incorporating Fine-designed Donor and Acceptor Materials.

PubMed

Ye, Long; Sun, Kai; Jiang, Wei; Zhang, Shaoqing; Zhao, Wenchao; Yao, Huifeng; Wang, Zhaohui; Hou, Jianhui

2015-05-06

Among the diverse nonfullerene acceptors, perylene bisimides (PBIs) have been attracting much attention due to their excellent electron mobility and tunable molecular and electronic properties by simply engineering the bay and head linkages. Herein, guided by two efficient small molecular acceptors, we designed, synthesized, and characterized a new nonfullerene small molecule PPDI with fine-tailored alkyl chains. Notably, a certificated PCE of 5.40% is realized in a simple structured fullerene-free polymer solar cell comprising PPDI as the electron acceptor and a fine-tailored 2D-conjugated polymer PBDT-TS1 as the electron donor. Moreover, the device behavior, morphological feature, and origin of high efficiency in PBDT-TS1/PPDI-based fullerene-free PSC were investigated. The synchronous selection and design of donor and acceptor materials reported here offer a feasible strategy for realizing highly efficient fullerene-free organic photovoltaics.

Electrical Manipulation of Donor Spin Qubits in Silicon and Germanium

NASA Astrophysics Data System (ADS)

Sigillito, Anthony James

Many proposals for quantum information devices rely on electronic or nuclear spins in semiconductors because of their long coherence times and compatibility with industrial fabrication processes. One of the most notable qubits is the electron spin bound to phosphorus donors in silicon, which offers coherence times exceeding seconds at low temperatures. These donors are naturally isolated from their environments to the extent that silicon has been coined a "semiconductor vacuum". While this makes for ultra-coherent qubits, it is difficult to couple two remote donors so quantum information proposals rely on high density arrays of qubits. Here, single qubit addressability becomes an issue. Ideally one would address individual qubits using electric fields which can be easily confined. Typically these schemes rely on tuning a donor spin qubit onto and off of resonance with a magnetic driving field. In this thesis, we measure the electrical tunability of phosphorus donors in silicon and use the extracted parameters to estimate the effects of electric-field noise on qubit coherence times. Our measurements show that donor ionization may set in before electron spins can be sufficiently tuned. We therefore explore two alternative options for qubit addressability. First, we demonstrate that nuclear spin qubits can be directly driven using electric fields instead of magnetic fields and show that this approach offers several advantages over magnetically driven spin resonance. In particular, spin transitions can occur at half the spin resonance frequency and double quantum transitions (magnetic-dipole forbidden) can occur. In a second approach to realizing tunable qubits in semiconductors, we explore the option of replacing silicon with germanium. We first measure the coherence and relaxation times for shallow donor spin qubits in natural and isotopically enriched germanium. We find that in isotopically enriched material, coherence times can exceed 1 ms and are limited by a single-phonon T1 process. At lower frequencies or lower temperatures the qubit coherence times should substantially increase. Finally, we measure the electric field tunability of donors in germanium and find a four order-of-magnitude enhancement in the spin-orbit Stark shift and confirm that the donors should be tunable by at least 4 times the electron spin ensemble linewidth (in isotopically enriched material). Germanium should therefore also be more sensitive to electrically driven nuclear magnetic resonance. Based on these results germanium is a promising alternative to silicon for spin qubits.

C–H arylation of unsubstituted furan and thiophene with acceptor bromides: access to donor–acceptor–donor-type building blocks for organic electronics.

PubMed

Matsidik, Rukiya; Martin, Johannes; Schmidt, Simon; Obermayer, Johannes; Lombeck, Florian; Nübling, Fritz; Komber, Hartmut; Fazzi, Daniele; Sommer, Michael

2015-01-16

Pd-catalyzed direct arylation (DA) reaction conditions have been established for unsubstituted furan (Fu) and thiophene (Th) with three popular acceptor building blocks to be used in materials for organic electronics, namely 4,7-dibromo-2,1,3-benzothiadiazole (BTBr2), N,N′-dialkylated 2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide) (NDIBr2), and 1,4-dibromotetrafluorobenzene (F4Br2). Reactions with BTBr2, F4Br2, and NDIBr2 require different solvents to obtain high yields. The use of dimethylacetamide (DMAc) is essential for the successful coupling of BTBr2 and F4Br2, but detrimental for NDIBr2, as the electron-deficient NDI core is prone to nucleophilic core substitution in DMAc as solvent but not in toluene. NDIFu2 is much more planar compared to NDITh2, resulting in an enhanced charge-transfer character, which makes it an interesting building block for conjugated systems designed for organic electronics. This study highlights direct arylation as a simple and inexpensive method to construct a series of important donor–acceptor–donor building blocks to be further used for the preparation of a variety of conjugated materials.

Properties of natural and synthetic hydroxyapatite and their surface free energy determined by the thin-layer wicking method

NASA Astrophysics Data System (ADS)

Szcześ, Aleksandra; Yan, Yingdi; Chibowski, Emil; Hołysz, Lucyna; Banach, Marcin

2018-03-01

Surface free energy is one of the parameters accompanying interfacial phenomena, occurring also in the biological systems. In this study the thin layer wicking method was used to determine surface free energy and its components for synthetic hydroxyapatite (HA) and natural one obtained from pig bones. The Raman, FTIR and X-Ray photoelectron spectroscopy, X-ray diffraction techniques and thermal analysis showed that both samples consist of carbonated hydroxyapatite without any organic components. Surface free energy and its apolar and polar components were found to be similar for both investigated samples and equalled γSTOT = 52.4 mJ/m2, γSLW = 40.2 mJ/m2 and γSAB = 12.3 mJ/m2 for the synthetic HA and γSTOT = 54.6 mJ/m2, γSLW = 40.3 mJ/m2 and γSAB = 14.3 mJ/m2 for the natural one. Both HA samples had different electron acceptor (γs+) and electron donor (γs-) parameters. The higher value of the electron acceptor was found for the natural HA whereas the electron donor one was higher for the synthetic HA

Influence of the Terminal Electron Donor in D-D-π-A Organic Dye-Sensitized Solar Cells: Dithieno[3,2-b:2',3'-d]pyrrole versus Bis(amine).

PubMed

Dai, Panpan; Yang, Lin; Liang, Mao; Dong, Huanhuan; Wang, Peng; Zhang, Chunyao; Sun, Zhe; Xue, Song

2015-10-14

With respect to the electron-withdrawing acceptors of D-A-π-A organic dyes, reports on the second electron-donating donors for D-D-π-A organic dyes are very limited. Both of the dyes have attracted significant attention in the field of dye-sensitized solar cells (DSCs). In this work, four new D-D-π-A organic dyes with dithieno[3,2-b:2',3'-d]pyrrole (DTP) or bis(amine) donor have been designed and synthesized for a investigation of the influence of the terminal electron donor in D-D-π-A organic dye-sensitized solar cells. It is found that DTP is a promising building block as the terminal electron donor when introduced in the dithiophenepyrrole direction, but not just a good bridge, which exhibits several characteristics: (i) efficiently increasing the maximum molar absorption coefficient and extending the absorption bands; (ii) showing stronger charge transfer interaction as compared with the pyrrole direction; (iii) beneficial to photocurrent generation of DSCs employing cobalt electrolytes. DSCs based on M45 with the Co-phen electrolyte exhibit good light-to-electric energy conversion efficiencies as high as 9.02%, with a short circuit current density (JSC) of 15.3 mA cm(-2), open circuit voltage (VOC) of 867 mV and fill factor (FF) of 0.68 under AM 1.5 illumination (100 mW cm(-2)). The results demonstrate that N,S-heterocycles such as DTP unit could be promising candidates for application in highly efficient DSCs employing cobalt electrolyte.

Photoluminescence Study of N-Type Thermal Conversion in Semi-Insulating GaAs.

DTIC Science & Technology

1982-12-01

free electron to the crystal. For example, in GaAs, a tellurium atom on an arsenic site (TeAs) or a silicon atom on a gallium site (SiGa) are donor atoms...Photoconductivity Photoluminescenc Silicon, SiGa 5.81 6.80 Germanium, GeGa 6.08 Sulfur, SAs 6.10 Selenium, SeAs 5.89 6.10 Tellurium , TeAs When an electron...34 to the neutral donor or acceptor (Ref 16:15). The following excitonic com- plexes have been observed in GaAs: (i) exciton bound to a neutron donor at

Synthesis and Characterization of Organic Dyes Containing Various Donors and Acceptors

PubMed Central

Wu, Tzi-Yi; Tsao, Ming-Hsiu; Chen, Fu-Lin; Su, Shyh-Gang; Chang, Cheng-Wen; Wang, Hong-Paul; Lin, Yuan-Chung; Ou-Yang, Wen-Chung; Sun, I-Wen

2010-01-01

New organic dyes comprising carbazole, iminodibenzyl, or phenothiazine moieties, respectively, as the electron donors, and cyanoacetic acid or acrylic acid moieties as the electron acceptors/anchoring groups were synthesized and characterized. The influence of heteroatoms on carbazole, iminodibenzyl and phenothiazine donors, and cyano-substitution on the acid acceptor is evidenced by spectral, electrochemical, photovoltaic experiments, and density functional theory calculations. The phenothiazine dyes show solar-energy-to-electricity conversion efficiency (η) of 3.46–5.53%, whereas carbazole and iminodibenzyl dyes show η of 2.43% and 3.49%, respectively. PMID:20162019

Electron Bifurcation: Thermodynamics and Kinetics of Two-Electron Brokering in Biological Redox Chemistry

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

Zhang, Peng; Yuly, Jonathon L.; Lubner, Carolyn E.

How can proteins drive two electrons from a redox active donor onto two acceptors at very different potentials and distances? And how can this transaction be conducted without dissipating very much energy or violating the laws of thermodynamics? Nature appears to have addressed these challenges by coupling thermodynamically uphill and downhill electron transfer reactions, using two-electron donor cofactors that have very different potentials for the removal of the first and second electron. Although electron bifurcation is carried out with near perfection from the standpoint of energy conservation and electron delivery yields, it is a biological energy transduction paradigm that hasmore » only come into focus recently. This Account provides an exegesis of the biophysical principles that underpin electron bifurcation.« less

Development of Medical Technology for Contingency Response to Marrow Toxic Agents

DTIC Science & Technology

2012-07-26

Confirmatory Testing DC Donor Center DIY Do it yourself DNA Deoxyribonucleic Acid DoD Department of Defense D/R Donor/Recipient EBMT European Group...recruitment support (Search screen redesign, New Donor Notes, HHQ enhancements, Site Maintenance redesign, Communications History, DIY ). National...Web and Do It Yourself ( DIY ) This project enables the ability to electronically contact the donors via email and allow them to update their contact

Catalytic Role Of Palladium And Relative Reactivity Of Substituted Chlorines During Adsorption And Treatment Of PCBs On Reactive Activated Carbon

EPA Science Inventory

The adsorption-mediated dechlorination of polychlorinated biphenyls (PCBs) is a unique feature of reactive activated cabon (RAC). Here, we address the RAC system, containing a tunable amount of Fe as a primary electron donor coupled with Pd as an electrochemical catalyst to pote...

Donor acceptor electronic couplings in π-stacks: How many states must be accounted for?

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.

2006-04-01

Two-state model is commonly used to estimate the donor-acceptor electronic coupling Vda for electron transfer. However, in some important cases, e.g. for DNA π-stacks, this scheme fails to provide accurate values of Vda because of multistate effects. The Generalized Mulliken-Hush method enables a multistate treatment of Vda. In this Letter, we analyze the dependence of calculated electronic couplings on the number of the adiabatic states included in the model. We suggest a simple scheme to determine this number. The superexchange correction of the two-state approximation is shown to provide good estimates of the electronic coupling.

Enhancement of diffraction efficiency and storage life of poly(vinyl chloride)-based optical recording medium with incorporation of an electron donor

NASA Astrophysics Data System (ADS)

John, Beena Mary; Ushamani, M.; Sreekumar, K.; Joseph, Rani; Sudha Kartha, C.

2007-01-01

The diffraction efficiency, sensitivity, and storage life of methylene blue-sensitized poly(vinyl chloride) film was improved by the addition of an electron donor in the matrix. The addition of pyridine enhanced the diffraction efficiency by two times, and storage life of the gratings was increased to 2-3 days.

Formation of tyrosine radicals in photosystem II under far-red illumination.

PubMed

Ahmadova, Nigar; Mamedov, Fikret

2018-04-01

Photosystem II (PS II) contains two redox-active tyrosine residues on the donor side at symmetrical positions to the primary donor, P 680 . Tyr Z , part of the water-oxidizing complex, is a preferential fast electron donor while Tyr D is a slow auxiliary donor to P 680 + . We used PS II membranes from spinach which were depleted of the water oxidation complex (Mn-depleted PS II) to study electron donation from both tyrosines by time-resolved EPR spectroscopy under visible and far-red continuous light and laser flash illumination. Our results show that under both illumination regimes, oxidation of Tyr D occurs via equilibrium with Tyr Z • at pH 4.7 and 6.3. At pH 8.5 direct Tyr D oxidation by P 680 + occurs in the majority of the PS II centers. Under continuous far-red light illumination these reactions were less effective but still possible. Different photochemical steps were considered to explain the far-red light-induced electron donation from tyrosines and localization of the primary electron hole (P 680 + ) on the Chl D1 in Mn-depleted PS II after the far-red light-induced charge separation at room temperature is suggested.

Extracellular Electron Uptake: Among Autotrophs and Mediated by Surfaces.

PubMed

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

2017-04-01

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

Photoinduced oxidation of a water-soluble manganese(III) porphyrin

PubMed Central

Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

1986-01-01

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly. PMID:16593699

Tunneling Statistics for Analysis of Spin-Readout Fidelity

NASA Astrophysics Data System (ADS)

Gorman, S. K.; He, Y.; House, M. G.; Keizer, J. G.; Keith, D.; Fricke, L.; Hile, S. J.; Broome, M. A.; Simmons, M. Y.

2017-09-01

We investigate spin and charge dynamics of a quantum dot of phosphorus atoms coupled to a radio-frequency single-electron transistor (SET) using full counting statistics. We show how the magnetic field plays a role in determining the bunching or antibunching tunneling statistics of the donor dot and SET system. Using the counting statistics, we show how to determine the lowest magnetic field where spin readout is possible. We then show how such a measurement can be used to investigate and optimize single-electron spin-readout fidelity.

Reactive Black 5 as electron donor and/or electron acceptor in dual chamber of solar photocatalytic fuel cell.

PubMed

Khalik, Wan Fadhilah; Ho, Li-Ngee; Ong, Soon-An; Voon, Chun-Hong; Wong, Yee-Shian; Yusuf, Sara Yasina; Yusoff, NikAthirah; Lee, Sin-Li

2018-07-01

The role of azo dye Reactive Black 5 (RB5) as an electron donor and/or electron acceptor could be distinguished in dual chamber of photocatalytic fuel cell (PFC). The introduction of RB5 in anode chamber increased the voltage generation in the system since degradation of RB5 might produce electrons which also would transfer through external circuit to the cathode chamber. The removal efficiency of RB5 with open and closed circuit was 8.5% and 13.6%, respectively and removal efficiency for open circuit was low due to the fact that recombination of electron-hole pairs might happen in anode chamber since without connection to the cathode, electron cannot be transferred. The degradation of RB5 in cathode chamber with absence of oxygen showed that electrons from anode chamber was accepted by dye molecules to break its azo bond. The presence of oxygen in cathode chamber would improve the oxygen reduction rate which occurred at Platinum-loaded carbon (Pt/C) cathode electrode. The V oc , J sc and P max for different condition of ultrapure water at cathode chamber also affected their fill factor. The transportation of protons to cathode chamber through Nafion membrane could decrease the pH of ultrapure water in cathode chamber and undergo hydrogen evolution reaction in the absence of oxygen which then increased degradation rate of RB5 as well as its electricity generation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

NASA Astrophysics Data System (ADS)

Zhang, Xian-Fu; Feng, Nan

2018-01-01

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 < δ ≤ 1), and the charge recombination induced the formation of triplet state (Dδ +-Aδ - → D-A (T1). These novel PCT- or PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems

PubMed Central

Teuscher, Joël; Brauer, Jan C.; Stepanov, Andrey; Solano, Alicia; Boziki, Ariadni; Chergui, Majed; Wolf, Jean-Pierre; Rothlisberger, Ursula; Banerji, Natalie; Moser, Jacques-E.

2017-01-01

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research “Molecular Ultrafast Science and Technology,” a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here. PMID:29308415

Balanced Ambipolar Organic Field-Effect Transistors by Polymer Preaggregation.

PubMed

Janasz, Lukasz; Luczak, Adam; Marszalek, Tomasz; Dupont, Bertrand G R; Jung, Jaroslaw; Ulanski, Jacek; Pisula, Wojciech

2017-06-21

Ambipolar organic field-effect transistors (OFETs) based on heterojunction active films still suffer from an imbalance in the transport of electrons and holes. This problem is related to an uncontrolled phase separation between the donor and acceptor organic semiconductors in the thin films. In this work, we have developed a concept to improve the phase separation in heterojunction transistors to enhance their ambipolar performance. This concept is based on preaggregation of the donor polymer, in this case poly(3-hexylthiophene) (P3HT), before solution mixing with the small-molecular-weight acceptor, phenyl-C61-butyric acid methyl ester (PCBM). The resulting heterojunction transistor morphology consists of self-assembled P3HT fibers embedded in a PCBM matrix, ensuring balanced mobilities reaching 0.01 cm 2 /V s for both holes and electrons. These are the highest mobility values reported so far for ambipolar OFETs based on P3HT/PCBM blends. Preaggregation of the conjugated polymer before fabricating binary blends can be regarded as a general concept for a wider range of semiconducting systems applicable in organic electronic devices.

Time-resolved EPR study on the photoexcited triplet state of the electron-donor-acceptor complex formed in the system of fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III) and tetracene.

PubMed

Zhebin, Fu; Shuhei, Yoshioka; Hisao, Murai

2014-01-09

The physical properties of the phosphorescent organic light-emitting diode material fac-tris(phenylpyridine) iridium(III), Ir(ppy)3, have been reported with experimental and theoretical studies. Here, the photochemical properties of the excited triplet state of partially modified fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III), Ir(C8ppy)3, were investigated using time-resolved electron paramagnetic resonance (tr-EPR) and optical methods by adding tetracene in the toluene solution. The tr-EPR observation at 77 K revealed the following two species: the excited triplet state of tetracene and another triplet species with zero field splitting parameters of |D| = 0.088 cm(-1) and |E| = 0.018 cm(-1) with characteristic spin polarization. The latter species was assigned to the electron-donor-acceptor (EDA) complex formed between Ir(C8ppy)3 and tetracene. The mechanism of formation and the properties of this EDA complex, including the information on the principal axes of (3)Ir(C8ppy)3*, are discussed.

Novel multistep BRET-FRET energy transfer using nanoconjugates of firefly proteins, quantum dots, and red fluorescent proteins

NASA Astrophysics Data System (ADS)

Alam, Rabeka; Zylstra, Joshua; Fontaine, Danielle M.; Branchini, Bruce R.; Maye, Mathew M.

2013-05-01

Sequential bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET) from firefly luciferase to red fluorescent proteins using quantum dot or rod acceptor/donor linkers is described. The effect of morphology and tuned optical properties on the efficiency of this unique BRET-FRET system was evaluated.Sequential bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET) from firefly luciferase to red fluorescent proteins using quantum dot or rod acceptor/donor linkers is described. The effect of morphology and tuned optical properties on the efficiency of this unique BRET-FRET system was evaluated. Electronic supplementary information (ESI) available: Experimental details, Fig. S1 and Table S1-S4. See DOI: 10.1039/c3nr01842c

Accelerated anaerobic dechlorination of DDT in slurry with Hydragric Acrisols using citric acid and anthraquinone-2,6-disulfonate (AQDS).

PubMed

Liu, Cuiying; Xu, Xianghua; Fan, Jianling

2015-12-01

The application of electron donor and electron shuttle substances has a vital influence on electron transfer, thus may affect the reductive dechlorination of 1,1,1-trichoro-2,2-bis(p-chlorophenyl)ethane (DDT) in anaerobic reaction systems. To evaluate the roles of citric acid and anthraquinone-2,6-disulfonate (AQDS) in accelerating the reductive dechlorination of DDT in Hydragric Acrisols that contain abundant iron oxide, a batch anaerobic incubation experiment was conducted in a slurry system with four treatments of (1) control, (2) citric acid, (3) AQDS, and (4) citric acid+AQDS. Results showed that DDT residues decreased by 78.93%-92.11% of the initial quantities after 20days of incubation, and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane (DDD) was the dominant metabolite. The application of citric acid accelerated DDT dechlorination slightly in the first 8days, while the methanogenesis rate increased quickly, and then the acceleration effect improved after the 8th day while the methanogenesis rate decreased. The amendment by AQDS decreased the Eh value of the reaction system and accelerated microbial reduction of Fe(III) oxides to generate Fe(II), which was an efficient electron donor, thus enhancing the reductive dechlorination rate of DDT. The addition of citric acid+AQDS was most efficient in stimulating DDT dechlorination, but no significant interaction between citric acid and AQDS on DDT dechlorination was observed. The results will be of great significance for developing an efficient in situ remediation strategy for DDT-contaminated sites. Copyright © 2015. Published by Elsevier B.V.

First-principles evaluation of electronic and optical properties of (Mo, C) codoped BaHfO3 for applications in photocatalysis

NASA Astrophysics Data System (ADS)

Akhtar, Shaheen; Alay-e-Abbas, Syed Muhammad; Abbas, Syed Muhammad Ghulam; Arshad, Muhammad Imran; Batool, Javaria; Amin, Nasir

2018-04-01

In this paper, we report first-principles spin-polarized density functional theory calculations for exploring the effect of aliovalent Mo and C dopants on the electronic properties and photocatalysis potential of doped modifications of wide-bandgap cubic perovskite oxide BaHfO3 for water splitting. The structural and thermodynamic properties are computed by using the generalized gradient approximation, whereas the modified Becke-Johnson local density approximation is used to calculate the electronic structures of pristine, cation (Mo), and anion (C) monodoped and cation-anion (Mo, C) codoped BaHfO3. The spin-polarized calculations reveal that substitutional dopants CO and MoHf in the BaHfO3 lattice are thermodynamically stable. The incorporation of C in the O site reduces the bandgap of BaHfO3 and acts as a double-acceptor system, whereas a metallic character is obtained when Mo is doped into the Hf site giving rise to a double-donor system. We show that the acceptor and donor states of the C- and Mo-monodoped BaHfO3 can be passivated by (Mo, C) codoping at nearest-neighbor Hf and O sites of the BaHfO3 lattice, respectively. Analysis of the calculated electronic structure and optical absorption of (Mo, C) codoped BaHfO3 with reference to the H2O oxidation and reduction potentials reveals that this system is a suitable candidate for efficient splitting of water through photocatalysis in the visible region of the electromagnetic spectrum.

Bioelectrical Perchlorate Remediation

NASA Astrophysics Data System (ADS)

Thrash, C.; Achenbach, L. A.; Coates, J. D.

2007-12-01

Several bioreactor designs are currently available for the ex-situ biological attenuation of perchlorate- contaminated waters and recently, some of these reactor designs were conditionally approved by the California Department of Health Services for application in the treatment of perchlorate contaminated drinking water. However, all of these systems are dependent on the continual addition of a chemical electron donor to sustain microbial activity and are always subject to biofouling and downstream water quality issues. In addition, residual labile electron donor in the reactor effluent can stimulate microbial growth in water distribution systems and contribute to the formation of potentially toxic trihalomethanes during disinfection by chlorination. As part of our ongoing studies into microbial perchlorate reduction we investigated the ability of dissimilatory perchlorate reducing bacteria (DPRB) to metabolize perchlorate using a negatively charged electrode (cathode) in the working chamber of a bioelectrical reactor (BER) as the primary electron donor. In this instance the DPRB use the electrons on the electrode surface either directly or indirectly in the form of electrolytically produced H2 as a source of reducing equivalents for nitrate and perchlorate reduction. As part of this investigation our fed-batch studies showed that DPRB could use electrons from a graphite cathode poised at -500mV (vs. Ag/AgCl) for the reduction of perchlorate and nitrate. We isolated a novel organism, Dechlorospirillum strain VDY, from the cathode surface after 70 days operation which readily reduced 100 mg.L-1 perchlorate in a mediatorless batch bioelectrical reactor (BER) in 6 days. Continuous up-flow BERs (UFBERs) seeded with active cultures of strain VDY continuously treated waters containing 100 mg.L-1 perchlorate with almost 100% efficiency throughout their operation achieving a non-optimized volumetric loading of 60 mg.L-1 reactor volume.day-1. The same UFBERs also treated low-level perchlorate (100 μg.L-1) influent as well as mixed-waste influents more typically found in the environment containing both nitrate and perchlorate. Through extended periods of operation (>70 days), no loss in treatment efficiency was noted and no measurable growth in biomass was observed. Gas phase analysis indicated that low levels of H2 produced at the cathode surface through electrolysis can provide enough reducing equivalents to mediate this metabolism. The results of these studies demonstrate that perchlorate remediation can be facilitated through the use of a cathode as the primary electron donor, and that continuous treatment in such a system approaches current industry standards. This has important implications for the continuous treatment of this critical contaminant in industrial waste streams and drinking water. Such a process has the advantage of long-term, low-maintenance operation with ease of online monitoring and control while limiting the injection of additional chemicals into the water treatment process and outgrowth of the microbial populations. This would negate the need for the continual removal and disposal of biomass produced during treatment and also the downstream issues associated with corrosion and biofouling of distribution systems and the production of toxic disinfection byproducts.

The role of amino acid electron-donor/acceptor atoms in host-cell binding peptides is associated with their 3D structure and HLA-binding capacity in sterile malarial immunity induction

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

Patarroyo, Manuel E., E-mail: mepatarr@mail.com; Universidad Nacional de Colombia, Bogota; Almonacid, Hannia

Highlights: Black-Right-Pointing-Pointer Fundamental residues located in some HABPs are associated with their 3D structure. Black-Right-Pointing-Pointer Electron-donor atoms present in {beta}-turn, random, distorted {alpha}-helix structures. Black-Right-Pointing-Pointer Electron-donor atoms bound to HLA-DR53. Black-Right-Pointing-Pointer Electron-acceptor atoms present in regular {alpha}-helix structure bound to HLA-DR52. -- Abstract: Plasmodium falciparum malaria continues being one of the parasitic diseases causing the highest worldwide mortality due to the parasite's multiple evasion mechanisms, such as immunological silence. Membrane and organelle proteins are used during invasion for interactions mediated by high binding ability peptides (HABPs); these have amino acids which establish hydrogen bonds between them in some of theirmore » critical binding residues. Immunisation assays in the Aotus model using HABPs whose critical residues had been modified have revealed a conformational change thereby enabling a protection-inducing response. This has improved fitting within HLA-DR{beta}1{sup Asterisk-Operator} molecules where amino acid electron-donor atoms present in {beta}-turn, random or distorted {alpha}-helix structures preferentially bound to HLA-DR53 molecules, whilst HABPs having amino acid electron-acceptor atoms present in regular {alpha}-helix structure bound to HLA-DR52. This data has great implications for vaccine development.« less

Resonance energy transfer: when a dipole fails.

PubMed

Andrews, David L; Leeder, Jamie M

2009-05-14

The Coulombic coupling of electric dipole (E1) transition moments is the most commonly studied and widely operative mechanism for energy migration in multichromophore systems. However a significant number of exceptions exist, in which donor decay and/or acceptor excitation processes are E1-forbidden. The alternative transfer mechanisms that can apply in such cases include roles for higher multipole transitions, exciton- or phonon-assisted interactions, and non-Coulombic interactions based on electron exchange. A quantum electrodynamical formulation provides a rigorous basis to assess the first of these, specifically addressing the relative significance of higher multipole contributions to the process of energy transfer in donor-acceptor systems where electric dipole transitions are precluded by symmetry. Working within the near-zone limit, where donor-acceptor separations are small in comparison to the chromophore scale, the analysis highlights the contributions of both electric quadrupole-electric quadrupole (E2-E2) coupling and the seldom considered second-order electric dipole-electric dipole (E1(2)-E1(2)) coupling. For both forms of interaction, experimentally meaningful rate equations are secured by the use of orientational averaging, and the mechanisms are analyzed with reference to systems in which E1-forbidden transitions are commonly reported.

Temperature dependent behavior of localized and delocalized electrons in nitrogen-doped 6H SiC crystals as studied by electron spin resonance

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

Savchenko, D., E-mail: dariyasavchenko@gmail.com; National Technical University of Ukraine “Kyiv Polytechnic Institute”, Kyiv 03056; Kalabukhova, E.

2016-01-28

We have studied the temperature behavior of the electron spin resonance (ESR) spectra of nitrogen (N) donors in n-type 6H SiC crystals grown by Lely and sublimation sandwich methods (SSM) with donor concentration of 10{sup 17 }cm{sup −3} at T = 60–150 K. A broad signal in the ESR spectrum was observed at T ≥ 80 K with Lorentzian lineshape and g{sub ||} = 2.0043(3), g{sub ⊥} = 2.0030(3), which was previously assigned in the literature to the N donors in the 1s(E) excited state. Based on the analysis of the ESR lineshape, linewidth and g-tensor we attribute this signal to the conduction electrons (CE). The emergence of the CE ESRmore » signal at T > 80 K was explained by the ionization of electrons from the 1s(A{sub 1}) ground and 1s(E) excited states of N donors to the conduction band while the observed reduction of the hyperfine (hf) splitting for the N{sub k1,k2} donors with the temperature increase is attributed to the motional narrowing effect of the hf splitting. The temperature dependence of CE ESR linewidth is described by an exponential law (Orbach process) with the activation energy corresponding to the energy separation between 1s(A{sub 1}) and 1s(E) energy levels for N residing at quasi-cubic sites (N{sub k1,k2}). The theoretical analysis of the temperature dependence of microwave conductivity measured by the contact-free method shows that due to the different position of the Fermi level in two samples the ionization of free electrons occurs from the energy levels of N{sub k1,k2} donors in Lely grown samples and from the energy level of N{sub h} residing at hexagonal position in 6H SiC grown by SSM.« less

Binding energy and photoionization cross-section of hydrogen-like donor impurity in strongly oblate ellipsoidal quantum dot

NASA Astrophysics Data System (ADS)

Hayrapetyan, D. B.; Ohanyan, G. L.; Baghdasaryan, D. A.; Sarkisyan, H. A.; Baskoutas, S.; Kazaryan, E. M.

