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Sample records for added electron acceptors

  1. Evidence on Anaerobic Methane Oxidation (AOM) in a boreal cultivated peatland with natural and added electron acceptors

    NASA Astrophysics Data System (ADS)

    Dorodnikov, Maxim; Silvennoinen, Hanna; Martikainen, Pertti; Dörsch, Peter

    2015-04-01

    Anaerobic oxidation of methane (AOM) is a process of methane (CH4) consumption under anoxic conditions driven by microorganisms, which oxidize CH4 with various alternate electron acceptors (AEA): sulfate, nitrate, nitrite, metals-(Fe, Mn, Cu), organic compounds. AOM is common in marine ecosystems, where microbial sulfate reduction (SR) consumes most of the CH4 produced in sediments. Despite the global significance of AOM, the exact mechanisms and relevance of the process in terrestrial ecosystems are almost unknown. In the current study the occurrence of AOM was tested for two organic soil horizons (30 and 40 cm depth) and one mineral sub-soil (sand, 50 cm depth) of a cultivated boreal peatland (Linnansuo, Eastern Finland, energy crop Phalaris arundinacea - reed canarygrass) under controlled conditions with the addition of 13C-labeled CH4 and two common AEAs - SO4-2 and Fe+3. Concentrations of CH4, CO2 and O2 were continuously measured during 10 days of incubation and CO2 was sampled periodically under anaerobic conditions for stable 13C analysis. Oxygen dynamics revealed negligible O2 contamination during incubation and its trace amounts (0.05-0.8% from the atmospheric) were accounted in the net CH4 uptake. Application of 13C-enriched CH4 (4.9 atom%) allowed to track the label in CO2 as the end-product of AOM. The highest 13CO2 enrichment (up to 60‰) was observed in mineral sub-soil, however AOM was quantitatively more pronounced in the upper 30 cm horizon (2.1 vs. 0.2 μg CO2 g soil DW-1 in the 50 cm sub-soil). The highest AOM rate of 8.9 ng CO2 g soil DW-1 h-1 was estimated for the control treatment where no AEAs were added indicating sufficient amount of naturally available AEAs, likely organic compounds. This rate was 50 times more intensive (on the C basis) than the CH4 production potential of the same soil. In contrast, external AEAs decreased AOM rates but added Fe+3 stimulated decomposition of native SOM (as seen from the most depleted 13CO2 signatures

  2. Anaerobic electron acceptor chemotaxis in Shewanella putrefaciens

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.; Moser, D. P.; Saffarini, D. A.

    1995-01-01

    Shewanella putrefaciens MR-1 can grow either aerobically or anaerobically at the expense of many different electron acceptors and is often found in abundance at redox interfaces in nature. Such redox interfaces are often characterized by very strong gradients of electron acceptors resulting from rapid microbial metabolism. The coincidence of S. putrefaciens abundance with environmental gradients prompted an examination of the ability of MR-1 to sense and respond to electron acceptor gradients in the laboratory. In these experiments, taxis to the majority of the electron acceptors that S. putrefaciens utilizes for anaerobic growth was seen. All anaerobic electron acceptor taxis was eliminated by the presence of oxygen, nitrate, nitrite, elemental sulfur, or dimethyl sulfoxide, even though taxis to the latter was very weak and nitrate and nitrite respiration was normal in the presence of dimethyl sulfoxide. Studies with respiratory mutants of MR-1 revealed that several electron acceptors that could not be used for anaerobic growth nevertheless elicited normal anaerobic taxis. Mutant M56, which was unable to respire nitrite, showed normal taxis to nitrite, as well as the inhibition of taxis to other electron acceptors by nitrite. These results indicate that electron acceptor taxis in S. putrefaciens does not conform to the paradigm established for Escherichia coli and several other bacteria. Carbon chemo-taxis was also unusual in this organism: of all carbon compounds tested, the only positive response observed was to formate under anaerobic conditions.

  3. Physiological and electrochemical effects of different electron acceptors on bacterial anode respiration in bioelectrochemical systems.

    PubMed

    Yang, Yonggang; Xiang, Yinbo; Xia, Chunyu; Wu, Wei-Min; Sun, Guoping; Xu, Meiying

    2014-07-01

    To understand the interactions between bacterial electrode respiration and the other ambient bacterial electron acceptor reductions, alternative electron acceptors (nitrate, Fe2O3, fumarate, azo dye MB17) were added singly or multiply into Shewanella decolorationis microbial fuel cells (MFCs). All the added electron acceptors were reduced simultaneously with current generation. Adding nitrate or MB17 resulted in more rapid cell growth, higher flavin concentration and higher biofilm metabolic viability, but lower columbic efficiency (CE) and normalized energy recovery (NER) while the CE and NER were enhanced by Fe2O3 or fumarate. The added electron acceptors also significantly influenced the cyclic voltammetry profile of anode biofilm probably via altering the cytochrome c expression. The highest power density was observed in MFCs added with MB17 due to the electron shuttle role of the naphthols from MB17 reduction. The results provided important information for MFCs applied in practical environments where contains various electron acceptors. PMID:24862003

  4. Electron Donor Acceptor Interactions. Final Progress Report

    SciTech Connect

    2002-08-16

    The Gordon Research Conference (GRC) on Electron Donor Acceptor Interactions was held at Salve Regina University, Newport, Rhode Island, 8/11-16/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  5. Tuning the Electron Acceptor in Phthalocyanine-Based Electron Donor-Acceptor Conjugates.

    PubMed

    Sekita, Michael; Jiménez, Ángel J; Marcos, M Luisa; Caballero, Esmeralda; Rodríguez-Morgade, M Salomé; Guldi, Dirk M; Torres, Tomás

    2015-12-21

    Zinc phthalocyanines (ZnPc) have been attached to the peri-position of a perylenemonoimide (PMI) and a perylenemonoanhydride (PMA), affording electron donor-acceptor conjugates 1 and 2, respectively. In addition, a perylene-monoimide-monoanhydride (PMIMA) has been connected to a ZnPc through its imido position to yield the ZnPc-PMIMA conjugate 10. The three conjugates have been studied for photoinduced electron transfer. For ZnPc-PMIMA 10, electron transfer occurs upon both ZnPc and PMIMA excitation, giving rise to a long-lived (340 ps) charge-separated state. For ZnPc-PMI 1 and ZnPc-PMA 2, stabilization of the radical ion pair states by using polar media is necessary. In THF, photoexcitation of either ZnPc or PMI/PMA produces charge-separated states with lifetimes of 375 and 163 ps, respectively. PMID:26593778

  6. Donor-acceptor electron transport mediated by solitons.

    PubMed

    Brizhik, L S; Piette, B M A G; Zakrzewski, W J

    2014-11-01

    We study the long-range electron and energy transfer mediated by solitons in a quasi-one-dimensional molecular chain (conjugated polymer, alpha-helical macromolecule, etc.) weakly bound to a donor and an acceptor. We show that for certain sets of parameter values in such systems an electron, initially located at the donor molecule, can tunnel to the molecular chain, where it becomes self-trapped in a soliton state, and propagates to the opposite end of the chain practically without energy dissipation. Upon reaching the end, the electron can either bounce back and move in the opposite direction or, for suitable parameter values of the system, tunnel to the acceptor. We estimate the energy efficiency of the donor-acceptor electron transport depending on the parameter values. Our calculations show that the soliton mechanism works for the parameter values of polypeptide macromolecules and conjugated polymers. We also investigate the donor-acceptor electron transport in thermalized molecular chains. PMID:25493866

  7. Donor-acceptor electron transport mediated by solitons

    NASA Astrophysics Data System (ADS)

    Brizhik, L. S.; Piette, B. M. A. G.; Zakrzewski, W. J.

    2014-11-01

    We study the long-range electron and energy transfer mediated by solitons in a quasi-one-dimensional molecular chain (conjugated polymer, alpha-helical macromolecule, etc.) weakly bound to a donor and an acceptor. We show that for certain sets of parameter values in such systems an electron, initially located at the donor molecule, can tunnel to the molecular chain, where it becomes self-trapped in a soliton state, and propagates to the opposite end of the chain practically without energy dissipation. Upon reaching the end, the electron can either bounce back and move in the opposite direction or, for suitable parameter values of the system, tunnel to the acceptor. We estimate the energy efficiency of the donor-acceptor electron transport depending on the parameter values. Our calculations show that the soliton mechanism works for the parameter values of polypeptide macromolecules and conjugated polymers. We also investigate the donor-acceptor electron transport in thermalized molecular chains.

  8. Mass transfer of electron acceptor aross the capillary fringe

    NASA Astrophysics Data System (ADS)

    Liu, S.; Piepenbrink, M.; Grathwohl, P.

    2005-12-01

    Transverse dispersion has been identified as a potentially limiting parameter controlling the mixing of electron donors and electron acceptors for natural attenuation of plumes originating from continuously emitting sources, however determining reactive transverse dispersion coefficients is not a simple task. The objective of this work is to elaborate the mass transfer of electron acceptor across the capillary fringe. A two-dimensional numerical reactive transport model and a fully controlled tank experiment are set up to investigate the mass transfer across the capillary and reactive fringe, where the oxygen supply is the limiting factor. The tank (77.9 times 14 times 0.8 cm) is made from acrylic-glass and filled with glass beads (0.5-0.75mm). Sodium dithionite, an easily oxidizable compound, is used as a surrogate for contaminants and is continuously injected from the inlets of the tank and reaches a steady state flow. Air circulates on the top of the glass beads. The oxygen concentrations as well as the reactive products (sulfate) are measured at the outlets of the tank with an oxygen sensor and via IC. In addition to that, resazurine, a redox indicator, is added to visualize the redox zones. These two-dimensional experimental results show quantitatively and qualitatively how the oxygen concentrations decrease at the plume fringe. Two dimensional numerical simulations with Min3P predicted oxygen distributions are compared with the experimental results. Acknowledgements: This work was funded by Helmholtz Association and Helmholtz Research Center UFZ; Project: `Virtual Institute for isotope biogeochemistry-biologically mediated processes at geochemical gradients and interfaces in soil - aquifer systems', Contract VH-VI-155.

  9. Electron acceptor-dependent respiratory and physiological stratifications in biofilms.

    PubMed

    Yang, Yonggang; Xiang, Yinbo; Sun, Guoping; Wu, Wei-Min; Xu, Meiying

    2015-01-01

    Bacterial respiration is an essential driving force in biogeochemical cycling and bioremediation processes. Electron acceptors respired by bacteria often have solid and soluble forms that typically coexist in the environment. It is important to understand how sessile bacteria attached to solid electron acceptors respond to ambient soluble alternative electron acceptors. Microbial fuel cells (MFCs) provide a useful tool to investigate this interaction. In MFCs with Shewanella decolorationis, azo dye was used as an alternative electron acceptor in the anode chamber. Different respiration patterns were observed for biofilm and planktonic cells, with planktonic cells preferred to respire with azo dye while biofilm cells respired with both the anode and azo dye. The additional azo respiration dissipated the proton accumulation within the anode biofilm. There was a large redox potential gap between the biofilms and anode surface. Changing cathodic conditions caused immediate effects on the anode potential but not on the biofilm potential. Biofilm viability showed an inverse and respiration-dependent profile when respiring with only the anode or azo dye and was enhanced when respiring with both simultaneously. These results provide new insights into the bacterial respiration strategies in environments containing multiple electron acceptors and support an electron-hopping mechanism within Shewanella electrode-respiring biofilms. PMID:25495895

  10. Electron acceptor dependence of electron shuttle secretion and extracellular electron transfer by Shewanella oneidensis MR-1.