2018-01-01

Hydrogen-like donor impurity states in strongly oblate ellipsoidal quantum dot have been studied. The hydrogen-like donor impurity states are investigated within the framework of variational method. The trial wave function constructed on the base of wave functions of the system without impurity. The dependence of the energy and binding energy for the ground and first excited states on the geometrical parameters of the ellipsoidal quantum dot and on the impurity position have been calculated. The behavior of the oscillator strength for different angles of incident light and geometrical parameters have been revealed. Photoionization cross-section of the electron transitions from the impurity ground state to the size-quantized ground and first excited states have been studied. The effects of impurity position and the geometrical parameters of the ellipsoidal quantum dot on the photoionization cross section dependence on the photon energy have been considered.

Effective Tuning of Ketocyanine Derivatives through Acceptor Substitution.

PubMed

Poe, Ambata; Della Pelle, Andrea; Byrnes, Sean; Thayumanavan, S

2015-05-18

A series of ketocyanine derivatives possessing bis(diarylamino)fluorenyl donors and variable acceptors installed at the bridging carbon atom were synthesized to investigate how the electronic structure of the dye can be systemically tuned through stabilization of the cyanine-like character of the donor by increasing the acceptor strength. Analysis of the (1) H NMR spectra indicates that the "charge-separated" species dominates in these dyes, given that carbons possessing a positive or negative charge in the resonance structures of this state purposefully shift downfield or upfield, respectively, depending on the strength of the acceptor moiety. In DAA-Fl-PI, the acceptor strength and the gain of acceptor aromaticity indicates a predisposition of the separated state, indicated by asymmetry in the (1) H NMR spectrum, as well as uneven distribution of the HOMO on the fluorenyl donor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geobacter sulfurreducens sp. nov., a hydrogen- and acetate-oxidizing dissimilatory metal-reducing microorganism.

PubMed Central

Caccavo, F; Lonergan, D J; Lovley, D R; Davis, M; Stolz, J F; McInerney, M J

1994-01-01

A dissimilatory metal- and sulfur-reducing microorganism was isolated from surface sediments of a hydrocarbon-contaminated ditch in Norman, Okla. The isolate, which was designated strain PCA, was an obligately anaerobic, nonfermentative nonmotile, gram-negative rod. PCA grew in a defined medium with acetate as an electron donor and ferric PPi, ferric oxyhydroxide, ferric citrate, elemental sulfur, Co(III)-EDTA, fumarate, or malate as the sole electron acceptor. PCA also coupled the oxidation of hydrogen to the reduction of Fe(III) but did not reduce Fe(III) with sulfur, glucose, lactate, fumarate, propionate, butyrate, isobutyrate, isovalerate, succinate, yeast extract, phenol, benzoate, ethanol, propanol, or butanol as an electron donor. PCA did not reduce oxygen, Mn(IV), U(VI), nitrate, sulfate, sulfite, or thiosulfate with acetate as the electron donor. Cell suspensions of PCA exhibited dithionite-reduced minus air-oxidized difference spectra which were characteristic of c-type cytochromes. Phylogenetic analysis of the 16S rRNA sequence placed PCA in the delta subgroup of the proteobacteria. Its closest known relative is Geobacter metallireducens. The ability to utilize either hydrogen or acetate as the sole electron donor for Fe(III) reduction makes strain PCA a unique addition to the relatively small group of respiratory metal-reducing microorganisms available in pure culture. A new species name, Geobacter sulfurreducens, is proposed. Images PMID:7527204

Photoinduced electron transfer in fixed distance chlorophyll-quinone donor-acceptor molecules

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

Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.

1987-01-01

A series of fixed distance chlorophyll-quinone donor-acceptor molecules have been prepared. The donor consists of either methyl pyropheophorbide a or methyl pyrochlorophyllide a, while the acceptor is either benzoquinone or naphthoquinone. The acceptors are fused to a triptycene spacer group, which in turn is attached to the donors at their vinyl groups. Picosecond transient absorption measurements have been used to identify electron transfer from the lowest excited singlet state of the donor to the acceptor as the mechanism of fluorescence quenching in these molecules. The charge separation rate constants increase from 2 x 10/sup 10/ s/sup -1/ to 4 xmore » 10/sup 11/ s/sup -1/ as the free energy of charge separation increases, while the radical pair recombination rate constants decrease from 1.2 x 10/sup 11/ s/sup -1/ to 2 x 10/sup 9/ s/sup -1/ as the free energy of recombination increases. The resulting total reorganization energy lambda = 0.9 eV.« less

Reducing exciton binding energy by increasing thin film permittivity: an effective approach to enhance exciton separation efficiency in organic solar cells.

PubMed

Leblebici, Sibel Y; Chen, Teresa L; Olalde-Velasco, Paul; Yang, Wanli; Ma, Biwu

2013-10-23

Photocurrent generation in organic solar cells requires that excitons, which are formed upon light absorption, dissociate into free carriers at the interface of electron acceptor and donor materials. The high exciton binding energy, arising from the low permittivity of organic semiconductor films, generally causes low exciton separation efficiency and subsequently low power conversion efficiency. We demonstrate here, for the first time, that the exciton binding energy in B,O-chelated azadipyrromethene (BO-ADPM) donor films is reduced by increasing the film permittivity by blending the BO-ADPM donor with a high dielectric constant small molecule, camphoric anhydride (CA). Various spectroscopic techniques, including impedance spectroscopy, photon absorption and emission spectroscopies, as well as X-ray spectroscopies, are applied to characterize the thin film electronic and photophysical properties. Planar heterojunction solar cells are fabricated with a BO-ADPM:CA film as the electron donor and C60 as the acceptor. With an increase in the dielectric constant of the donor film from ∼4.5 to ∼11, the exciton binding energy is reduced and the internal quantum efficiency of the photovoltaic cells improves across the entire spectrum, with an ∼30% improvement in the BO-ADPM photoactive region.

Donor impurity-related photoionization cross section in GaAs cone-like quantum dots under applied electric field

NASA Astrophysics Data System (ADS)

Iqraoun, E.; Sali, A.; Rezzouk, A.; Feddi, E.; Dujardin, F.; Mora-Ramos, M. E.; Duque, C. A.

2017-06-01

The donor impurity-related electron states in GaAs cone-like quantum dots under the influence of an externally applied static electric field are theoretically investigated. Calculations are performed within the effective mass and parabolic band approximations, using the variational procedure to include the electron-impurity correlation effects. The uncorrelated Schrödinger-like electron states are obtained in quasi-analytical form and the entire electron-impurity correlated states are used to calculate the photoionisation cross section. Results for the electron state energies and the photoionisation cross section are reported as functions of the main geometrical parameters of the cone-like structures as well as of the electric field strength.

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

DOE PAGES

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; ...

2016-09-09

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

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

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.

PubMed

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurélien; Blumberger, Jochen; Elstner, Marcus

2016-10-11

In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

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

Bose, A; Gardel, EJ; Vidoudez, C

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

Synthesis, and spectroscopic studies of charge transfer complex of 1,2-dimethylimidazole as an electron donor with π-acceptor 2,4-dinitro-1-naphthol in different polar solvents

NASA Astrophysics Data System (ADS)

Miyan, Lal; Khan, Ishaat M.; Ahmad, Afaq

2015-07-01

The charge transfer (CT) complex of 1,2-dimethylimidazole (DMI) as an electron donor with π acceptor 2,4-dinitro-1-naphthol (DNN) has been studied spectrophotometrically in different solvents like chloroform, acetonitrile, methanol, methylene chloride, etc. at room temperature. The CT complex which is formed through the transfer of lone pair electrons from DMI to DNN exhibits well resolved CT bands and the regions of these bands were remarkably different from those of the donor and acceptor. The stoichiometry of the CT complex was found to be 1:1 by a straight-line method between donor and acceptor with maximum absorption bands. The novel CT complex has been characterized by FTIR, TGA-DTA, powder XRD, 1H NMR and 13C NMR spectroscopic techniques. The Benesi-Hildebrand equation has been used to determine the formation constant (KCT), molar extinction coefficient (εCT), standard gibbs free energy (ΔG°) and other physical parameters of the CT complex. The formation constant recorded higher values and molar extinction coefficient recorded lower values in chloroform compared with methylene chloride, methanol and acetonitrile, confirming the strong interaction between the molecular orbital's of donor and acceptor in the ground state in less polar solvent. This CT complex has been studied by absorption spectra of donor 1,2-dimethylimidazole (DMI) and acceptor 2,4-dinitro-1-naphthol (DNN) by using the spectrophotometric technique in various solvents at room temperature.

The electronic spectra of benzo[b]thiete and transient o-thiobenzoquinonemethide. Spectral assignments on the basis of the electronic spectra of aniline, thiophenol, thioanisole, all-trans-octatetraene and transient o-xylylene in conjunction with quantum-chemical calculations

NASA Astrophysics Data System (ADS)

Schweig, Armin; Diehl, Frank; Kesper, Karl; Meyer, Hermann

1989-07-01

The electronic absorption spectra of benzo[b]thiete ( 1) and of transient o-thiobenzoquinonemethide ( 2) have been obtained. Semiempirical valence-electron calculations using the CNDO/S SECI, CNDO/S PERTCI and LNDO/S PERTCI methods and correlation diagrams using suitable reference compounds ad aniline, thiophenol, thioanisole, all-trans-octatetraene and o-xylylene are applied to the interpretation of the spectra. The results clearly reveal 1 as a typically donor-substituted benzene derivative and 2 as a polyene-like system closely related to o-xylylene.

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

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

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

2015-03-30

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

Complete Oxidation of Propionate, Valerate, Succinate, and Other Organic Compounds by Newly Isolated Types of Marine, Anaerobic, Mesophilic, Gram-Negative, Sulfur-Reducing Eubacteria

PubMed Central

Finster, Kai; Bak, Friedhelm

1993-01-01

Anaerobic enrichment cultures with either propionate, succinate, lactate, or valerate and elemental sulfur and inocula from shallow marine or deep-sea sediments were dominated by rod-shaped motile bacteria after three transfers. By application of deep-agar dilutions, five eubacterial strains were obtained in pure culture and designated Kyprop, Gyprop, Kysw2, Gylac, and Kyval. All strains were gram negative and grew by complete oxidation of the electron donors and concomitant stoichiometric reduction of elemental sulfur to hydrogen sulfide. The isolates used acetate, propionate, succinate, lactate, pyruvate, oxaloacetate, maleate, glutamate, alanine, aspartate, and yeast extract. All isolates, except strain Gylac, used citrate as an electron donor but valerate was oxidized only by strain Kyval. Fumarate and malate were degraded by all strains without an additional electron donor or acceptor. Kyprop, Gyprop, and Gylac utilized elemental sulfur as the sole inorganic electron acceptor, while Kysw2 and Kyval also utilized nitrate, dimethyl sulfoxide, or Fe(III)-citrate as an electron acceptor. Images PMID:16348934

Hydride vapor phase GaN films with reduced density of residual electrons and deep traps

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

Polyakov, A. Y., E-mail: aypolyakov@gmail.com; Smirnov, N. B.; Govorkov, A. V.

2014-05-14

Electrical properties and deep electron and hole traps spectra are compared for undoped n-GaN films grown by hydride vapor phase epitaxy (HVPE) in the regular process (standard HVPE samples) and in HVPE process optimized for decreasing the concentration of residual donor impurities (improved HVPE samples). It is shown that the residual donor density can be reduced by optimization from ∼10{sup 17} cm{sup −3} to (2–5) × 10{sup 14} cm{sup −3}. The density of deep hole traps and deep electron traps decreases with decreased donor density, so that the concentration of deep hole traps in the improved samples is reduced to ∼5 × 10{sup 13} cm{sup −3} versusmore » 2.9 × 10{sup 16} cm{sup −3} in the standard samples, with a similar decrease in the electron traps concentration.« less

Adrenodoxin supports reactions catalyzed by microsomal steroidogenic cytochrome P450s

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

Pechurskaya, Tatiana A.; Harnastai, Ivan N.; Grabovec, Irina P.

2007-02-16

The interaction of adrenodoxin (Adx) and NADPH cytochrome P450 reductase (CPR) with human microsomal steroidogenic cytochrome P450s was studied. It is found that Adx, mitochondrial electron transfer protein, is able to support reactions catalyzed by human microsomal P450s: full length CYP17, truncated CYP17, and truncated CYP21. CPR, but not Adx, supports activity of truncated CYP19. Truncated and the full length CYP17s show distinct preference for electron donor proteins. Truncated CYP17 has higher activity with Adx compared to CPR. The alteration in preference to electron donor does not change product profile for truncated enzymes. The electrostatic contacts play a major rolemore » in the interaction of truncated CYP17 with either CPR or Adx. Similarly electrostatic contacts are predominant in the interaction of full length CYP17 with Adx. We speculate that Adx might serve as an alternative electron donor for CYP17 at the conditions of CPR deficiency in human.« less

Computer-assisted audiovisual health history self-interviewing. Results of the pilot study of the Hoxworth Quality Donor System.

PubMed

Zuck, T F; Cumming, P D; Wallace, E L

2001-12-01

The safety of blood for transfusion depends, in part, on the reliability of the health history given by volunteer blood donors. To improve reliability, a pilot study evaluated the use of an interactive computer-based audiovisual donor interviewing system at a typical midwestern blood center in the United States. An interactive video screening system was tested in a community donor center environment on 395 volunteer blood donors. Of the donors using the system, 277 completed surveys regarding their acceptance of and opinions about the system. The study showed that an interactive computer-based audiovisual donor screening system was an effective means of conducting the donor health history. The majority of donors found the system understandable and favored the system over a face-to-face interview. Further, most donors indicated that they would be more likely to return if they were to be screened by such a system. Interactive computer-based audiovisual blood donor screening is useful and well accepted by donors; it may prevent a majority of errors and accidents that are reportable to the FDA; and it may contribute to increased safety and availability of the blood supply.

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions

DOE PAGES

Kwon, Man Jae; O’Loughlin, Edward J.; Boyanov, Maxim I.; ...

2016-01-22

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over timemore » revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. As a result, these data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.« less

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE PAGES

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.; ...

2017-09-13

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions

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

Kwon, Man Jae; O’Loughlin, Edward J.; Boyanov, Maxim I.

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over timemore » revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. As a result, these data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.« less

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

PubMed

Thomson, Stuart A J; Niklas, Jens; Mardis, Kristy L; Mallares, Christopher; Samuel, Ifor D W; Poluektov, Oleg G

2017-10-19

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2 ) 2 , DTS(F 2 BTTh 2 ) 2 , DTS(PTTh 2 ) 2 , DTG(FBTTh 2 ) 2 and DTG(F 2 BTTh 2 ) 2 ) with the fullerene derivative PC 61 BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2 ) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2 ) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh 2 ) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions.

PubMed

Kwon, Man Jae; O'Loughlin, Edward J; Boyanov, Maxim I; Brulc, Jennifer M; Johnston, Eric R; Kemner, Kenneth M; Antonopoulos, Dionysios A

2016-01-01

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over time revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. These data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

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

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Super electron donor-mediated reductive transformation of nitrobenzenes: a novel strategy to synthesize azobenzenes and phenazines.

PubMed

Nozawa-Kumada, Kanako; Abe, Erina; Ito, Shungo; Shigeno, Masanori; Kondo, Yoshinori

2018-05-02

The transformation of nitrobenzenes into azobenzenes by pyridine-derived super electron donor 2 is described. This method provides an efficient synthesis of azobenzenes because of not requiring the use of expensive transition-metals, toxic or flammable reagents, or harsh conditions. Moreover, when using 2-fluoronitrobenzenes as substrates, phenazines were found to be obtained. The process affords a novel synthesis of phenazines.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Enhanced biodegradation of hexachlorocyclohexane in upflow anaerobic sludge blanket reactor using methanol as an electron donor.

PubMed

Bhatt, Praveena; Kumar, M Suresh; Mudliar, Sandeep; Chakrabarti, Tapan

2008-05-01

Anaerobic dechlorination of technical grade hexachlorocyclohexane (THCH) was studied in a continuous upflow anaerobic sludge blanket (UASB) reactor with methanol as a supplementary substrate and electron donor. A reactor without methanol served as the experimental control. The inlet feed concentration of THCH in both the experimental and the control UASB reactor was 100 mg l(-1). After 60 days of continuous operation, the removal of THCH was >99% in the methanol-supplemented reactor as compared to 20-35% in the control reactor. THCH was completely dechlorinated in the methanol fed reactor at 48 h HRT after 2 months of continuous operation. This period was also accompanied by increase in biomass in the reactor, which was not observed in the experimental control. Batch studies using other supplementary substrates as well as electron donors namely acetate, butyrate, formate and ethanol showed lower % dechlorination (<85%) and dechlorination rates (<3 mg g(-1)d(-1)) as compared to methanol (98%, 5 mg g(-1)d(-1)). The optimum concentration of methanol required, for stable dechlorination of THCH (100 mg l(-1)) in the UASB reactor, was found to be 500 mg l(-1). Results indicate that addition of methanol as electron donor enhances dechlorination of THCH at high inlet concentration, and is also required for stable UASB reactor performance.

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

PubMed Central

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

2015-01-01

Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds new light on how oxidative enzymes present in plant degraders may act in concert. PMID:26686263

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

PubMed

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

An intermolecular heterobimetallic system for photocatalytic water reduction.

PubMed

Hansen, Sven; Klahn, Marcus; Beweries, Torsten; Rosenthal, Uwe

2012-04-01

Teamwork: A new intermolecular heterobimetallic system for photocatalytic water reduction, consisting of a photosensitizer of the type [Ru(bpy)(2)(L)](PF(6))(2) (L=bidentate ligand), a dichloro palladium complex PdCl(2)(L) serving as the water reduction catalyst, and triethyl amine as electron donor, is presented. Variations of the ligand as well as of the palladium source results in a significant improvement of the performance of the catalyst system. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-photon or higher-order absorbing optical materials and methods of use

NASA Technical Reports Server (NTRS)

Perry, Joseph (Inventor); Marder, Seth (Inventor)

2001-01-01

Compositions capable of simultaneous two-photon absorption and higher order absorptivities are disclosed. Many of these compositions are compounds satisfying the formulae D-.PI.-D, A-.PI.-A, D-A-D and A-D-A, wherein D is an electron donor group, A is an electron acceptor group and .PI. comprises a bridge of .pi.-conjugated bonds connecting the electron donor groups and electron acceptor groups. In A-D-A and D-A-D compounds, the .pi. bridge is substituted with electron donor groups and electron acceptor groups, respectively. Also disclosed are methods that generate an electronically excited state of a compound, including those satisfying one of these formulae. The electronically excited state is achieved in a method that includes irradiating the compound with light. Then, the compound is converted to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of light. The sum of the energies of all of the absorbed photons is greater than or equal to the transition energy from a ground state of the compound to the multi-photon excited state. The energy of each absorbed photon is less than the transition energy between the ground state and the lowest single-photon excited state of the compound is less than the transition energy between the multi-photon excited state and the ground state.

Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems

NASA Astrophysics Data System (ADS)

Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

Humic Acid-Oxidizing, Nitrate-Reducing Bacteria in Agricultural Soils

PubMed Central

Van Trump, J. Ian; Wrighton, Kelly C.; Thrash, J. Cameron; Weber, Karrie A.; Andersen, Gary L.; Coates, John D.

2011-01-01

ABSTRACT This study demonstrates the prevalence, phylogenetic diversity, and physiology of nitrate-reducing microorganisms capable of utilizing reduced humic acids (HA) as electron donors in agricultural soils. Most probable number (MPN) enumeration of agricultural soils revealed large populations (104 to 106 cells g−1 soil) of microorganisms capable of reducing nitrate while oxidizing the reduced HA analog 2,6-anthrahydroquinone disulfonate (AH2DS) to its corresponding quinone. Nitrate-dependent HA-oxidizing organisms isolated from agricultural soils were phylogenetically diverse and included members of the Alphaproteobacteria, Betaproteobacteria, and Gammaproteobacteria. Advective up-flow columns inoculated with corn plot soil and amended with reduced HA and nitrate supported both HA oxidation and enhanced nitrate reduction relative to no-donor or oxidized HA controls. The additional electron donating capacity of reduced HA could reasonably be attributed to the oxidation of reduced functional groups. Subsequent 16S rRNA gene-based high-density oligonucleotide microarray (PhyloChip) indicated that reduced HA columns supported the development of a bacterial community enriched with members of the Acidobacteria, Firmicutes, and Betaproteobacteria relative to the no-donor control and initial inoculum. This study identifies a previously unrecognized role for HA in stimulating denitrification processes in saturated soil systems. Furthermore, this study indicates that reduced humic acids impact soil geochemistry and the indigenous bacterial community composition. PMID:21750120

An Electron-Deficient Building Block Based on the B←N Unit: An Electron Acceptor for All-Polymer Solar Cells.

PubMed

Dou, Chuandong; Long, Xiaojing; Ding, Zicheng; Xie, Zhiyuan; Liu, Jun; Wang, Lixiang

2016-01-22

A double B←N bridged bipyridyl (BNBP) is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells. The B←N bridging units endow BNBP with fixed planar configuration and low-lying LUMO/HOMO energy levels. As a result, the polymer based on BNBP units (P-BNBP-T) exhibits high electron mobility, low-lying LUMO/HOMO energy levels, and strong absorbance in the visible region, which is desirable for polymer electron acceptors. Preliminary all-polymer solar cell (all-PSC) devices with P-BNBP-T as the electron acceptor and PTB7 as the electron donor exhibit a power conversion efficiency (PCE) of 3.38%, which is among the highest values of all-PSCs with PTB7 as the electron donor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organ Procurement Organizations and the Electronic Health Record.

PubMed

Howard, R J; Cochran, L D; Cornell, D L

2015-10-01

The adoption of electronic health records (EHRs) has adversely affected the ability of organ procurement organizations (OPOs) to perform their federally mandated function of honoring the donation decisions of families and donors who have signed the registry. The difficulties gaining access to potential donor medical record has meant that assessment, evaluation, and management of brain dead organ donors has become much more difficult. Delays can occur that can lead to potential recipients not receiving life-saving organs. For over 40 years, OPO personnel have had ready access to paper medical records. But the widespread adoption of EHRs has greatly limited the ability of OPO coordinators to readily gain access to patient medical records and to manage brain dead donors. Proposed solutions include the following: (1) hospitals could provide limited access to OPO personnel so that they could see only the potential donor's medical record; (2) OPOs could join with other transplant organizations to inform regulators of the problem; and (3) hospital organizations could be approached to work with Center for Medicare and Medicaid Services (CMS) to revise the Hospital Conditions of Participation to require OPOs be given access to donor medical records. © Copyright 2015 The American Society of Transplantation and the American Society of Transplant Surgeons.

Electron Bifurcation: Thermodynamics and Kinetics of Two-Electron Brokering in Biological Redox Chemistry.

PubMed

Zhang, Peng; Yuly, Jonathon L; Lubner, Carolyn E; Mulder, David W; King, Paul W; Peters, John W; Beratan, David N

2017-09-19

How can proteins drive two electrons from a redox active donor onto two acceptors at very different potentials and distances? And how can this transaction be conducted without dissipating very much energy or violating the laws of thermodynamics? Nature appears to have addressed these challenges by coupling thermodynamically uphill and downhill electron transfer reactions, using two-electron donor cofactors that have very different potentials for the removal of the first and second electron. Although electron bifurcation is carried out with near perfection from the standpoint of energy conservation and electron delivery yields, it is a biological energy transduction paradigm that has only come into focus recently. This Account provides an exegesis of the biophysical principles that underpin electron bifurcation. Remarkably, bifurcating electron transfer (ET) proteins typically send one electron uphill and one electron downhill by similar energies, such that the overall reaction is spontaneous, but not profligate. Electron bifurcation in the NADH-dependent reduced ferredoxin: NADP + oxidoreductase I (Nfn) is explored in detail here. Recent experimental progress in understanding the structure and function of Nfn allows us to dissect its workings in the framework of modern ET theory. The first electron that leaves the two-electron donor flavin (L-FAD) executes a positive free energy "uphill" reaction, and the departure of this electron switches on a second thermodynamically spontaneous ET reaction from the flavin along a second pathway that moves electrons in the opposite direction and at a very different potential. The singly reduced ET products formed from the bifurcating flavin are more than two nanometers distant from each other. In Nfn, the second electron to leave the flavin is much more reducing than the first: the potentials are said to be "crossed." The eventually reduced cofactors, NADH and ferredoxin in the case of Nfn, perform crucial downstream redox processes of their own. We dissect the thermodynamics and kinetics of electron bifurcation in Nfn and find that the key features of electron bifurcation are (1) spatially separated transfer pathways that diverge from a two-electron donor, (2) one thermodynamically uphill and one downhill redox pathway, with a large negative shift in the donor's reduction potential after departure of the first electron, and (3) electron tunneling and activation factors that enable bifurcation, producing a 1:1 partitioning of electrons onto the two pathways. Electron bifurcation is found in the CO 2 reducing pathways of methanogenic archaea, in the hydrogen pathways of hydrogenases, in the nitrogen fixing pathway of Fix, and in the mitochondrial charge transfer chain of complex III, cytochrome bc 1 . While crossed potentials may offer the biological advantage of producing tightly regulated high energy reactive species, neither kinetic nor thermodynamic considerations mandate crossed potentials to generate successful electron bifurcation. Taken together, the theoretical framework established here, focusing on the underpinning electron tunneling barriers and activation free energies, explains the logic of electron bifurcation that enables energy conversion and conservation in Nfn, points toward bioinspired schemes to execute multielectron redox chemistry, and establishes a roadmap for examining novel electron bifurcation networks in nature.

U(VI) bioreduction with emulsified vegetable oil as the electron donor--model application to a field test.

PubMed

Tang, Guoping; Watson, David B; Wu, Wei-Min; Schadt, Christopher W; Parker, Jack C; Brooks, Scott C

2013-04-02

We amended a shallow fast-flowing uranium (U) contaminated aquifer with emulsified vegetable oil (EVO) and subsequently monitored the biogeochemical responses for over a year. Using a biogeochemical model developed in a companion article (Tang et al., Environ. Sci. Technol.2013, doi: 10.1021/es304641b) based on microcosm tests, we simulated geochemical and microbial dynamics in the field test during and after the 2-h EVO injection. When the lab-determined parameters were applied in the field-scale simulation, the estimated rate coefficient for EVO hydrolysis in the field was about 1 order of magnitude greater than that in the microcosms. Model results suggested that precipitation of long-chain fatty acids, produced from EVO hydrolysis, with Ca in the aquifer created a secondary long-term electron donor source. The model predicted substantial accumulation of denitrifying and sulfate-reducing bacteria, and U(IV) precipitates. The accumulation was greatest near the injection wells and along the lateral boundaries of the treatment zone where electron donors mixed with electron acceptors in the groundwater. While electron acceptors such as sulfate were generally considered to compete with U(VI) for electrons, this work highlighted their role in providing electron acceptors for microorganisms to degrade complex substrates thereby enhancing U(VI) reduction and immobilization.

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

PubMed

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

2016-10-07

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

Ammonification in Bacillus subtilis Utilizing Dissimilatory Nitrite Reductase Is Dependent on resDE

PubMed Central

Hoffmann, Tamara; Frankenberg, Nicole; Marino, Marco; Jahn, Dieter

1998-01-01

During anaerobic nitrate respiration Bacillus subtilis reduces nitrate via nitrite to ammonia. No denitrification products were observed. B. subtilis wild-type cells and a nitrate reductase mutant grew anaerobically with nitrite as an electron acceptor. Oxygen-sensitive dissimilatory nitrite reductase activity was demonstrated in cell extracts prepared from both strains with benzyl viologen as an electron donor and nitrite as an electron acceptor. The anaerobic expression of the discovered nitrite reductase activity was dependent on the regulatory system encoded by resDE. Mutation of the gene encoding the regulatory Fnr had no negative effect on dissimilatory nitrite reductase formation. PMID:9422613

Doping of the step-edge Si chain: Ag on a Si(557)-Au surface

NASA Astrophysics Data System (ADS)

Krawiec, M.; Jałochowski, M.

2010-11-01

Structural and electronic properties of monatomic Ag chains on the Au-induced, highly ordered Si(557) surface are investigated by scanning tunneling microscopy (STM)/spectroscopy and first-principles density functional theory (DFT) calculations. The STM topography data show that a small amount of Ag (0.25 ML) very weakly modifies the one-dimensional structure induced by Au atoms. However, the bias-dependent STM topography and spectroscopy point to the importance of the electronic effects in this system, which are further corroborated by the DFT calculations. The obtained results suggest that Ag atoms act as electron donors leaving the geometry of the surface almost unchanged.

Design of a New Fused-Ring Electron Acceptor with Excellent Compatibility to Wide-Bandgap Polymer Donors for High-Performance Organic Photovoltaics.

PubMed

Liu, Wenrui; Zhang, Jianyun; Zhou, Zichun; Zhang, Dongyang; Zhang, Yuan; Xu, Shengjie; Zhu, Xiaozhang

2018-05-16

Fused-ring electron acceptors (FREAs) have recently received intensive attention. Besides the continuing development of new FREAs, the demand for FREAs featuring good compatibility to donor materials is becoming more and more urgent, which is highly desirable for screening donor materials and achieving new breakthroughs. In this work, a new FREA is developed, ZITI, featuring an octacyclic dithienocyclopentaindenoindene central core. The core is designed by linking 2,7-dithienyl substituents and indenoindene with small methylene groups, in which the indeno[1,2-b]thiophene-2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile part provides a large and unoccupied π-surface. Most notably, ZITI possesses an excellent compatibility with commercially available polymer donors, delivering very high power conversion efficiencies of over 13%. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic photosensitive devices

DOEpatents

Peumans, Peter; Forrest, Stephen R.

2013-01-22

A photoactive device is provided. The device includes a first electrode, a second electrode, and a photoactive region disposed between and electrically connected to the first and second electrodes. The photoactive region further includes an organic donor layer and an organic acceptor layer that form a donor-acceptor heterojunction. The mobility of holes in the organic donor region and the mobility of electrons in the organic acceptor region are different by a factor of at least 100, and more preferably a factor of at least 1000. At least one of the mobility of holes in the organic donor region and the mobility of electrons in the organic acceptor region is greater than 0.001 cm.sup.2/V-sec, and more preferably greater than 1 cm.sup.2/V-sec. The heterojunction may be of various types, including a planar heterojunction, a bulk heterojunction, a mixed heterojunction, and a hybrid planar-mixed heterojunction.

Study of intermediates from transition metal excited-state electron-transfer reactions

NASA Astrophysics Data System (ADS)

Hoffman, M. Z.

1984-03-01

Attention during the past year focused on MV(+)., the reduced methyl viologen radical cation, which is a precursor to the formation of H2 in the photosensitized reduction of water. Through the use of photochemical and radiation chemical techniques, the efficiency of interaction of MV(+). with colloidal Pt, the stability of MV(+). as a function of pH, the quantum yield of formation of MV(+). in the Ru(bpy)3(2+)/MV(2+)/EDTA system, and the formation of photoactive charge-transfer complexes between MV(2+) and sacrificial electron donors were studied.

A general framework for the solvatochromism of pyridinium phenolate betaine dyes

NASA Astrophysics Data System (ADS)

Rezende, Marcos Caroli; Aracena, Andrés

2013-02-01

A general framework for the solvatochromic behavior of pyridinium phenolate betaine dyes is presented, based on the variations with the medium of the electrophilic Fukui functions of their electron-pair donor and acceptor moieties. The model explains the ‘anomalous' solvatochromic behavior of large betaines, which change their behavior from negative to inverted, when electron-pair donor and acceptor groups are separated by a conjugated chain of variable size.

Infrared Detector Research

DTIC Science & Technology

1976-08-01

Bratt, Howard Davis, Frank Renda , Paul Chia, Arthur Lockwood. Bell Telephone Labs Leo F. Johnson, Alfred U. MacRae, Paul Norton. Texas Ins truments Werner...impurities which can "donate" their extra electron not required for bonding with the silicon atoms. When there are more acceptors than donors the material...will be p-type. The extra electrons from the donors can complete the bond missing due to the boron atoms. This process is call compensation. The

Gradient ascent pulse engineering approach to CNOT gates in donor electron spin quantum computing

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

Tsai, D.-B.; Goan, H.-S.

2008-11-07

In this paper, we demonstrate how gradient ascent pulse engineering (GRAPE) optimal control methods can be implemented on donor electron spin qubits in semiconductors with an architecture complementary to the original Kane's proposal. We focus on the high fidelity controlled-NOT (CNOT) gate and we explicitly find the digitized control sequences for a controlled-NOT gate by optimizing its fidelity using the effective, reduced donor electron spin Hamiltonian with external controls over the hyperfine A and exchange J interactions. We then simulate the CNOT-gate sequence with the full spin Hamiltonian and find that it has an error of 10{sup -6} that ismore » below the error threshold of 10{sup -4} required for fault-tolerant quantum computation. Also the CNOT gate operation time of 100 ns is 3 times faster than 297 ns of the proposed global control scheme.« less

Origin of background electron concentration in In xGa 1-xN alloys

DOE PAGES

Pantha, B. N.; Wang, H.; Khan, N.; ...

2011-08-15

The origin of high background electron concentration (n) in In xGa 1-xN alloys has been investigated. A shallow donor was identified as having an energy level (E D1) that decreases with x (E D1 = 16 meV at x = 0 and E D1 = 0 eV at x ~ 0.5) and that crossover the conduction band at x ~ 0.5. This shallow donor is believed to be the most probable cause of high n in InGaN. This understanding is consistent with the fact that n increases sharply with an increase in x and becomes constant for x > 0.5.more » A continuous reduction in n was obtained by increasing the V/III ratio during the epilayer growth, suggesting that nitrogen vacancy-related impurities are a potential cause of the shallow donors and high background electron concentration in InGaN« less

Heterogeneous semiconductor photocatalysts for hydrogen production from aqueous solutions of electron donors

NASA Astrophysics Data System (ADS)

Kozlova, E. A.; Parmon, V. N.

2017-09-01

Current views on heterogeneous photocatalysts for visible- and near-UV-light-driven production of molecular hydrogen from water and aqueous solutions of inorganic and organic electron donors are analyzed and summarized. Main types of such photocatalysts and methods for their preparation are considered. Particular attention is paid to semiconductor photocatalysts based on sulfides that are known to be sensitive to visible light. The known methods for increasing the quantum efficiency of the target process are discussed, including design of the structure, composition and texture of semiconductor photocatalysts and variation of the medium pH and the substrate and photocatalyst concentrations. Some important aspects of the activation and deactivation of sulfide photocatalysts and the evolution of their properties in the course of hydrogen production processes in the presence of various types of electron donors are analyzed. The bibliography includes 276 references.

Dissimilatory arsenate reduction with sulfide as electron donor: Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate respirer

USGS Publications Warehouse

Hoeft, S.E.; Kulp, T.R.; Stolz, J.F.; Hollibaugh, J.T.; Oremland, R.S.

2004-01-01

Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3- into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the ??-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

Physiological function of hydrogen metabolism during growth of sulfidogenic bacteria on organic substrates.

PubMed Central

Lupton, F S; Conrad, R; Zeikus, J G

1984-01-01

Desulfovibrio vulgaris Madison and Thermodesulfobacterium commune contained functionally distinct hydrogenase activities, one which exchanged 3H2 into 3H2O and was inhibited by carbon monoxide and a second activity which produced H2 in the presence of CO. Cell suspensions of D. vulgaris used either lactate, pyruvate, or CO as the electron donor for H2 production in the absence of sulfate. Both sulfidogenic species produced and consumed hydrogen as a trace gas during growth on lactate or pyruvate as electron donors and on thiosulfate or sulfate as electron acceptors. Higher initial levels of hydrogen were detected during growth on lactate-sulfate than on pyruvate-sulfate. D. vulgaris but not T. commune also produced and then consumed CO during growth on organic electron donors and sulfate or thiosulfate. High partial pressures of exogenous H2 inhibited growth and substrate consumption when D. vulgaris was cultured on pyruvate alone but not when it was metabolizing pyruvate plus sulfate or lactate plus sulfate. The data are discussed in relation to supporting two different models for the physiological function of H2 metabolism during growth of sulfidogenic bacteria on organic electron donors plus sulfate. A trace H2 transformation model is proposed for control of redox processes during growth on either pyruvate or lactate plus sulfate, and an obligate H2 cycling model is proposed for chemiosmotic energy coupling during growth on CO plus sulfate. PMID:6480553

Outcomes of red blood cell transfusions prescribed in organ donors by the Digital Intern, an electronic decision support algorithm.

PubMed

Connor, Joseph P; Raife, Thomas; Medow, Joshua E

2018-02-01

The Digital Intern (DI) is an electronic decision support tool for the management of organ donors. One algorithm determines the dose, in units of red blood cells to be transfused, based on hematocrit (Hct) thresholds and targets. The effectiveness of the transfusion dose calculated by the DI in terms of achieving the selected Hct target and the duration of the targeted dose is not known. This was a retrospective study to describe the outcomes of transfusions prescribed by the DI. Pre- and posttransfusion Hct levels were compared to define response and all posttransfusion Hct values were plotted to evaluate the duration of the prescribed dose. A total of 120 organ donors were studied and 22 donors had 28 transfusions (six were transfused twice). The transfused donors were a mix of trauma and medical admissions and brain death and cardiac death donors. The transfusion target of 24% Hct was attained in 96% of transfusions. The mean number of units transfused was 1.4 and the mean time from transfusion to procurement was 19.8 hours. There was a decline in Hct over time after transfusion in all but one case with a mean decline of 1.9% Hct over 13 hours. Six donors were transfused twice, likely due to a longer donor time period (41.7 hr vs. 27 hr). The DI provided transfusion dosing that achieved the desired threshold in the majority of organ donors transfused. Ongoing work focuses on application of this technology to transfusions in general patient populations. © 2017 AABB.

Electronic Structure and Bonding in Transition Metal Inorganic and Organometallic Complexes: New Basis Sets, Linear Semibridging Carbonyls and Thiocarbonyls, and Oxidative Addition of Molecular Hydrogen to Square - Iridium Complexes.

NASA Astrophysics Data System (ADS)

Sargent, Andrew Landman

Approximate molecular orbital and ab initio quantum chemical techniques are used to investigate the electronic structure, bonding and reactivity of several transition metal inorganic and organometallic complexes. Modest-sized basis sets are developed for the second-row transition metal atoms and are designed for use in geometry optimizations of inorganic and organometallic complexes incorporating these atoms. The basis sets produce optimized equilibrium geometries which are slightly better than those produced with standard 3-21G basis sets, and which are significantly better than those produced with effective core potential basis sets. Linear semibridging carbonyl ligands in heterobimetallic complexes which contain a coordinatively unsaturated late transition metal center are found to accept electron density from, rather than donate electron density to, these centers. Only when the secondary metal center is a coordinatively unsaturated early transition metal center does the semibridging ligand donate electron density to this center. Large holes in the d shell around the metal center are more prominent and prevalent in early than in late transition metal centers, and the importance of filling in these holes outweighs the importance of mitigating the charge imbalance due to the dative metal-metal interaction. Semibridging thiocarbonyl ligands are more effective donors of electron density than the carbonyl ligands since the occupied donor orbitals of pi symmetry are higher in energy. The stereoselectivity of H_2 addition to d^8 square-planar transition metal complexes is controlled by the interactions between the ligands in the plane of addition and the concentrations of electronic charge around the metal center as the complex evolves from a four-coordinate to a six-coordinate species. Electron -withdrawing ligands help stabilize the five-coordinate species while strong electron donor ligands contribute only to the destabilizing repulsive interactions. The relative thermodynamic stabilities of the final complexes can be predicted based on the relative orientations of the strongest sigma-donor ligands.

Energetic Limitations on Microbial Respiration of Organic Compounds using Aqueous Fe(III) Complexes

NASA Astrophysics Data System (ADS)

Naughton, H.; Fendorf, S. E.

2015-12-01

Soil organic matter constitutes up to 75% of the terrestrial carbon stock. Microorganisms mediate the breakdown of organic compounds and the return of carbon to the atmosphere, predominantly through respiration. Microbial respiration requires an electron acceptor and an electron donor such as small fatty acids, organic acids, alcohols, sugars, and other molecules that differ in oxidation state of carbon. Carbon redox state affects how much energy is required to oxidize a molecule through respiration. Therefore, different organic compounds should offer a spectrum of energies to respiring microorganisms. However, microbial respiration has traditionally focused on the availability and reduction potential of electron acceptors, ignoring the organic electron donor. We found through incubation experiments that the organic compound serving as electron donor determined how rapidly Shewanella putrefaciens CN32 respires organic substrate and the extent of reduction of the electron acceptor. We simulated a range of energetically favorable to unfavorable electron acceptors using organic chelators bound to Fe(III) with equilibrium stability constants ranging from log(K) of 11.5 to 25.0 for the 1:1 complex, where more stable complexes are less favorable for microbial respiration. Organic substrates varied in nominal oxidation state of carbon from +2 to -2. The most energetically favorable substrate, lactate, promoted up to 30x more rapid increase in percent Fe(II) compared to less favorable substrates such as formate. This increased respiration on lactate was more substantial with less stable Fe(III)-chelate complexes. Intriguingly, this pattern contradicts respiration rate predicted by nominal oxidation state of carbon. Our results suggest that organic substrates will be consumed so long as the energetic toll corresponding to the electron donor half reaction is counterbalanced by the energy available from the electron accepting half reaction. We propose using the chemical structure of organic matter, elucidated with techniques such as FT-ICR MS, to improve microbial decomposition and carbon cycling models by incorporating energetic limitations due to carbon oxidation.

Resonant electronic excitation energy transfer by exchange mechanism in the quantum dot system

NASA Astrophysics Data System (ADS)

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

2017-11-01

A microscopic theory of nonradiative resonance energy transfer between spherical A3B5 semiconductor quantum dots by the exchange mechanism is suggested. The interdot Coulomb interaction is taken into consideration. It is assumed that the quantum dot-donor and the quantum dot-acceptor are made from the same A3B5 compound and are embedded in the matrix of another material that produces potential barriers for electrons and holes. The dependences of the energy transfer rate on the quantum-dot system parameters are found in the frame of the Kane model that provides the most adequate description of the real spectra of A3B5 semiconductors. The analytical treatment is carried out with using the density matrix method, which enabled us to perform an energy transfer analysis both in the weak-interaction approximation and in the strong-interaction approximation. The numerical calculations showed the saturation of the energy transfer rate at the distances between the donor and the acceptor approaching the contact one. The contributions of the exchange and direct Coulomb intractions can be of the same order at the small distances and can have the same value in the saturation range.

Is Oxidized Thioredoxin a Major Trigger for Cysteine Oxidation? Clues from a Redox Proteomics Approach

PubMed Central

García-Santamarina, Sarela; Boronat, Susanna; Calvo, Isabel A.; Rodríguez-Gabriel, Miguel; Ayté, José; Molina, Henrik

2013-01-01

Abstract Cysteine oxidation mediates oxidative stress toxicity and signaling. It has been long proposed that the thioredoxin (Trx) system, which consists of Trx and thioredoxin reductase (Trr), is not only involved in recycling classical Trx substrates, such as ribonucleotide reductase, but it also regulates general cytoplasmic thiol homeostasis. To investigate such a role, we have performed a proteome-wide analysis of cells expressing or not the two components of the Trx system. We have compared the reversibly oxidized thiol proteomes of wild-type Schizosaccharomyces pombe cells with mutants lacking Trx or Trr. Specific Trx substrates are reversibly-oxidized in both strain backgrounds; however, in the absence of Trr, Trx can weakly recycle its substrates at the expense of an alternative electron donor. A massive thiol oxidation occurs only in cells lacking Trr, with 30% of all cysteine-containing peptides being reversibly oxidized; this oxidized cysteine proteome depends on the presence of Trxs. Our observations lead to the hypothesis that, in the absence of its reductase, the natural electron donor Trx becomes a powerful oxidant and triggers general thiol oxidation. Antioxid. Redox Signal. 18, 1549–1556. PMID:23121505

High-Resolution Two-Dimensional Optical Spectroscopy of Electron Spins

NASA Astrophysics Data System (ADS)

Salewski, M.; Poltavtsev, S. V.; Yugova, I. A.; Karczewski, G.; Wiater, M.; Wojtowicz, T.; Yakovlev, D. R.; Akimov, I. A.; Meier, T.; Bayer, M.

2017-07-01

Multidimensional coherent optical spectroscopy is one of the most powerful tools for investigating complex quantum mechanical systems. While it was conceived decades ago in magnetic resonance spectroscopy using microwaves and radio waves, it has recently been extended into the visible and UV spectral range. However, resolving MHz energy splittings with ultrashort laser pulses still remains a challenge. Here, we analyze two-dimensional Fourier spectra for resonant optical excitation of resident electrons to localized trions or donor-bound excitons in semiconductor nanostructures subject to a transverse magnetic field. Particular attention is devoted to Raman coherence spectra, which allow one to accurately evaluate tiny splittings of the electron ground state and to determine the relaxation times in the electron spin ensemble. A stimulated steplike Raman process induced by a sequence of two laser pulses creates a coherent superposition of the ground-state doublet which can be retrieved only optically because of selective excitation of the same subensemble with a third pulse. This provides the unique opportunity to distinguish between different complexes that are closely spaced in energy in an ensemble. The related experimental demonstration is based on photon-echo measurements in an n -type CdTe /(Cd ,Mg )Te quantum-well structure detected by a heterodyne technique. The difference in the sub-μ eV range between the Zeeman splittings of donor-bound electrons and electrons localized at potential fluctuations can be resolved even though the homogeneous linewidth of the optical transitions is larger by 2 orders of magnitude.

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells.

PubMed

Capodilupo, Agostina L; Fabiano, Eduardo; De Marco, Luisa; Ciccarella, Giuseppe; Gigli, Giuseppe; Martinelli, Carmela; Cardone, Antonio

2016-04-15

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

Improving first-time donor attendance rates through the use of enhanced donor preparation materials.

PubMed

Masser, Barbara; France, Christopher R; Foot, Jayne; Rozsa, Amy; Hayman, Jane; Waller, Daniel; Hunder, Everard

2016-06-01

Many nondonors are positive about blood donation and this motivates booking an appointment to donate. However, as their appointment approaches barriers to donating-such as anxiety-may become salient and deter attendance. Building on research of France and colleagues demonstrating the positive effect of enhanced preparation materials on donor recruitment, this study sought to determine whether these materials could effectively boost first donation appointment attendance. A field study comprising a 3 (brochure: none, e-mail, hard copy) × 2 (national call center [NCC] contact: none, call) between-subjects design was conducted with 3646 nondonors who had scheduled their first appointment. Participants in the brochure conditions received either a hard copy or an e-mailed link to electronic materials modeled on the donor preparation research of France and colleagues. Participants in the NCC call condition also received a call scripted in line with these preparation materials. The key outcome was new donor attendance rate. Although first-appointment attendance rates were high in the control (no additional contact) condition at 85.07% of those not canceling in advance, dual exposure to the preparation materials through a NCC call and an electronic brochure boosted attendance. The relative risk of attending in the NCC call and electronic brochure condition was 1.0836 (95% confidence interval, 1.0352-1.1343; p = 0.0006), with attendance 8.36% higher than in the control. This gain in attendance came at a relative increase in recruitment costs of 2%. The use of tailored communication to address new donors' concerns and prepare them for donating bolsters attendance rates. © 2016 AABB.

Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions

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

Ihly, Rachelle; Mistry, Kevin S.; Ferguson, Andrew J.

2016-04-25

Understanding the kinetics and energetics of interfacial electron transfer in molecular systems is crucial for the development of a broad array of technologies, including photovoltaics, solar fuel systems and energy storage. The Marcus formulation for electron transfer relates the thermodynamic driving force and reorganization energy for charge transfer between a given donor/acceptor pair to the kinetics and yield of electron transfer. Here we investigated the influence of the thermodynamic driving force for photoinduced electron transfer (PET) between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives by employing time-resolved microwave conductivity as a sensitive probe of interfacial exciton dissociation. For the firstmore » time, we observed the Marcus inverted region (in which driving force exceeds reorganization energy) and quantified the reorganization energy for PET for a model SWCNT/acceptor system. The small reorganization energies (about 130 meV, most of which probably arises from the fullerene acceptors) are beneficial in minimizing energy loss in photoconversion schemes.« less

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

NASA Technical Reports Server (NTRS)

Parusel, A. B.

2000-01-01

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Ac Conduction in Mixed Oxides Al-In2O3-SnO2-Al Structure Deposited by Co-Evaporation

NASA Astrophysics Data System (ADS)

Anwar, M.; Siddiqi, S. A.; Ghauri, I. M.

Conductivity-frequency and capacitance-frequency characteristics of mixed oxides Al-In2O3-SnO2-Al structure are examined to elicit any correlation with the conduction mechanisms most often observed in thin film work. The existence of Schottky barriers is believed to be due to a strong donor band in the insulator established during the vacuum evaporation when a layer of mixed oxides In2O3-SnO2 system is sandwiched between two metal electrodes. Low values of activation energy at low temperatures indicate that the transport of the carriers between localized states is mainly due to electronic hopping over the barrier separating the two nearest neighbor sites. The increase in the formation of ionized donors with increase in temperature during electrical measurements indicates that electronic part of the conductivity is higher than the ionic part. The initial increase in conductivity with increase in Sn content in In2O3 lattice is caused by the Sn atom substitution of In atom, giving out one extra electron. The decrease in electrical conductivity above the critical Sn content (10 mol% SnO2) is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in electrical conductivity with film thickness is caused by the increase in free carriers density, which is generated by oxygen vacancy acting as two electron donor. The increase in conductivity with substrate and annealing temperatures is due to either the severe deficiency of oxygen, which deteriorates the film properties and reduces the mobility of the carriers or to the diffusion of Sn atoms from interstitial locations into the In cation sites and formation of indium species of lower oxidation state (In2+). Calculations of C and σac from tan δ measurements suggest that there is some kind of space-charge polarization in the material, caused by the storage of carriers at the electrodes. Capacitance decreases not only with the rise of frequency but also with the lowering of temperature. At low temperatures the major contribution to capacitance arises from the ionic polarization, however, with the increase of temperature the contribution from orientation polarization would considerably increase. The decrease in capacitance with the increase in frequency may be attributed to interfacial polarization.

Trehalose protects Mn-depleted photosystem 2 preparations against the donor-side photoinhibition.

PubMed

Yanykin, D V; Khorobrykh, A A; Mamedov, M D; Klimov, V V

2016-11-01

Recently, it has been shown that the addition of 1M trehalose leads to the increase of the rate of oxygen photoconsumption associated with activation of electron transport in the reaction center of photosystem 2 (PS2) in Mn-depleted PS2 membranes (apo-WOC-PS2) [37]. In the present work the effect of trehalose on photoinhibition of apo-WOC-PS2 preparations (which are characterized by a high sensitivity to the donor side photoinhibition of PS2) was investigated. The degree of photoinhibition was estimated by the loss of the capability of exogenous electron donor (sodium ascorbate) to reactivate the electron transport (measured by light-induced changes of chlorophyll fluorescence yield (∆F)) in apo-WOC-PS2. It was found that 1M trehalose enhanced the Mn 2+ -dependent suppression of photoinhibition of apo-WOC-PS2: in the presence of trehalose the addition of 0.2μM Mn 2+ (corresponding to 2 Mn 2+ per one reaction center) was sufficient for an almost complete suppression of the donor side photoinhibition of the complex. In the absence of trehalose it was necessary to add 100μM Mn 2+ to achieve a similar result. The effect of trehalose was observed during photoinhibition of apo-WOC-PS2 at low (15μmolphotons -1 m -2 ) and high (200μmolphotons -1 m -2 ) light intensity. When Mn 2+ was replaced by other PS2 electron donors (ferrocyanide, DPC) as well as by Ca 2+ the protective effect of trehalose was not observed. It was also found that 1M trehalose decreased photoinhibition of apo-WOC-PS2 if the samples contained endogenous manganese (1-2 Mn ions per one RC was enough for the maximum protection effect). It is concluded that structural changes in PS2 caused by the addition of trehalose enhance the capability of photochemical reaction centers of apo-WOC-PS2 to accept electrons from manganese (both exogenous and endogenous), which in turn leads to a considerable suppression of the donor side photoinhibition of PS2. Copyright © 2016 Elsevier B.V. All rights reserved.

Distributions of microbial activities in deep subseafloor sediments

NASA Technical Reports Server (NTRS)

D'Hondt, Steven; Jorgensen, Bo Barker; Miller, D. Jay; Batzke, Anja; Blake, Ruth; Cragg, Barry A.; Cypionka, Heribert; Dickens, Gerald R.; Ferdelman, Timothy; Hinrichs, Kai-Uwe;

Photoinduced electron transfer in rigidly linked dimethoxynapthalene-N-methylpyridinium donor-acceptor molecules

NASA Astrophysics Data System (ADS)

Clayton, Andrew H. A.; Ghiggino, Kenneth P.; Wilson, Gerard J.; Keyte, Peter J.; Paddon-Row, Michael N.

1992-07-01

Photoinduced electron transfer (ET) is studied in a series of novel molecules containing a dimethoxynaphthalene (DMN) donor and either a pyridine (P) or N-methylpyridinium (P-Me +) acceptor covalently linked via a rigid nonbornalogous bridge ( n sigma bonds in length). ET rates of the order of 10 10 s -1 were measured for the DMN- n-P-Me + series ( n = 4, 6), while no appreciable ET was observed for the DMN- n-P compounds. Electronic and nuclear factors are discussed and the results rationalized in terms of Marcus—Hush and non-adiabatic ET theories.

Quasiclassical description of the nearest-neighbor hopping dc conduction via hydrogen-like donors in intermediately compensated GaAs crystals

NASA Astrophysics Data System (ADS)

Poklonski, N. A.; Vyrko, S. A.; Zabrodskii, A. G.

2010-08-01

Expressions for the pre-exponential factor σ3 and the thermal activation energy ɛ3 of hopping electric conductivity of electrons via hydrogen-like donors in n-type gallium arsenide are obtained in the quasiclassical approximation. Crystals with the donor concentration N and the acceptor concentration KN at the intermediate compensation ratio K (approximately from 0.25 to 0.75) are considered. We assume that the donors in the charge states (0) and (+1) and the acceptors in the charge state (-1) form a joint nonstoichiometric simple cubic 'sublattice' within the crystalline matrix. In such sublattice the distance between nearest impurity atoms is Rh = [(1 + K)N]-1/3 which is also the length of an electron hop between donors. To take into account orientational disorder of hops we assume that the impurity sublattice randomly and smoothly changes orientation inside a macroscopic sample. Values of σ3(N) and ɛ3(N) calculated for the temperature of 2.5 K agree with known experimental data at the insulator side of the insulator-metal phase transition.

Effective treatment of alkaline Cr(VI) contaminated leachate using a novel Pd-bionanocatalyst: Impact of electron donor and aqueous geochemistry

PubMed Central

Watts, Mathew P.; Coker, Victoria S.; Parry, Stephen A.; Thomas, Russell A.P.; Kalin, Robert; Lloyd, Jonathan R.

2015-01-01

Palladium catalysts offer the potential for the effective treatment of a variety of priority reducible pollutants in natural waters. In this study, microbially synthesized magnetite nanoparticles were functionalized with Pd(0), creating a highly reactive, magnetically recoverable, nano-scale catalyst (Pd-BnM). This was then investigated for the treatment of model Cr(VI) contaminated solutions at a range of pH values, and also alkaline Cr(VI) contaminated leachates from chromite ore processing residue (COPR); a contaminant issue of global concern. The sample of COPR used in this study was obtained from a site in Glasgow, UK, where extensive Cr(VI) contamination has been reported. In initial experiments Pd-BnM was supplied with H2 gas or formate as electron donors, and Cr(VI) removal from model synthetic solutions was quantified at various pH values (2–12). Effective removal was noted at neutral to environmentally relevant alkaline (pH 12) pH values, while the use of formate as an electron donor resulted in loss of performance under acidic conditions (pH 2). Reaction kinetics were then assessed with increasing Pd-BnM loading in both model pH 12 Cr(VI) solutions and the COPR leachate. When formate was used as the electron donor for Pd-BnM, to treat COPR leachate, there was significant inhibition of Cr(VI) removal. In contrast, a promotion of reaction rate, was observed when H2 was employed. Upon sustained reaction with model Cr(VI) solutions, in the presence of excess electron donor (formate or H2), appreciable quantities of Cr(VI) were removed before eventual inactivation of the catalyst. Faster onset of inactivation was reported in the COPR leachates, removing 4% and 64% of Cr(VI) observed from model Cr(VI) solutions, when formate and H2 were used as electron donors, respectively. XAS, TEM-EDX and XPS analysis of the catalysts that had been inactivated in the model solution, showed that the surface had an extensive covering of reduced Cr(III), most likely as a CrOOH phase. COPR reacted catalysts recorded a lower abundance of Cr(III) alongside a high abundance of the leachate components Ca and Si, implicating these elements in the faster onset of inactivation. PMID:26146457

Ultrafast photoinduced charge transport in Pt(II) donor-acceptor assembly bearing naphthalimide electron acceptor and phenothiazine electron donor.

PubMed

Sazanovich, Igor V; Best, Jonathan; Scattergood, Paul A; Towrie, Michael; Tikhomirov, Sergei A; Bouganov, Oleg V; Meijer, Anthony J H M; Weinstein, Julia A

2014-12-21

Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor-chromophore-donor, (NDI-phen)Pt(II)(-C≡C-Ph-CH2-PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(-C≡C-Ph-)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a (3)MLCT/LL'CT, with {Pt(II)-acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI(-)-phen-[Pt-(C≡C)2](+)-PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of ∼15 ps during which the hole migrates from the [Pt-(C≡C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C≡C-Ph-CH2-PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C≡C-Ph-C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed.

Enhanced performance of polymer solar cells by employing a ternary cascade energy structure.

PubMed

An, Qiaoshi; Zhang, Fujun; Li, Lingliang; Zhuo, Zuliang; Zhang, Jian; Tang, Weihua; Teng, Feng

2014-08-14

We present a route to successfully tackle the two main limitations, low open circuit voltage (Voc) and limited short circuit-density (Jsc), of polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) as an electron-donor. The indene-C60 bisadduct (ICBA) was selected as an electron acceptor to improve the open circuit voltage (Voc). The narrow band gap polymer poly[(4,8-bis-(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2,6-diyl] (PBDTTT-C), as a complementary electron-donor material, was doped into the host system of P3HT:ICBA to form ternary cascade energy structured PSCs with increased Jsc. The power conversion efficiency (PCE) of P3HT:ICBA-based cells was improved from 3.32% to 4.38% by doping with 3 wt% PBDTTT-C with 1 min 150 °C annealing treatment. The 4.38% PCE of ternary PSCs is still larger than the 3.79% PCE of PSCs based on P3HT:ICBA with 10 minutes 150 °C annealing treatment.

Exciplex and excimer molecular probes: detection of conformational flip in a myo-inositol chair.

PubMed

Kadirvel, Manikandan; Arsic, Biljana; Freeman, Sally; Bichenkova, Elena V

2008-06-07

2-O-tert-Butyldimethylsilyl-4,6-bis-O-pyrenoyl-myo-inositol-1,3,5-orthoformate (6) and 2-O-tert-butyldimethylsilyl-4-O-[4-(dimethylamino)benzoyl]-6-O-pyrenoyl-myo-inositol-1,3,5-orthoacetate (10) adopt conformationally restricted unstable chairs with five axial substituents. In the symmetrical diester 6, the two pi-stacked pyrenoyl groups are electron acceptor-donor partners, giving a strong intramolecular excimer emission. In the mixed ester 10, the pyrenoyl group is the electron acceptor and the 4-(dimethylamino)benzoyl ester is the electron donor, giving a strong intramolecular exciplex emission. The conformation of the mixed ester 10 was assessed using 1H NMR spectroscopy (1H-NOESY) and computational studies. which showed the minimum inter-centroid distance between the two aromatic systems to be approximately 3.9 A. Upon addition of acid, the orthoformate/orthoacetate trigger in 6 and 10 was cleaved, which caused a switch of the conformation of the myo-inositol ring to the more stable penta-equatorial chair, leading to separation of the aromatic ester groups and loss of excimer and exciplex fluorescence, respectively. This study provides proof of principle for the development of novel fluorescent molecular probes.