    PubMed

    Wu, Chao; Cheng, Yuan-Yuan; Li, Bing-Bing; Li, Wen-Wei; Li, Dao-Bo; Yu, Han-Qing

    2013-05-01

    Shewanella oneidensis MR-1 is an extensively studied dissimilatory metal-reducing bacterium with a great potential for bioremediation and electricity generation. It secretes flavins as electron shuttles which play an important role in extracellular electron transfer. However, the influence of various environmental factors on the secretion of flavins is largely unknown. Here, the effects of electron acceptors, including fumarate, ferrihydrite, Fe(III)-nitrilotriacetic acid (NTA), nitrate and trimethylamine oxide (TMAO), on the secretion of flavins were investigated. The level of riboflavin and riboflavin-5'-phosphate (FMN) secreted by S. oneidensis MR-1 varied considerably with different electron acceptors. While nitrate and ferrihydrite suppressed the secretion of flavins in relative to fumarate, Fe(III)-NTA and TMAO promoted such a secretion and greatly enhanced ferrihydrite reduction and electricity generation. This work clearly demonstrates that electron acceptors could considerably affect the secretion of flavins and consequent microbial EET. Such impacts of electron acceptors in the environment deserve more attention. PMID:23558182

  11. Anaerobic methanotrophy in tidal wetland: Effects of electron acceptors

    NASA Astrophysics Data System (ADS)

    Lin, Li-Hung; Yu, Zih-Huei; Wang, Pei-Ling

    2016-04-01

    Wetlands have been considered to represent the largest natural source of methane emission, contributing substantially to intensify greenhouse effect. Despite in situ methanogenesis fueled by organic degradation, methanotrophy also plays a vital role in controlling the exact quantity of methane release across the air-sediment interface. As wetlands constantly experience various disturbances of anthropogenic activities, biological burrowing, tidal inundation, and plant development, rapid elemental turnover would enable various electron acceptors available for anaerobic methanotrophy. The effects of electron acceptors on stimulating anaerobic methanotrophy and the population compositions involved in carbon transformation in wetland sediments are poorly explored. In this study, sediments recovered from tidally influenced, mangrove covered wetland in northern Taiwan were incubated under the static conditions to investigate whether anaerobic methanotrophy could be stimulated by the presence of individual electron acceptors. Our results demonstrated that anaerobic methanotrophy was clearly stimulated in incubations amended with no electron acceptor, sulfate, or Fe-oxyhydroxide. No apparent methane consumption was observed in incubations with nitrate, citrate, fumarate or Mn-oxides. Anaerobic methanotrophy in incubations with no exogenous electron acceptor appears to proceed at the greatest rates, being sequentially followed by incubations with sulfate and Fe-oxyhydroxide. The presence of basal salt solution stimulated methane oxidation by a factor of 2 to 3. In addition to the direct impact of electron acceptor and basal salts, incubations with sediments retrieved from low tide period yielded a lower rate of methane oxidation than from high tide period. Overall, this study demonstrates that anaerobic methanotrophy in wetland sediments could proceed under various treatments of electron acceptors. Low sulfate content is not a critical factor in inhibiting methane

  12. Rigid Conjugated Twisted Truxene Dimers and Trimers as Electron Acceptors.

    PubMed

    Zhang, Gang; Lami, Vincent; Rominger, Frank; Vaynzof, Yana; Mastalerz, Michael

    2016-03-14

    A new class of rigid twisted truxenone oligomers with an enlarged π backbone has been established by oxidative dimerization reactions. The resulting extended conjugated systems have large extinction coefficients and low-lying LUMO levels and show good solubility in common organic solvents, thus making them attractive compounds as new electron acceptors in organic electronics. Their suitability as electron acceptors has been demonstrated in bulk-heterojunction organic solar cells with poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7) as the donor material. PMID:26891096

  13. Mechanisms of electron acceptor utilization: Implications for simulating anaerobic biodegradation

    USGS Publications Warehouse

    Schreiber, M.E.; Carey, G.R.; Feinstein, D.T.; Bahr, J.M.

    2004-01-01

    Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum- contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and

  14. Mechanisms of electron acceptor utilization: implications for simulating anaerobic biodegradation.

    PubMed

    Schreiber, M E; Carey, G R; Feinstein, D T; Bahr, J M

    2004-09-01

    Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum-contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and

  15. 2012 ELECTRON DONOR-ACCEPTOR INTERACTIONS GORDON RESEARCH CONFERENCE, AUGUST 5-10, 2012

    SciTech Connect

    McCusker, James

    2012-08-10

    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.

  16. Virtual screening of electron acceptor materials for organic photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Halls, Mathew D.; Djurovich, Peter J.; Giesen, David J.; Goldberg, Alexander; Sommer, Jonathan; McAnally, Eric; Thompson, Mark E.

    2013-10-01

    Virtual screening involves the generation of structure libraries, automated analysis to predict properties related to application performance and subsequent screening to identify lead systems and estimate critical structure-property limits across a targeted chemical design space. This approach holds great promise for informing experimental discovery and development efforts for next-generation materials, such as organic semiconductors. In this work, the virtual screening approach is illustrated for nitrogen-substituted pentacene molecules to identify systems for development as electron acceptor materials for use in organic photovoltaic (OPV) devices. A structure library of tetra-azapentacenes (TAPs) was generated by substituting four nitrogens for CH at 12 sites on the pentacene molecular framework. Molecular properties (e.g. ELUMO, Eg and μ) were computed for each candidate structure using hybrid DFT at the B3LYP/6-311G** level of theory. The resulting TAPs library was then analyzed with respect to intrinsic properties associated with OPV acceptor performance. Marcus reorganization energies for charge transport for the most favorable TAP candidates were then calculated to further determine suitability as OPV electron acceptors. The synthesis, characterization and OPV device testing of TAP materials is underway, guided by these results.

  17. Fullerene derivatives as electron acceptors for organic photovoltaic cells.

    PubMed

    Mi, Dongbo; Kim, Ji-Hoon; Kim, Hee Un; Xu, Fei; Hwang, Do-Hoon

    2014-02-01

    Energy is currently one of the most important problems humankind faces. Depletion of traditional energy sources such as coal and oil results in the need to develop new ways to create, transport, and store electricity. In this regard, the sun, which can be considered as a giant nuclear fusion reactor, represents the most powerful source of energy available in our solar system. For photovoltaic cells to gain widespread acceptance as a source of clean and renewable energy, the cost per watt of solar energy must be decreased. Organic photovoltaic cells, developed in the past two decades, have potential as alternatives to traditional inorganic semiconductor photovoltaic cells, which suffer from high environmental pollution and energy consumption during production. Organic photovoltaic cells are composed of a blended film of a conjugated-polymer donor and a soluble fullerene-derivative acceptor sandwiched between a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)-coated indium tin oxide positive electrode and a low-work-function metal negative electrode. Considerable research efforts aim at designing and synthesizing novel fullerene derivatives as electron acceptors with up-raised lowest unoccupied molecular orbital energy, better light-harvesting properties, higher electron mobility, and better miscibility with the polymer donor for improving the power conversion efficiency of the organic photovoltaic cells. In this paper, we systematically review novel fullerene acceptors synthesized through chemical modification for enhancing the photovoltaic performance by increasing open-circuit voltage, short-circuit current, and fill factor, which determine the performance of organic photovoltaic cells. PMID:24749413

  18. Nitrite and nitrate as electron acceptors for biological sulphide oxidation.

    PubMed

    Munz, G; Mannucci, A; Arreola-Vargas, J; Alatriste-Mondragon, F; Giaccherini, F; Mori, G

    2015-01-01

    Autotrophic denitrification with sulphide using nitrate (R1) and nitrite (R2) as electron acceptor was investigated at bench scale. Different solids retention times (SRT) (5 and 20 d) have been tested in R1 while R2 was operated at SRT=13 d. The results indicated that the process allows complete sulphide removal to be achieved in all tested conditions. Tested sulphide loads were estimated from the H2S produced in a pilot-scale anaerobic digester treating vegetable tannery primary sludge; nitrogen loads originated from the nitrification of the supernatant. Average nitrogen removal efficiencies higher than 80% were observed in all the tested conditions once steady state was reached. A maximum specific nitrate removal rate equal to 0.35 g N-NO3- g VSS(-1) d(-1) was reached in R1. Due to sulphide limitation, incomplete denitrification was observed and nitrite and thiosulphate tend to accumulate especially in the presence of variable environmental conditions in both R1 and R2. Lower SRT caused higher NO2accumulated/NO3reduced ratios (0.22 and 0.24, with SRT of 5 d and 20 d, respectively) using nitrate as electron acceptor in steady-state condition. Temperature decrease caused sudden NO2accumulated/NO3reduced ratio increase in R1 and NO2- removal decrease in R2. PMID:26247758

  19. Three Redox States of a Diradical Acceptor-Donor-Acceptor Triad: Gating the Magnetic Coupling and the Electron Delocalization.

    PubMed

    Souto, Manuel; Lloveras, Vega; Vela, Sergi; Fumanal, Maria; Ratera, Imma; Veciana, Jaume

    2016-06-16

    The diradical acceptor-donor-acceptor triad 1(••), based on two polychlorotriphenylmethyl (PTM) radicals connected through a tetrathiafulvalene(TTF)-vinylene bridge, has been synthesized. The generation of the mixed-valence radical anion, 1(•-), and triradical cation species, 1(•••+), obtained upon electrochemical reduction and oxidation, respectively, was monitored by optical and ESR spectroscopy. Interestingly, the modification of electron delocalization and magnetic coupling was observed when the charged species were generated and the changes have been rationalized by theoretical calculations. PMID:27231856

  20. Development of imide- and imidazole-containing electron acceptors for use in donor-acceptor conjugated compounds and polymers

    NASA Astrophysics Data System (ADS)

    Li, Duo

    Conjugated organic compounds and polymers have attracted significant attention due to their potential application in electronic devices as semiconducting materials, such as organic solar cells (OSCs). In order to tune band gaps, donor-acceptor (D-A) structure is widely used, which has been proved to be one of the most effective strategies. This thesis consists of three parts: 1) design, syntheses and characterization of new weak acceptors based on imides and the systematic study of the structure-property relationship; (2) introduction of weak and strong acceptors in one polymer to achieve a broad coverage of light absorption and improve the power conversion efficiency (PCE); (3) modification of benzothiadiazole (BT) acceptor in order to increase the electron withdrawing ability. Imide-based electron acceptors, 4-(5-bromothiophen-2-y1)-2-(2-ethylhexyl)-9- phenyl- 1H-benzo[f]isoindole-1,3(2H)-dione (BIDO-1) and 4,9-bis(5-bromothiophen-2-yl)-2-(2-ethylhexyl)-benzo[f]isoindole-1,3-dione (BIDO-2), were designed and synthesized. In this design, naphthalene is selected as its main core to maintain a planar structure, and thienyl groups are able to facilitate the bromination reaction and lower the band gap. BIDO-1 and BIDO-2 were successfully coupled with different donors by both Suzuki cross-coupling and Stille cross-coupling reactions. Based on the energy levels and band gaps of the BIDO-containing compounds and polymers, BIDO-1 and BIDO-2 are proved to be weak electron acceptors. Pyromellitic diimide (PMDI) was also studied and found to be a stronger electron acceptor than BIDO . In order to obtain broad absorption coverage, both weak acceptor ( BIDO-2) and strong acceptor diketopyrrolopyrrole (DPP) were introduced in the same polymer. The resulting polymers show two absorption bands at 400 and 600 nm and two emission peaks at 500 and 680 nm. The band gaps of the polymers are around 1.6 eV, which is ideal for OSC application. The PCE of 1.17% was achieved. Finally

  1. Rates of primary electron transfer reactions in the photosystem I reaction center reconstituted with different quinones as the secondary acceptor

    SciTech Connect

    Kumazaki, Shigeichi; Kandori, Hideki; Yoshihara, Keitaro ); Iwaki, Masayo; Itoh, Shigeru ); Ikegamu, Isamu )

    1994-10-27

    Rates of sequential electron transfer reactions from the primary electron donor chlorophyll dimer (P700) to the electron acceptor chlorophyll a-686 (A[sub 0]) and to the secondary acceptor quinone (Q[sub [phi

  2. Fate of microbial metabolites of hydrocarbons in a coastal plain aquifer: The role of electron acceptors

    USGS Publications Warehouse

    Cozzarelli, I.M.; Herman, J.S.; Baedecker, M. Jo

    1995-01-01

    A combined field and laboratory study was undertaken to understand the distribution and geochemical conditions that influence the prevalence of low molecular weight organic acids in groundwater of a shallow aquifer contaminated with gasoline. Aromatic hydrocarbons from gasoline were degraded by microbially mediated oxidation-reduction reactions, including reduction of nitrate, sulfate, and Fe(III). The biogeochemical reactions changed overtime in response to changes in the hydrogeochemical conditions in the aquifer. Aliphatic and aromatic organic acids were associated with hydrocarbon degradation in anoxic zones of the aquifer. Laboratory microcosms demonstrated that the biogeochemical fate of specific organic acids observed in groundwater varied with the structure of the acid and the availability of electron acceptors. Benzoic and phenylacetic acid were degraded by indigenous aquifer microorganisms when nitrate was supplied as an electron acceptor. Aromatic acids with two or more methyl substituants on the benzene ring persisted under nitrate-reducing conditions. Although iron reduction and sulfate reduction were important processes in situ and occurred in the microcosms, these reactions were not coupled to the biological oxidation of aromatic organic acids that were added to the microcosms as electron donors. ?? 1995 American Chemical Society.