Effect of proton transfer on the electronic coupling in DNA

NASA Astrophysics Data System (ADS)

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

2006-06-01

The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, Vda, in DNA are studied on the bases of quantum chemical calculations. Four dimers [AT,AT], [GC,GC], [GC,AT] and [GC,TA)] are considered. Three techniques - the generalized Mulliken-Hush scheme, the fragment charge method and the diabatic states method - are employed to estimate Vda for hole transfer between base pairs. We show that both single- and double proton transfer (PT) reactions may substantially affect the electronic coupling in DNA. The electronic coupling in [AT,AT] is predicted to be most sensitive to PT. Single PT within the first base pair in the dimer leads to increase in the hole transfer efficiency by a factor of 4, while proton transfer within the second pair should substantially, by 2.7 times, decrease the rate of charge transfer. Thus, directional asymmetry of the PT effects on the electronic coupling is predicted. The changes in the Vda matrix elements correlate with the topological properties of orbitals of donor and acceptor and can be qualitatively rationalized in terms of resonance structures of donor and acceptor. Atomic pair contributions to the Vda matrix elements are also analyzed.

Comparative Demonstration of Active and Semi-Passive in Situ Bioremediation Approaches for Perchlorate-Impacted Groundwater at Longhorn Army Ammunitions Plant

DTIC Science & Technology

2009-01-01

wells in order to achieve the desired electron donor coverage. Soluble electron donors such as sodium lactate, citric acid , or ethanol have been used in...ORP) Monitoring.............39 6.7.5 Results of Volatile Fatty Acids (VFA) Analysis............................39 6.7.6 Results of Sulfate Analysis...VC vinyl chloride VFA volatile fatty acid VOC volatile organic compounds Technical material contained in this report has been approved for

Implanted bismuth donors in 28-Si: Process development and electron spin resonance measurements

NASA Astrophysics Data System (ADS)

Weis, C. D.; Lo, C. C.; Lang, V.; George, R. E.; Tyryshkin, A. M.; Bokor, J.; Lyon, S. A.; Morton, J. J. L.; Schenkel, T.

2012-02-01

Spins of donor atoms in silicon are excellent qubit candidates. Isotope engineered substrates provide a nuclear spin free host environment, resulting in long spin coherence times [1,2]. The capability of swapping quantum information between electron and nuclear spins can enable quantum communication and gate operation via the electron spin and quantum memory via the nuclear spin [2]. Spin properties of donor qubit candidates in silicon have been studied mostly for phosphorous and antimony [1-3]. Bismuth donors in silicon exhibit a zero field splitting of 7.4 GHz and have attracted attention as potential nuclear spin memory and spin qubit candidates [4,5] that could be coupled to superconducting resonators [4,6]. We report on progress in the formation of bismuth doped 28-Si epi layers by ion implantation, electrical dopant activation and their study via pulsed electron spin resonance measurements showing narrow linewidths and good coherence times. [4pt] [1] A. M. Tyryshkin, et al. arXiv: 1105.3772 [2] J. J. L. Morton, et al. Nature (2008) [3] T. Schenkel, et al APL 2006; F. R. Bradbury, et al. PRL (2006) [4] R. E. George, et al. PRL (2010) [5] G. W. Morley, et al. Nat Mat (2010) [6] M. Hatridge, et al. PRB (2011), R. Vijay, et al. APL (2010) This work was supported by NSA (100000080295) and DOE (DE-AC02-05CH11231).

Interaction of proflavin with aromatic amines in homogeneous and micellar media: Photoinduced electron transfer probed by magnetic field effect

NASA Astrophysics Data System (ADS)

Chakraborty, Brotati; Basu, Samita

2010-02-01

Photoinduced electron transfer (PET) between proflavin (PF +) and two aromatic amines viz., dimethylaniline (DMA) and 4,4'-bis(dimethylamino)diphenylmethane (DMDPM) is studied in homogeneous and heterogeneous media using steady-state as well as time-resolved fluorescence spectroscopy and laser flash photolysis with an associated magnetic field. Ionic micelles have been used to study the effect of charge of proflavin on PET with amines. Magnetic field effect on PET reactions reveals that the parent spin-state of precursors of PET for DMA-PF + system is singlet while for DMDPM-PF + system is triplet, implying that the dynamics of PET is influenced by the structure of the donor.

Density Functional Study on A-Units Based on Thieno[3,4- c]pyrrole-4,6-dione for Organic Solar Cells

NASA Astrophysics Data System (ADS)

Tang, Xiaoqin; Shen, Wei; Fu, Zhiyong; Liu, Xiaorui; Li, Ming

2017-08-01

The use of polymer donor materials has allowed great progress in organic solar cells. To search for potential donor materials, we have designed a series of donor-acceptor (D-A)-type alternating polymers composed of dithieno[3,2- b:2',3'- d]pyrrole (DTP) electron-rich units and thieno[3,4- c]pyrrole-4,6-dione (TPD) electron-deficient units. Their electronic and optical properties have been investigated using density functional theory and Marcus theory. The calculation results demonstrate that introduction of cyclic compounds (furyl, thienyl, and phenyl) into electron-deficient units of the molecules can result in lower highest occupied molecular orbital (HOMO) levels and reorganization energies compared with the experimental molecule ( X 0 ). To investigate the effects of electron-withdrawing units, three electron-withdrawing substituents (-OCH3, -F, and -CN) were introduced into the thienyl. The results indicated that the polymer X 2-3 will show the best performance among the designed polymers, offering low-lying HOMO energy level (-5.47 eV), narrow energy gap (1.97 eV), and high hole mobility (7.45 × 10-2 cm2 V-1 s-1). This work may provide a guideline for the design of efficient D-A polymers for organic solar cells with enhanced performance.

Rational Design of High-Performance Wide-Bandgap (≈2 eV) Polymer Semiconductors as Electron Donors in Organic Photovoltaics Exhibiting High Open Circuit Voltages (≈1 V).

PubMed

Chochos, Christos L; Katsouras, Athanasios; Gasparini, Nicola; Koulogiannis, Chrysanthos; Ameri, Tayebeh; Brabec, Christoph J; Avgeropoulos, Apostolos

2017-01-01

Systematic optimization of the chemical structure of wide-bandgap (≈2.0 eV) "donor-acceptor" copolymers consisting of indacenodithiophene or indacenodithieno[3,2-b]thiophene as the electron-rich unit and thieno[3,4-c]pyrrole-4,6-dione as the electron-deficient moiety in terms of alkyl side chain engineering and distance of the electron-rich and electron-deficient monomers within the repeat unit of the polymer chain results in high-performance electron donor materials for organic photovoltaics. Specifically, preliminary results demonstrate extremely high open circuit voltages (V oc s) of ≈1.0 V, reasonable short circuit current density (J sc ) of around 11 mA cm -2 , and moderate fill factors resulting in efficiencies close to 6%. All the devices are fabricated in an inverted architecture with the photoactive layer processed by doctor blade equipment, showing the compatibility with roll-to-roll large-scale manufacturing processes. From the correlation of the chemical structure-optoelectronic properties-photovoltaic performance, a rational guide toward further optimization of the chemical structure in this family of copolymers, has been achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Halogen bond: a long overlooked interaction.

PubMed

Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

2015-01-01

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

Modeling the long-term fate of agricultural nitrate in groundwater in the San Joaquin Valley, California

USGS Publications Warehouse

Chapelle, Francis H.; Campbell, Bruce G.; Widdowson, Mark A.; Landon, Mathew K.

2013-01-01

Nitrate contamination of groundwater systems used for human water supplies is a major environmental problem in many parts of the world. Fertilizers containing a variety of reduced nitrogen compounds are commonly added to soils to increase agricultural yields. But the amount of nitrogen added during fertilization typically exceeds the amount of nitrogen taken up by crops. Oxidation of reduced nitrogen compounds present in residual fertilizers can produce substantial amounts of nitrate which can be transported to the underlying water table. Because nitrate concentrations exceeding 10 mg/L in drinking water can have a variety of deleterious effects for humans, agriculturally derived nitrate contamination of groundwater can be a serious public health issue. The Central Valley aquifer of California accounts for 13 percent of all the groundwater withdrawals in the United States. The Central Valley, which includes the San Joaquin Valley, is one of the most productive agricultural areas in the world and much of this groundwater is used for crop irrigation. However, rapid urbanization has led to increasing groundwater withdrawals for municipal public water supplies. That, in turn, has led to concern about how contaminants associated with agricultural practices will affect the chemical quality of groundwater in the San Joaquin Valley. Crop fertilization with various forms of nitrogen-containing compounds can greatly increase agricultural yields. However, leaching of nitrate from soils due to irrigation has led to substantial nitrate contamination of shallow groundwater. That shallow nitrate-contaminated groundwater has been moving deeper into the Central Valley aquifer since the 1960s. Denitrification can be an important process limiting the mobility of nitrate in groundwater systems. However, substantial denitrification requires adequate sources of electron donors in order to drive the process. In many cases, dissolved organic carbon (DOC) and particulate organic carbon (POC) are the primary electron donors driving active denitrification in groundwater. The purpose of this chapter is to use a numerical mass balance modeling approach to quantitatively compare sources of electron donors (DOC, POC) and electron acceptors (dissolved oxygen, nitrate, and ferric iron) in order to assess the potential for denitrification to attenuate nitrate migration in the Central Valley aquifer.

An overview of the first half-century of molecular electronics.

PubMed

Hush, Noel S

2003-12-01

The seminal ideas from which molecular electronics has developed were the theories of molecular conduction advanced in the late 1940s by Robert S. Mulliken and Albert Szent-Gyorgi. These were, respectively, the concept of donor-acceptor charge transfer complexes and the possibility that proteins might in fact not be insulators The next two decades saw a burgeoning of experimental and theoretical work on electron transfer systems, together with a lone effort by D.D. Eley on conduction in proteins. The call by Feynman in his famous 1959 lecture There's Plenty of Room at the Bottom for chemists, engineers and physicists to combine to build up structures from the molecular level was influential in turning attention to the possibility of engineering single molecules to function as elements in information-processing systems. This was made tangible by the proposal of Aviram and Ratner in 1974 to use a Mulliken-like electron donor-acceptor molecule as a molecular diode, generalizing molecular conduction into molecular electronics. In the early 1970s the remarkably visionary work of Forrest L. Carter of the U.S. Naval Research Laboratories began to appear: designs for molecular wires, switches, complex molecular logic elements, and a host of related ideas were advanced. Shortly after that, conferences on molecular electronics began to be held, and the interdisciplinary programs that Feynman envisaged. There was a surge in both experimental and theoretical work in molecular electronics, and the establishment of many research centres. The past five years or so have seen extraordinarily rapid progress in fabrication and theoretical understanding. The history of how separate lines of research emanating from fundamental insights of about 50 years ago have coalesced into a thriving international research program in what might be called the ultimate nanotechnology is the subject of this review; it concentrates on the lesser-appreciated early developments in the field.

Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers.

PubMed

Lei, Ting; Wang, Jie-Yu; Pei, Jian

2014-04-15

Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor-acceptor (D-A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure-property relationships. Recently, isoindigo has been used as a new acceptor of D-A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure-property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using farther branched alkyl chains can effectively decrease interchain π-π stacking distance and improve carrier mobility. When we introduce electron-deficient functional groups on the isoindigo core, the LUMO levels of the polymers markedly decrease, which significantly improves the electron mobility and device stability. In addition, we present a new polymer system called BDOPV, which is based on the concept of π-extended isoindigo. By application of some strategies successfully used in isoindigo-based polymers, BDOPV-based polymers exhibit high mobility and good stability both in n-type and in ambipolar FETs. We believe that a synergy of molecular engineering strategies towards the isoindigo core, donor units, and side chains may further improve the performance and broaden the application of isoindigo-based polymers.

Rotaxanes and Photovoltaic Materials Based on Pi-Conjugated Donors and Acceptors: Toward Energy Transduction on the Nanoscale

NASA Astrophysics Data System (ADS)

Bruns, Carson J.

The flow of energy between its various forms is central to our understanding of virtually all natural phenomena, from the origins and fate of the universe to the mechanisms that underpin Life. Therefore, a deeper fundamental understanding of how to manage energy processes at the molecular scale will open new doors in science and technology. This dissertation describes organic molecules and materials that are capable of transducing various forms of energy on the nanoscale, namely, a class of mechanically interlocked molecules known as rotaxanes for electrochemical-to-mechanical energy transduction (Part I), and a class of thin films known as organic photovoltaics (OPVs) for solar-to-electric energy transduction (Part II). These materials are all based on conjugated molecules with a capacity to donate or accept pi-electrons. A contemporary challenge in molecular nanotechnology is the development of artificial molecular machines (AMMs) that mimic the ability of motor proteins (e.g. myosin, kinesin) to perform mechanical work by leveraging a combination of energy sources and rich structural chemistry. Part I describes the synthesis, characterization, molecular dynamics, and switching properties of a series of `daisy chain' and oligorotaxane AMM prototypes. All compounds are templated by charge transfer and hydrogen bonding interactions between pi-associated 1,5-dioxynaphthlene donors appended with polyether groups and pi-acceptors of either neutral (naphthalenediimide) or charged (4,4´-bipyridinium) varieties, and are synthesized using efficient one-pot copper(I)-catalyzed azide-alkyne cycloaddition `click chemistry' protocols. The interlocked architectures of these rotaxanes enable them to express sophisticated secondary structures (i.e. foldamers) and mechanical motions in solution, which have been elucidated using dynamic 1H NMR spectroscopy. Furthermore, molecular dynamics simulations, cyclic voltammetry, and spectroelectrochemistry experiments have demonstrated that the muscle-like contractile-extensile motions of the daisy chains can be controlled by redox or thermal stimuli. It is concluded that donor-acceptor daisy chains and oligorotaxanes of unprecendented complexity can be readily prepared using click chemistry and actuated in solution. Motivated by the global demand for low-cost renewable energy, novel pi-donor molecules based on thiophene and diketopyrrolopyrrole (DPP) moieties are investigated in the context of thin-film materials for OPV technologies in Part II. Homologous families of small-molecule donors have been synthesized to investigate the effects of various molecular design principles on the morphological, optical, electronic, and photovoltaic properties of the corresponding thin-film materials. This strategy has been executed in the context of inorganic-organic hybrid OPVs and also more conventional bulk heterojunction (BHJ) OPVs. In the former case, a series of terthiophene surfactants with systematic variations in valency, geometry, and flexibility are electrodeposited on transparent electrodes from aqueous solutions to yield lamellar Zn(OH)2 materials with nanoscale periodicity, which are characterized by scanning electron miscroscopy and two-dimensional grazing incidence X-ray scattering. It is concluded that monovalent, flexible, linear surfactants yield the most dense and anisotropic nanostructures that are ideal for OPVs. For BHJ OPVs, the family of compounds under investigation are small molecule (SM) donors based on electron-rich heterocyclic acenes (benzodithiophene, benzodifuran, naphtho-dithiophene) and electron-poor thiophene-flanked DPP units. Single crystal X-ray structures of the SM donors are compared with morphological, hole mobility, photovoltaic efficiency data on their blends with a common fullerene acceptor to elucidate the optimal molecular design principles for this class of OPVs. It is concluded that the best-performing molecules have a symmetric architecture in which the central acene core comprises an extended pi-system.

Next Generation Highly Conducting Organic Films Using Novel Donor-Acceptor Molecules for Opto-electronic Applications

DTIC Science & Technology

2010-06-01

addition, a new class of donor molecules was invented in the course of the DRI program. 2.1 Polymer Based Donor-acceptor Material The following work by...average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data...information, including suggestions for reducing the burden, to Department of Defense, Washington Headquarters Services, Directorate for Information

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

Norris, J.R.; Budil, D.E.; Gast, P.

The orientation of the principal axes of the primary electron donor triplet state measured in single crystals of photosynthetic reaction centers is compared to the x-ray structures of the bacteria Rhodobacter (Rb.) sphaeroides R-26 and Rhodopseudomonas (Rps.) viridis. The primary donor of Rps. viridis is significantly different from that of Rb. sphaeroides. The measured directions of the axes indicate that triplet excitation is almost completely localized on the L-subunit half of the dimer in Rps. viridis but is more symmetrically distributed on the dimeric donor in Rb. sphaeroides R-26. The large reduction of the zero field splitting parameters relative tomore » monomeric bacteriochlorophyll triplet in vitro suggests significant participation of asymmetrical charge transfer electronic configurations in the special pair triplet state of both organisms.« less

The impact of donor policies in Europe: a steady increase, but not everywhere

PubMed Central

Coppen, Remco; Friele, Roland D; Gevers, Sjef KM; Blok, Geke A; van der Zee, Jouke

2008-01-01

Background Transplantable organs are scarce everywhere. Therefore, countries have developed policies to support the efficient use of potential donors. Nevertheless, the shortage of organs remains. Were these policies in vain? The aim of this study is to assess the impact of donor policies on donor procurement in 10 Western European countries from 1995 to 2005. Method To assess the impact of the donor policies we studied the conversion of potential donors into effectuated donors. 80% of the donors died from CVAs or a (traffic) accident. We considered these mortality rates to be a good proxy for potential donors. Here we call the conversion of potential donors into actual donors 'the donor efficiency rate by proxy'. Results The mortality rates for CVA and (traffic) accidents have decreased in the countries under study. At the same time, in most countries the donor efficiency rates have steadily increased. The variance in donor efficiency rates between countries has also increased from 1995 to 2005. Four countries introduced a new consent system or changed their existing system, without (visible) long-term effects. Conclusion The overall increase in donor efficiency means that the efforts to improve donor policies have paid off. However, substantial differences between countries were found. The success of donor policies in terms of the number of absolute donors is blurred by the success of policies on traffic safety and CVA treatment. It remains unclear which specific policy measures are responsible for the increase in donor efficiency rates. This increase is not related to having a presumed consent system. Furthermore, an analysis of countries that introduced a new consent system or changed their system showed no effect on donor efficiency. PMID:19014536

Scalable quantum computer architecture with coupled donor-quantum dot qubits

DOEpatents

Schenkel, Thomas; Lo, Cheuk Chi; Weis, Christoph; Lyon, Stephen; Tyryshkin, Alexei; Bokor, Jeffrey

2014-08-26

A quantum bit computing architecture includes a plurality of single spin memory donor atoms embedded in a semiconductor layer, a plurality of quantum dots arranged with the semiconductor layer and aligned with the donor atoms, wherein a first voltage applied across at least one pair of the aligned quantum dot and donor atom controls a donor-quantum dot coupling. A method of performing quantum computing in a scalable architecture quantum computing apparatus includes arranging a pattern of single spin memory donor atoms in a semiconductor layer, forming a plurality of quantum dots arranged with the semiconductor layer and aligned with the donor atoms, applying a first voltage across at least one aligned pair of a quantum dot and donor atom to control a donor-quantum dot coupling, and applying a second voltage between one or more quantum dots to control a Heisenberg exchange J coupling between quantum dots and to cause transport of a single spin polarized electron between quantum dots.

Electronic messaging and communication with living kidney donors.

PubMed

Ruck, Jessica M; Zhou, Sheng; Thomas, Alvin G; Cramm, Shannon L; Massie, Allan B; Montgomery, John R; Berger, Jonathan C; Henderson, Macey L; Segev, Dorry L

2018-02-01

New regulations require living kidney donor (LKD) follow-up for 2 years, but donor retention remains poor. Electronic communication (eg, text messaging and e-mail) might improve donor retention. To explore the possible impact of electronic communication, we recruited LKDs to participate in an exploratory study of communication via telephone, e-mail, or text messaging postdonation; communication through this study was purely optional and did not replace standard follow-up. Of 69 LKDs recruited, 3% requested telephone call, 52% e-mail, and 45% text messaging. Telephone response rate was 0%; these LKDs were subsequently excluded from analysis. Overall response rates with e-mail or text messaging at 1 week, 1 month, 6 months, 1 year, and 2 years were 94%, 87%, 81%, 72%, and 72%. Lower response rates were seen in African Americans, even after adjusting for age, sex, and contact method (incidence rate ratio (IRR) nonresponse 2.07 5.81 16.36 , P = .001). Text messaging had higher response rates than e-mail (IRR nonresponse 0.11 0.28 0.71 , P = .007). Rates of nonresponse were similar by sex (IRR 0.68, P = .4) and age (IRR 1.00, P > .9). In summary, LKDs strongly preferred electronic messaging over telephone and were highly responsive 2 years postdonation, even in this nonrequired, nonincentivized exploratory research study. These electronic communication tools can be automated and may improve regulatory compliance and postdonation care. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Dissimilatory arsenate reduction with sulfide as the electron donor--Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate-respirer

USGS Publications Warehouse

Hoeft, Shelley E.; Kulp, Thomas R.; Stolz, John F.; Hollibaugh, James T.; Oremland, Ronald S.

2004-01-01

Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3− into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the δ-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

Magnetite production and transformation in the methanogenic consortia from coastal riverine sediments.

PubMed

Zheng, Shiling; Wang, Bingchen; Liu, Fanghua; Wang, Oumei

2017-11-01

Minerals that contain ferric iron, such as amorphous Fe(III) oxides (A), can inhibit methanogenesis by competitively accepting electrons. In contrast, ferric iron reduced products, such as magnetite (M), can function as electrical conductors to stimulate methanogenesis, however, the processes and effects of magnetite production and transformation in the methanogenic consortia are not yet known. Here we compare the effects on methanogenesis of amorphous Fe (III) oxides (A) and magnetite (M) with ethanol as the electron donor. RNA-based terminal restriction fragment length polymorphism with a clone library was used to analyse both bacterial and archaeal communities. Iron (III)-reducing bacteria including Geobacteraceae and methanogens such as Methanosarcina were enriched in iron oxide-supplemented enrichment cultures for two generations with ethanol as the electron donor. The enrichment cultures with A and non-Fe (N) dominated by the active bacteria belong to Veillonellaceae, and archaea belong to Methanoregulaceae and Methanobacteriaceae, Methanosarcinaceae (Methanosarcina mazei), respectively. While the enrichment cultures with M, dominated by the archaea belong to Methanosarcinaceae (Methanosarcina barkeri). The results also showed that methanogenesis was accelerated in the transferred cultures with ethanol as the electron donor during magnetite production from A reduction. Powder X-ray diffraction analysis indicated that magnetite was generated from microbial reduction of A and M was transformed into siderite and vivianite with ethanol as the electron donor. Our data showed the processes and effects of magnetite production and transformation in the methanogenic consortia, suggesting that significantly different effects of iron minerals on microbial methanogenesis in the iron-rich coastal riverine environment were present.

A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation.

PubMed

Shaw, Wendy J; Helm, Monte L; DuBois, Daniel L

2013-01-01

This review discusses the development of molecular electrocatalysts for H2 production and oxidation based on nickel. A modular approach is used in which the structure of the catalyst is divided into first, second, and outer coordination spheres. The first coordination sphere consists of the ligands bound directly to the metal center, and this coordination sphere can be used to control such factors as the presence or absence of vacant coordination sites, redox potentials, hydride donor abilities and other important thermodynamic parameters. The second coordination sphere includes functional groups such as pendent acids or bases that can interact with bound substrates such as H2 molecules and hydride ligands, but that do not form strong bonds with the metal center. These functional groups can play diverse roles such as assisting the heterolytic cleavage of H2, controlling intra- and intermolecular proton transfer reactions, and providing a physical pathway for coupling proton and electron transfer reactions. By controlling both the hydride donor ability of the catalysts using the first coordination sphere and the proton donor abilities of the functional groups in the second coordination sphere, catalysts can be designed that are biased toward H2 production, oxidation, or bidirectional (catalyzing both H2 oxidation and production). The outer coordination sphere is defined as that portion of the catalytic system that is beyond the second coordination sphere. This coordination sphere can assist in the delivery of protons and electrons to and from the catalytically active site, thereby adding another important avenue for controlling catalytic activity. Many features of these simple catalytic systems are good models for enzymes, and these simple systems provide insights into enzyme function and reactivity that may be difficult to probe in enzymes. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Spin and charge ordering in organic conductors investigated by electron spin resonance

NASA Astrophysics Data System (ADS)

Tokumoto, Takahisa D.

This dissertation presents systematic studies on ordered states of organic conductors investigated mainly by Electron Spin Resonance (ESR). First, we describe an introduction to organic conductors. Organic conductors are based on conducting layers of highly planar donor molecules, separated by insulating layers of acceptors. The donor arrangements in the conducting layers determine the three simple parameters, transfer integral t between the donor molecules, onsite Coulomb interaction U and next neighboring Coulomb interaction V. Depending on the values of the above three parameters, a variety of ground states is realized and hence the organic conductors has become a main stream of condensed matter physics. Among many ground states, the main focus is on magnetic orders in this dissertation. Therefore we have employed ESR to probe local magnetic structures. And we cover a basic theory of ESR in paramagnetic/antiferromagnetically ordered states and the experimental realizations. Next, after an introduction to a system with an exchange interaction between d magnetic moments embedded at acceptor sites and pi spins at donor molecules is given, we discuss the effectiveness of systematic studies on isostructural magnetic and non-magnetic acceptor based organic conductors. Then, we go over one of the "exchange coupled" materials, beta-(BDA-TTP)2MCl 4 (M=Fe3+,Ga3+). We examine the origins of the Metal-Insulator transition and the long range antiferromangetic order in the magnetic acceptor based material, where we found the critical importance of the quantum fluctuations of pi spins. Finally, we delineate the magnetic order of alternating easy axes of a class of an organic conductor, tau-(P-(S,S)-DMEDT)2(AuBr2) 1+y, at low temperature/field by ESR. We briefly discuss the origin of this unprecedented magnetic structure in terms of the unstoichiometric ratio of donors to acceptors and the tetragonal symmetry of the unit cell. Then, we report the results of the ultra high field ESR to probe the magnetic structure changes around a hysteretic field induced metal insulator transition.

Highly Selective Coupling of Alkenes and Aldehydes Catalyzed by NHC–Ni–P(OPh)3: Synergy Between a Strong σ-Donor and a Strong π-Acceptor**

PubMed Central

Ho, Chun-Yu; Jamison, Timothy F.

2011-01-01

Both a strong electron donor (IPr) and a strong electron acceptor (P(OPh)3) are necessary for a highly selective, nickel-catalyzed coupling reaction between alkenes, aldehydes, and silyltriflates. Without the phosphite, catalysis is not observed and several side reactions are observed. The phosphite appears to suppress the formation of these byproducts and rescue the catalytic cycle by accelerating reductive elimination from an (IPr–Ni–H)(OTf) complex. PMID:17154217

Impurity-assisted terahertz photoluminescence in quantum wells under conditions of interband stimulated emission

NASA Astrophysics Data System (ADS)

Makhov, I. S.; Panevin, V. Yu; Firsov, D. A.; Vorobjev, L. E.; Sofronov, A. N.; Vinnichenko, M. Ya; Maleev, N. A.; Vasil'ev, A. P.

2018-03-01

Terahertz and near-infrared photoluminescence under conditions of interband stimulated emission are studied in n-GaAs/AlGaAs quantum well laser structure. The observed terahertz emission is related to the optical transitions of nonequilibrium electrons from the first electron subband and excited donor states to donor ground states in quantum wells. The opportunity to increase the intensity of impurity-assisted terahertz emission due to interband stimulated emission with the participation of impurity centres is demonstrated.

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

Park Y. S.; Kale, T.; Wu, Q.

A series of diketopyrrolopyrrole(DPP)-based small molecules have been synthesized by palladium-catalyzed coupling reactions. Electron-donating moieties (benzothiophene, benzoselenophene, and benzotellurophene) are bridged by an electron-withdrawing DPP unit to generate donor-acceptor-donor (D-A-D) type molecules. We observe red-shifts in absorption spectra of these compounds by varying heteroatoms from sulfur to tellurium. In bulk heterojunction solar cells with [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor, we obtain power conversion efficiencies of 2.4% (benzothiophene), 4.1% (benzoselenophene), and 3.0% (benzotellurophene), respectively.

Mixed oxide nanoparticles and method of making

DOEpatents

Lauf, Robert J.; Phelps, Tommy J.; Zhang, Chuanlun; Roh, Yul

2002-09-03

Methods and apparatus for producing mixed oxide nanoparticulates are disclosed. Selected thermophilic bacteria cultured with suitable reducible metals in the presence of an electron donor may be cultured under conditions that reduce at least one metal to form a doped crystal or mixed oxide composition. The bacteria will form nanoparticles outside the cell, allowing easy recovery. Selection of metals depends on the redox potentials of the reducing agents added to the culture. Typically hydrogen or glucose are used as electron donors.

Medicare and state health care programs: fraud and abuse; electronic health records safe harbor under the anti-kickback statute. Final rule.

PubMed

2013-12-27

In this final rule, the Office of Inspector General (OIG) amends the safe harbor regulation concerning electronic health records items and services, which defines certain conduct that is protected from liability under the Federal anti-kickback statute, section 1128B(b) of the Social Security Act (the Act). Amendments include updating the provision under which electronic health records software is deemed interoperable; removing the electronic prescribing capability requirement; extending the sunset provision until December 31, 2021; limiting the scope of protected donors to exclude laboratory companies; and clarifying the condition that prohibits a donor from taking any action to limit or restrict the use, compatibility, or interoperability of the donated items or services.

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

PubMed

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

Donor-impurity-related optical response and electron Raman scattering in GaAs cone-like quantum dots

NASA Astrophysics Data System (ADS)

Gil-Corrales, A.; Morales, A. L.; Restrepo, R. L.; Mora-Ramos, M. E.; Duque, C. A.

2017-02-01

The donor-impurity-related optical absorption, relative refractive index changes, and Raman scattering in GaAs cone-like quantum dots are theoretically investigated. Calculations are performed within the effective mass and parabolic band approximations, using the variational procedure to include the electron-impurity correlation effects. The study involves 1 s -like, 2px-like, and 2pz-like states. The conical structure is chosen in such a way that the cone height is large enough in comparison with the base radius thus allowing the use a quasi-analytic solution of the uncorrelated Schrödinger-like electron states.

Simulation study on the effects of chemical structure and molecular size on the acceptor strength in poly(3-hexylthiophene)-based copolymer with alternating donor and acceptor for photovoltaic applications

NASA Astrophysics Data System (ADS)

Rassamesard, Areefen; Pengpan, Teparksorn

2017-02-01

This research assessed the effects of various chemical structures and molecular sizes on the simulated geometric parameters, electron structures, and spectroscopic properties of single-chain complex alternating donor-acceptor (D-A) monomers and copolymers that are intended for use as photoactive layer in a polymer solar cell by using Kohn-Sham density functional theory with B3LYP exchange-correlation functional. The 3-hexylthiophene (3HT) was selected for electron donor, while eight chemicals, namely thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), benzothiadiazole (BT), thiadiazolothieno-pyrazine (TPD), oxadiazole (OXD) and 5-diphenyl-1,2,4-triazole (TAZ), were employed as electron acceptor functional groups. The torsional angle, bridge bond length, intramolecular charge transfer, energy levels, and molecular orbitals were analyzed. The simulation results reveal that the geometry and electron structure of donor-acceptor monomer and copolymer are significantly impacted by heterocyclic rings, heteroatoms, fused rings, degree of steric hindrance and coplanarity of the acceptor molecular structure. Planar conformation was obtained from the D copolymer, and a pseudo-planar structure with the TD copolymer. The TAZ acceptor exhibited strong steric hindrance due to its bulky structure and non-planarity of its structure. An analysis of the electron structures indicated that the degree of intramolecular electron-withdrawing capability had the rank order TAZ  <  Z  <  D  <  TPD  <  OXD  <  TP  <  BT  <  TD. The TD is indicated as the most effective acceptor among those that were simulated. However, the small energy gaps of TD as well as TPD copolymer indicate that these two copolymers can be used in transparent conducting materials. The copolymer based on BT acceptor exhibited good intramolecular charge transfer and absorbed at 656 nm wavelength which is close to the maximum flux of solar spectrum. Hence, the BT acceptor functional group provides a compromise in the characteristics of a donor-acceptor copolymer, useful in a polymeric candidate material for the photoactive layer in a polymer solar cell.

Applying Thienyl Side Chains and Different π-Bridge to Aromatic Side-Chain Substituted Indacenodithiophene-Based Small Molecule Donors for High-Performance Organic Solar Cells.

PubMed

Wang, Jin-Liang; Liu, Kai-Kai; Liu, Sha; Liu, Feng; Wu, Hong-Bin; Cao, Yong; Russell, Thomas P

2017-06-14

A pair of linear tetrafluorinated small molecular donors, named as ThIDTTh4F and ThIDTSe4F, which are with tetrathienyl-substituted IDT as electron-rich central core, electron-deficient difluorobenzothiadiazole as acceptor units, and donor end-capping groups, but having differences in the π-bridge (thiophene and selenophene), were successfully synthesized and evaluated as donor materials in organic solar cells. Such π-bridge and core units in these small molecules play a decisive role in the formation of the nanoscale separation of the blend films, which were systematically investigated through absorption spectra, grazing incidence X-ray diffraction pattern, transmission electron microscopy images, resonant soft X-ray scattering profiles, and charge mobility measurement. The ThIDTSe4F (with selenophene π-bridge)-based device exhibited superior performance than devices based on ThIDTh4F (with thiophene π-bridge) after post annealing treatment owing to optimized film morphology and improved charge transport. Power conversion efficiency of 7.31% and fill factor of ∼0.70 were obtained by using a blend of ThIDTSe4F and PC 71 BM with thermal annealing and solvent vapor annealing treatments, which is the highest PCE from aromatic side-chain substituted IDT-based small molecular solar cells. The scope of this study is to reveal the structure-property relationship of the aromatic side-chain substituted IDT-based donor materials as a function of π-bridge and the post annealing conditions.

New acceptor-bridge-donor strategy for enhancing NLO response with long-range excess electron transfer from the NH2...M/M3O donor (M = Li, Na, K) to inside the electron hole cage C20F19 acceptor through the unusual σ chain bridge (CH2)4.

PubMed

Bai, Yang; Zhou, Zhong-Jun; Wang, Jia-Jun; Li, Ying; Wu, Di; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2013-04-04

Using the strong electron hole cage C20F19 acceptor, the NH2...M/M3O (M = Li, Na, and K) complicated donors with excess electron, and the unusual σ chain (CH2)4 bridge, we construct a new kind of electride molecular salt e(-)@C20F19-(CH2)4-NH2...M(+)/M3O(+) (M = Li, Na, and K) with excess electron anion inside the hole cage (to be encapsulated excess electron-hole pair) serving as a new A-B-D strategy for enhancing nonlinear optical (NLO) response. An interesting push-pull mechanism of excess electron generation and its long-range transfer is exhibited. The excess electron is pushed out from the (super)alkali atom M/M3O by the lone pair of NH2 in the donor and further pulled inside the hole cage C20F19 acceptor through the efficient long σ chain (CH2)4 bridge. Owing to the long-range electron transfer, the new designed electride molecular salts with the excess electron-hole pair exhibit large NLO response. For the e(-)@C20F19-(CH2)4-NH2...Na(+), its large first hyperpolarizability (β0) reaches up to 9.5 × 10(6) au, which is about 2.4 × 10(4) times the 400 au for the relative e(-)@C20F20...Na(+) without the extended chain (CH2)4-NH2. It is shown that the new strategy is considerably efficient in enhancing the NLO response for the salts. In addition, the effects of different bridges and alkali atomic number on β0 are also exhibited. Further, three modulating factors are found for enhancing NLO response. They are the σ chain bridge, bridge-end group with lone pair, and (super)alkali atom. The new knowledge may be significant for designing new NLO materials and electronic devices with electrons inside the cages. They may also be the basis of establishing potential organic chemistry with electron-hole pair.

Synthesis and Characterization of SF-PPV-I

NASA Technical Reports Server (NTRS)

Wang, Y.; Fan, Z.; Taft, C.; Sun, S.

2001-01-01

Conjugated electro-active polymers find their potential applications in developing variety inexpensive and flexible shaped electronic and photonic devices, such as photovoltaic or photo/electro light emitting devices. In many of these opto-electronic polymeric materials, certain electron rich donors and electron deficient acceptors are needed in order to fine-tune the electronic or photonic properties of the desired materials and structures. While many donor type of conjugated polymers have been widely studied and developed in the past decades, there are relatively fewer acceptor type of conjugated polymers have been developed. Key acceptor type conjugated polymers developed so far include C60 and CN-PPV, and each has its limitations. Due to the complexity and diversity of variety future electronic materials and structural needs, alternative and synthetically amenable acceptor conjugated polymers need to be developed. In this paper, we present the synthesis and characterization of a new acceptor conjugated polymer, a sulfone derivatized polyphenylenevinylene "SF-PPV".

Increasing Saturated Electron-Drift Velocity in Donor-Acceptor Doped pHEMT Heterostructures

NASA Astrophysics Data System (ADS)

Protasov, D. Yu.; Gulyaev, D. V.; Bakarov, A. K.; Toropov, A. I.; Erofeev, E. V.; Zhuravlev, K. S.

2018-03-01

Field dependences of the electron-drift velocity in typical pseudomorphic high-electron-mobility transistor (pHEMT) heteroepitaxial structures (HESs) and in those with donor-acceptor doped (DApHEMT) heterostructures with quantum-well (QW) depth increased by 0.8-0.9 eV with the aid of acceptor layers have been studied by a pulsed technique. It is established that the saturated electron-drift velocity in DA-pHEMT-HESs is 1.2-1.3 times greater than that in the usual pHEMT-HESs. The electroluminescence (EL) spectra of DA-pHEMT-HESs do not contain emission bands related to the recombination in widebandgap layers (QW barriers). The EL intensity in these HESs is not saturated with increasing electric field. This is indicative of a suppressed real-space transfer of hot electrons from QW to barrier layers, which accounts for the observed increase in the saturated electron-drift velocity.

Homogeneity and variation of donor doping in Verneuil-grown SrTiO3:Nb single crystals

PubMed Central

Rodenbücher, C.; Luysberg, M.; Schwedt, A.; Havel, V.; Gunkel, F.; Mayer, J.; Waser, R.

2016-01-01

The homogeneity of Verneuil-grown SrTiO3:Nb crystals was investigated. Due to the fast crystal growth process, inhomogeneities in the donor dopant distribution and variation in the dislocation density are expected to occur. In fact, for some crystals optical studies show variations in the density of Ti3+ states on the microscale and a cluster-like surface conductivity was reported in tip-induced resistive switching studies. However, our investigations by TEM, EDX mapping, and 3D atom probe reveal that the Nb donors are distributed in a statistically random manner, indicating that there is clearly no inhomogeneity on the macro-, micro-, and nanoscale in high quality Verneuil-grown crystals. In consequence, the electronic transport in the bulk of donor-doped crystals is homogeneous and it is not significantly channelled by extended defects such as dislocations which justifies using this material, for example, as electronically conducting substrate for epitaxial oxide film growth. PMID:27577508

The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes - A detailed investigation of structure-property relationships

NASA Technical Reports Server (NTRS)

Stiegman, A. E.; Graham, Eva; Khundkar, Lutfur R.; Perry, Joseph W.; Cheng, L.-T.; Perry, Kelly J.

1991-01-01

A series of donor-acceptor acetylene compounds was synthesized in which systematic changes in both the conjugation length and the donor-acceptor strength were made. The effect of these structural changes on the spectroscopic and electronic properties of the molecules and, ultimately, on the measured second-order molecular hyperpolarizabilities (beta) was investigated. It was found that increases in the donor-acceptor strength resulted in increases in the magnitude of beta. For this class of molecules, the increase is dominated by the energy of the intramolecular charge-transfer transition, while factors such as the ground to excited-state dipole moment change and the transition-moment integral are much less important. Increasing the conjugation length from one to two acetylene linkers did not result in an increase in the value of beta; however, beta increased sharply in going from two acetylenes to three. This increase is attributed to the superposition of several nearly isoenergetic excited states.

Structural correlations in the generation of polaron pairs in low-bandgap polymers for photovoltaics

NASA Astrophysics Data System (ADS)

Tautz, Raphael; da Como, Enrico; Limmer, Thomas; Feldmann, Jochen; Egelhaaf, Hans-Joachim; von Hauff, Elizabeth; Lemaur, Vincent; Beljonne, David; Yilmaz, Seyfullah; Dumsch, Ines; Allard, Sybille; Scherf, Ullrich

2012-07-01

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

Sulfur-based autotrophic denitrification from the micro-polluted water.

PubMed

Zhou, Weili; Liu, Xu; Dong, Xiaojing; Wang, Zheng; Yuan, Ying; Wang, Hui; He, Shengbing

2016-06-01

Eutrophication caused by high concentrations of nutrients is a huge problem for many natural lakes and reservoirs. Removing the nitrogen contamination from the low C/N water body has become an urgent need. Autotrophic denitrification with the sulfur compound as electron donor was investigated in the biofilter reactors. Through the lab-scale experiment, it was found that different sulfur compounds and different carriers caused very different treatment performances. Thiosulfate was selected to be the best electron donor and ceramsite was chosen as the suitable carrier due to the good denitrification efficiency, low cost and the good resistibility against the high hydraulic loads. Later the optimum running parameters of the process were determined. Then the pilot-scale experiment was carried out with the real micro-polluted water from the West Lake, China. The results indicated that the autotrophic denitrification with thiosulfate as electron donor was feasible and applicable for the micro-polluted lake water. Copyright © 2016. Published by Elsevier B.V.

Organic photochemical storage of solar energy. Progress report, July 1, 1977--Feburary 28, 1978

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

Jones, G. II

1978-03-01

The prospects for driving endoergic reactions of simple, relatively abundant organic chemicals by photochemical means have been examined. Strategies for utilization of light of varying wavelength involve sensitization mechanisms which depend on the redox properties of energy storing substrates and photosensitizers. Of principal interest is valence isomerization which can be induced by electron donor-acceptor interaction between substrate and sensitizer in an excited complex or exciplex. Photophysical studies show that potentially isomerizable substrates efficiently intercept redox photosensitizers. The quenching of emission of electron acceptor sensitizers by non conjugated hydrocarbon dienes is indeed a function of the reduction potential of the acceptorsmore » (a series of aromatics with varying absorption characteristics) and the oxidation potentials of the substrates. Electron deficient dienes have been shown alternatively to be efficient quenchers of excited donor sensitizers. That exciplexes are formed between isomerizable substrates and donor or acceptor sensitizers has been confirmed by emission spectroscopy. The rearrangement of hexamethyldewarbenzene, a model exciplex isomerization has been examined in some detail.« less

Spectrophotometric and spectroscopic studies of charge transfer complex of 1-Naphthylamine as an electron donor with picric acid as an electron acceptor in different polar solvents

NASA Astrophysics Data System (ADS)

Singh, Neeti; Ahmad, Afaq

2010-08-01

The charge transfer complex of 1-Naphthylamine as a donor with π-acceptor picric acid has been studied spectrophotometrically in different solvents at room temperature. The results indicate that the formation of charge transfer complex is high in less polar solvent. The stoichiometry of the complex was found to be 1:1 by straight line method. The data are analysed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G o), oscillator strength ( ƒ), transition dipole moment ( μ EN), resonance energy ( R N) and ionization potential ( I D). It is concluded that the formation constant ( KCT) of the complex is found to be depends upon the nature of both electron acceptor and donor and also on the polarity of solvents. Further the charge transfer molecular complex between picric acid and 1-Naphthylamine is stabilized by hydrogen bonding.

Organic substrates as electron donors in permeable reactive barriers for removal of heavy metals from acid mine drainage.

PubMed

Kijjanapanich, P; Pakdeerattanamint, K; Lens, P N L; Annachhatre, A P

2012-12-01

This research was conducted to select suitable natural organic substrates as potential carbon sources for use as electron donors for biological sulphate reduction in a permeable reactive barrier (PRB). A number of organic substrates were assessed through batch and continuous column experiments under anaerobic conditions with acid mine drainage (AMD) obtained from an abandoned lignite coal mine. To keep the heavy metal concentration at a constant level, the AMD was supplemented with heavy metals whenever necessary. Under anaerobic conditions, sulphate-reducing bacteria (SRB) converted sulphate into sulphide using the organic substrates as electron donors. The sulphide that was generated precipitated heavy metals as metal sulphides. Organic substrates, which yielded the highest sulphate reduction in batch tests, were selected for continuous column experiments which lasted over 200 days. A mixture of pig-farm wastewater treatment sludge, rice husk and coconut husk chips yielded the best heavy metal (Fe, Cu, Zn and Mn) removal efficiencies of over 90%.

First-principles calculation of photo-induced electron transfer rate constants in phthalocyanine-C60 organic photovoltaic materials: Beyond Marcus theory

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

Classical Marcus theory is commonly adopted in solvent-mediated charge transfer (CT) process to obtain the CT rate constant, but it can become questionable when the intramolecular vibrational modes dominate the CT process as in OPV devices because Marcus theory treats these modes classically and therefore nuclear tunneling is not accounted for. We present a computational scheme to obtain the electron transfer rate constant beyond classical Marcus theory. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided. Ab initio calculations are used to obtain the basic parameters needed for calculating the electron transfer rate constant. We apply our methodology to phthalocyanine(H2PC)-C60 organic photovoltaic system where one C60 acceptor and one or two H2PC donors are included to model the donor-acceptor interface configuration. We obtain the electron transfer and recombination rate constants for all accessible charge transfer (CT) states, from which the CT exciton dynamics is determined by employing a master equation. The role of higher lying excited states in CT exciton dynamics is discussed. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

Tuning the physical properties of organic sensitizers by replacing triphenylamine with new donors for dye sensitized solar cells - a theoretical approach.

PubMed

Ramkumar, Sekar; Manidurai, Paulraj

2017-02-15

New donor molecules with low ionization potential have been theoretically designed by replacing the benzene moieties in triphenylamine (TPA) with thiophene as well as furan. The designed new donors also exhibited planar structure, making an angle of 120° around the nitrogen atom that results in resonance effects through π-bonds of aryl rings. New sensitizers have been theoretically studied using DFT and TD-DFT by adopting these designed donors. UV-Vis absorption spectra, light harvesting ability (LHE) and electron injection ability (ΔG inject ) of the designed sensitizers have been calculated by taking L0 as reference. Orbital overlapping between donor and acceptor facilitates intra-molecular charge transfer, thereby increasing the interfacial electron injection from the sensitizer to the semiconductor nanoparticles. Our theoretical results demonstrate that sensitizers DTPA-AA and DFPA-AA have broader absorption and lower ΔG inject respectively compare to L0, this opens a new way for designing sensitizers for dye sensitized solar cells (DSSCs). All the dyes designed were found to be good light harvesters. Copyright © 2016 Elsevier B.V. All rights reserved.

Fullerene C{sub 70} as a p-type donor in organic photovoltaic cells

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

Zhuang, Taojun; Wang, Xiao-Feng, E-mail: charles1976110@hotmail.com, E-mail: zrhong@ucla.edu, E-mail: kid@yz.yamagata-u.ac.jp; Sano, Takeshi

2014-09-01

Fullerenes and their derivatives have been widely used as n-type materials in organic transistor and photovoltaic devices. Though it is believed that they shall be ambipolar in nature, there have been few direct experimental proofs for that. In this work, fullerene C{sub 70}, known as an efficient acceptor, has been employed as a p-type electron donor in conjunction with 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile as an electron acceptor in planar-heterojunction (PHJ) organic photovoltaic (OPV) cells. High fill factors (FFs) of more than 0.70 were reliably achieved with the C{sub 70} layer even up to 100 nm thick in PHJ cells, suggesting the superior potentialmore » of fullerene C{sub 70} as the p-type donor in comparison to other conventional donor materials. The optimal efficiency of these unconventional PHJ cells was 2.83% with a short-circuit current of 5.33 mA/cm{sup 2}, an open circuit voltage of 0.72 V, and a FF of 0.74. The results in this work unveil the potential of fullerene materials as donors in OPV devices, and provide alternative approaches towards future OPV applications.« less

Radiobiological Effectiveness of Ultrashort Laser-Driven Electron Bunches: Micronucleus Frequency, Telomere Shortening and Cell Viability.

PubMed

Andreassi, Maria Grazia; Borghini, Andrea; Pulignani, Silvia; Baffigi, Federica; Fulgentini, Lorenzo; Koester, Petra; Cresci, Monica; Vecoli, Cecilia; Lamia, Debora; Russo, Giorgio; Panetta, Daniele; Tripodi, Maria; Gizzi, Leonida A; Labate, Luca

2016-09-01

Laser-driven electron accelerators are capable of producing high-energy electron bunches in shorter distances than conventional radiofrequency accelerators. To date, our knowledge of the radiobiological effects in cells exposed to electrons using a laser-plasma accelerator is still very limited. In this study, we compared the dose-response curves for micronucleus (MN) frequency and telomere length in peripheral blood lymphocytes exposed to laser-driven electron pulse and X-ray radiations. Additionally, we evaluated the effects on cell survival of in vitro tumor cells after exposure to laser-driven electron pulse compared to electron beams produced by a conventional radiofrequency accelerator used for intraoperative radiation therapy. Blood samples from two different donors were exposed to six radiation doses ranging from 0 to 2 Gy. Relative biological effectiveness (RBE) for micronucleus induction was calculated from the alpha coefficients for electrons compared to X rays (RBE = alpha laser/alpha X rays). Cell viability was monitored in the OVCAR-3 ovarian cancer cell line using trypan blue exclusion assay at day 3, 5 and 7 postirradiation (2, 4, 6, 8 and 10 Gy). The RBE values obtained by comparing the alpha values were 1.3 and 1.2 for the two donors. Mean telomere length was also found to be reduced in a significant dose-dependent manner after irradiation with both electrons and X rays in both donors studied. Our findings showed a radiobiological response as mirrored by the induction of micronuclei and shortening of telomere as well as by the reduction of cell survival in blood samples and cancer cells exposed in vitro to laser-generated electron bunches. Additional studies are needed to improve preclinical validation of the radiobiological characteristics and efficacy of laser-driven electron accelerators in the future.

Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

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

Luo, Wensui; Zhou, Jizhong; Wu, Weimin

2007-01-01

A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonatemore » (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.« less

Arsenite as an electron donor for anoxygenic photosynthesis: Description of three strains of Ectothiorhodospria from Mono Lake, California, and Big Soda Lake, Nevada

USGS Publications Warehouse

McCann, Shelley; Boren, Alison; Hernandez-Maldonado, Jaime; Stoneburner, Brendon; Saltikov, Chad W; Stolz, John F.; Oremland, Ronald S.

2017-01-01

Three novel strains of photosynthetic bacteria from the family Ectothiorhodospiraceae were isolated from soda lakes of the Great Basin Desert, USA by employing arsenite (As(III)) as the sole electron donor in the enrichment/isolation process. Strain PHS-1 was previously isolated from a hot spring in Mono Lake, while strain MLW-1 was obtained from Mono Lake sediment, and strain BSL-9 was isolated from Big Soda Lake. Strains PHS-1, MLW-1, and BSL-9 were all capable of As(III)-dependent growth via anoxygenic photosynthesis and contained homologs of arxA, but displayed different phenotypes. Comparisons were made with three related species: Ectothiorhodospira shaposhnikovii DSM 2111, Ectothiorhodospira shaposhnikovii DSM 243T, and Halorhodospira halophila DSM 244. All three type cultures oxidized arsenite to arsenate but did not grow with As(III) as the sole electron donor. DNA–DNA hybridization indicated that strain PHS-1 belongs to the same species as Ect. shaposhnikovii DSM 2111 (81.1% sequence similarity), distinct from Ect. shaposhnikovii DSM 243T (58.1% sequence similarity). These results suggest that the capacity for light-driven As(III) oxidation is a common phenomenon among purple photosynthetic bacteria in soda lakes. However, the use of As(III) as a sole electron donor to sustain growth via anoxygenic photosynthesis is confined to novel isolates that were screened for by this selective cultivation criterion.

Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater

NASA Astrophysics Data System (ADS)

Goltz, M. N.; Secody, R. E.; Huang, J.; Hatzinger, P. B.

2007-12-01

Perchlorate-contaminated groundwater is a significant national problem. An innovative technology was recently developed which uses a pair of dual-screened treatment wells to mix an electron donor into perchlorate- contaminated groundwater in order to effect in situ bioremediation of the perchlorate by indigenous perchlorate reducing bacteria (PRB) without the need to extract the contaminated water from the subsurface. The two treatment wells work in tandem to establish a groundwater recirculation zone in the subsurface. Electron donor is added and mixed into perchlorate-contaminated groundwater flowing through each well. The donor serves to stimulate biodegradation of the perchlorate by PRB in bioactive zones that form adjacent to the injection screens of the treatment wells. In this study, a model that simulates operation of the technology was calibrated using concentration data obtained from a field-scale technology evaluation project at a perchlorate-contaminated site. The model simulates transport of perchlorate, the electron donor (citrate, for this study), and competing electron acceptors (oxygen and nitrate) in the groundwater flow field induced by operation of the treatment well pair. A genetic algorithm was used to derive a set of best-fit model parameters to describe the perchlorate reduction kinetics in this field-scale evaluation project. The calibrated parameter values were then used to predict technology performance. The model qualitatively predicted the salient characteristics of the observed data. It appears the model may be a useful tool for designing and operating this technology at other perchlorate-contaminated sites.

Direct view at colossal permittivity in donor-acceptor (Nb, In) co-doped rutile TiO2

NASA Astrophysics Data System (ADS)

Mandal, Suman; Pal, Somnath; Kundu, Asish K.; Menon, Krishnakumar S. R.; Hazarika, Abhijit; Rioult, Maxime; Belkhou, Rachid

2016-08-01

Topical observations of colossal permittivity (CP) with low dielectric loss in donor-acceptor cations co-doped rutile TiO2 have opened up several possibilities in microelectronics and energy-storage devices. Yet, the precise origin of the CP behavior, knowledge of which is essential to empower the device integration suitably, is highly disputed in the literature. From spectromicroscopic approach besides dielectric measurements, we explore that microscopic electronic inhomogeneities along with the nano-scale phase boundaries and the low temperature polaronic relaxation are mostly responsible for such a dielectric behavior, rather than electron-pinned defect-dipoles/grain-boundary effects as usually proposed. Donor-acceptor co-doping results in a controlled carrier-hopping inevitably influencing the dielectric loss while invariably upholding the CP value.

Transport through an impurity tunnel coupled to a Si/SiGe quantum dot

DOE PAGES

Foote, Ryan H.; Ward, Daniel R.; Prance, J. R.; ...

2015-09-11

Achieving controllable coupling of dopants in silicon is crucial for operating donor-based qubit devices, but it is difficult because of the small size of donor-bound electron wavefunctions. Here in this paper, we report the characterization of a quantum dot coupled to a localized electronic state and present evidence of controllable coupling between the quantum dot and the localized state. A set of measurements of transport through the device enable the determination that the most likely location of the localized state is consistent with a location in the quantum well near the edge of the quantum dot. Finally, our results aremore » consistent with a gate-voltage controllable tunnel coupling, which is an important building block for hybrid donor and gate-defined quantum dot devices.« less

Computational study on the effects of substituent and heteroatom on physical properties and solar cell performance in donor-acceptor conjugated polymers based on benzodithiophene.

PubMed

Zhang, Lvyong; Shen, Wei; He, Rongxing; Liu, Xiaorui; Fu, Zhiyong; Li, Ming

2014-11-01

Computationally driven material design has attracted increasing interest to accelerate the search for optimal conjugated donor materials in bulk heterojunction organic solar cells. A series of novel copolymers containing benzo[1,2-b:4,5-b']dithiophene (BDT) and thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives were simulated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). We performed a systematic study on the influences on molecular geometry parameters, electronic properties, optical properties, photovoltaic performances, and intermolecular stacking as well as hole mobility when different chalcogenophenes in TPD derivatives were used and functional groups with different electron-withdrawing abilities such as alkyl, fluorine, sufonyl, and cyano were introduced to the nitrogen positions in electron-deficient units. The substitution position of electron-withdrawing groups may cause little steric hindrance to the neighboring donor units, especially fluorine and cyano group. It was found that the incorporation of these new electron-deficient substituents and sulfur-selenium exchange can be applicable to further modify and optimize existing molecular structures. Our findings will provide valuable guidance and chemical methodologies for a judicious material design of conjugated polymers for solar cell applications with desirable photovoltaic characteristics.

Isolation of Geobacter species from diverse sedimentary environments

USGS Publications Warehouse

Coaxes, J.D.; Phillips, E.J.P.; Lonergan, D.J.; Jenter, H.; Lovley, D.R.

1996-01-01

In an attempt to better understand the microorganisms responsible for Fe(III) reduction in sedimentary environments, Fe(III)-reducing microorganisms were enriched for and isolated from freshwater aquatic sediments, a pristine deep aquifer, and a petroleum-contaminated shallow aquifer. Enrichments were initiated with acetate or toluene as the electron donor and Fe(III) as the electron acceptor. Isolations were made with acetate or benzoate. Five new strains which could obtain energy for growth by dissimilatory Fe(III) reduction were isolated. All five isolates are gram- negative strict anaerobes which grow with acetate as the electron donor and Fe(III) as the electron acceptor. Analysis of the 16S rRNA sequence of the isolated organisms demonstrated that they all belonged to the genus Geobacter in the delta subdivision of the Proteobacteria. Unlike the type strain, Geobacter metallireducens, three of the five isolates could use H2 as an electron donor fur Fe(III) reduction. The deep subsurface isolate is the first Fe(III) reducer shown to completely oxidize lactate to carbon dioxide, while one of the freshwater sediment isolates is only the second Fe(III) reducer known that can oxidize toluene. The isolation of these organisms demonstrates that Geobacter species are widely distributed in a diversity of sedimentary environments in which Fe(III) reduction is an important process.

Shifting the balance of fermentation products between hydrogen and volatile fatty acids: microbial community structure and function.

PubMed

Miceli, Joseph F; Torres, César I; Krajmalnik-Brown, Rosa

2016-12-01

Fermentation is a key process in many anaerobic environments. Varying the concentration of electron donor fed to a fermenting community is known to shift the distribution of products between hydrogen, fatty acids and alcohols. Work to date has focused mainly on the fermentation of glucose, and how the microbial community structure is affected has not been explored. We fed ethanol, lactate, glucose, sucrose or molasses at 100 me- eq. L -1 , 200 me- eq. L -1 or 400 me- eq. L -1 to batch-fed cultures with fermenting, methanogenic communities. In communities fed high concentrations of electron donor, the fraction of electrons channeled to methane decreased, from 34% to 6%, while the fraction of electrons channeled to short chain fatty acids increased, from 52% to 82%, averaged across all electron donors. Ethanol-fed cultures did not produce propionate, but did show an increase in electrons directed to acetate as initial ethanol concentration increased. In glucose, sucrose, molasses and lactate-fed cultures, propionate accumulation co-occurred with known propionate producing organisms. Overall, microbial communities were determined by the substrate provided, rather than its initial concentration, indicating that a change in community function, rather than community structure, is responsible for shifts in the fermentation products produced. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Structure and electronic properties of Alq3 derivatives with electron acceptor/donor groups at the C4 positions of the quinolate ligands: a theoretical study.

PubMed

Rao, Joshi Laxmikanth; Bhanuprakash, Kotamarthi

2011-12-01

The molecular structures of the ground (S(0)) and first singlet excited (S(1)) states of Alq3 derivatives in which pyrazolyl and 3-methylpyrazolyl groups are substituted at the C4 positions of the 8-hydroxyquinolate ligands as electron acceptors, and piperidinyl and N-methylpiperazinyl groups are substituted at the same positions as electron donors, have been optimized using the B3LYP/6-31G and CIS/6-31G methods, respectively. In order to analyze the electronic transitions in these derivatives, the frontier molecular orbital characteristics were analyzed systematically, and it was found that the highest occupied molecular orbital is localized on the A ligand while the lowest unoccupied molecular orbital is localized on the B ligand in their ground states, similar to what is seen for mer-Alq3. The absorption and emission spectra were evaluated at the TD-PBE0/6-31G level, and it was observed that electron acceptor substitution causes a red-shift in the emission spectra, which is also seen experimentally. The reorganization energies were calculated at the B3LYP/6-31G level and the results show that acceptor/donor substitution has a significant effect on the intrinsic charge mobilities of these derivatives as compared to mer-Alq3.

An Obvious Improvement in the Performance of Ternary Organic Solar Cells with "Guest" Donor Present at the "Host" Donor/Acceptor Interface.

PubMed

Bi, Peng-Qing; Wu, Bo; Zheng, Fei; Xu, Wei-Long; Yang, Xiao-Yu; Feng, Lin; Zhu, Furong; Hao, Xiao-Tao

2016-09-07

A small-molecule material, 7,7-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5-yl)benzo-[c] [1,2,5]thiadiazole) (p-DTS(FBTTH2)2), was used to modify the morphology and electron-transport properties of the polymer blend of poly(3-hexythiophene) (P3HT) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) bulk heterojunctions. As a result, a 24% increase in the power-conversion efficiency (PCE) of the p-DTS(FBTTH2)2:P3HT:PC71BM ternary organic solar cells (OSCs) is obtained. The improvement in the performance of OSCs is attributed to the constructive energy cascade path in the ternary system that benefits an efficient Förster resonance energy/charge transfer process between P3HT and p-DTS(FBTTH2)2, thereby improving photocurrent generation. It is shown that p-DTS(FBTTH2)2 molecules engage themselves at the P3HT/PC71BM interface. A combination of absorption enhancement, efficient energy transfer process, and ordered nanomorphology in the ternary system favors exciton dissociation and charge transportation in the polymer bulk heterojunction. The finding of this work reveals that distribution of the appropriate "guest" donor at the "host" donor/acceptor interface is an effective approach for attaining high-performance OSCs.