  3. [Effects of carbon sources, temperature and electron acceptors on biological phosphorus removal].

    PubMed

    Han, Yun; Xu, Song; Dong, Tao; Wang, Bin-Fan; Wang, Xian-Yao; Peng, Dang-Cong

    2015-02-01

    Effects of carbon sources, temperature and electron acceptors on phosphorus uptake and release were investigated in a pilot-scale oxidation ditch. Phosphorus uptake and release rates were measured with different carbon sources (domestic sewage, sodium acetate, glucose) at 25 degrees C. The results showed that the minimum phosphorus uptake and release rates of glucose were 5.12 mg x (g x h)(-1) and 6.43 mg x (g x h)(-1), respectively, and those of domestic sewage are similar to those of sodium acetate. Phosphorus uptake and release rates increased with the increase of temperature (12, 16, 20 and 25 degrees C) using sodium acetate as carbon sources. Anoxic phosphorus uptake rate decreased with added COD. Electron acceptors (oxygen, nitrate, nitrite) had significant effects on phosphorus uptake rate and their order was in accordance with oxygen > nitrate > nitrite. The mass ratio of anoxic P uptake and N consumption (P(uptake)/N (consumption)) of nitrate and nitrite were 0.96 and 0.65, respectively. PMID:26031087

  4. Biosynthetic Pathways of Vibrio succinogenes growing with fumarate as terminal electron acceptor and sole carbon source.

    PubMed

    Bronder, M; Mell, H; Stupperich, E; Kröger, A

    1982-05-01

    1. With fumarate as the terminal electron acceptor and either H2 or formate as donor, Vibrio succinogenes could grow anaerobically in a mineral medium using fumarate as the sole carbon source. Both the growth rate and the cell yield were increased when glutamate was also present in the medium. 2. Glutamate was incorporated only into the amino acids of the glutamate family (glutamate, glutamine, proline and arginine) of the protein. The residual cell constituents were synthesized from fumarate. 3. Pyruvate and phosphoenolpyruvate, as the central intermediates of most of the cell constituents, were formed through the action of malic enzyme and phosphoenolpyruvate synthetase. Fructose-1,6-bisphosphate aldolase was present in the bacterium suggesting that this enzyme is involved in carbohydrate synthesis. 4. In the absence of added glutamate the amino acids of the glutamate family were synthesized from fumarate via citrate. The enzymes involved in glutamate synthesis were present. 5. During growth in the presence of glutamate, net reducing equivalents were needed for cell synthesis. Glutamate and not H2 or formate was used as the source of these reducing equivalents. For this purpose part of the glutamate was oxidized to yield succinate and CO2. 6. The alpha-ketoglutarate dehydrogenase involved in this reaction was found to use ferredoxin as the electron acceptor. The ferredoxin of the bacterium was reoxidized by means of a NADP-ferredoxin oxidoreductase. Enzymes catalyzing the reduction of NAD, NADP or ferredoxin by H2 or formate were not detected in the bacterium. PMID:7103660

  5. Donor-Acceptor-Type Semiconducting Polymers Consisting of Benzothiadiazole Derivatives as Electron-Acceptor Units for Organic Photovoltaic Cells.

    PubMed

    Kim, Hee Su; Park, Jong Baek; Kim, Ji-Hoon; Hwang, Do-Hoon

    2015-11-01

    We synthesized two fused pentacyclic donor-acceptor structures, where the two different outer electron rich thiophene (DTPBT) and electron poor benzene (ICTh) moieties are covalently bonded to the central electron-deficient benzothiadiazole core by two nitrogen bridges. These new electron-acceptor DTPBT and ICTh building blocks were copolymerized with fluorene, as the electron donor group, via Suzuki coupling polymerization, to produce two new alternating copolymers, PFDTPBT and PFICTh, respectively. The average molecular weights of the synthesized polymers were determined by GPC. The number-average molecular weights of PFDTPBT and PFICTh were 19,000 (PDI = 2.5) and 20,000 (PDI = 4.0), respectively. The optical bandgap energies of the polymers were measured from their absorption onsets to be 2.15 and 2.55 eV, depending on the polymer structure. The HOMO energy levels of the polymers were determined, by measuring the oxidation onsets of the polymer films by cyclic voltammetry. The measured HOMO energy levels of PFDTPBT and PFICTh were -5.10 and -5.57 eV, respectively. When the polymers were blended with PC71BM, as the active layer for bulk-heterojunction photovoltaic devices, power conversion efficiencies were 2.08% and 0.34%, respectively, under AM 1.5 G (100 mW cm(-2)) conditions. PMID:26726610

  6. Analysis of Shewanella oneidensis Membrane Protein Expression in Response to Electron Acceptor Availability

    SciTech Connect

    Giometti, Carol S.; Khare, Tripti; Verberkmoes, Nathan; O'Loughlin, Ed; Lindberg, Carl; Thompson, Melissa; Hettich, Robert

    2006-04-05

    Shewanella oneidensis MR-1, a gram negative metal-reducing bacterium, can utilize a large number of electron acceptors. In the natural environment, S. oneidensis utilizes insoluble metal oxides as well as soluble terminal electron acceptors. The purpose of this ERSP project is to identify differentially expressed proteins associated with the membranes of S. oneidensis MR-1 cells grown with different electron acceptors, including insoluble metal oxides. We hypothesize that through the use of surface labeling, subcellular fractionation, and a combination of proteome analysis tools, proteins involved in the reduction of different terminal electron acceptors will be elucidated. We are comparing the protein profiles from cells grown with the soluble electron acceptors oxygen and fumarate and with those from cells grown with the insoluble iron oxides goethite, ferrihydrite and lepidocrocite. Comparison of the cell surface proteins isolated from cells grown with oxygen or anaerobically with fumarate revealed an increase in the abundance of over 25 proteins in anaerobic cells, including agglutination protein and flagellin proteins along with the several hypothetical proteins. In addition, the surface protein composition of cells grown with the insoluble iron oxides varies considerably from the protein composition observed with either soluble electron acceptor as well as between the different insoluble acceptors.

  7. Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

  8. Photoinduced electron tunneling between randomly dispersed donors and acceptors in frozen glasses and other rigid matrices.

    PubMed

    Wenger, Oliver S

    2013-07-14

    In fluid solution un-tethered donors and acceptors can diffuse freely, and consequently the donor-acceptor distance is usually not fixed on the timescale of an electron transfer event. When attempting to investigate the influence of driving-force changes or donor-acceptor distance variations on electron transfer rates this can be a problem. In rigid matrices diffusion is suppressed, and it becomes possible to investigate fixed-distance electron transfer. This method represents an attractive alternative to investigate rigid rod-like donor-bridge-acceptor molecules which have to be made in elaborate syntheses. This perspective focuses specifically on the distance dependence of photoinduced electron transfer which occurs via tunneling of charge carriers through rigid matrices over distances between 1 and 33 Å. Some key aspects of the theoretical models commonly used for analyzing kinetic data of electron tunneling through rigid matrices are recapitulated. New findings from this rather mature field of research are emphasized. PMID:23722299

  9. Electron-Donor-Acceptor (EDA) Complexes Of Aromatic Hydrocarbons With Organic Acceptors In Solution And In The Solid State. A Quantitative FT-IR Investigation.

    NASA Astrophysics Data System (ADS)

    Bruni, Paolo; Giorgini, Elisabetta; Tosi, Giorgio; Zampini, Angela

    1989-12-01

    Liquid phase FT-IR investigation on π-π Electron-Donor-Acceptor (EDA) complexes between arenes and organic acceptors leads to values of formation constants that are in good agreement with the ones from other techniques (UV-Vis and NMR). In addition solid state FT-IR and UV-Vis determinations on the complexes are also reported and discussed.

  10. INFLUENCE OF ALTERNATIVE ELECTRON ACCEPTORS ON THE ANAEROBIC BIODEGRADABILITY OF CHLORINATED PHENOLS AND BENZOIC ACIDS

    EPA Science Inventory

    Nitrate, sulfate, and carbonate were used as electron acceptors to examine the anaerobic biodegradability of chlorinated aromatic compounds in estuarine and freshwater sediments. he respective denitrifying, sulfidogenic, and methanogenic enrichment cultures were established on ea...

  11. TIO2 ADVANCED PHOTO-OXIDATION TECHNOLOGY: EFFECT OF ELECTRON ACCEPTORS

    EPA Science Inventory

    The effects of electron acceptors (additives) such as hydrogen peroxide, ammonium persulphate, potassium bromate and potassium peroxymonosulphate (ozone) on the TiO2 photocatalytic degradation of various organic pollutants were examined at various conditions. he individual and th...

  12. Candidatus Accumulibacter phosphatis clades enriched under cyclic anaerobic and microaerobic conditions simultaneously use different electron acceptors.

    PubMed

    Camejo, Pamela Y; Owen, Brian R; Martirano, Joseph; Ma, Juan; Kapoor, Vikram; Santo Domingo, Jorge; McMahon, Katherine D; Noguera, Daniel R

    2016-10-01

    Lab- and pilot-scale simultaneous nitrification, denitrification and phosphorus removal-sequencing batch reactors were operated under cyclic anaerobic and micro-aerobic conditions. The use of oxygen, nitrite, and nitrate as electron acceptors by Candidatus Accumulibacter phosphatis during the micro-aerobic stage was investigated. A complete clade-level characterization of Accumulibacter in both reactors was performed using newly designed qPCR primers targeting the polyphosphate kinase gene (ppk1). In the lab-scale reactor, limited-oxygen conditions led to an alternated dominance of Clade IID and IC over the other clades. Results from batch tests when Clade IC was dominant (i.e., >92% of Accumulibacter) showed that this clade was capable of using oxygen, nitrite and nitrate as electron acceptors for P uptake. A more heterogeneous distribution of clades was found in the pilot-scale system (Clades IIA, IIB, IIC, IID, IA, and IC), and in this reactor, oxygen, nitrite and nitrate were also used as electron acceptors coupled to phosphorus uptake. However, nitrite was not an efficient electron acceptor in either reactor, and nitrate allowed only partial P removal. The results from the Clade IC dominated reactor indicated that either organisms in this clade can simultaneously use multiple electron acceptors under micro-aerobic conditions, or that the use of multiple electron acceptors by Clade IC is due to significant microdiversity within the Accumulibacter clades defined using the ppk1 gene. PMID:27340814

  13. Natural organic matter as electron acceptor: experimental evidence for its important role in anaerobic respiration

    NASA Astrophysics Data System (ADS)

    Lau, Maximilian Peter; Sander, Michael; Gelbrecht, Jörg; Hupfer, Michael

    2014-05-01

    Microbial respiration is a key driver of element cycling in oxic and anoxic environments. Upon depletion of oxygen as terminal electron acceptor (TEA), a number of anaerobic bacteria can employ alternative TEA for intracellular energy generation. Redox active quinone moieties in dissolved organic matter (DOM) are well known electron acceptors for microbial respiration. However, it remains unclear whether quinones in adsorbed and particulate OM accept electrons in a same way. In our studies we aim to understand the importance of natural organic matter (NOM) as electron acceptors for microbial energy gain and its possible implications for methanogenesis. Using a novel electrochemical approach, mediated electrochemical reduction and -oxidation, we can directly quantify reduced hydroquinone and oxidized quionone moieties in dissolved and particulate NOM samples. In a mesocosm experiment, we rewetted sediment and peat soil and followed electron transfer to the inorganic and organic electron acceptors over time. We found that inorganic and organic electron acceptor pools were depleted over the same timescales. More importantly, we showed that organic, NOM-associated electron accepting moieties represent as much as 21 40% of total TEA inventories. These findings support earlier studies that propose that the reduction of quinone moieties in particulate organic matter competitively suppresses methanogenesis in wetland soils. Our results indicate that electron transfer to organic, particulate TEA in inundated ecosystems has to be accounted for when establishing carbon budgets in and projecting greenhouse gas emissions from these systems.

  14. Dissimilatory Reduction of Fe(III) and Other Electron Acceptors by a Thermus Isolate

    PubMed Central

    Kieft, T. L.; Fredrickson, J. K.; Onstott, T. C.; Gorby, Y. A.; Kostandarithes, H. M.; Bailey, T. J.; Kennedy, D. W.; Li, S. W.; Plymale, A. E.; Spadoni, C. M.; Gray, M. S.

    1999-01-01

    A thermophilic bacterium that can use O2, NO3−, Fe(III), and S0 as terminal electron acceptors for growth was isolated from groundwater sampled at a 3.2-km depth in a South African gold mine. This organism, designated SA-01, clustered most closely with members of the genus Thermus, as determined by 16S rRNA gene (rDNA) sequence analysis. The 16S rDNA sequence of SA-01 was >98% similar to that of Thermus strain NMX2 A.1, which was previously isolated by other investigators from a thermal spring in New Mexico. Strain NMX2 A.1 was also able to reduce Fe(III) and other electron acceptors. Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus strain SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could reduce only relatively small quantities (0.5 mM) of hydrous ferric oxide except when the humic acid analog 2,6-anthraquinone disulfonate was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II); reduction of Fe(III)-NTA was coupled to the oxidation of lactate and supported growth through three consecutive transfers. Suspensions of Thermus strain SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and U(VI). Mn(IV)-oxide was reduced in the presence of either lactate or H2. Both strains were also able to mineralize NTA to CO2 and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus strains SA-01 and NMX2 A.1 is approximately 65°C; their optimum pH is 6.5 to 7.0. This is the first report of a Thermus sp. being able to couple the oxidation of organic compounds to the reduction of Fe, Mn, or S. PMID:10049886

  15. Dissimilatory Reduction of Fe(III) and Other Electron Acceptors by a Thermus Isolate

    SciTech Connect

    Kieft, T. L.; Fredrickson, J. K.; Onstott, T. C.; Gorby, Y. A.; Kostandarithes, H. M.; Bailey, T. J.; Kennedy, D. W.; Li, S. W.; Plymale, A. E.; Spadoni, C. M.; Gray, M. S.

    1995-10-25

    A thermophilic bacterium that could use O{sub 2}, NO{sub 3}{sup -}, Fe(III), or S{sup o} as terminal electron acceptors for growth was isolated from groundwater sampled at 3.2 km depth in a South African gold mine. This organism, designated SA-01, clustered most closely with members of the genus Thermus, as determined by 16S rDNA gene sequence analysis. The 16S rDNA sequence of SA-01 was >98% similar to that of Thermus strain NMX2 A.1, which was previously isolated by other investigators from a thermal spring in New Mexico. Strain NMX2 A.1 was also able to reduce Fe(III) and other electron acceptors, whereas Thermus aquaticus (ATCC 25104) and Thermus filiformis (ATCC 43280) did not reduce NO{sub 3}{sup -} or Fe(III). Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could only reduce relatively small quantities (0.5 mM) of hydrous ferric oxide (HFO) except when the humic acid analog 2,6-anthraquinone disulfonate (AQDS) was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II), was coupled to the oxidation of lactate, and could support growth through three consecutive transfers. Suspensions of Thermus SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and AQDS. Mn(IV)-oxide was reduced in the presence of either lactate or H{sub 2}. Both strains were also able to mineralize NTA to CO{sub 2} and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus SA-01 and NMX2 A.1 is approximately 65 C; optimum pH is 6.5 to 7.0. This is the first report of a Thermus sp. being able to couple the oxidation of organic compounds to the reduction of Fe, Mn or S.

  16. Effect of Electronic Acceptor Segments on Photophysical Properties of Low-Band-Gap Ambipolar Polymers

    PubMed Central

    Li, Yuanzuo; Cui, Jingang; Zhao, Jianing; Liu, Jinglin; Song, Peng; Ma, Fengcai

    2013-01-01

    Stimulated by a recent experimental report, charge transfer and photophysical properties of donor-acceptor ambipolar polymer were studied with the quantum chemistry calculation and the developed 3D charge difference density method. The effects of electronic acceptor strength on the structure, energy levels, electron density distribution, ionization potentials, and electron affinities were also obtained to estimate the transporting ability of hole and electron. With the developed 3D charge difference density, one visualizes the charge transfer process, distinguishes the role of molecular units, and finds the relationship between the role of DPP and excitation energy for the three polymers during photo-excitation. PMID:23365549

  17. Conduction electrons in acceptor-doped GaAs/GaAlAs heterostructures: a review

    NASA Astrophysics Data System (ADS)

    Zawadzki, Wlodek; Raymond, Andre; Kubisa, Maciej

    2016-05-01

    We review magneto-optical and magneto-transport effects in GaAs/GaAlAs heterostructures doped in GaAlAs barriers with donors, providing two-dimensional (2D) electron gas (2DEG) in GaAs quantum wells (QWS), and additionally doped with smaller amounts of acceptors (mostly Be atoms) in the vicinity of 2DEG. One may also deal with residual acceptors (mostly C atoms). The behavior of such systems in the presence of a magnetic field differs appreciably from those doped in the vicinity of 2DEG with donors. Three subjects related to the acceptor-doped heterostructures are considered. First is the problem of bound states of conduction electrons confined to the vicinity of negatively charged acceptors by the joint effect of a QW and an external magnetic field parallel to the growth direction. A variational theory of such states is presented, demonstrating that an electron turning around a repulsive center has discrete energies above the corresponding Landau levels. Experimental evidence for the discrete electron energies comes from the work on interband photo-magneto-luminescence, intraband cyclotron resonance and quantum magneto-transport (the Quantum Hall and Shubnikov-de Haas effects). An electron rain-down effect at weak electric fields and a boil-off effect at strong electric fields are introduced. It is demonstrated, both theoretically and experimentally, that a negatively charged acceptor can localize more than one electron. The second subject describes experiment and theory of asymmetric quantized Hall and Shubnikov-de Haas plateaus in acceptor-doped GaAs/GaAlAs heterostructures. It is shown that the main features of the plateau asymmetry can be attributed to asymmetric density of Landau states in the presence of acceptors. However, at high magnetic fields, the rain-down effect is also at work. The third subject deals with the so-called disorder modes (DMs) in the cyclotron resonance of conduction electrons. The DMs originate from random distributions of negatively

  18. [Effect of C/N ratio on nitrous oxide production during denitrification with different electron acceptors].

    PubMed

    Shang, Hui-Lai; Peng, Yong-Zhen; Zhang, Jing-Rong; Wang, Shu-Ying

    2009-07-15

    The experiment investigated the nitrous oxide production under different C/N ratios during denitrification, taking nitrate and nitrite as electron acceptor respectively. Ethanol was selected as carbon source. The C/N ratios were 0, 1.2, 2.4, 3.5, 5.0 and 20 when nitrate was taken as electron acceptor and C/N ratios 0, 1.8, 2.4, 3.0, 4.3, 5.2, 6.6, 20.6 when electron acceptor was nitrite. The results indicated that: the optimum C/N ratio was 3.0 taking nitrite as electron acceptor and the N2O production was 0.044 mg x L(-1); the optimum C/N ratio was 5.0 taking nitrate as electron acceptor and the N2O production was 0.135 mg x L(-1) which was 3 times higher than that of nitrite as electron acceptor. Though the electron acceptor changed, the trend of N2O production was similar: when carbon source was badly insufficient, the production of N2O and denitrification rate were both quite small; the N2O production increased with the increasing of the quantity of carbon source; when the carbon source was excessive, the N2O production sharply raised. Consequently, compared to complete nitrification and denitrification, short-cut nitrification and denitrification could save 40% carbon source. Moreover, controlling C/N = 3 could reduce the production of N2O in short-cut nitrification. PMID:19775000

  19. Insights on the design and electron-acceptor properties of conjugated organophosphorus materials.

    PubMed

    Baumgartner, Thomas

    2014-05-20

    The development of conjugated organic materials has become a rapidly evolving field of research, particularly with a view toward practical applications in so-called organic electronics that encompass a variety of device types, such as OLEDs, OPVs, and OFETs. Almost all of these devices minimally require the presence of electron-donor and -acceptor components that act as p- and n-type semiconductors, respectively. Research over the past two decades has shown that while there is an abundant resource of organic p-type materials, suitable n-type species are few and far between. To overcome this severe bottleneck for the further development of organic electronics, researchers have identified organo-main-group avenues as valuable alternatives toward organic electron-acceptor materials that may ultimately be used as n-type components in practical devices. One particular element of interest in this context is phosphorus, which at first glance may not necessarily suggest such properties. In this Account, I provide detailed insights on the origin of the electron-acceptor properties of organophosphorus-based conjugated materials and include an overview of important molecular species that have been developed by my group and others. To this end, I explain that the electron-acceptor properties of conjugated organophosphorus materials originate from an interaction known as negative hyperconjugation. While this particular interaction creates a simply inductively withdrawing phosphoryl substituent for π-conjugated scaffolds, incorporation of a phosphorus atom as an integral part of a cyclic substructure within a π-conjugated system provides a much more complex, versatile, and consequently highly valuable tool for the tuning of the electron-acceptor properties of the materials. Notably, the degree of negative hyperconjugation can effectively be tailored in various ways via simple substitution at the phosphorus center. This is now well established for phosphole-based molecular

  20. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    PubMed Central

    Zhong, Yu; Trinh, M. Tuan; Chen, Rongsheng; Purdum, Geoffrey E.; Khlyabich, Petr P.; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y.; Black, Charles T.; Steigerwald, Michael L.; Loo, Yueh-Lin; Ng, Fay; Zhu, X.-Y.; Nuckolls, Colin

    2015-01-01

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor−acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. PMID:26382113

  1. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    DOE PAGESBeta

    Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; Chen, Rongsheng; Purdum, Geoffrey E.; Khlyabich, Petr P.; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; et al

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealedmore » both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.« less

  2. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells.

    PubMed

    Zhong, Yu; Trinh, M Tuan; Chen, Rongsheng; Purdum, Geoffrey E; Khlyabich, Petr P; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y; Black, Charles T; Steigerwald, Michael L; Loo, Yueh-Lin; Ng, Fay; Zhu, X-Y; Nuckolls, Colin

    2015-01-01

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. PMID:26382113

  3. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    SciTech Connect

    Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; Chen, Rongsheng; Purdum, Geoffrey E.; Khlyabich, Petr P.; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Sfeir, Matthew Y.; Black, Charles T.; Steigerwald, Michael L.; Loo, Yueh -Lin; Ng, Fay; Zhu, X. -Y.; Nuckolls, Colin

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.

  4. Non-fullerene electron acceptors for use in organic solar cells.

    PubMed

    Nielsen, Christian B; Holliday, Sarah; Chen, Hung-Yang; Cryer, Samuel J; McCulloch, Iain

    2015-11-17

    The active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure-property relationships that are emerging. The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together, forming dimers with

  5. Non-Fullerene Electron Acceptors for Use in Organic Solar Cells

    PubMed Central

    2015-01-01

    Conspectus The active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure–property relationships that are emerging. The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together

  6. Catalytic reaction of cytokinin dehydrogenase: preference for quinones as electron acceptors.

    PubMed Central

    Frébortová, Jitka; Fraaije, Marco W; Galuszka, Petr; Sebela, Marek; Pec, Pavel; Hrbác, Jan; Novák, Ondrej; Bilyeu, Kristin D; English, James T; Frébort, Ivo

    2004-01-01

    The catalytic reaction of cytokinin oxidase/dehydrogenase (EC 1.5.99.12) was studied in detail using the recombinant flavoenzyme from maize. Determination of the redox potential of the covalently linked flavin cofactor revealed a relatively high potential dictating the type of electron acceptor that can be used by the enzyme. Using 2,6-dichlorophenol indophenol, 2,3-dimethoxy-5-methyl-1,4-benzoquinone or 1,4-naphthoquinone as electron acceptor, turnover rates with N6-(2-isopentenyl)adenine of approx. 150 s(-1) could be obtained. This suggests that the natural electron acceptor of the enzyme is quite probably a p-quinone or similar compound. By using the stopped-flow technique, it was found that the enzyme is rapidly reduced by N6-(2-isopentenyl)adenine (k(red)=950 s(-1)). Re-oxidation of the reduced enzyme by molecular oxygen is too slow to be of physiological relevance, confirming its classification as a dehydrogenase. Furthermore, it was established for the first time that the enzyme is capable of degrading aromatic cytokinins, although at low reaction rates. As a result, the enzyme displays a dual catalytic mode for oxidative degradation of cytokinins: a low-rate and low-substrate specificity reaction with oxygen as the electron acceptor, and high activity and strict specificity for isopentenyladenine and analogous cytokinins with some specific electron acceptors. PMID:14965342

  7. Enhanced anaerobic fermentation with azo dye as electron acceptor: simultaneous acceleration of organics decomposition and azo decolorization.