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

PubMed

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

2018-04-04

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

An Overview of Electron Acceptors in Microbial Fuel Cells

PubMed Central

Ucar, Deniz; Zhang, Yifeng; Angelidaki, Irini

2017-01-01

Microbial fuel cells (MFC) have recently received increasing attention due to their promising potential in sustainable wastewater treatment and contaminant removal. In general, contaminants can be removed either as an electron donor via microbial catalyzed oxidization at the anode or removed at the cathode as electron acceptors through reduction. Some contaminants can also function as electron mediators at the anode or cathode. While previous studies have done a thorough assessment of electron donors, cathodic electron acceptors and mediators have not been as well described. Oxygen is widely used as an electron acceptor due to its high oxidation potential and ready availability. Recent studies, however, have begun to assess the use of different electron acceptors because of the (1) diversity of redox potential, (2) needs of alternative and more efficient cathode reaction, and (3) expanding of MFC based technologies in different areas. The aim of this review was to evaluate the performance and applicability of various electron acceptors and mediators used in MFCs. This review also evaluated the corresponding performance, advantages and disadvantages, and future potential applications of select electron acceptors (e.g., nitrate, iron, copper, perchlorate) and mediators. PMID:28469607

Endo-Fullerene and Doped Diamond Nanocrystallite Based Models of Qubits for Solid-State Quantum Computers

NASA Technical Reports Server (NTRS)

Park, Seongjun; Srivastava, Deepak; Cho, Kyeongjae; Biegel, Bryan (Technical Monitor)

2001-01-01

Models of encapsulated 1/2 nuclear spin H-1 and P-31 atoms in fullerene and diamond nanocrystallite, respectively, are proposed and examined with ab-initio local density functional method for possible applications as single quantum bits (qubits) in solid-state quantum computers. A H-1 atom encapsulated in a fully deuterated fullerene, C(sub 20)D(sub 20), forms the first model system and ab-initio calculation shows that H-1 atom is stable in atomic state at the center of the fullerene with a barrier of about 1 eV to escape. A P-31 atom positioned at the center of a diamond nanocrystallite is the second model system, and 3 1P atom is found to be stable at the substitutional site relative to interstitial sites by 15 eV, Vacancy formation energy is 6 eV in diamond so that substitutional P-31 atom will be stable against diffusion during the formation mechanisms within the nanocrystallite. The coupling between the nuclear spin and weakly bound (valance) donor electron coupling in both systems is found to be suitable for single qubit applications, where as the spatial distributions of (valance) donor electron wave functions are found to be preferentially spread along certain lattice directions facilitating two or more qubit applications. The feasibility of the fabrication pathways for both model solid-state qubit systems within practical quantum computers is discussed with in the context of our proposed solid-state qubits.

Design and Feasibility Analysis of a Self-Sustaining Biofiltration System for Removal of Low Concentration N2O Emitted from Wastewater Treatment Plants.

PubMed

Yoon, Hyun; Song, Min Joon; Yoon, Sukhwan

2017-09-19

N 2 O is a potent greenhouse gas and ozone-depletion agent. In this study, a biofiltration system was designed for removal of N 2 O emitted at low concentrations (<200 ppmv) from wastewater treatment plants. The proposed biofiltration system utilizes untreated wastewater from the primary sedimentation basin as the source of electron donor and nutrients and energy requirement is minimized by utilizing gravitational force and pressure differential to direct liquid medium and gas through the biofilter. The experiments performed with laboratory-scale biofilter in two different configurations confirmed the feasibility of the biofiltration system. The biofilter operated with cycling of raw wastewater exhibited up to 94% and 53% removal efficiency with 100 ppmv N 2 O in N 2 and air, respectively, as the feed gas, corroborating that untreated wastewater can serve as a robust source of electron donor and nutrients. The laboratory-scale biofilter operated with a continuous flow-through of synthetic wastewater attained >99.9% removal of N 2 O from N 2 background at the gas flow rate up to 2,000 mL·min -1 and >50% N 2 O removal from air background at the gas flow rate of 200 mL·min -1 . nosZ-containing bacterial genera including Flavobacterium (5.92%), Pseudomonas (4.26%) and Bosea (2.39%) were identified in the biofilm samples collected from the oxic biofilter, indicating these organisms were responsible for N 2 O removal.

Thio-arylglycosides with Various Aglycon Para-Substituents, a Probe for Studying Chemical Glycosylation Reactions

PubMed Central

Li, Xiaoning; Huang, Lijun; Hu, Xiche; Huang, Xuefei

2009-01-01

Summary Three series of thioglycosyl donors differing only in their respective aglycon substituents within each series have been prepared as representatives of typical glycosyl donors. The relative anomeric reactivities of these donors were quantified under competitive glycosylation conditions with various reaction time, promoters, solvents and acceptors. Over three orders of magnitude reactivity difference were generated by simple transformation of the para-substituent on the aglycon with methanol as the acceptor, while chemoselectivities became lower with carbohydrate acceptors. Excellent linear correlations were attained between relative reactivity values of donors and σp values of the substituents in the Hammett plots. This indicates that the glycosylation mechanism remains the same over a wide range of reactivities and glycosylation conditions. The negative slopes of the Hammett plots suggested that electron donating substituents expedite the reactions and the magnitudes of slopes can be rationalized by neighboring group participation as well as electronic properties of the glycon protective groups. Within the same series of donors, less nucleophilic acceptors gave smaller slopes in their Hammett plots. This is consistent with the notion that acceptor nucleophilic attack onto the reactive intermediate is part of the rate limiting step of the glycosylation reaction. Excellent linear Hammett correlations were obtained between relative reactivity values of three series of donors differing only in their aglycon substituents and σp values of the substituents. PMID:19081954

Computer applications in the search for unrelated stem cell donors.

PubMed

Müller, Carlheinz R

2002-08-01

The majority of patients which are eligible for a blood stem cell transplantation from an allogeneic donor do not have a suitable related donor so that an efficient unrelated donor search is a prerequisite for this treatment. Currently, there are over 7 million volunteer donors in the files of 50 registries in the world and in most countries the majority of transplants are performed from a foreign donor. Evidently, computer and communication technology must play a crucial role in the complex donor search process on the national and international level. This article describes the structural elements of the donor search process and discusses major systematic and technical issues to be addressed in the development and evolution of the supporting telematic systems. The theoretical considerations are complemented by a concise overview over the current state of the art which is given by describing the scope, relevance, interconnection and technical background of three major national and international computer appliances: The German Marrow Donor Information System (GERMIS) and the European Marrow Donor Information System (EMDIS) are interoperable business-to-business e-commerce systems and Bone Marrow Donors World Wide (BMDW) is the basic international donor information desk on the web.

Do thermal donors reduce the lifetimes of Czochralski-grown silicon crystals?

NASA Astrophysics Data System (ADS)

Miyamura, Y.; Harada, H.; Nakano, S.; Nishizawa, S.; Kakimoto, K.

2018-05-01

High-performance electronics require long carrier lifetimes within their silicon crystals. This paper reports the effects of thermal donors on the lifetimes of carriers in as-grown n-type silicon crystals grown by the Czochralski method. We grew silicon crystals with two different concentrations of thermal donors using the following two cooling processes: one was cooled with a 4-h halt after detaching the crystal from the melt, and the other was cooled continuously. The crystal grown with the cooling halt contained higher concentrations of thermal donors of the order of 1 × 1013 cm-3, while the crystal without the halt had no thermal donors. The measured bulk lifetimes were in the range of 15-18 ms. We concluded that thermal donors in Czochralski-grown silicon crystals do not act to reduce their lifetimes.

Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

PubMed

McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

2015-02-11

Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

Anaerobic bioremediation of hexavalent uranium in groundwater by reductive precipitation with methanogenic granular sludge.

PubMed

Tapia-Rodriguez, Aida; Luna-Velasco, Antonia; Field, Jim A; Sierra-Alvarez, Reyes

2010-04-01

Uranium has been responsible for extensive contamination of groundwater due to releases from mill tailings and other uranium processing waste. Past evidence has confirmed that certain bacteria can enzymatically reduce soluble hexavalent uranium (U(VI)) to insoluble tetravalent uranium (U(IV)) under anaerobic conditions in the presence of appropriate electron donors. This paper focuses on the evaluation of anaerobic granular sludge as a source of inoculum for the bioremediation of uranium in water. Batch experiments were performed with several methanogenic anaerobic granular sludge samples and different electron donors. Abiotic controls consisting of heat-killed inoculum and non-inoculated treatments confirmed the biological removal process. In this study, unadapted anaerobic granular sludge immediately reduced U(VI), suggesting an intrinsic capacity of the sludge to support this process. The high biodiversity of anaerobic granular sludge most likely accounts for the presence of specific microorganisms capable of reducing U(VI). Oxidation by O(2) was shown to resolubilize the uranium. This observation combined with X-ray diffraction evidence of uraninite confirmed that the removal during anaerobic treatment was due to reductive precipitation. The anaerobic removal activity could be sustained after several respikes of U(VI). The U(VI) removal was feasible without addition of electron donors, indicating that the decay of endogenous biomass substrates was contributing electron equivalents to the process. Addition of electron donors, such as H(2) stimulated the removal of U(VI) to varying degrees. The stimulation was greater in sludge samples with lower endogenous substrate levels. The present work reveals the potential application of anaerobic granular sludge for continuous bioremediation schemes to treat uranium-contaminated water. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Non-Condon nonequilibrium Fermi’s golden rule rates from the linearized semiclassical method

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

Sun, Xiang; Geva, Eitan

2016-08-14

The nonequilibrium Fermi’s golden rule describes the transition between a photoexcited bright donor electronic state and a dark acceptor electronic state, when the nuclear degrees of freedom start out in a nonequilibrium state. In a previous paper [X. Sun and E. Geva, J. Chem. Theory Comput. 12, 2926 (2016)], we proposed a new expression for the nonequilibrium Fermi’s golden rule within the framework of the linearized semiclassical approximation and based on the Condon approximation, according to which the electronic coupling between donor and acceptor is assumed constant. In this paper we propose a more general expression, which is applicable tomore » the case of non-Condon electronic coupling. We test the accuracy of the new non-Condon nonequilibrium Fermi’s golden rule linearized semiclassical expression on a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering the following: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary-mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions, in both normal and inverted regions, and over a wide range of initial nonequilibrium states, temperatures, and frictions.« less

Compared microbiology of granular sludge under autotrophic, mixotrophic and heterotrophic denitrification conditions.

PubMed

Fernández, N; Sierra-Alvarez, R; Amils, R; Field, J A; Sanz, J L

2009-01-01

Water contamination by nitrate is a wideworld extended phenomena. Biological autotrophic denitrification has a real potential to face this problem and presents less drawbacks than the most extended heterotrophic denitrification. Three bench-scale UASB reactors were operated under autotrophic (R1, H2S as electron donor), mixotrophic (R2, H2S plus p-cresol as electron donors) and heterotrophic (R3, p-cresol as electron donor) conditions using nitrate as terminal electron acceptor. 16S rDNA genetic libraries were built up to compare their microbial biodiversity. Six different bacteria phyla and three archaeal classes were observed. Proteobacteria was the main phyla in all reactors standing out the presence of denitrifiers. Microorganisms similar to Thiobacillus denitrificans and Acidovorax sp. performed the autotrophic denitification. These OTUs were displaced by chemoheterotrophic denitrifiers, especially by Limnobacter-like and Ottowia-like OTUs. Other phyla were Bacteroidetes, Chloroflexi, Firmicutes and Actinobacteria that--as well as Archaea members--were implicated in the degradation of organic matter, as substrate added as coming from endogenous sludge decay under autotrophic conditions. Archaea diversity remained low in all the reactors being Methanosaeta concilii the most abundant one.

Impurity and phonon scattering in silicon nanowires

NASA Astrophysics Data System (ADS)

Zhang, W.; Persson, M. P.; Mera, H.; Delerue, C.; Niquet, Y. M.; Allan, G.; Wang, E.

2011-03-01

We model the scattering of electrons by phonons and dopant impurities in ultimate [110]-oriented gate-all-around silicon nanowires with an atomistic valence force field and tight-binding approach. All electron-phonons interactions are included. We show that impurity scattering can reduce with decreasing nanowire diameter due to the enhanced screening by the gate. Donors and acceptors however perform very differently : acceptors behave as tunnel barriers for the electrons, while donors behave as quantum wells which introduce Fano resonances in the conductance. As a consequence the acceptors are much more limiting the mobility than the donors. The resistances of single acceptors are also very dependent on their radial position in the nanowire, which might be a significant source of variability in ultimate silicon nanowire devices. Concerning phonons, we show that, as a result of strong confinement, i) electrons couple to a wide and complex distribution of phonons modes, and ii) the mobility has a non-monotonic variation with wire diameter and is strongly reduced with respect to bulk. French National Research Agency ANR project QUANTAMONDE Contract No. ANR-07-NANO-023-02 and by the Délégation Générale pour l'Armement, French Ministry of Defense under Grant No. 2008.34.0031.

Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol.

PubMed

Azofra, Luis Miguel; Alkorta, Ibon; Toro-Labbé, Alejandro; Elguero, José

2013-09-07

The mechanism of the S(N)2 model glycosylation reaction between ethanol, 1,2-ethanediol and methoxymethanol has been studied theoretically at the B3LYP/6-311+G(d,p) computational level. Three different types of reactions have been explored: (i) the exchange of hydroxyl groups between these model systems; (ii) the basic catalysis reactions by combination of the substrates as glycosyl donors (neutral species) and acceptors (enolate species); and (iii) the effect on the reaction profile of an explicit H2O molecule in the reactions considered in (ii). The reaction force, the electronic chemical potential and the reaction electronic flux have been characterized for the reaction path in each case. Energy calculations show that methoxymethanol is the worst glycosyl donor model among the ones studied here, while 1,2-ethanediol is the best, having the lowest activation barrier of 74.7 kJ mol(-1) for the reaction between this one and the ethanolate as the glycosyl acceptor model. In general, the presence of direct interactions between the atoms involved in the penta-coordinated TS increases the activation energies of the processes.

Spatially resolved resonant tunneling on single atoms in silicon.

PubMed

Voisin, B; Salfi, J; Bocquel, J; Rahman, R; Rogge, S

2015-04-22

The ability to control single dopants in solid-state devices has opened the way towards reliable quantum computation schemes. In this perspective it is essential to understand the impact of interfaces and electric fields, inherent to address coherent electronic manipulation, on the dopants atomic scale properties. This requires both fine energetic and spatial resolution of the energy spectrum and wave-function, respectively. Here we present an experiment fulfilling both conditions: we perform transport on single donors in silicon close to a vacuum interface using a scanning tunneling microscope (STM) in the single electron tunneling regime. The spatial degrees of freedom of the STM tip provide a versatility allowing a unique understanding of electrostatics. We obtain the absolute energy scale from the thermal broadening of the resonant peaks, allowing us to deduce the charging energies of the donors. Finally we use a rate equations model to derive the current in presence of an excited state, highlighting the benefits of the highly tunable vacuum tunnel rates which should be exploited in further experiments. This work provides a general framework to investigate dopant-based systems at the atomic scale.

The Roles of Biofilm Conductivity and Donor Substrate Kinetics in a Mixed-Culture Biofilm Anod

EPA Science Inventory

We experimentally assessed kinetics and thermodynamics of electron transfer (ET) from the donor substrate (acetate) to the anode for a mixed-culture biofilm anode. We interpreted the results with a modified biofilm-conduction model consisting of three ET steps: (1) intracellular...

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Non-fullerene electron acceptors for organic photovoltaic devices

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

Jenekhe, Samson A.; Li, Haiyan; Earmme, Taeshik

Non-fullerene electron acceptors for highly efficient organic photovoltaic devices are described. The non-fullerene electron acceptors have an extended, rigid, .pi.-conjugated electron-deficient framework that can facilitate exciton and charge derealization. The non-fullerene electron acceptors can physically mix with a donor polymer and facilitate improved electron transport. The non-fullerene electron acceptors can be incorporated into organic electronic devices, such as photovoltaic cells.

Mixing-Chamber Preamplifier for Spin Qubit Readout

NASA Astrophysics Data System (ADS)

Curry, Matthew; Mounce, Andrew; England, Troy; Manginell, Ronald; Wendt, Joel; Pluym, Tammy; Carr, Stephen; Carroll, Malcolm

Spin qubit states are often read out with a nearby charge sensor. To improve signal-to-noise ratio (SNR) and bandwidth, we amplify a charge sensor with a low-current-bias, silicon-germanium heterojunction-bipolar-transistor (HBT). The HBT is located at the mixing chamber of a dilution refrigerator, which minimizes parasitic capacitance and amplifies signal before fridge noise is introduced. Using the HBT-charge-sensor circuit, we tune a few-electron quantum dot (QD) into resonance with a donor-like object and observe singlet-triplet (ST) behavior. ST separation in this MOS donor-implanted-QD molecular system is measured using magnetospectroscopy to be approximately 100 μeV. The low current bias of the HBT minimizes both heating of the charge-sensed QD as well as maintains an overall low power at the mixing chamber. HBT bias impact on QD electron temperature is examined and we find that the HBT preamplifier can operate at around 100 nW with a current gain of around 500 without influencing the electron temperature, which is around 150 mK. We will also examine single-shot readout of a charge state using the HBT preamplifier. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the U. S. Department of Energy under Contract No. DE-AC04-94AL85000.

Quantum point contacts for electrons on H-Si(111) surfaces using a Ga focused-ion beam for direct-write implant lithography

NASA Astrophysics Data System (ADS)

Robertson, Luke D.; Kane, B. E.

Quantum point contacts (QPCs) realized in materials with anisotropic electron mass, such as Si, may exhibit valley filter phenomena leading to extreme sensitivity to single donor occupancy, and thus are of interest to measurement schemes for donor-based quantum information processing. To this end, we have developed ambipolar devices on a H-Si(111):Si(100)/SiO2 flip-chip assembly which utilize in-plane, degenerately doped n+ (P) and p+ (B) contacts to probe transport in a 2D electron system (2DES). In addition to providing electrostatic isolation of carriers, these p-type contacts can be used as lateral depletion gates to modulate the 2DES conductance, and if extended to the nanoscale can lead to 1D confinement and quantized conductance of the 2DES. In this talk, I will describe our efforts to use a Ga focused-ion beam for direct-write implant lithography to pattern QPCs and Ga nanowires on H-Si(111) surfaces. I will present low temperature (4.2K) conductance data collected on 30nm Ga nanowires to demonstrate their effectiveness as lateral depletion gates, and discuss on going measurements to confine and modulate the conductance of the 2DES using Ga QPCs.

Fine-tuning of electronic properties in donor-acceptor conjugated polymers based on oligothiophenes

NASA Astrophysics Data System (ADS)

Imae, Ichiro; Sagawa, Hitoshi; Harima, Yutaka

2018-03-01

A novel series of donor-acceptor conjugated polymers having oligothiophenes with well-defined structures were synthesized and their optical, electrochemical, and photovoltaic properties were investigated. It was found that the absorption bands of polymers were red-shifted with increasing number of ethylenedioxy groups added to each oligothiophene unit and that their band edges reached over 1000 nm. The systematical fine-tuning of the electronic properties was achieved using the chemical structures of oligothiophene units. Photovoltaic cells based on polymer/(6,6)-phenyl C61 butyric acid methyl ester (PC61BM) exhibited power conversion efficiencies in the range from 0.004 to 1.10%, reflecting the electronic properties of the polymers.

Coenzyme preference of Streptococcus pyogenes δ1-pyrroline-5-carboxylate reductase: evidence supporting NADPH as the physiological electron donor.

PubMed

Petrollino, Davide; Forlani, Giuseppe

2012-07-01

The streptococcal enzyme that catalyzes the last step in proline biosynthesis was heterologously expressed and the recombinant protein was purified to electrophoretic homogeneity and characterized thoroughly. As for δ1-pyrroline-5-carboxylate reductases from other sources, it was able to use either NADH or NADPH as the electron donor in vitro. However, with NADH the activity was markedly inhibited by physiological levels of NADP+. Results also strengthen the possibility that an unusual ordered substrate binding occurs, in which the dinucleotide binds last.

Time-dependent transition density matrix for visualizing charge-transfer excitations in photoexcited organic donor-acceptor systems

NASA Astrophysics Data System (ADS)

Li, Yonghui; Ullrich, Carsten

2013-03-01

The time-dependent transition density matrix (TDM) is a useful tool to visualize and interpret the induced charges and electron-hole coherences of excitonic processes in large molecules. Combined with time-dependent density functional theory on a real-space grid (as implemented in the octopus code), the TDM is a computationally viable visualization tool for optical excitation processes in molecules. It provides real-time maps of particles and holes which gives information on excitations, in particular those that have charge-transfer character, that cannot be obtained from the density alone. Some illustration of the TDM and comparison with standard density difference plots will be shown for photoexcited organic donor-acceptor molecules. This work is supported by NSF Grant DMR-1005651

Why the apparent order of bimolecular recombination in blend organic solar cells can be larger than two: A topological consideration

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

Nenashev, A. V.; Dvurechenskii, A. V.; Novosibirsk State University, 630090 Novosibirsk

2016-07-18

The apparent order δ of non-geminate recombination higher than δ = 2 has been evidenced in numerous experiments on organic bulk heterojunction (BHJ) structures intensively studied for photovoltaic applications. This feature is claimed puzzling, since the rate of the bimolecular recombination in organic BHJ systems is proportional to the product of the concentrations of recombining electrons and holes and therefore the reaction order δ = 2 is expected. In organic BHJ structures, electrons and holes are confined to two different material phases: electrons to the acceptor material (usually a fullerene derivative) while holes to the donor phase (usually a polymer). The non-geminatemore » recombination of charge carriers can therefore happen only at the interfaces between the two phases. Considering a simple geometrical model of the BHJ system, we show that the apparent order of recombination can deviate from δ = 2 due solely to the topological structure of the system.« less

Single shot spin readout using a cryogenic high-electron-mobility transistor amplifier at sub-Kelvin temperatures

NASA Astrophysics Data System (ADS)

Tracy, L. A.; Luhman, D. R.; Carr, S. M.; Bishop, N. C.; Ten Eyck, G. A.; Pluym, T.; Wendt, J. R.; Lilly, M. P.; Carroll, M. S.

2016-02-01

We use a cryogenic high-electron-mobility transistor circuit to amplify the current from a single electron transistor, allowing for demonstration of single shot readout of an electron spin on a single P donor in Si with 100 kHz bandwidth and a signal to noise ratio of ˜9. In order to reduce the impact of cable capacitance, the amplifier is located adjacent to the Si sample, at the mixing chamber stage of a dilution refrigerator. For a current gain of ˜ 2.7 × 10 3 , the power dissipation of the amplifier is 13 μW, the bandwidth is ˜ 1.3 MHz, and for frequencies above 300 kHz the current noise referred to input is ≤ 70 fA/ √{ Hz } . With this amplification scheme, we are able to observe coherent oscillations of a P donor electron spin in isotopically enriched 28Si with 96% visibility.

Optical and electronic structure description of metal-doped phthalocyanines.

PubMed

Leal, Luciano Almeida; da Cunha, Wiliam Ferreira; Ribeiro Junior, Luiz Antonio; Pereira, Tamires Lima; Blawid, Stefan Michael; de Sousa Junior, Rafael Timóteo; da Silva Filho, Demétrio Antonio

2017-05-01

Phthalocyanines represent a crucial class of organic compounds with high technological appeal. By doping the center of these systems with metals, one obtains the so-called metal-phthalocyanines, whose property of being an effective electron donor allows for potentially interesting uses in organic electronics. In this sense, investigating optical and electronic structure changes in the phthalocyanine profiles in the presence of different metals is of fundamental importance for evaluating the appropriateness of the resulting system as far as these uses are concerned. In the present work, we carry out this kind of effort for phthalocyanines doped with different metals, namely, copper, nickel, and magnesium. Density functional theory was applied to obtain the absorption spectra, and electronic and structural properties of the complexes. Our results suggest that depending on the dopant, a different level of change is achieved. Moreover, electrostatic potential energy mapping shows how the charge distribution can be affected by solar radiation. Our contribution is crucial in describing the best possible candidates for use in different organic photovoltaic applications. Graphical Abstract Representation of meta-phthalocyanine systems. All calculations of this work are based on varying metal position along z axis, considering the z-axis has its zero point matching with the center of phthalocyanine cavityconsidering.

Single molecule-level study of donor-acceptor interactions and nanoscale environment in blends

NASA Astrophysics Data System (ADS)

Quist, Nicole; Grollman, Rebecca; Rath, Jeremy; Robertson, Alex; Haley, Michael; Anthony, John; Ostroverkhova, Oksana

2017-02-01

Organic semiconductors have attracted considerable attention due to their applications in low-cost (opto)electronic devices. The most successful organic materials for applications that rely on charge carrier generation, such as solar cells, utilize blends of several types of molecules. In blends, the local environment strongly influences exciton and charge carrier dynamics. However, relationship between nanoscale features and photophysics is difficult to establish due to the lack of necessary spatial resolution. We use functionalized fluorinated pentacene (Pn) molecule as single molecule probes of intermolecular interactions and of the nanoscale environment in blends containing donor and acceptor molecules. Single Pn donor (D) molecules were imaged in PMMA in the presence of acceptor (A) molecules using wide-field fluorescence microscopy. Two sample configurations were realized: (i) a fixed concentration of Pn donor molecules, with increasing concentration of acceptor molecules (functionalized indenflouorene or PCBM) and (ii) a fixed concentration of acceptor molecules with an increased concentration of the Pn donor. The D-A energy transfer and changes in the donor emission due to those in the acceptor- modified polymer morphology were quantified. The increase in the acceptor concentration was accompanied by enhanced photobleaching and blinking of the Pn donor molecules. To better understand the underlying physics of these processes, we modeled photoexcited electron dynamics using Monte Carlo simulations. The simulated blinking dynamics were then compared to our experimental data, and the changes in the transition rates were related to the changes in the nanoscale environment. Our study provides insight into evolution of nanoscale environment during the formation of bulk heterojunctions.

Negative polarity of phenyl-C{sub 61} butyric acid methyl ester adjacent to donor macromolecule domains

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

Alley, Olivia J.; Dawidczyk, Thomas J.; Hardigree, Josué F. Martínez

2015-01-19

Interfacial fields within organic photovoltaics influence the movement of free charge carriers, including exciton dissociation and recombination. Open circuit voltage (V{sub oc}) can also be dependent on the interfacial fields, in the event that they modulate the energy gap between donor HOMO and acceptor LUMO. A rise in the vacuum level of the acceptor will increase the gap and the V{sub oc}, which can be beneficial for device efficiency. Here, we measure the interfacial potential differences at donor-acceptor junctions using Scanning Kelvin Probe Microscopy, and quantify how much of the potential difference originates from physical contact between the donor andmore » acceptor. We see a statistically significant and pervasive negative polarity on the phenyl-C{sub 61} butyric acid methyl ester (PCBM) side of PCBM/donor junctions, which should also be present at the complex interfaces in bulk heterojunctions. This potential difference may originate from molecular dipoles, interfacial interactions with donor materials, and/or equilibrium charge transfer due to the higher work function and electron affinity of PCBM. We show that the contact between PCBM and poly(3-hexylthiophene) doubles the interfacial potential difference, a statistically significant difference. Control experiments determined that this potential difference was not due to charges trapped in the underlying substrate. The direction of the observed potential difference would lead to increased V{sub oc}, but would also pose a barrier to electrons being injected into the PCBM and make recombination more favorable. Our method may allow unique information to be obtained in new donor-acceptor junctions.« less

Donors' blood group declaration before donation can be used as a tool for electronic crossmatching.

PubMed

Arslan, O

2005-12-01

Electronic crossmatching (E-XM) is used to detect ABO incompatibility. In developing countries, as many of the donations are from first-time donors, it is difficult to guarantee the accuracy of the ABO/Rh label on these units to use them for E-XM. This problem was overcome with a new software 'hemosoft', using donors' blood group declaration before donation as a tool for E-XM. During registration, donors either declare their blood group or give no comment. For, ABO/Rh grouping, either two results from different donations or only one in concordant with the declaration before donation is needed. If there is a conflict, second typing is performed from the unit segment. If donors give no declaration, two different technicians perform typing, one from the sample tube and the other from the unit segment. Of 18,618 donations performed, 640 (3%) were repeated and the rest were first-time donations. In 16,327, typing was performed once, as the blood group declaration and the typing results were identical. In 2407, grouping was performed twice, as donors gave no declaration or conflicts between declaration and typing results were found. No labelling or wrong unit-release errors were detected in units donated, typed and labelled in our centre. In 26,402 donations, 16,314 (61.8%) E-XMs were performed. No major haemolytic transfusion reaction was recorded. Donors' ABO/Rh declaration before donation can be used as a tool for E-XM, instead of the requirement for serological confirmation or a second donation to guarantee grouping.

Light and colour as analytical detection tools: a journey into the periodic table using polyamines to bio-inspired systems as chemosensors.

PubMed

Lodeiro, Carlos; Capelo, José Luis; Mejuto, Juan Carlos; Oliveira, Elisabete; Santos, Hugo M; Pedras, Bruno; Nuñez, Cristina

2010-08-01

This critical review describes some developments on the chemistry of fluorescent and colorimetric molecular probes or chemosensors, based on polyamines and associated compounds having oxygen and/or sulfur as donor atoms. The reported systems are essentially based on some selected published work in this field in the last five years, and in the work developed by the authors from 2000 onwards. Some interesting properties beyond sensing molecules, ions or/and cations by fluorescence, colorimetry as well as by MALDI-TOF MS spectrometry can arise from these systems. A short brief on different examples activated by PET (photoinduced electron transfer), ICT (internal charge transfer) and EET (electronic energy transfer) phenomena will be provided. Finally the introduction of bio-inspired compounds derived from emissive amino acid or short peptide systems and nanoparticle devices to detect metal ions will be reviewed (202 references).