    PubMed

    Li, Yang; Zhang, Yaobin; Quan, Xie; Zhang, Jingxin; Chen, Shuo; Afzal, Shahzad

    2014-10-01

    Accumulation of hydrogen during anaerobic processes usually results in low decomposition of volatile organic acids (VFAs). On the other hand, hydrogen is a good electron donor for dye reduction, which would help the acetogenic conversion in keeping low hydrogen concentration. The main objective of the study was to accelerate VFA composition through using azo dye as electron acceptor. The results indicated that the azo dye serving as an electron acceptor could avoid H2 accumulation and accelerate anaerobic digestion of VFAs. After adding the azo dye, propionate decreased from 2400.0 to 689.5mg/L and acetate production increased from 180.0 to 519.5mg/L. It meant that the conversion of propionate into acetate was enhanced. Fluorescence in situ hybridization analysis showed that the abundance of propionate-utilizing acetogens with the presence of azo dye was greater than that in a reference without azo dye. The experiments via using glucose as the substrate further demonstrated that the VFA decomposition and the chemical oxygen demand (COD) removal increased by 319.7mg/L and 23.3% respectively after adding the azo dye. Therefore, adding moderate azo dye might be a way to recover anaerobic system from deterioration due to the accumulation of H2 or VFAs. PMID:25288539

  8. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods.

    PubMed

    Dolgounitcheva, O; Díaz-Tinoco, Manuel; Zakrzewski, V G; Richard, Ryan M; Marom, Noa; Sherrill, C David; Ortiz, J V

    2016-02-01

    Comparison of ab initio electron-propagator predictions of vertical ionization potentials and electron affinities of organic, acceptor molecules with benchmark calculations based on the basis set-extrapolated, coupled cluster single, double, and perturbative triple substitution method has enabled identification of self-energy approximations with mean, unsigned errors between 0.1 and 0.2 eV. Among the self-energy approximations that neglect off-diagonal elements in the canonical, Hartree-Fock orbital basis, the P3 method for electron affinities, and the P3+ method for ionization potentials provide the best combination of accuracy and computational efficiency. For approximations that consider the full self-energy matrix, the NR2 methods offer the best performance. The P3+ and NR2 methods successfully identify the correct symmetry label of the lowest cationic state in two cases, naphthalenedione and benzoquinone, where some other methods fail. PMID:26730459

  9. Effect of cathode electron acceptors on simultaneous anaerobic sulfide and nitrate removal in microbial fuel cell.

    PubMed

    Cai, Jing; Zheng, Ping; Mahmood, Qaisar

    2016-01-01

    The current investigation reports the effect of cathode electron acceptors on simultaneous sulfide and nitrate removal in two-chamber microbial fuel cells (MFCs). Potassium permanganate and potassium ferricyanide were common cathode electron acceptors and evaluated for substrate removal and electricity generation. The abiotic MFCs produced electricity through spontaneous electrochemical oxidation of sulfide. In comparison with abiotic MFC, the biotic MFC showed better ability for simultaneous nitrate and sulfide removal along with electricity generation. Keeping external resistance of 1,000 Ω, both MFCs showed good capacities for substrate removal where nitrogen and sulfate were the main end products. The steady voltage with potassium permanganate electrodes was nearly twice that of with potassium ferricyanide. Cyclic voltammetry curves confirmed that the potassium permanganate had higher catalytic activity than potassium ferricyanide. The potassium permanganate may be a suitable choice as cathode electron acceptor for enhanced electricity generation during simultaneous treatment of sulfide and nitrate in MFCs. PMID:26901739

  10. Growth of strain SES-3 with arsenate and other diverse electron acceptors

    USGS Publications Warehouse

    Laverman, A.M.; Blum, J.S.; Schaefer, J.K.; Phillips, E.J.P.; Lovley, D.R.; Oremland, R.S.

    1995-01-01

    The selenate-respiring bacterial strain SES-3 was able to use a variety of inorganic electron acceptors to sustain growth. SES-3 grew with the reduction of arsenate to arsenite, Fe(III) to Fe(II), or thiosulfate to sulfide. It also grew in medium in which elemental sulfur, Mn(IV), nitrite, trimethylamine N-oxide, or fumarate was provided as an electron acceptor. Growth on oxygen was microaerophilic. There was no growth with arsenite or chromate. Washed suspensions of cells grown on selenate or nitrate had a constitutive ability to reduce arsenate but were unable to reduce arsenite. These results suggest that strain SES-3 may occupy a niche as an environmental opportunist by being able to take advantage of a diversity of electron acceptors.

  11. Photocurrent generation through electron-exciton interaction at the organic semiconductor donor/acceptor interface.

    PubMed

    Chen, Lijia; Zhang, Qiaoming; Lei, Yanlian; Zhu, Furong; Wu, Bo; Zhang, Ting; Niu, Guoxi; Xiong, Zuhong; Song, Qunliang

    2013-10-21

    In this work, we report our effort to understand the photocurrent generation that is contributed via electron-exciton interaction at the donor/acceptor interface in organic solar cells (OSCs). Donor/acceptor bi-layer heterojunction OSCs, of the indium tin oxide/copper phthalocyanine (CuPc)/fullerene (C60)/molybdenum oxide/Al type, were employed to study the mechanism of photocurrent generation due to the electron-exciton interaction, where CuPc and C60 are the donor and the acceptor, respectively. It is shown that the electron-exciton interaction and the exciton dissociation processes co-exist at the CuPc/C60 interface in OSCs. Compared to conventional donor/acceptor bi-layer OSCs, the cells with the above configuration enable holes to be extracted at the C60 side while electrons can be collected at the CuPc side, resulting in a photocurrent in the reverse direction. The photocurrent thus observed is contributed to primarily by the charge carriers that are generated by the electron-exciton interaction at the CuPc/C60 interface, while charges derived from the exciton dissociation process also exist at the same interface. The mechanism of photocurrent generation due to electron-exciton interaction in the OSCs is further investigated, and it is manifested by the transient photovoltage characteristics and the external quantum efficiency measurements. PMID:24002235

  12. Electronic and Chemical Properties of Donor, Acceptor Centers in Graphene.

    PubMed

    Telychko, Mykola; Mutombo, Pingo; Merino, Pablo; Hapala, Prokop; Ondráček, Martin; Bocquet, François C; Sforzini, Jessica; Stetsovych, Oleksandr; Vondráček, Martin; Jelínek, Pavel; Švec, Martin

    2015-09-22

    Chemical doping is one of the most suitable ways of tuning the electronic properties of graphene and a promising candidate for a band gap opening. In this work we report a reliable and tunable method for preparation of high-quality boron and nitrogen co-doped graphene on silicon carbide substrate. We combine experimental (dAFM, STM, XPS, NEXAFS) and theoretical (total energy DFT and simulated STM) studies to analyze the structural, chemical, and electronic properties of the single-atom substitutional dopants in graphene. We show that chemical identification of boron and nitrogen substitutional defects can be achieved in the STM channel due to the quantum interference effect, arising due to the specific electronic structure of nitrogen dopant sites. Chemical reactivity of single boron and nitrogen dopants is analyzed using force-distance spectroscopy by means of dAFM. PMID:26256407

  13. Pyridine as proton acceptor in the concerted proton electron transfer oxidation of phenol.

    PubMed

    Bonin, Julien; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

    2011-06-01

    Taking pyridine as a prototypal example of biologically important nitrogen bases involved in proton-coupled electron transfers, it is shown with the example of the photochemically triggered oxidation of phenol by Ru(III)(bpy)(3) that this proton acceptor partakes in a concerted pathway whose kinetic characteristics can be extracted from the overall kinetic response. The treatment of these data, implemented by the results of a parallel study carried out in heavy water, allowed the determination of the intrinsic kinetic characteristics of this proton acceptor. Comparison of the reorganization energies and of the pre-exponential factors previously derived for hydrogen phosphate and water (in water) as proton acceptors suggests that, in the case of pyridine, the proton charge is delocalized over a primary shell of water molecules firmly bound to the pyridinium cation. PMID:21499600

  14. Electronic structure of sub-surface Boron acceptors in silicon for potential qubits

    NASA Astrophysics Data System (ADS)

    Rahman, Rajib; Mol, Jan; Klimeck, Gerhard; Rogge, Sven

    2013-03-01

    Single acceptors in silicon are investigated as potential qubits. Due to the p-type nature of the valence band (VB), the acceptor states are less susceptible to the hyperfine interaction of the neighboring nuclear spins. The presence of a stronger spin-orbit coupling in the VB also enables the possibility of an all-electric qubit control. Whereas donor qubits exhibit exchange oscillation with separation distance due to conduction band valleys, Boron acceptors are expected to have smoother exchange curves. We investigate the electronic structure of single Boron acceptors in silicon in the presence of electric field, strain, magnetic field, and interfaces. Bulk Boron acceptors have a four-fold degenerate ground state 45 meV above the VB with angular momentum states of 3/2 and 1/2. An interface splits this manifold into Kramer's doublets. Application of E and B fields allow several possibilities for forming a two-level qubit driven by an ac electric field. We compare calculations from atomistic tight-binding theory to scanning tunneling microscope (STM) measurements and k.p calculations. The tight-binding method captures additional wavefunction symmetries due to the crystal that help to explain the STM measurements.

  15. High performance weak donor-acceptor polymers in thin film transistors: effect of the acceptor on electronic properties, ambipolar conductivity, mobility, and thermal stability.

    PubMed

    Yuen, Jonathan D; Fan, Jian; Seifter, Jason; Lim, Bogyu; Hufschmid, Ryan; Heeger, Alan J; Wudl, Fred

    2011-12-28

    We have studied the electronic, physical, and transistor properties of a family of donor-acceptor polymers consisting of diketopyrrolopyrrole (DPP) coupled with different accepting companion units in order to determine the effects of donor-acceptor interaction. Using the electronically neutral benzene (B), the weakly accepting benzothiadiazole (BT), and the strongly accepting benzobisthiadiazole (BBT), the accepting strength of the companion unit was systematically modulated. All polymers exhibited excellent transistor performance, with mobilities above 0.1 cm(2)V(-1)s(-1), even exceeding 1 cm(2)V(-1)s(-1) for one of the BBT-containing polymers. We find that the BBT is the strongest acceptor, enabling the BBT-containing polymers to be strongly ambipolar. The BBT moiety also strengthens interchain interactions, which provides higher thermal stability and performance for transistors with BBT-containing polymers as the active layer. PMID:22043809

  16. Photoinduced electron transfer across fixed distances in chlorophyll donor-acceptor molecules

    SciTech Connect

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

    1987-06-01

    The primary events of photosynthesis are a series of rapid, unidirectional electron transfer events between donors and acceptors that are positioned in the reaction center protein at precise spatial orientations and distances relative to one another. Recent work suggests that electron transfer rates depend on distance and free energy of reaction in porphyrin-quinone models in which the distance and orientation of the donor relative to the acceptor is highly restricted. Spacer molecules were developed which were used to link chlorophyll donors with either chlorophyll or quinone acceptors to produce models in which the donor-acceptor distance is well-defined. Recent theoretical studies and photochemical hole-burning experiments have suggested that the actual primary event of photosynthesis is the production of an intramolecular charge transfer state involving the two bacteriochlorophyll molecules of the special pair dimer. This possibility was explored with symmetric, fixed distance chlorophyll dimer. The chlorophyll macrocycles share a common vinyl group at the 2-position. This linkage serves to increase the degree of electronic coupling between the macrocycles. This dimer exhibits a remarkable decrease in fluorescence quantum yield as the dielectric constant of the medium in which it is dissolved increases. This decrease is accompanied by a proportional decrease in the lowest excited singlet state lifetime as measured by picosecond fluorescence and absorption. 11 refs., 2 figs.

  17. Rationally designed donor-acceptor scheme based molecules for applications in opto-electronic devices.

    PubMed

    Subash Sundar, T; Sen, R; Johari, P

    2016-04-01

    Several donor (D)-acceptor (A) based molecules are rationally designed by adopting three different schemes in which the conjugation length, strength of the donor and acceptor moieties, and planarity of the molecules are varied. These variations are made by introducing a π-conjugated linkage unit, terminating the ends of the moieties by different electron donating and accepting functional groups, and fusing the donor and acceptor moieties, respectively. Our DFT and TDDFT based calculations reveal that using the above-mentioned design schemes, the electronic and optical properties of the D-A based molecules can be largely tuned. While introduction of a linkage and fusing of moieties enhance the π-π interaction, addition of electron donating groups (-CH3, -OH, and -NH2) and electron accepting groups (-CF3, -CN, -NO2, and -NH3(+)) varies the strength of the donor and acceptor moieties. These factors lead to modulation of the HOMO and LUMO energy levels and facilitate the engineering of the HOMO-LUMO gap and the optical gap over a wide range of ∼0.7-3.7 eV. Moreover, on the basis of calculated ionization potential and reorganization energy, most of the investigated molecules are predicted to be air stable and to exhibit high electron mobility, with the possibility of the presence of ambipolar characteristics in a few of them. The results of our calculations not only demonstrate the examined molecules to be the potential materials for organic opto-electronic devices, but also establish an understanding of the composition-structure-property correlation, which will provide guidelines for designing and synthesizing new materials of choice. PMID:26972386

  18. Influence of different electron donors and acceptors on dehalorespiration of tetrachloroethene by Desulfitobacterium frappieri TCE1

    SciTech Connect

    Gerritse, J.; Drzyzga, O.; Kloetstra, G.; Keijmel, M.; Wiersum, L.P.; Hutson, R.; Collins, M.D.; Gottschal, J.C.

    1999-12-01

    Strain TCE1, a strictly anaerobic bacterium that can grow by reductive dechlorination of tetrachloroethene (PCE) and trichloroethane (TCE), was isolated by selective enrichment from a PCE-dechlorinating chemostat mixed culture. Strain TCE1 is a gram-positive, motile, curved rod-shaped organism that is 2 to 4 by 0.6 to 0.8 {micro}m and has approximately six lateral flagella. The pH and temperature optima for growth are 7.2 and 35 C, respectively. On the basis of a comparative 16S rRNA sequence analysis, this bacterium was identified as a new strain of Desulfitobacterium frappieri, because it exhibited 99.7% relatedness to the D. frappieri type strain, strain PCP-1. Growth with H{sub 2}, format, L-lactate, butyrate, crotonate, or ethanol as the electron donor depends on the availability of an external electron acceptor. Pyruvate and serine can also be used fermentatively. Electron donors (except format and H{sub 2}) are oxidized to acetate and CO{sub 2}. when L-lactate is the growth substrate, strain TCE1 can use the following electron acceptors: PCE and TCE (to produce cis-1,2-dichloroethene), sulfite and thiosulfate (to produce sulfide), nitrate (to produce nitrite), and fumarate (to produce succinate). Strain TCE1 is not able to reductively dechlorinate 3-chloro-4-hydroxyphenylacetate. The growth yields of the newly isolated bacterium when PCE is the electron acceptor are similar to those obtained for other dehalorespiring anaerobes (e.g., Desulfitobacterium sp. strain PCE1 and Desulfitobacterium hafniense) and the maximum specific reductive dechlorination rates are 4 to 16 times higher. Dechlorination of PCE and TCE is an inducible process. In PCE-limited chemostat cultures of strain TCE1, dechlorination is strongly inhibited by sulfite but not by other alternative electron acceptors, such as fumate or nitrate.

  19. Influence of alternative electron acceptors on the anaerobic biodegradability of chlorinated phenols and benzoic acids

    SciTech Connect

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y. )

    1993-04-01

    Methanogeneic conditions can promote the biodegradation of a number of halogenated aromatic compounds. This study, using sediments from freshwater and estuarine sites, is an evaluation of the anaerobic biodegradability of monochlorinated phenols and benzoic acids coupled to denitrification, sulfidogenesis, and methanogenesis. The results indicate that chlorinated phenols and benzoic acids are biodegradable under at least one set of anaerobic conditions. Metabolism depends both on the electron acceptor available and on the position of the chlorine substituent. Presence of alternative electron acceptors, nitrate, sulfate, and carbonate, can affect degradation rates and substrate specificities. Since contaminated sites usually have mixtures of wastes, bioremediation efforts may need to consider the activities of diverse anaerobic communities to carry out effective treatment of all components. 37 refs., 4 figs., 4 tabs.

  20. Electron acceptors for energy generation in microbial fuel cells fed with wastewaters: A mini-review.

    PubMed

    He, Chuan-Shu; Mu, Zhe-Xuan; Yang, Hou-Yun; Wang, Ya-Zhou; Mu, Yang; Yu, Han-Qing

    2015-12-01

    Microbial fuel cells (MFCs) have gained tremendous global interest over the last decades as a device that uses bacteria to oxidize organic and inorganic matters in the anode with bioelectricity generation and even for purpose of bioremediation. However, this prospective technology has not yet been carried out in field in particular because of its low power yields and target compounds removal which can be largely influenced by electron acceptors contributing to overcome the potential losses existing on the cathode. This mini review summarizes various electron acceptors used in recent years in the categories of inorganic and organic compounds, identifies their merits and drawbacks, and compares their influences on performance of MFCs, as well as briefly discusses possible future research directions particularly from cathode aspect. PMID:25907762

  1. Influence of alternative electron acceptors on the anaerobic biodegradability of chlorinated phenols and benzoic acids

    SciTech Connect

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y.

    1993-01-01

    Nitrate, sulfate, and carbonate were used as electron acceptors to examine the anaerobic biodegradability of chlorinated aromatic compounds in estuarine and freshwater sediments. The respective denitrifying, sulfidogenic, and methanogenic enrichment cultures were established on each of the monochlorinated phenol and monochlorinated benzoic acid isomers, using sediment from the upper (freshwater) and lower (estuarine) Hudson River and the East River (estuarine) as source materials. Utilization of each chlorophenol and chlorobenzoate isomer was observed under at least one reducing condition; however, no single reducing condition permitted the metabolism of all six compounds tested. The anaerobic biodegradation of the chlorophenols and chlorobenzoates depended on the electron acceptor available and on the position of the chlorine substituent. In general, similar activities were observed under the different reducing conditions in both the freshwater and estuarine sediments.

  2. Influence of various nitrogenous electron acceptors on the anaerobic sulfide oxidation.

    PubMed

    Jing, Cai; Ping, Zheng; Mahmood, Qaisar

    2010-05-01

    The effect of nitrate and nitrite as electron acceptors on the performance of anaerobic sulfide oxidizing process (ASO process) was investigated. For nitrate-ASO process, the maximum influent nitrogen concentration was lower than that in nitrite-ASO process, but the maximum influent sulfur concentration was higher than that of nitrite-ASO process. The half saturation values for nitrogen and sulfur in both processes were similar. The minimum reaction time taken for nitrite and sulfide was relatively shorter than in nitrite-ASO reactor. As indicated by sensitivity ratio, activated sludge was more tolerant to sulfide, which had no significant differences between two processes; while it was relatively more sensitive to nitrite over nitrate. PCR-DGGE fingerprints, Dice and Shannon similarity indices and sequencing results all suggested that the microbial communities in both reactors were similar. The use of nitrate as an electron acceptor may be preferable over nitrite to treat sulfide-rich wastewaters. PMID:20047830

  3. Humic acids as electron acceptors for anaerobic microbial oxidation of vinyl chloride and dichloroethene

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.; Lovley, D.R.

    1998-01-01

    Anaerobic oxidation of [1,2-14C]vinyl chloride and [1,2- 14C]dichloroethene to 14CO2 under humic acid-reducing conditions was demonstrated. The results indicate that waterborne contaminants can be oxidized by using humic acid compounds as electron acceptors and suggest that natural aquatic systems have a much larger capacity for contaminant oxidation than previously thought.

  4. Humic acids as electron acceptors for anaerobic microbial oxidation of vinyl chloride and dichloroethane

    SciTech Connect

    Bradley, P.M.; Chapelle, F.H.; Lovley, D.R.

    1998-08-01

    Anaerobic oxidation of [1,2-{sup 14}C]vinyl chloride and [1,2-{sup 14}C]dichloroethene to {sup 14}CO{sub 2} under humic acid-reducing conditions was demonstrated. The results indicate that waterborne contaminants can be oxidized by using humic acid compounds as electron acceptors and suggest that natural aquatic systems have a much larger capacity for contaminant oxidation than previously thought.

  5. Influence of alternative electron acceptors on the anaerobic biodegradability of chlorinated phenols and benzoic acids

    SciTech Connect

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y.

    1993-01-01

    Nitrate, sulfate, and carbonate were used as electron acceptors to examine the anaerobic biodegradability of chlorinated aromatic compounds in estuarine and freshwater sediments. The respective denitrifying, sulfidogenic, and methanogenic enrichment cultures were established on each of the monochlorinated phenol and monochlorinated benzoic acid isomers, using sediment from the upper (freshwater) and lower (estuarine) Hudson River and the East River (estuarine) as source materials. (Copyright (c) 1993 American Society for Microbiology.)

  6. Electron scattering by acceptor centers in p-Ag{sub 2}Te at low temperatures

    SciTech Connect

    Aliev, F. F. Jafarov, M. B.; Askerova, G. Z.; Gojaev, E. M.

    2010-08-15

    Resonant electron scattering in p-Ag{sub 2}Te at acceptor concentrations N{sub a} < 4.2 x 10{sup 16} cm{sup -3} has been observed in the temperature range of 50-80 K. The contribution of the resonant scattering to the temperature dependences of the conductivity {sigma}(T) and thermopower {alpha}{sub 0}(T) has been calculated. It is shown that this contribution exceeds that of charge carrier scattering by acoustic phonons.

  7. Metals as electron acceptors in single-chamber microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Yan; Wu, Yining; Puranik, Sampada; Lei, Yu; Vadas, Timothy; Li, Baikun

    2014-12-01

    Two typical oxidized-status metals (Fe(III) and Cr(VI)) were studied as electron acceptors on cathodes in single chamber microbial fuel cells (SCMFCs) to explore novel sustainable technology for metal treatment. The batch-mode tests indicated that the voltages of SCMFCs steadily increased with Fe(III) concentrations (10, 30, and 50 mg L-1) and Cr(VI) concentrations (1, 3, and 10 mg L-1). The maximum power density was 658 ± 6 mW m-2 at 50 mg L-1 of Fe(III), and 419 ± 4 mW m-2 at 10 mg L-1 Cr(VI). The conversion efficiency of Cr(VI) and Fe(III) were high (>89%), and coulombic efficiency ranged 23-100%. Cr(VI) concentration of 10 mg L-1 started to irreversibly inhibit SCMFCs. The open circuit potentials (OCPs) well reflected the organic substrate removal in anode and metal reduction on cathode. Cathode liner sweep voltammetry (LSV) showed the electrochemical activity increased with metal concentrations, and the cathode of Fe(III) had better LSV performance than Cr(VI). Microbial community analysis of biofilms showed that the DNA band patterns of anode biofilms were similar, while cathode biofilms varied with electron acceptors. This study demonstrated the high power generation of SCMFCs with metals as electron acceptors, and revealed the great potential of expanding MFCs for diverse waste treatment.