Multiple-component covalent organic frameworks

NASA Astrophysics Data System (ADS)

Huang, Ning; Zhai, Lipeng; Coupry, Damien E.; Addicoat, Matthew A.; Okushita, Keiko; Nishimura, Katsuyuki; Heine, Thomas; Jiang, Donglin

2016-07-01

Covalent organic frameworks are a class of crystalline porous polymers that integrate molecular building blocks into periodic structures and are usually synthesized using two-component [1+1] condensation systems comprised of one knot and one linker. Here we report a general strategy based on multiple-component [1+2] and [1+3] condensation systems that enable the use of one knot and two or three linker units for the synthesis of hexagonal and tetragonal multiple-component covalent organic frameworks. Unlike two-component systems, multiple-component covalent organic frameworks feature asymmetric tiling of organic units into anisotropic skeletons and unusually shaped pores. This strategy not only expands the structural complexity of skeletons and pores but also greatly enhances their structural diversity. This synthetic platform is also widely applicable to multiple-component electron donor-acceptor systems, which lead to electronic properties that are not simply linear summations of those of the conventional [1+1] counterparts.

A Two-component NADPH Oxidase (NOX)-like System in Bacteria Is Involved in the Electron Transfer Chain to the Methionine Sulfoxide Reductase MsrP*

PubMed Central

Juillan-Binard, Céline; Picciocchi, Antoine; Andrieu, Jean-Pierre; Petit-Hartlein, Isabelle; Caux-Thang, Christelle; Vivès, Corinne; Nivière, Vincent

2017-01-01

MsrPQ is a newly identified methionine sulfoxide reductase system found in bacteria, which appears to be specifically involved in the repair of periplasmic proteins oxidized by hypochlorous acid. It involves two proteins: a periplasmic one, MsrP, previously named YedY, carrying out the Msr activity, and MsrQ, an integral b-type heme membrane-spanning protein, which acts as the specific electron donor to MsrP. MsrQ, previously named YedZ, was mainly characterized by bioinformatics as a member of the FRD superfamily of heme-containing membrane proteins, which include the NADPH oxidase proteins (NOX/DUOX). Here we report a detailed biochemical characterization of the MsrQ protein from Escherichia coli. We optimized conditions for the overexpression and membrane solubilization of an MsrQ-GFP fusion and set up a purification scheme allowing the production of pure MsrQ. Combining UV-visible spectroscopy, heme quantification, and site-directed mutagenesis of histidine residues, we demonstrated that MsrQ is able to bind two b-type hemes through the histidine residues conserved between the MsrQ and NOX protein families. In addition, we identify the E. coli flavin reductase Fre, which is related to the dehydrogenase domain of eukaryotic NOX enzymes, as an efficient cytosolic electron donor to the MsrQ heme moieties. Cross-linking experiments as well as surface Plasmon resonance showed that Fre interacts with MsrQ to form a specific complex. Taken together, these data support the identification of the first prokaryotic two-component protein system related to the eukaryotic NOX family and involved in the reduction of periplasmic oxidized proteins. PMID:28028176

Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

Experimental confirmation of the predicted shallow donor hydrogen state in zinc oxide.

PubMed

Cox, S F; Davis, E A; Cottrell, S P; King, P J; Lord, J S; Gil, J M; Alberto, H V; Vilão, R C; Piroto Duarte, J; Ayres de Campos, N; Weidinger, A; Lichti, R L; Irvine, S J

2001-03-19

We confirm the recent prediction that interstitial protium may act as a shallow donor in zinc oxide, by direct spectroscopic observation of its muonium counterpart. On implantation into ZnO, positive muons--chemically analogous to protons in this context--form paramagnetic centers below about 40 K. The muon-electron contact hyperfine interaction, as well as the temperature and activation energy for ionization, imply a shallow level. Similar results for the cadmium chalcogenides suggest that such shallow donor states are generic to the II-VI compounds. The donor level depths should serve as a guide for the electrical activity of interstitial hydrogen.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion

DOE PAGES

Wang, Peng; Chang, Angela Y.; Novosad, Valentyn; ...

2017-06-11

We report on entirely man-made nanobio hybrid fabricated through assembly of cell-free expressed transmembrane proton pump and semiconductor nanoparticles as an efficient nanocatalysis for photocatalytic H 2 evolution. The system produces H 2 at a turnover rate of 239 (μmole protein) -1 h -1 under green and 17742 (μmole protein) -1 h -1 under white light at ambient conditions, in water at neutral pH with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allows for systemic manipulation at nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion

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

Wang, Peng; Chang, Angela Y.; Novosad, Valentyn

We report on entirely man-made nanobio hybrid fabricated through assembly of cell-free expressed transmembrane proton pump and semiconductor nanoparticles as an efficient nanocatalysis for photocatalytic H 2 evolution. The system produces H 2 at a turnover rate of 239 (μmole protein) -1 h -1 under green and 17742 (μmole protein) -1 h -1 under white light at ambient conditions, in water at neutral pH with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allows for systemic manipulation at nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Novel processes for anaerobic sulfate production from elemental sulfur by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1994-01-01

Sulfate reducers and related organisms which had previously been found to reduce Fe(III) with H2 or organic electron donors oxidized S0 to sulfate when Mn(IV) was provided as an electron acceptor. Organisms catalyzing this reaction in washed cell suspensions included Desulfovibrio desulfuricans, Desulfomicrobium baculatum. Desulfobacterium autotrophicum, Desulfuromonas acetoxidans, and Geobacter metallireducens. These organisms produced little or no sulfate from S0 with Fe(III) as a potential electron acceptor or in the absence of an electron acceptor. In detailed studies with Desulfovibrio desulfuricans, the stoichiometry of sulfate and Mn(II) production was consistent with the reaction S0 + 3 MnO2 + 4H+ ???SO42- + 3Mn(II) + 2H2O. None of the organisms evaluated could be grown with S0 as the sole electron donor and Mn(IV) as the electron acceptor. In contrast to the other sulfate reducers evaluated, Desulfobulbus propionicus produced sulfate from S0 in the absence of an electron acceptor and Fe(III) oxide stimulated sulfate production. Sulfide also accumulated in the absence of Mn(IV) or Fe(III). The stoichiometry of sulfate and sulfide production indicated that Desulfobulbus propionicus disproportionates S0 as follows: 4S0 + 4H2O???SO42- + 3HS- + 5 H+. Growth of Desulfobulbus propionicus with S0 as the electron donor and Fe(III) as a sulfide sink and/or electron acceptor was very slow. The S0 oxidation coupled to Mn(IV) reduction described here provides a potential explanation for the Mn(IV)-dependent sulfate production that previous studies have observed in anoxic marine sediments. Desulfobulbus propionicus is the first example of a pure culture known to disproportionate S0.

Donor-acceptor cocrystal based on hexakis(alkoxy)triphenylene and perylenediimide derivatives with an ambipolar transporting property

NASA Astrophysics Data System (ADS)

Su, Yajun; Li, Yan; Liu, Jiangang; Xing, Rubo; Han, Yanchun

2015-01-01

An organic donor-acceptor cocrystal with an ambipolar transporting property was constructed based on N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) and 2,3,6,7,10,11-hexakis-(hexyloxy)-triphenylene (H6TP). The cocrystal with an alternating stacking of H6TP and EP-PDI molecules was formed through both drop-casting and spin-coating processes, especially at the optimized ratios of H6TP/EP-PDI (2/1, 1/1). The formation of the cocrystal was driven by the strong π-π interaction and the weaker steric hindrance, resulting from the smaller side groups, between the donor and acceptor molecules. Field effect transistors (FETs) based on the H6TP/EP-PDI cocrystal exhibited relatively balanced hole/electron transport, with a hole mobility of 1.14 × 10-3 cm2 V-1 s-1 and an electron mobility of 1.40 × 10-3 cm2 V-1 s-1.An organic donor-acceptor cocrystal with an ambipolar transporting property was constructed based on N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) and 2,3,6,7,10,11-hexakis-(hexyloxy)-triphenylene (H6TP). The cocrystal with an alternating stacking of H6TP and EP-PDI molecules was formed through both drop-casting and spin-coating processes, especially at the optimized ratios of H6TP/EP-PDI (2/1, 1/1). The formation of the cocrystal was driven by the strong π-π interaction and the weaker steric hindrance, resulting from the smaller side groups, between the donor and acceptor molecules. Field effect transistors (FETs) based on the H6TP/EP-PDI cocrystal exhibited relatively balanced hole/electron transport, with a hole mobility of 1.14 × 10-3 cm2 V-1 s-1 and an electron mobility of 1.40 × 10-3 cm2 V-1 s-1. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05915h

Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

DOEpatents

Shelnutt, John A.

1986-01-01

A method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation which comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a gas hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound .pi.--.pi. complexes which can develop.

Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

DOEpatents

Shelnutt, J.A.

1984-11-29

A method is disclosed improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation. The method comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound ..pi..-..pi.. complexes which can develop.

Molecular Engineering Strategy for High Efficiency Fullerene-Free Organic Solar Cells Using Conjugated 1,8-Naphthalimide and Fluorenone Building Blocks.

PubMed

Do, Thu Trang; Pham, Hong Duc; Manzhos, Sergei; Bell, John M; Sonar, Prashant

2017-05-24

We designed, synthesized, and characterized a series of novel electron deficient small molecule nonfullerene acceptors based on 1,8-naphthalimide (NAI) and 9-fluorenone (FN) with different branched alkyl chains using various techniques. These molecules are based on an acceptor-donor-acceptor-donor-acceptor (A1-D-A2-D-A1) molecular design configuration with NAI as the end-capping acceptor (A1), FN as electron-withdrawing central (A2) group, and thiophene ring as a donor (D) unit. These materials are named as NAI-FN-NAI (BO) and NAI-FN-NAI (HD) where BO and HD represent butyloctyl and hexyldecyl alkyl groups, respectively. To further modify energy levels of these materials, we converted the weak electron withdrawing ketonic group (C═O) attached to the FN moiety of NAI-FN-NAI (BO) to a stronger electron withdrawing cyano group (C≡N) to obtain the compound NAI-FCN-NAI (BO) by keeping the same alkyl chain. The optical, electrochemical, and thermal properties of the new acceptors were studied. The materials exhibited higher to medium band gaps, low lowest unoccupied molecular orbital (LUMO) energy levels, and highly thermally stable properties. Organic solar cell devices employing conventional poly(3-hexylthiophene) (P3HT) a donor polymer and the newly designed small molecules as the acceptor were investigated. Among all new materials, organic solar cell devices based on NAI-FN-NAI (BO) as an acceptor exhibit the highest performance with an open circuit voltage (V OC ) of 0.88 V, a short-circuit current density (J SC ) of 9.1 mAcm -2 , a fill factor (FF) of 45%, and an overall power conversion efficiency (PCE) of 3.6%. This is the first report of 9-fluorenone based nonfullerene acceptor with P3HT donor in organic solar cell devices with such a promising performance.

Isoindigo-Based Small Molecules with Varied Donor Components for Solution-Processable Organic Field Effect Transistor Devices.

PubMed

Patil, Hemlata; Chang, Jingjing; Gupta, Akhil; Bilic, Ante; Wu, Jishan; Sonar, Prashant; Bhosale, Sheshanath V

2015-09-18

Two solution-processable small organic molecules, (E)-6,6'-bis(4-(diphenylamino)phenyl)-1,1'-bis(2-ethylhexyl)-(3,3'-biindolinylidene)-2,2'-dione (coded as S10) and (E)-6,6'-di(9H-carbazol-9-yl)-1,1'-bis(2-ethylhexyl)-(3,3'-biindolinylidene)-2,2'-dione (coded as S11) were successfully designed, synthesized and fully characterized. S10 and S11 are based on a donor-acceptor-donor structural motif and contain a common electron accepting moiety, isoindigo, along with different electron donating functionalities, triphenylamine and carbazole, respectively. Ultraviolet-visible absorption spectra revealed that the use of triphenylamine donor functionality resulted in an enhanced intramolecular charge transfer transition and reduction of optical band gap, when compared with its carbazole analogue. Both of these materials were designed to be donor semiconducting components, exerted excellent solubility in common organic solvents, showed excellent thermal stability, and their promising optoelectronic properties encouraged us to scrutinize charge-carrier mobilities using solution-processable organic field effect transistors. Hole mobilities of the order of 2.2 × 10(-4) cm²/Vs and 7.8 × 10(-3) cm²/Vs were measured using S10 and S11 as active materials, respectively.

Electric-field control of a hydrogenic donor's spin in a semiconductor

NASA Astrophysics Data System (ADS)

de, Amrit; Pryor, Craig E.; Flatté, Michael E.

2009-03-01

The orbital wave function of an electron bound to a single donor in a semiconductor can be modulated by an applied AC electric field, which affects the electron spin dynamics via the spin-orbit interaction. Numerical calculations of the spin dynamics of a single hydrogenic donor (Si) using a real-space multi-band k.p formalism show that in addition to breaking the high symmetry of the hydrogenic donor state, the g-tensor has a strong nonlinear dependence on the applied fields. By explicitly integrating the time dependent Schr"odinger equation it is seen that Rabi oscillations can be obtained for electric fields modulated at sub-harmonics of the Larmor frequency. The Rabi frequencies obtained from sub-harmonic modulation depend on the magnitudes of the AC and DC components of the electric field. For a purely AC field, the highest Rabi frequency is obtained when E is driven at the 2nd sub-harmonic of the Larmor frequency. Apart from suggesting ways to measure g-tensor anisotropies and nonlinearities, these results also suggest the possibility of direct frequency domain measurements of Rabi frequencies.

Dynamical photo-induced electronic properties of molecular junctions

NASA Astrophysics Data System (ADS)

Beltako, K.; Michelini, F.; Cavassilas, N.; Raymond, L.

2018-03-01

Nanoscale molecular-electronic devices and machines are emerging as promising functional elements, naturally flexible and efficient, for next-generation technologies. A deeper understanding of carrier dynamics in molecular junctions is expected to benefit many fields of nanoelectronics and power devices. We determine time-resolved charge current flowing at the donor-acceptor interface in molecular junctions connected to metallic electrodes by means of quantum transport simulations. The current is induced by the interaction of the donor with a Gaussian-shape femtosecond laser pulse. Effects of the molecular internal coupling, metal-molecule tunneling, and light-donor coupling on photocurrent are discussed. We then define the time-resolved local density of states which is proposed as an efficient tool to describe the absorbing molecule in contact with metallic electrodes. Non-equilibrium reorganization of hybridized molecular orbitals through the light-donor interaction gives rise to two phenomena: the dynamical Rabi shift and the appearance of Floquet-like states. Such insights into the dynamical photoelectronic structure of molecules are of strong interest for ultrafast spectroscopy and open avenues toward the possibility of analyzing and controlling the internal properties of quantum nanodevices with pump-push photocurrent spectroscopy.

Systematic Analysis of Polymer Molecular Weight Influence on the Organic Photovoltaic Performance.

PubMed

Katsouras, Athanasios; Gasparini, Nicola; Koulogiannis, Chrysanthos; Spanos, Michael; Ameri, Tayebeh; Brabec, Christoph J; Chochos, Christos L; Avgeropoulos, Apostolos

2015-10-01

The molecular weight of an electron donor-conjugated polymer is as essential as other well-known parameters in the chemical structure of the polymer, such as length and the nature of any side groups (alkyl chains) positioned on the polymeric backbone, as well as their placement, relative strength, the ratio of the donor and acceptor moieties in the backbone of donor-acceptor (D-A)-conjugated polymers, and the arrangement of their energy levels for organic photovoltaic performance. Finding the "optimal" molecular weight for a specific conjugated polymer is an important aspect for the development of novel photovoltaic polymers. Therefore, it is evident that the chemistry of functional conjugated polymers faces major challenges and materials have to adopt a broad range of specifications in order to be established for high photovoltaic performance. In this review, the approaches followed for enhancing the molecular weight of electron-donor polymers are presented in detail, as well as how this influences the optoelectronic properties, charge transport properties, structural conformation, morphology, and the photovoltaic performance of the active layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic solid state optical switches and method for producing organic solid state optical switches

DOEpatents

Wasielewski, M.R.; Gaines, G.L.; Niemczyk, M.P.; Johnson, D.G.; Gosztola, D.J.; O`Neil, M.P.

1993-01-01

This invention consists of a light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, and a method for making said compound.

Recovery of Elemental Palladium by Shewanella putrefaciens

NASA Astrophysics Data System (ADS)

Akasaka, S.; Xia, X.; Sawada, K.; Enokida, Y.; Yamamoto, I.; Ohnuki, T.

2006-12-01

Microbial reduction of metals plays an important role in environmental behavior and provides a technique for the recovery of metals from industrial wastewater. Recently, demand for platinum group metals (PGMs) increases by their catalytic properties. The extreme rarity of PGMs have led to a growing interest in their recovery. Palladium, one of PGMs, has different oxidation states of Pd(II) and Pd(0). The oxidized form of Pd(II) is soluble, while the reduced form of Pd(0) is insoluble. In this study, microbial reduction of palladium by Fe(III)- reducing bacterium, Shewanella putrefaceins was conducted. This bacterium is known to be capable of reducing metals, such as Mn(IV), U(VI), or Tc(VII) with organic C or H2 as an electron donor. In order to investigate the potential of S. putrefaciens to reduce Pd(II) in solution, resting cells or heat-killed cells were suspended under anaerobic conditions with lactate or H2 as an electron donor. The cells of S. putrefaciens (NBRC3908) were grown in aerobic medium, harvested by centrifugation, and then washed with 25 mmol/dm3 HEPES and 100 mmol/dm3 NaCl (HEPES-NaCl) solution (pH 7.0). The heat-killed cells were autoclaved for 20 min at 121 degrees C. The cell suspension (21.5 mg in dry weight) was resuspended in the HEPES-NaCl solution which contained 1.0 mmol/dm3 Na2PdCl4 (Wako Pure chemical Industries, Ltd). The suspensions were bubbled with N2 for 15 min before 10 mmol/dm3 lactate or 4.8 v/v% H2 was added. The suspensions were then incubated at 30 degrees C. Redox potential (Eh) and pH of the solutions were measured in an inert glove box with Ar gas. Concentration of Pd(II) was measured by Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Deposited Pd and cells were analyzed by X-ray powder diffraction (XRD) and Scanning Electron Microscope (SEM) with Energy-Dispersive Spectroscopy (EDS). Approximately 86% of Pd(II) of the initial concentration was removed from solution by the resting cells within 24 h when lactate was used as an electron donor. A black precipitates were observed in the solution, that was confirmed as Pd(0) by XRD analysis. SEM and EDS analyses identified that Pd bearing precipitates were present on and/or in the cells. The size of the precipitates associated with cells was approximately 100 nm in diameter. Approximately 23% of Pd(II) was removed by the heat-killed cells within 24 h. The precipitates between 200 and 300 nm in diameter were observed to be associated with the heat-killed cells by SEM and EDS analyses. No removal of Pd(II) was obtained without cells. On the contrary, complete removal of Pd(II) was occurred within 4 h after exposure of the resting cells to Pd(II) solution when H2 was used as an electron donor. Approximately 88 and 80% of Pd(II) was removed within 4 h with the heat-killed cells and without cells, respectively. The measured Eh and pH values were plotted in the Eh-pH diagram calculated for Pd-Cl-H2O system indicated that chemical conditions in the solutions were saturated with respect to Pd(0) at 24 or 4 h of incubation regardless the electron donor. These findings indicate that S. putrefaciens is capable to enhance the precipitation of palladium from solution by reducing Pd(II) to Pd(0) with lactate or H2 as an electron donor.

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

NASA Astrophysics Data System (ADS)

Gorby, Y. A.; Senko, J.

2011-12-01

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

Phosphorus and carrier density of heavily n-type doped germanium

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

Takinai, K.; Wada, K.

2016-05-14

The threshold current density of n-type, tensile-strained Ge lasers strongly depends on the electron density. Although optical net gain analyses indicate that the optimum electron density should be on the order of 1 × 10{sup 20} cm{sup −3} to get the lowest threshold, it is not a simple task to increase the electron density beyond the mid range of 10{sup 19} cm{sup −3}. The present paper analyzes the phenomenon where electron density is not proportional to phosphorus donor density, i.e., “saturation” phenomenon, by applying the so-called amphoteric defect model. The analyses indicate that the saturation phenomenon can be well explained by the charge compensationmore » between the phosphorus donors (P{sup +}) and doubly negative charged Ge vacancies (V{sup 2−}).« less

Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

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

Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

2014-01-28

The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

Effect of Donor Strength and Bulk on Thieno[3,4-b]-pyrazine-Based Panchromatic Dyes in Dye-Sensitized Solar Cells.

PubMed

Liyanage, Nalaka P; Cheema, Hammad; Baumann, Alexandra R; Zylstra, Alexa R; Delcamp, Jared H

2017-06-22

Near-infrared-absorbing organic dyes are critically needed in dye-sensitized solar cells (DSCs). Thieno[3,4-b]pyrazine (TPz) based dyes can access the NIR spectral region and show power conversion efficiencies (PCEs) of up to 8.1 % with sunlight being converted at wavelengths up to 800 nm for 17.6 mA cm -2 of photocurrent in a co-sensitized DSC device. Precisely controlling dye excited-state energies is critical for good performances in NIR DSCs. Strategies to control TPz dye energetics with stronger donor groups and TPz substituent choice are evaluated here. Additionally, donor size influence versus dye loading on TPz dyes is analyzed with respect to the TiO 2 surface protection designed to prevent recombination of electrons in TiO 2 with the redox shuttle. Importantly, the dyes evaluated were demonstrated to work well with low Li + concentration electrolytes, with iodine and cobalt redox shuttle systems, and efficiently as part of co-sensitized devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Incorporating fluorinated moieties in fully conjugated donor-acceptor block copolymers

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Wang, Qing; Gomez, Enrique D.

Fully conjugated donor-acceptor block copolymers are promising candidates for photovoltaics due to their ability to microphase separate at length scales commensurate with exciton diffusion lengths. These materials can also serve as model systems to study the relationship between molecular structure, microstructure, and optoelectronic properties of conjugated polymers. The development of new donor-acceptor block copolymers relies on the manipulation of the chemical structure to fine tune properties and improve overall performance when employed in photovoltaic devices. To this end, we have demonstrated the incorporation of fluorinated moieties in conjugated block copolymers. The introduction of fluorine, a strong electron withdrawing element, is known to influence phase separation and the bandgap, and as a result, optoelectronic properties. Fluorine was introduced to the acceptor block of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5 ',5?-diyl) (P3HT- b-PFTBT). PFTBTs were prepared with di-fluorinated and mono-fluorinated TBT. We find that fluorination impacts the bandgap, morphology and performance in devices.

Denitrification of the anaerobic membrane bioreactor (AnMBR) effluent with alternative electron donors in domestic wastewater treatment.

PubMed

Pelaz, L; Gómez, A; Garralón, G; Letona, A; Fdz-Polanco, M

2017-11-01

A fixed film bioreactor for the denitrification of the effluent from an anaerobic membrane bioreactor (AnMBR) treating domestic wastewater was designed, built and investigated. After anaerobic treatment, the wastewater usually has a low C/N ratio (∼1.3), and a remaining chemical oxygen demand of around 117mg O 2 /L, which is not enough to make conventional heterotrophic denitrification possible. That effluent also holds methane and sulfide dissolved and oversaturated after leaving the AnMBR. This paper demonstrates the feasibility of using these reduced compounds as electron donors in order to remove 80mg NO x - -N/L at 18°C and 2h of hydraulic retention time. In addition, the influence of the NO 2 - /NO 3 - ratios in the feed was studied. Total nitrogen removal was achieved in all the cases studied, except for a feed with 100% NO 3 - . Methane was the main electron donor used to remove the nitrites and nitrates, with a participation rate of over 70%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anaerobic oxidation of arsenite in Mono Lake water and by a facultative, arsenite-oxidizing chemoautotroph, strain MLHE-1

USGS Publications Warehouse

Oremland, R.S.; Hoeft, S.E.; Santini, J.M.; Bano, N.; Hollibaugh, R.A.; Hollibaugh, J.T.

2002-01-01

Arsenite [As(III)]-enriched anoxic bottom water from Mono Lake, California, produced arsenate [As(V)] during incubation with either nitrate or nitrite. No such oxidation occurred in killed controls or in live samples incubated without added nitrate or nitrite. A small amount of biological As(III) oxidation was observed in samples amended with Fe(III) chelated with nitrolotriacetic acid, although some chemical oxidation was also evident in killed controls. A pure culture, strain MLHE-1, that was capable of growth with As(III) as its electron donor and nitrate as its electron acceptor was isolated in a defined mineral salts medium. Cells were also able to grow in nitrate-mineral salts medium by using H2 or sulfide as their electron donor in lieu of As(III). Arsenite-grown cells demonstrated dark 14CO2 fixation, and PCR was used to indicate the presence of a gene encoding ribulose-1,5-biphosphate carboxylase/oxygenase. Strain MLHE-1 is a facultative chemoautotroph, able to grow with these inorganic electron donors and nitrate as its electron acceptor, but heterotrophic growth on acetate was also observed under both aerobic and anaerobic (nitrate) conditions. Phylogenetic analysis of its 16S ribosomal DNA sequence placed strain MLHE-1 within the haloalkaliphilic Ectothiorhodospira of the ??-Proteobacteria. Arsenite oxidation has never been reported for any members of this subgroup of the Proteobacteria.

Towards Sustainable H2 Production: Rational Design of Hydrophobic Triphenylamine-based Dyes for Sensitized Ethanol Photoreforming.

PubMed

Dessì, Alessio; Monai, Matteo; Bessi, Matteo; Montini, Tiziano; Calamante, Massimo; Mordini, Alessandro; Reginato, Gianna; Trono, Cosimo; Fornasiero, Paolo; Zani, Lorenzo

2018-02-22

Donor-acceptor dyes are a well-established class of photosensitizers, used to enhance visible-light harvesting in solar cells and in direct photocatalytic reactions, such as H 2 production by photoreforming of sacrificial electron donors (SEDs). Amines-typically triethanolamine (TEOA)-are commonly employed as SEDs in such reactions. Dye-sensitized photoreforming of more sustainable, biomass-derived alcohols, on the other hand, was only recently reported by using methanol as the electron donor. In this work, several rationally designed donor-acceptor dyes were used as sensitizers in H 2 photocatalytic production, comparing the efficiency of TEOA and EtOH as SEDs. In particular, the effect of hydrophobic chains in the spacer and/or the donor unit of the dyes was systematically studied. The H 2 production rates were higher when TEOA was used as SED, whereas the activity trends depended on the SED used. The best performance was obtained with TEOA by using a sensitizer with just one bulky hydrophobic moiety, propylenedioxythiophene, placed on the spacer unit. In the case of EtOH, the best-performing sensitizers were the ones featuring a thiazolo[5,4-d]thiazole internal unit, needed for enhancing light harvesting, and carrying alkyl chains on both the donor part and the spacer unit. The results are discussed in terms of reaction mechanism, interaction with the SED, and structural/electrochemical properties of the sensitizers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping the Reactivity and Selectivity of 2-Azidofucosyl Donors for the Assembly of N-Acetylfucosamine-Containing Bacterial Oligosaccharides.

PubMed

Hagen, Bas; Ali, Sara; Overkleeft, Herman S; van der Marel, Gijsbert A; Codée, Jeroen D C

2017-01-20

The synthesis of complex oligosaccharides is often hindered by a lack of knowledge on the reactivity and selectivity of their constituent building blocks. We investigated the reactivity and selectivity of 2-azidofucosyl (FucN 3 ) donors, valuable synthons in the synthesis of 2-acetamido-2-deoxyfucose (FucNAc) containing oligosaccharides. Six FucN 3 donors, bearing benzyl, benzoyl, or tert-butyldimethylsilyl protecting groups at the C3-O and C4-O positions, were synthesized, and their reactivity was assessed in a series of glycosylations using acceptors of varying nucleophilicity and size. It was found that more reactive nucleophiles and electron-withdrawing benzoyl groups on the donor favor the formation of β-glycosides, while poorly reactive nucleophiles and electron-donating protecting groups on the donor favor α-glycosidic bond formation. Low-temperature NMR activation studies of Bn- and Bz-protected donors revealed the formation of covalent FucN 3 triflates and oxosulfonium triflates. From these results, a mechanistic explanation is offered in which more reactive acceptors preferentially react via an S N 2-like pathway, while less reactive acceptors react via an S N 1-like pathway. The knowledge obtained in this reactivity study was then applied in the construction of α-FucN 3 linkages relevant to bacterial saccharides. Finally, a modular synthesis of the Staphylococcus aureus type 5 capsular polysaccharide repeating unit, a trisaccharide consisting of two FucNAc units, is described.

Development of Spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene]-Based A-π-D-π-A Small Molecules with Different Acceptor Units for Efficient Organic Solar Cells.

PubMed

Wang, Wengong; Shen, Ping; Dong, Xinning; Weng, Chao; Wang, Guo; Bin, Haijun; Zhang, Jing; Zhang, Zhi-Guo; Li, Yongfang

2017-02-08

Three acceptor-π-donor-π-acceptor (A-π-D-π-A) small molecules (STFYT, STFRDN, and STFRCN) with spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene] (STF) as the central donor unit, terthiophene as the π-conjugated bridge, indenedione, 3-ethylrhodanine, or 2-(1,1-dicyanomethylene)rhodanine as the acceptor unit are designed, synthesized, and characterized as electron donor materials in solution-processing organic solar cells (OSCs). The effects of the spiro STF-based central core and different acceptors on the molecular configuration, absorption properties, electronic energy levels, carrier transport properties, the morphology of active layers, and photovoltaic properties are investigated in detail. The three molecules exhibit desirable physicochemical features: wide absorption bands (300-850 nm) and high molar absorption coefficients (4.82 × 10 4 to 7.56 × 10 4 M -1 cm -1 ) and relatively low HOMO levels (-5.15 to -5.38 eV). Density functional theory calculations reveal that the spiro STF central core benefits to reduce the steric hindrance effect between the central donor block and terthiophene bridge and suppress excessive intermolecular aggregations. The optimized OSCs based on these molecules deliver power conversion efficiencies (PCEs) of 6.68%, 3.30%, and 4.33% for STFYT, STFRDN, and STFRCN, respectively. The higher PCE of STFYT-based OSCs should be ascribed to its better absorption ability, higher and balanced hole and electron mobilities, and superior active layer morphology as compared to the other two compounds. So far, this is the first example of developing the A-π-D-π-A type small molecules with a spiro central donor core for high-performance OSC applications. Meanwhile, these results demonstrate that using spiro central block to construct A-π-D-π-A molecule is an alternative and effective strategy for achieving high-performance small molecule donor materials.