  8. High-Performance Electron Acceptor with Thienyl Side Chains for Organic Photovoltaics.

    PubMed

    Lin, Yuze; Zhao, Fuwen; He, Qiao; Huo, Lijun; Wu, Yang; Parker, Timothy C; Ma, Wei; Sun, Yanming; Wang, Chunru; Zhu, Daoben; Heeger, Alan J; Marder, Seth R; Zhan, Xiaowei

    2016-04-13

    We develop an efficient fused-ring electron acceptor (ITIC-Th) based on indacenodithieno[3,2-b]thiophene core and thienyl side-chains for organic solar cells (OSCs). Relative to its counterpart with phenyl side-chains (ITIC), ITIC-Th shows lower energy levels (ITIC-Th: HOMO = -5.66 eV, LUMO = -3.93 eV; ITIC: HOMO = -5.48 eV, LUMO = -3.83 eV) due to the σ-inductive effect of thienyl side-chains, which can match with high-performance narrow-band-gap polymer donors and wide-band-gap polymer donors. ITIC-Th has higher electron mobility (6.1 × 10(-4) cm(2) V(-1) s(-1)) than ITIC (2.6 × 10(-4) cm(2) V(-1) s(-1)) due to enhanced intermolecular interaction induced by sulfur-sulfur interaction. We fabricate OSCs by blending ITIC-Th acceptor with two different low-band-gap and wide-band-gap polymer donors. In one case, a power conversion efficiency of 9.6% was observed, which rivals some of the highest efficiencies for single junction OSCs based on fullerene acceptors. PMID:27015115

  9. Copper Toxicity Affects Photosystem II Electron Transport at the Secondary Quinone Acceptor, QB1

    PubMed Central

    Mohanty, Narendranath; Vass, Imre; Demeter, Sándor

    1989-01-01

    The nature of Cu2+ inhibition of photosystem II (PSII) photochemistry in pea (Pisum sativum L.) thylakoids was investigated monitoring Hill activity and light emission properties of photosystem II. In Cu2+-inhibited thylakoids, diphenyl carbazide addition does not relieve the loss of Hill activity. The maximum yield of fluorescence induction restored by hydroxylamine in Tris-inactivated thylakoids is markedly reduced by Cu2+. This suggests that Cu2+ does not act on the donor side of PSII but on the reaction center of PSII or on components beyond. Thermoluminescence and delayed luminescence studies show that charge recombination between the positively charged intermediate in water oxidation cycle (S2) and negatively charged primary quinone acceptor of pSII (QA−) is largely unaffected by Cu2+. The S2QB− charge recombination, however, is drastically inhibited which parallels the loss of Hill activity. This indicates that Cu2+ inhibits photosystem II photochemistry primarily affecting the function of the secondary quinone electron acceptor, QB. We suggest that Cu2+ does not block electron flow between the primary and secondary quinone acceptor but modifies the QB site in such a way that it becomes unsuitable for further photosystem II photochemistry. PMID:16666731

  10. Easy Access to NO2 -Containing Donor-Acceptor-Acceptor Electron Donors for High Efficiency Small-Molecule Organic Solar Cells.

    PubMed

    Ting, Hao-Chun; Yang, Ya-Ting; Chen, Chia-Hsun; Lee, Jiun-Haw; Chang, Jung-Hung; Wu, Chih-I; Chiu, Tien-Lung; Lin, Chi-Feng; Chung, Chin-Lung; Wong, Ken-Tsung

    2016-06-22

    Two donor-acceptor-acceptor (D-A-A)-type molecules incorporating nitrobenzoxadiazole (NBO) as the A-A block and ditolylamine as the D block bridged through a phenylene (PNBO) and a thiophene (TNBO) spacer were synthesized in a one-step coupling reaction. Their electronic, photophysical, and thermal properties; crystallographic analysis; and theoretical calculations were studied to establish a clear structure-property relationship. The results indicate that the quinoidal character of the thiophene bridge strongly governs the structural features and crystal packings (herringbone vs. brickwork) and thus the physical properties of the compounds. PNBO and TNBO were utilized as electron donors combined with C70 as the electron acceptor in the active layer of vacuum-processed bulk heterojunction small-molecule organic solar cells (SMOSCs). The power conversion efficiency of both PNBO- and TNBO-based OSCs exceeded 5 %. The ease of accessibility of PNBO and TNBO demonstrates the potential for simple and economical synthesis of electron donors in vacuum-processed SMOSCs. PMID:27213296

  11. XeF(2) /fluoride acceptors as versatile one-electron oxidants.

    PubMed

    Poleschner, Helmut; Seppelt, Konrad

    2013-12-01

    No phlogiston but xenon is released when XeF2 /F(-) acceptors act as new one-electron oxidants. F(-) acceptors are Lewis acids BF3 , B(C6 F5 )3 , and Al{OC(CF3 )3 }3 , and silyl derivatives TfOSiMe3 , Tf2 NSiMe3 , Me3 Si(+)  B(C6 F5 )4 (-) , and Me3 Si(+)  CHB11 Cl11 (-) . The anions BF4 (-) , TfO(-) , Tf2 N(-) , FB(C6 F5 )3 (-) , FAl{OC(CF3 )3 }3 (-) , B(C6 F5 )4 (-) , or CHB11 Cl11 (-) can be introduced into oxidation products of R2 E2 (E=S, Se, Te), [FeCp2 ], [(FeCpS)4 ], tetrathiafulvalene, thianthrene, and (2,4-Br2 C6 H3 )3 N. PMID:24127390

  12. Efficient photoinduced orthogonal energy and electron transfer reactions via phospholipid membrane-bound donors and acceptors

    SciTech Connect

    Clapp, P.J.; Armitage, B.; Roosa, P.; O'Brien, D.F. )

    1994-10-05

    A three component, liposome-bound photochemical molecular device (PMD) consisting of energy and electron transfer reactions is described. Bilayer membrane surface-associated dyes, 5,10,15,20-tetrakis[4-(trimethylammonio)-phenyl]-21H,2 3H-porphine tetra-p-tosylate salt and N,N[prime]-bis[(3-trimethylammonio)propyl]thiadicarbocya nine tribromide, are the energy donor and acceptor, respectively, in a blue light stimulated energy transfer reaction along the vesicle surface. The electronically excited cyanine is quenched by electron transfer from the phospholipid membrane bound triphenylbenzyl borate anion, which is located in the lipid bilayer interior. The PMD exhibits sequential reactions following electronic excitation with the novel feature that the steps proceed with orthogonal orientation: energy transfer occurs parallel to the membrane surface, and electron transfer occurs perpendicular to the surface. Photobleaching and fluorescence quenching experiments verify the transfer reactions, and Stern-Volmer analysis was used to estimate the reaction rate constants. At the highest concentrations examined of energy and electron acceptor ca. 60% of the photoexcited porphyrins were quenched by energy transfer to the cyanine. 56 refs., 6 figs., 3 tabs.

  13. An inner membrane cytochrome required only for reduction of high redox potential extracellular electron acceptors

    SciTech Connect

    Levar, Caleb E.; Chan, Chi Ho; Mehta-Kolte, Misha G.; Bond, Daniel R.

    2014-10-28

    Dissimilatory metal-reducing bacteria, such as Geobacter sulfurreducens, transfer electrons beyond their outer membranes to Fe(III) and Mn(IV) oxides, heavy metals, and electrodes in electrochemical devices. In the environment, metal acceptors exist in multiple chelated and insoluble forms that span a range of redox potentials and offer different amounts of available energy. Despite this, metal-reducing bacteria have not been shown to alter their electron transfer strategies to take advantage of these energy differences. Disruption of imcH, encoding an inner membrane c-type cytochrome, eliminated the ability of G. sulfurreducens to reduce Fe(III) citrate, Fe(III)-EDTA, and insoluble Mn(IV) oxides, electron acceptors with potentials greater than 0.1 V versus the standard hydrogen electrode (SHE), but the imcH mutant retained the ability to reduce Fe(III) oxides with potentials of ≤–0.1 V versus SHE. The imcH mutant failed to grow on electrodes poised at +0.24 V versus SHE, but switching electrodes to –0.1 V versus SHE triggered exponential growth. At potentials of ≤–0.1 V versus SHE, both the wild type and the imcH mutant doubled 60% slower than at higher potentials. Electrodes poised even 100 mV higher (0.0 V versus SHE) could not trigger imcH mutant growth. These results demonstrate that G. sulfurreducens possesses multiple respiratory pathways, that some of these pathways are in operation only after exposure to low redox potentials, and that electron flow can be coupled to generation of different amounts of energy for growth. Redox potentials that trigger these behaviors mirror those of metal acceptors common in subsurface environments where Geobacter is found.

  14. An inner membrane cytochrome required only for reduction of high redox potential extracellular electron acceptors

    DOE PAGESBeta

    Levar, Caleb E.; Chan, Chi Ho; Mehta-Kolte, Misha G.; Bond, Daniel R.

    2014-10-28

    Dissimilatory metal-reducing bacteria, such as Geobacter sulfurreducens, transfer electrons beyond their outer membranes to Fe(III) and Mn(IV) oxides, heavy metals, and electrodes in electrochemical devices. In the environment, metal acceptors exist in multiple chelated and insoluble forms that span a range of redox potentials and offer different amounts of available energy. Despite this, metal-reducing bacteria have not been shown to alter their electron transfer strategies to take advantage of these energy differences. Disruption of imcH, encoding an inner membrane c-type cytochrome, eliminated the ability of G. sulfurreducens to reduce Fe(III) citrate, Fe(III)-EDTA, and insoluble Mn(IV) oxides, electron acceptors with potentialsmore » greater than 0.1 V versus the standard hydrogen electrode (SHE), but the imcH mutant retained the ability to reduce Fe(III) oxides with potentials of ≤–0.1 V versus SHE. The imcH mutant failed to grow on electrodes poised at +0.24 V versus SHE, but switching electrodes to –0.1 V versus SHE triggered exponential growth. At potentials of ≤–0.1 V versus SHE, both the wild type and the imcH mutant doubled 60% slower than at higher potentials. Electrodes poised even 100 mV higher (0.0 V versus SHE) could not trigger imcH mutant growth. These results demonstrate that G. sulfurreducens possesses multiple respiratory pathways, that some of these pathways are in operation only after exposure to low redox potentials, and that electron flow can be coupled to generation of different amounts of energy for growth. Redox potentials that trigger these behaviors mirror those of metal acceptors common in subsurface environments where Geobacter is found.« less

  15. Biogenic hydroxysulfate green rust, a potential electron acceptor for SRB activity

    NASA Astrophysics Data System (ADS)

    Zegeye, Asfaw; Huguet, Lucie; Abdelmoula, Mustapha; Carteret, Cédric; Mullet, Martine; Jorand, Frédéric

    2007-11-01

    Microbiological reduction of a biogenic sulfated green rust (GR2(SO42-)), was examined using a sulfate reducing bacterium ( Desulfovibrio alaskensis). Experiments investigated whether GR2(SO42-) could serve as a sulfate source for D. alaskensis anaerobic respiration by analyzing mineral transformation. Batch experiments were conducted using lactate as the electron donor and biogenic GR2(SO42-) as the electron acceptor, at circumneutral pH in unbuffered medium. GR2(SO42-) transformation was monitored with time by X-ray diffraction (XRD), Transmission Mössbauer Spectroscopy (TMS), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The reduction of sulfate anions and the formation of iron sulfur mineral were clearly identified by XPS analyses. TMS showed the formation of additional mineral as green rust (GR) and vivianite. XRD analyses discriminated the type of the newly formed GR as GR1. The formed GR1 was GR1(CO32-) as indicated by DRIFTS analysis. Thus, the results presented in this study indicate that D. alaskensis cells were able to use GR2(SO42-) as an electron acceptor. GR1(CO32-), vivianite and an iron sulfur compound were formed as a result of GR2(SO42-) reduction by D. alaskensis. Hence, in environments where geochemical conditions promote biogenic GR2(SO42-) formation, this mineral could stimulate the anaerobic respiration of sulfate reducing bacteria.

  16. The Tetrathiafulvalene-based Donor-acceptor Diads for Molecular Electronics

    NASA Astrophysics Data System (ADS)

    Perepichka, Dmitrii F.; Bryce, Martin R.; Ho, Gregory; Heath, James R.; Pearson, Christopher; Petty, Michael C.

    2004-03-01

    The challenge of covalent linking a strong electron donor (as tetrathiafulvalene, TTF) to a strong acceptor (as tetracyanoquinodimethane, TCNQ) was laid down by Aviram and Ratner, who proposed that a single donor-sigma-acceptor molecule could rectify an electric current. Although numerous organic compounds have been tested in metal-molecule-metal junctions, they had substantially higher HOMO-LUMO gap (Eg >0.5 eV) and, in most cases, high dipole moment due to conjugated character of the linker. Those molecules re-orient in the electric field limiting the device stability. Recently, we have pioneered the synthesis of DsigmaA molecules with the HOMO-LUMO gap 0.17-0.3 eV, including the original TTF-TCNQ.* We will present the intriguing electronic properties of these compounds, including the conformational control of the Eg and the thermoexcited electron transfer. The compounds form high-quality LB films, suitable for molecular electronics applications. In Si-molecule-Ti junctions, the rectification ratio increases as molecules align perpendicularly to the surface, and the device stability override significantly the related system based on D-pi-A molecules. * Perepichka, et al., Angew. Chem. Int. Ed. 2003, 42, 4635.