Tumor cell death induced by the inhibition of mitochondrial electron transport: The effect of 3-hydroxybakuchiol

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

Jaña, Fabián; Faini, Francesca; Lapier, Michel

Changes in mitochondrial ATP synthesis can affect the function of tumor cells due to the dependence of the first step of glycolysis on mitochondrial ATP. The oxidative phosphorylation (OXPHOS) system is responsible for the synthesis of approximately 90% of the ATP in normal cells and up to 50% in most glycolytic cancers; therefore, inhibition of the electron transport chain (ETC) emerges as an attractive therapeutic target. We studied the effect of a lipophilic isoprenylated catechol, 3-hydroxybakuchiol (3-OHbk), a putative ETC inhibitor isolated from Psoralea glandulosa. 3-OHbk exerted cytotoxic and anti-proliferative effects on the TA3/Ha mouse mammary adenocarcinoma cell line andmore » induced a decrease in the mitochondrial transmembrane potential, the activation of caspase-3, the opening of the mitochondrial permeability transport pore (MPTP) and nuclear DNA fragmentation. Additionally, 3-OHbk inhibited oxygen consumption, an effect that was completely reversed by succinate (an electron donor for Complex II) and duroquinol (electron donor for Complex III), suggesting that 3-OHbk disrupted the electron flow at the level of Complex I. The inhibition of OXPHOS did not increase the level of reactive oxygen species (ROS) but caused a large decrease in the intracellular ATP level. ETC inhibitors have been shown to induce cell death through necrosis and apoptosis by increasing ROS generation. Nevertheless, we demonstrated that 3-OHbk inhibited the ETC and induced apoptosis through an interaction with Complex I. By delivering electrons directly to Complex III with duroquinol, cell death was almost completely abrogated. These results suggest that 3-OHbk has antitumor activity resulting from interactions with the ETC, a system that is already deficient in cancer cells. - Highlights: • We studied the anticancer activity of a natural compound, 3-OHbk, on TA3/Ha cells. • 3-OHbk inhibited mitochondrial electron flow by interacting with Complex I. • Complex I inhibition did not induce ROS generation. • 3-OHbk induced apoptosis in tumor cells with no effect on mammary epithelial cells. • Mitochondrial bioenergetics is implicated in anticancer action of 3-OHbk.« less

Substituent Dependence of Third-Order Optical Nonlinearity in Chalcone Derivatives

NASA Astrophysics Data System (ADS)

Kiran, Anthony John; Satheesh Rai, Nooji; Chandrasekharan, Keloth; Kalluraya, Balakrishna; Rotermund, Fabian

2008-08-01

The third-order nonlinear optical properties of derivatives of dibenzylideneacetone were investigated using the single beam z-scan technique at 532 nm. A strong dependence of third-order optical nonlinearity on electron donor and acceptor type of substituents was observed. An enhancement in χ(3)-value of one order of magnitude was achieved upon the substitution of strong electron donors compared to that of the molecule substituted with an electron acceptor. The magnitude of nonlinear refractive index of these chalcones is as high as of 10-11 esu. Their nonlinear optical coefficients are larger than those of widely used thiophene oligomers and trans-1-[p-(p-dimethylaminobenzyl-azo)-benzyl]-2-(N-methyl-4-pyridinium)-ethene iodide (DABA-PEI) organic compounds.

Modification of indole by electron-rich atoms and their application in novel electron donor materials

NASA Astrophysics Data System (ADS)

Zhang, Maolin; Qin, Guangjiong; Liu, Jialei; Zhen, Zhen; Fedorchuk, A. A.; Lakshminarayana, G.; Albassam, A. A.; El-Naggar, A. M.; Ozga, Katarzyna; Kityk, I. V.

2017-08-01

Novel nonlinear optical (NLO) chromophore based on 6-(pyrrolidin-1-yl)-1H-indole as the electron donor group was designed and synthesized. The molecular structure of this chromophore was characterized by 1H NMR spectra, 13C NMR spectra, and MS spectra. The delocalized energy level was estimated by UV-Vis. spectra. The thermal property was studied by thermogravimetric analysis (TGA). The poled films containing chromophores ZML-1 with a loading density of 10 wt% in amorphous polycarbonate (APC) afford an average electro-optic (EO) coefficient (r33) of 19 pm/V at 1310 nm. Compared to the reported aniline-based chromophore (r33 = 12 pm/V) analogues, chromophore ZML-1 exhibits enhanced electro-optical activity.

Donor-derived infections among Chinese donation after cardiac death liver recipients.

PubMed

Ye, Qi-Fa; Zhou, Wei; Wan, Qi-Quan

2017-08-21

To investigate blood cultures of deceased donors and report the confirmed transmission of bacterial infection from donors to liver recipients. We retrospectively studied the results of blood cultures among our donation after cardiac death (DCD) donors and calculated the donor-derived bacterial infection rates among liver recipients. Study participants underwent liver transplantation between January 1, 2010 and February 1, 2017. The study involved a total of 67 recipients of liver grafts from 67 DCD donors. We extracted the data of donors' and patients' characteristics, culture results and clinical outcomes, especially the post-transplant complications in liver recipients, from electronic medical records. We analyzed the characteristics of the donors and the corresponding liver recipients with emphasis put on donor-derived infections. Head trauma was the most common origin of death among our 67 DCD donors (46.3%). Blood taken prior to the procurement operation was cultured for 53 of the donors, with 17 episodes of bloodstream infections developing from 13 donors. The predominant organism isolated from the blood of donors was Gram-positive bacteria (70.6%). Only three (4.5%) of 67 liver recipients developed confirmed donor-derived bacterial infections, with two isolates of multidrug-resistant Klebsiella pneumoniae and one isolate of multidrug-resistant Enterobacter aerogenes. The liver recipients with donor-derived infections showed relation to higher crude mortality and graft loss rates (33.3% each) within 3 mo post transplantation, as compared to those without donor-derived infections (9.4% and 4.7%, respectively). All three liver recipients received appropriate antimicrobial therapy. Liver recipients have high occurrence of donor-derived infections. The liver recipients with donor-derived multidrug-resistant Enterobacteriaceae infections can have good outcome if appropriate antimicrobial therapy is given.

Dipole and Coulomb forces in electron capture dissociation and electron transfer dissociation mass spectroscopy.

PubMed

Świerszcz, Iwona; Skurski, Piotr; Simons, Jack

2012-02-23

Ab initio electronic structure calculations were performed on a doubly charged polypeptide model H(+)-Lys(Ala)(19)-CO-CH(NH(2))-CH(2)-SS-CH(2)-(NH(2))CH-CO-(Ala)(19)-Lys-H(+) consisting of a C-terminal protonated Lys followed by a 19-Ala α-helix with a 20th Ala-like unit whose side chain is linked by a disulfide bond to a corresponding Ala-like unit connected to a second 19-Ala α-helix terminated by a second C-terminal-protonated Lys. The Coulomb potentials arising from the two charged Lys residues and dipole potentials arising from the two oppositely directed 72 D dipoles of the α-helices act to stabilize the SS bond's σ* orbital. The Coulomb potentials provide stabilization of 1 eV, while the two large dipoles generate an additional 4 eV. Such stabilization allows the SS σ* orbital to attach an electron and thereby generate disulfide bond cleavage products. Although calculations are performed only on SS bond cleavage, discussion of N-C(α) bond cleavage caused by electron attachment to amide π* orbitals is also presented. The magnitudes of the stabilization energies as well as the fact that they arise from Coulomb and dipole potentials are supported by results on a small model system consisting of a H(3)C-SS-CH(3) molecule with positive and negative fractional point charges to its left and right designed to represent (i) two positive charges ca. 32 Å distant (i.e., the two charged Lys sites of the peptide model) and (ii) two 72 D dipoles (i.e., the two α-helices). Earlier workers suggested that internal dipole forces in polypeptides could act to guide incoming free electrons (i.e., in electron capture dissociation (ECD)) toward the positive end of the dipole and thus affect the branching ratios for cleaving various bonds. Those workers argued that, because of the huge mass difference between an anion donor and a free electron, internal dipole forces would have a far smaller influence over the trajectory of a donor (i.e., in electron transfer dissociation (ETD)). The present findings suggest that, in addition to their effects on guiding electron or donor trajectories, dipole potentials (in combination with Coulomb potentials) also alter the energies of SS σ* and amide π* orbitals, which then affects the ability of these orbitals to bind an electron. Thus, both by trajectory-guiding and by orbital energy stabilization, Coulomb and dipole potentials can have significant influences on the branching ratios of ECD and ETC in which disulfide or N-C(α) bonds are cleaved. © 2012 American Chemical Society

The expectations and attitudes of patients with chronic kidney disease toward living kidney donor transplantation: a thematic synthesis of qualitative studies.

PubMed

Hanson, Camilla S; Chadban, Steve J; Chapman, Jeremy R; Craig, Jonathan C; Wong, Germaine; Ralph, Angelique F; Tong, Allison

2015-03-01

Living kidney donation offers superior outcomes over deceased organ donation, but incurs psychosocial and ethical challenges for recipients because of the risks imposed on their donor. We aimed to describe the beliefs, attitudes, and expectations of patients with chronic kidney disease toward receiving a living kidney donor transplant. We conducted a systematic review of qualitative studies of patients' attitudes toward living kidney donation using a comprehensive literature search of electronic databases to February 2013. The findings were analyzed using thematic synthesis. Thirty-nine studies (n ≥ 1791 participants) were included. We identified six themes: prioritizing own health (better graft survival, accepting risk, and desperate aversion to dialysis), guilt and responsibility (jeopardizing donor health, anticipating donor regret, and causing donor inconvenience), ambivalence and uncertainty (doubting transplant urgency, insufficient information, confronted by unfamiliarity, and prognostic uncertainty), seeking decisional validation (a familial obligation, alleviating family burden, reciprocal benefits for donors, respecting donor autonomy, external reassurance, and religious approval), needing social support (avoiding family conflict, unrelenting indebtedness, and emotional isolation), and cautious donor recruitment (self-advocacy, lacking self-confidence, avoiding donor coercion, emotional vulnerability, respecting cultural, and religious taboos). Enhanced education and psychosocial support may help clarify, validate, and address patients' concerns regarding donor outcomes, guilt, relationship tensions, and donor recruitment. This may encourage informed decision-making, increase access to living kidney donation, and improve psychosocial adjustment for transplant recipients.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

High-resolution photoluminescence spectroscopy of Sn-doped ZnO single crystals

DOE PAGES

Kumar, E. Senthil; Mohammadbeigi, F.; Boatner, Lynn A.; ...

2016-01-01

Here, Group IV donors in ZnO are poorly understood, despite evidence that they are effective n-dopants. We present high-resolution photoluminescence spectroscopy studies of unintentionally doped and Sn doped ZnO single crystals grown by the chemical vapor transport method. Doped samples showed greatly increased emission from the I10 bound exciton transition which was recently proven to be related to the incorporation of Sn impurities based on radio-isotope studies. PL linewidths are exceptionally sharp for these samples, enabling clear identification of several donor species. Temperature dependent PL measurements of the I10 line emission energy and intensity dependence reveal a behavior similar tomore » other shallow donors in ZnO. Ionized donor bound exciton and two electron satellite transitions of the I10 transition are unambiguously identified and yield a donor binding energy of 71 meV. In contrast to recent reports of Ge-related donors in ZnO, the spectroscopic binding energy for the Sn-related donor bound exciton follows a linear relationship with donor binding energy (Haynes rule), confirming the shallow nature of this defect center, which we attribute to a SnZn double donor compensated by an unknown single acceptor.« less

Nature-Inspired, Highly Durable CO2 Reduction System Consisting of a Binuclear Ruthenium(II) Complex and an Organic Semiconductor Using Visible Light.

PubMed

Kuriki, Ryo; Matsunaga, Hironori; Nakashima, Takuya; Wada, Keisuke; Yamakata, Akira; Ishitani, Osamu; Maeda, Kazuhiko

2016-04-20

A metal-free organic semiconductor of mesoporous graphitic carbon nitride (C3N4) coupled with a Ru(II) binuclear complex (RuRu') containing photosensitizer and catalytic units selectively reduced CO2 into HCOOH under visible light (λ > 400 nm) in the presence of a suitable electron donor with high durability, even in aqueous solution. Modification of C3N4 with Ag nanoparticles resulted in a RuRu'/Ag/C3N4 photocatalyst that exhibited a very high turnover number (>33000 with respect to the amount of RuRu'), while maintaining high selectivity for HCOOH production (87-99%). This turnover number was 30 times greater than that reported previously using C3N4 modified with a mononuclear Ru(II) complex, and by far the highest among the metal-complex/semiconductor hybrid systems reported to date. The results of photocatalytic reactions, emission decay measurements, and time-resolved infrared spectroscopy indicated that Ag nanoparticles on C3N4 collected electrons having lifetimes of several milliseconds from the conduction band of C3N4, which were transferred to the excited state of RuRu', thereby promoting photocatalytic CO2 reduction driven by two-step photoexcitation of C3N4 and RuRu'. This study also revealed that the RuRu'/Ag/C3N4 hybrid photocatalyst worked efficiently in water containing a proper electron donor, despite the intrinsic hydrophobic nature of C3N4 and low solubility of CO2 in an aqueous environment.

Zwitterion mediator/quenchers. Coulombic minimization of the back-reaction in photocatalysis

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

Brugger, P.A.; Graetzel, M.; Guarr, T.

1982-03-18

Zwitterionic analogues of methyl viologen, N,N'-bis(carboxyethyl)-4,4'-bipyridyl (CEB), and N,N'-bis(sulfonatopropyl)-4,4'-bipyridyl (SPB) have been studied as electron-transfer quenchers of excited-state photocatalysts. The molecules are formally neutral when oxidized but become negatively charged when reduced. This charge buildup minimizes undesirable back-recombination of the photogenerated redox products. This Coulombic effect is demonstrated both by direct flash photolysis measurements of back-recombination and by catalytic studies of water reduction. Results are compared for the zwitterion quenchers and methyl viologen, reacting with soluble anionic porphyrins and with micelle-associated reactants. For the anionic porphyrin system zinc tetrakis (sulfonatophenyl)porphyrin(4-) the rates of back-recombination are as follows: ZnTSPP/sup 3 -/more » + MV/sup +/...-->.. ZnTSPP/sup 4 -/ + MV/sup 2 +/ (k), k = 2 x 10/sup 9/M/sup -1/s/sup -1/; ZnTSPP/sup 3 -/ + CEB/sup -/. ..-->.. ZnTSPP/sup 4 -/ + CEB +- (k), k = 6 x 10/sup 8/ M/sup -1/ s/sup -1/. In a corresponding catalytic system incorporating ZnTPPS as the photoacceptor, CEB or methyl viologen as the quencher, and N-phenylglycine as the electron donor, a >2-fold enhancement of catalysis is observed by replacing MV/sup 2 +/ with CEB. These events can be greatly accentuated by increasing the charge on the components, via micellar localization. Thus, by using an amphiphilic derivative of Ru(bpy)/sub 3//sup 2 +/ as photoactive donor solubilized in anionic micelles and SPB as electron acceptor, one can achieve 200-fold reduction in the rate of the back-reaction.« less

Apheresis for Collection of Ebola Convalescent Plasma in Liberia

PubMed Central

Brown, Jerry F.; Rowe, Kathleen; Zacharias, Peter; van Hasselt, James; Dye, John M.; Wohl, David A.; Fischer, William A.; Cunningham, Coleen K.; Thielman, Nathan M.; Hoover, David L.

2017-01-01

Purpose This report describes initiation of apheresis capability in Liberia, Africa to support a clinical trial of convalescent plasma therapy for Ebola Virus Disease. Methods A bloodmobile was outfitted in the United States as a four-bed apheresis unit with capabilities including pathogen reduction, electronic blood establishment computer system, designated areas for donor counseling and laboratory testing, and onboard electrical power generation. After air transport to Liberia, the bloodmobile was positioned at ELWA Hospital, Monrovia, and connected to the hospital’s power grid. Liberian staff were trained to conduct donor screening, which included questionnaire and onsite blood typing and transfusion transmitted infection (TTI) testing, and plasma collection and processing. Results The bloodmobile was operational within three weeks after arrival of the advance team. Of 101 donors who passed the pre-screening questionnaire, 32 were deferred. Twenty-eight of 99 tested survivors were deferred for positive transfusion transmitted infection (TTI) tests; 21 were positive for hepatitis B, hepatitis C, or human immunodeficiency virus. The majority of donors had type O blood; all but one were Rh positive. Forty-three survivors donated at least once; 89 apheresis attempts resulted in 81 successful collections. Conclusions Apheresis capability was emergently established in Liberia to support an efficacy trial of Ebola Convalescent Plasma. Extensive cooperation among multinational team members, engineers, logisticians and blood safety technical personnel at the operational site was required to surmount challenges to execution posed by logistical factors. The high proportion of positive TTI tests supported the use of a pathogen reduction system to enhance product safety. PMID:27393614

Donor-π-Acceptor Polymer with Alternating Triarylborane and Triphenylamine Moieties.

PubMed

Li, Haiyan; Jäkle, Frieder

2010-05-12

A luminescent main chain donor-π-acceptor-type polymer (4) was prepared via organometallic polycondensation reaction followed by post modification. With both electron-rich amine and electron-deficient borane moieties embedded in the main chain, 4 exhibits an interesting ambipolar character: it can be reduced and oxidized electrochemically at moderate potentials and shows a strong solvatochromic effect in the emission spectra. Complexation studies show that 4 selectively binds to fluoride and cyanide; quantitative titration with cyanide reveals a two-step binding process. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microbiology: A microbial arsenic cycle in a salt-saturated, extreme environment

USGS Publications Warehouse

Oremland, R.S.; Kulp, T.R.; Blum, J.S.; Hoeft, S.E.; Baesman, S.; Miller, L.G.; Stolz, J.F.

2005-01-01

Searles Lake is a salt-saturated, alkaline brine unusually rich in the toxic element arsenic. Arsenic speciation changed from arsenate [As(V)] to arsenite [As(III)] with sediment depth. Incubated anoxic sediment slurries displayed dissimilatory As(V)-reductase activity that was markedly stimulated by H2 or sulfide, whereas aerobic slurries had rapid As(III)-oxidase activity. An anaerobic, extremely haloalkaliphilic bacterium was isolated from the sediment that grew via As(V) respiration, using either lactate or sulfide as its electron donor. Hence, a full biogeochemical cycle of arsenic occurs in Searles Lake, driven in part by inorganic electron donors.

Anionic Four Electron Donor-Based Palladacycles as Catalysts for Addition Reactions of Arylboronic Acids with α,β-Unsaturated Ketones, Aldehydes and α-Ketoesters

PubMed Central

He, Ping; Lu, Yong; Dong, Cheng-Guo; Hu, Qiao-Sheng

2008-01-01

Anionic four electron donor-based palladacycle-catalyzed 1,4-additions of arylboronic acids with α,β-unsaturated ketones and 1,2-additions of arylboronic acids with aldehydes and α-ketoesters are described. Our study demonstrated that palladacycles were highly efficient, practical catalysts for these addition reactions. The work described here not only opened a new paradigm for the application of palladacycles, but may also pave the road for other metalacycles as practically useful catalysts for such addition reactions including asymmetric ones. PMID:17217300

¹³C Pathway Analysis for the Role of Formate in Electricity Generation by Shewanella Oneidensis MR-1 Using Lactate in Microbial Fuel Cells.

PubMed

Luo, Shuai; Guo, Weihua; Nealson, Kenneth H; Feng, Xueyang; He, Zhen

2016-02-12

Microbial fuel cell (MFC) is a promising technology for direct electricity generation from organics by microorganisms. The type of electron donors fed into MFCs affects the electrical performance, and mechanistic understanding of such effects is important to optimize the MFC performance. In this study, we used a model organism in MFCs, Shewanella oneidensis MR-1, and (13)C pathway analysis to investigate the role of formate in electricity generation and the related microbial metabolism. Our results indicated a synergistic effect of formate and lactate on electricity generation, and extra formate addition on the original lactate resulted in more electrical output than using formate or lactate as a sole electron donor. Based on the (13)C tracer analysis, we discovered decoupled cell growth and electricity generation in S. oneidensis MR-1 during co-utilization of lactate and formate (i.e., while the lactate was mainly metabolized to support the cell growth, the formate was oxidized to release electrons for higher electricity generation). To our best knowledge, this is the first time that (13)C tracer analysis was applied to study microbial metabolism in MFCs and it was demonstrated to be a valuable tool to understand the metabolic pathways affected by electron donors in the selected electrochemically-active microorganisms.

Geovibrio ferrireducens, a phylogenetically distinct dissimilatory Fe(III)-reducing bacterium

USGS Publications Warehouse

Caccavo, F.; Coates, J.D.; Rossello-Mora, R. A.; Ludwig, W.; Schleifer, K.H.; Lovley, D.R.; McInerney, M.J.

1996-01-01

A new, phylogenetically distinct, dissimilatory, Fe(III)-reducing bacterium was isolated from surface sediment of a hydrocarbon-contaminated ditch. The isolate, designated strain PAL-1, was an obligately anaerobic, non-fermentative, motile, gram-negative vibrio. PAL-1 grew in a defined medium with acetate as electron donor and ferric pyrophosphate, ferric oxyhydroxide, ferric citrate, Co(III)-EDTA, or elemental sulfur as sole electron acceptor. PAL-1 also used proline, hydrogen, lactate, propionate, succinate, fumarate, pyruvate, or yeast extract as electron donors for Fe(III) reduction. It is the first bacterium known to couple the oxidation of an amino acid to Fe(III) reduction. PAI-1 did not reduce oxygen, Mn(IV), U(VI), Cr(VI), nitrate, sulfate, sulfite, or thiosulfate with acetate as the electron donor. Cell suspensions of PAL-1 exhibited dithionite-reduced minus air-oxidized difference spectra that were characteristic of c-type cytochromes. Analysis of the 16S rRNA gene sequence of PAL-1 showed that the strain is not related to any of the described metal-reducing bacteria in the Proteobacteria and, together with Flexistipes sinusarabici, forms a separate line of descent within the Bacteria. Phenotypically and phylogenetically, strain PAI-1 differs from all other described bacteria, and represents the type strain of a new genus and species. Geovibrio ferrireducens.

Tuning the electronic and optical properties of NDT-based conjugated polymers by adopting fused heterocycles as acceptor units: a theoretical study.

PubMed

Cheng, Na; Zhang, Changqiao; Liu, Yongjun

2017-08-01

Donor-acceptor conjugated polymers have been successfully applied in bulk heterojunction solar cell devices. Tuning their donor and acceptor units allows the design of new polymers with desired electronic and optical properties. Here, to screen new candidate polymers based on a newly synthesized donor unit, dithieo[2,3-d:2',3'-d']naphtho[1,2-b:3,4-b']dithiophene (NDT), a series of model polymers with different acceptor units were designed and denoted NDT-A 0 to NDT-A 12 , and the structures and optical properties of those polymers were investigated using DFT and TDDFT calculations. The results of the calculations revealed that the electronic and optical properties of these polymers depend on the acceptor unit present; specifically, their HOMO energies ranged from -4.89 to -5.38 eV, their HOMO-LUMO gaps ranged from 1.30 to 2.80 eV, and their wavelengths of maximum absorption ranged from 538 to 1212 nm. The absorption spectra of NDT-A 1 to NDT-A 6 , NDT-A 8 , NDT-A 9 , and NDT-A 12 occur within the visible region (<900 nm), indicating that these polymers are potential candidates for use in solar cells. On the other hand, the absorption spectra of NDT-A 7 , NDT-A 10 , and NDT-A 11 extend much further into the near-infrared region, implying that they absorb near-infrared light. These polymers could meet the requirements of donor units for use in tandem and ternary solar cells. Graphical abstract Theoretical calculations by TD-DFT reveal that the optical properties of NDT-based conjugated polymers can be well tuned by adopting different acceptor units, and these ploymers are potential donor materials for tandem and ternary solar cells.

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

Ponomarenko, Nina S.; Li, Liang; Marino, Antony R.

Heterodimer mutant reaction centers (RCs) of Blastochloris viridis were crystallized using microfluidic technology. In this mutant, a leucine residue replaced the histidine residue which had acted as a fifth ligand to the bacteriochlorophyll (BChl) of the primary electron donor dimer M site (HisM200). With the loss of the histidine-coordinated Mg, one bacteriochlorophyll of the special pair was converted into a bacteriopheophytin (BPhe), and the primary donor became a heterodimer supermolecule. The crystals had dimensions 400 x 100 x 100 {micro}m, belonged to space group P4{sub 3}2{sub 1}2, and were isomorphous to the ones reported earlier for the wild type (WT)more » strain. The structure was solved to a 2.5 {angstrom} resolution limit. Electron-density maps confirmed the replacement of the histidine residue and the absence of Mg. Structural changes in the heterodimer mutant RC relative to the WT included the absence of the water molecule that is typically positioned between the M side of the primary donor and the accessory BChl, a slight shift in the position of amino acids surrounding the site of the mutation, and the rotation of the M194 phenylalanine. The cytochrome subunit was anchored similarly as in the WT and had no detectable changes in its overall position. The highly conserved tyrosine L162, located between the primary donor and the highest potential heme C{sub 380}, revealed only a minor deviation of its hydroxyl group. Concomitantly to modification of the BChl molecule, the redox potential of the heterodimer primary donor increased relative to that of the WT organism (772 mV vs. 517 mV). The availability of this heterodimer mutant and its crystal structure provides opportunities for investigating changes in light-induced electron transfer that reflect differences in redox cascades.« less

Diketopyrrolopyrrole-based π-bridged donor-acceptor polymer for photovoltaic applications.

PubMed

Li, Wenting; Lee, Taegweon; Oh, Soong Ju; Kagan, Cherie R

2011-10-01

We report the synthesis, properties, and photovoltaic applications of a new conjugated copolymer (C12DPP-π-BT) containing a donor group (bithiophene) and an acceptor group (2,5-didodecylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione), bridged by a phenyl group. Using cyclic voltammetry, we found the energy levels of C12DPP-π-BT are intermediate to common electron donor and acceptor photovoltaic materials, poly (3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), respectively. Whereas P3HT and PCBM are exclusively electron donating or accepting, we predict C12DPP-π-BT may uniquely serve as either an electron donor or an acceptor when paired with PCBM or P3HT forming junctions with large built-in potentials. We confirmed the ambipolar nature of C12DPP-π-BT in space charge limited current measurements and in C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT bulk heterojunction solar cells, achieving power conversion efficiencies of 1.67% and 0.84%, respectively, under illumination of AM 1.5G (100 mW/cm(2)). Adding diiodooctane to C12DPP-π-BT:PCBM improved donor-acceptor inter-mixing and film uniformity, and therefore enhanced charge separation and overall device efficiency. Using higher-molecular-weight polymer C12DPP-π-BT in both C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT devices improved charge transport and hence the performance of the solar cells. In addition, we compared the structural and electronic properties of C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT blends, representing the materials classes of polymer:fullerene and polymer:polymer blends. In C12DPP-π-BT:PCBM blends, higher short circuit currents were obtained, consistent with faster charge transfer and balanced electron and hole transport, but lower open circuit voltages may be reduced by trap-assisted recombination and interfacial recombination losses. In contrast, C12DPP-π-BT:P3HT blends exhibit higher open circuit voltage, but short circuit currents were limited by charge transfer between the polymers. In conclusion, C12DPP-π-BT is a promising material with intrinsic ambipolar characteristics for organic photovoltaics and may operate as either a donor or acceptor in the design of bulk heterojunction solar cells. © 2011 American Chemical Society

Electrical Manipulation of Spin Qubits in Li-doped Si

NASA Astrophysics Data System (ADS)

Petukhov, Andre; Pendo, Luke; Handberg, Erin; Smelyanskiy, Vadim

2011-03-01

We propose a complete quantum computing scheme based on Li donors in Si under external biaxial stress. The qubits are encoded on the ground state Zeeman doublets and coupled via long-range spin-spin interaction mediated by acoustic phonons. This interaction is unique for Li donors in Si due to their inverted electronic structure. Our scheme takes advantage of the fact that the energy level spacing in 1 s Li-donor manifold is comparable with the magnitude of the spin-orbit interaction. As a result the Li spin qubits can be placed 100 nm apart and manipulated by a combination of external electric field and microwave field impulses. We present a specially-designed sequence of the electric field impulses which allows for a typical time of a two-qubit gate ~ ~1~ μ s and a quality factor ~10-6 . These estimates are derived from detailed microscopic calculations of the quadratic Stark effect and electron-phonon decoherence times.

Donor-derived infections among Chinese donation after cardiac death liver recipients

PubMed Central

Ye, Qi-Fa; Zhou, Wei; Wan, Qi-Quan

2017-01-01

AIM To investigate blood cultures of deceased donors and report the confirmed transmission of bacterial infection from donors to liver recipients. METHODS We retrospectively studied the results of blood cultures among our donation after cardiac death (DCD) donors and calculated the donor-derived bacterial infection rates among liver recipients. Study participants underwent liver transplantation between January 1, 2010 and February 1, 2017. The study involved a total of 67 recipients of liver grafts from 67 DCD donors. We extracted the data of donors’ and patients’ characteristics, culture results and clinical outcomes, especially the post-transplant complications in liver recipients, from electronic medical records. We analyzed the characteristics of the donors and the corresponding liver recipients with emphasis put on donor-derived infections. RESULTS Head trauma was the most common origin of death among our 67 DCD donors (46.3%). Blood taken prior to the procurement operation was cultured for 53 of the donors, with 17 episodes of bloodstream infections developing from 13 donors. The predominant organism isolated from the blood of donors was Gram-positive bacteria (70.6%). Only three (4.5%) of 67 liver recipients developed confirmed donor-derived bacterial infections, with two isolates of multidrug-resistant Klebsiella pneumoniae and one isolate of multidrug-resistant Enterobacter aerogenes. The liver recipients with donor-derived infections showed relation to higher crude mortality and graft loss rates (33.3% each) within 3 mo post transplantation, as compared to those without donor-derived infections (9.4% and 4.7%, respectively). All three liver recipients received appropriate antimicrobial therapy. CONCLUSION Liver recipients have high occurrence of donor-derived infections. The liver recipients with donor-derived multidrug-resistant Enterobacteriaceae infections can have good outcome if appropriate antimicrobial therapy is given. PMID:28883707

Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

2012-01-01

A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…