  17. Work function increase of transparent conductive electrodes by solution processed electron acceptor molecular monolayers

    NASA Astrophysics Data System (ADS)

    Castellani, Mauro; Winkler, Stefanie; Bröker, Benjamin; Baumgarten, Martin; Müllen, Klaus; Koch, Norbert

    2014-02-01

    We show how the work function of transparent conductive oxide surfaces can be increased by more than 1 eV by solution-depositing strong electron acceptor monolayers comprising tetrafluoro-tetracyanoquinodimethane (F4TCNQ) or hexaazatriphenylene-hexacarbonitrile (HATCN). The effects of ambient atmosphere on the work function are investigated by comparing Kelvin probe measurements in air and ultraviolet photoelectron spectroscopy in ultrahigh vacuum. In this way, important technological issues related to the influence of ambient moisture on electrode properties are elucidated.

  18. TiO2 advanced photo-oxidation technology: Effect of electron acceptors

    SciTech Connect

    Al-Ekabi, H.; Butters, B.; Delany, D.; Powell, T.; Ireland, J.

    1993-01-01

    The effects of electron acceptors (additives) such as hydrogen peroxide, ammonium persulphate, potassium bromate and potassium peroxymonosulphate (oxone) on the TiO2 photocatalytic degradation of various organic pollutants were examined at various conditions. The individual and the collective effects of these additives on the degradation rates of two different concentrations (40 and 200 ppm) of 2,4-dichlorophenol (2,4-DCP) were investigated in single-pass and multi-pass operational modes at 3 L/min flow. (Copyright (c) 1993 Elsevier Science Publishers B.V.)

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

    PubMed Central

    Kato, Yuki; Nagao, Ryo; Noguchi, Takumi

    2016-01-01

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

  20. Electron acceptor redox potential globally regulates transcriptomic profiling in Shewanella decolorationis S12.

    PubMed

    Lian, Yingli; Yang, Yonggang; Guo, Jun; Wang, Yan; Li, Xiaojing; Fang, Yun; Gan, Lixia; Xu, Meiying

    2016-01-01

    Electron acceptor redox potential (EARP) was presumed to be a determining factor for microbial metabolism in many natural and engineered processes. However, little is known about the potentially global effects of EARP on bacteria. In this study, we compared the physiological and transcriptomic properties of Shewanella decolorationis S12 respiring with different EARPs in microbial electrochemical systems to avoid the effects caused by the other physicochemical properties of real electron acceptor. Results showed that the metabolic activities of strain S12 were nonlinear responses to EARP. The tricarboxylic acid cycle for central carbon metabolism was down-regulated while glyoxylate shunt was up-regulated at 0.8 V compared to 0.2 and -0.2 V, which suggested that EARP is an important but not the only determinant for metabolic pathways of strain S12. Moreover, few cytochrome c genes were differentially expressed at different EARPs. The energy intensive flagella assembly and assimilatory sulfur metabolism pathways were significantly enriched at 0.8 V, which suggested strain S12 had stronger electrokinesis behavior and oxidative stress-response at high EARP. This study provides the first global information of EARP regulations on microbial metabolism, which will be helpful for understanding microorganism respiration. PMID:27503002

  1. Electron acceptor redox potential globally regulates transcriptomic profiling in Shewanella decolorationis S12

    PubMed Central

    Lian, Yingli; Yang, Yonggang; Guo, Jun; Wang, Yan; Li, Xiaojing; Fang, Yun; Gan, Lixia; Xu, Meiying

    2016-01-01

    Electron acceptor redox potential (EARP) was presumed to be a determining factor for microbial metabolism in many natural and engineered processes. However, little is known about the potentially global effects of EARP on bacteria. In this study, we compared the physiological and transcriptomic properties of Shewanella decolorationis S12 respiring with different EARPs in microbial electrochemical systems to avoid the effects caused by the other physicochemical properties of real electron acceptor. Results showed that the metabolic activities of strain S12 were nonlinear responses to EARP. The tricarboxylic acid cycle for central carbon metabolism was down-regulated while glyoxylate shunt was up-regulated at 0.8 V compared to 0.2 and −0.2 V, which suggested that EARP is an important but not the only determinant for metabolic pathways of strain S12. Moreover, few cytochrome c genes were differentially expressed at different EARPs. The energy intensive flagella assembly and assimilatory sulfur metabolism pathways were significantly enriched at 0.8 V, which suggested strain S12 had stronger electrokinesis behavior and oxidative stress-response at high EARP. This study provides the first global information of EARP regulations on microbial metabolism, which will be helpful for understanding microorganism respiration. PMID:27503002

  2. Electron acceptor redox potential globally regulates transcriptomic profiling in Shewanella decolorationis S12

    NASA Astrophysics Data System (ADS)

    Lian, Yingli; Yang, Yonggang; Guo, Jun; Wang, Yan; Li, Xiaojing; Fang, Yun; Gan, Lixia; Xu, Meiying

    2016-08-01

    Electron acceptor redox potential (EARP) was presumed to be a determining factor for microbial metabolism in many natural and engineered processes. However, little is known about the potentially global effects of EARP on bacteria. In this study, we compared the physiological and transcriptomic properties of Shewanella decolorationis S12 respiring with different EARPs in microbial electrochemical systems to avoid the effects caused by the other physicochemical properties of real electron acceptor. Results showed that the metabolic activities of strain S12 were nonlinear responses to EARP. The tricarboxylic acid cycle for central carbon metabolism was down-regulated while glyoxylate shunt was up-regulated at 0.8 V compared to 0.2 and ‑0.2 V, which suggested that EARP is an important but not the only determinant for metabolic pathways of strain S12. Moreover, few cytochrome c genes were differentially expressed at different EARPs. The energy intensive flagella assembly and assimilatory sulfur metabolism pathways were significantly enriched at 0.8 V, which suggested strain S12 had stronger electrokinesis behavior and oxidative stress-response at high EARP. This study provides the first global information of EARP regulations on microbial metabolism, which will be helpful for understanding microorganism respiration.

  3. Effect of electron acceptor structure on stability and efficiency in polymer photovoltaics: a library approach

    NASA Astrophysics Data System (ADS)

    Tro, Michael; Oparko, David; Lewis, Emma; Sarabia, Alexis; Giammona, Maxwell; Isaac, Justin; Adalsteinsson, Thorsteinn; McNelis, Brian; Barber, Richard

    2014-03-01

    A commonly studied polymer photovoltaic system is prepared using a mixture of poly[3-hexylthiophene] (P3HT) as the electron donor and [6,6]-Phenyl C61 butyric acid methyl ester (PCBM) as the electron acceptor. We have prepared a series of PCBM analogs, making a variety of fullerene esters using commercially available primary alcohols. The first studies involved attaching an eight- or eighteen-carbon chain in place of the single carbon in PCBM. Solar cells made from these compounds exhibited improved lifetimes, motivating further exploration in the domain of possible attachments. We have now created a small library of these acceptor compounds and blended them with P3HT to prepare and measure solar cells. We collect current-voltage data over hours or days for each sample under ambient air conditions. These data provide not only the standard figures of merit, but also reveal the time dependence of these values. We have already observed significant differences between fullerene esters that are very similar in structure. Support for this work provided by an SCU Sustainability Research Grant and an SCU IBM Faculty Research Grant

  4. In situ generation of electron acceptor for photoelectrochemical biosensing via hemin-mediated catalytic reaction.

    PubMed

    Zang, Yang; Lei, Jianping; Zhang, Lei; Ju, Huangxian

    2014-12-16

    A novel photoelectrochemical sensing strategy is designed for DNA detection on the basis of in situ generation of an electron acceptor via the catalytic reaction of hemin toward H2O2. The photoelectrochemical platform was established by sequential assembly of near-infrared CdTe quantum dots, capture DNA, and a hemin-labeled DNA probe to form a triple-helix molecular beacon (THMB) structure on an indium tin oxide electrode. According to the highly catalytic capacity of hemin toward H2O2, a photoelectrochemical mechanism was then proposed, in which the electron acceptor of O2 was in situ-generated on the electrode surface, leading to the enhancement of the photocurrent response. The utilization of CdTe QDs can extend the absorption edge to the near-infrared band, resulting in an increase in the light-to-electricity efficiency. After introducing target DNA, the THMB structure is disassembled and releases hemin and, thus, quenches the photocurrent. Under optimized conditions, this biosensor shows high sensitivity with a linear range from 1 to 1000 pM and detection limit of 0.8 pM. Moreover, it exhibits good performance of excellent selectivity, high stability, and acceptable fabrication reproducibility. This present strategy opens an alternative avenue for photoelectrochemical signal transduction and expands the applications of hemin-based materials in photoelectrochemical biosensing and clinical diagnosis. PMID:25393151

  5. Triazole bridges as versatile linkers in electron donor-acceptor conjugates

    PubMed Central

    de Miguel, Gustavo; Wielopolski, Mateusz; Schuster, David I.; Fazio, Michael A; Lee, Olivia P.; Haley, Christopher K.; Ortiz, Angy L.; Echegoyen, Luis; Clark, Timothy; Guldi, Dirk M.

    2011-01-01

    Aromatic triazoles have been frequently used as π-conjugated linkers in intramolecular electron transfer processes. To gain a deeper understanding of the electron mediating function of triazoles, we have synthesized a family of new triazole-based electron donor-acceptor conjugates. We have connected porphyrins and fullerenes through a central triazole moiety – (ZnP-Tri-C60) – each with a single change in their connection through the linker. An extensive photophysical and computational investigation reveals that the electron transfer dynamics – charge separation and charge recombination – in the different ZnP-Tri-C60 conjugates reflect a significant influence of the connectivity at the triazole linker. Except for m4m-ZnP-Tri-C60 17, the conjugates exhibit through-bond electron transfer with varying rate constants. Since the through-bond distance is nearly equal in the ZnP-Tri-C60 conjugates, the variation in charge separation and charge recombination dynamics is mainly associated with the electronic properties of the conjugates, including orbital energies, electron affinity, and the energies of the excited states. The changes of the electronic couplings are, in turn, a consequence of the different connectivity patterns at the triazole moieties. PMID:21702513

  6. Donor-acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions.

    PubMed

    Stergiou, Anastasios; Pagona, Georgia; Tagmatarchis, Nikos

    2014-01-01

    Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor-acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor-acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor-acceptor graphene-based hybrids, will be discussed. PMID:25247140

  7. Donor–acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions

    PubMed Central

    Stergiou, Anastasios; Pagona, Georgia

    2014-01-01

    Summary Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor–acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor–acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor–acceptor graphene-based hybrids, will be discussed. PMID:25247140

  8. Spectral Fine Tuning of Cyanine Dyes: Electron Donor-Acceptor Substituted Analogues of Thiazole Orange†

    PubMed Central

    Rastede, Elizabeth E.; Tanha, Matteus; Yaron, David; Watkins, Simon C.; Waggoner, Alan S.; Armitage, Bruce A.

    2015-01-01

    The introduction of electron donor and acceptor groups at strategic locations on a fluorogenic cyanine dye allows fine-tuning of the absorption and emission spectra while preserving the ability of the dye to bind to biomolecular hosts such as double-stranded DNA and a single-chain antibody fragment originally selected for binding to the parent unsubstituted dye, thiazole orange (TO). The observed spectral shifts are consistent with calculated HOMO-LUMO energy gaps and reflect electron density localization on the quinoline half of TO in the LUMO. A dye bearing donating methoxy and withdrawing trifluoromethyl groups on the benzothiazole and quinoline rings, respectively, shifts the absorption spectrum to sufficiently longer wavelengths to allow excitation at green wavelengths as opposed to the parent dye, which is optimally excited in the blue. PMID:26171668

  9. Spectral fine tuning of cyanine dyes: electron donor-acceptor substituted analogues of thiazole orange.

    PubMed

    Rastede, Elizabeth E; Tanha, Matteus; Yaron, David; Watkins, Simon C; Waggoner, Alan S; Armitage, Bruce A

    2015-09-26

    The introduction of electron donor and acceptor groups at strategic locations on a fluorogenic cyanine dye allows fine-tuning of the absorption and emission spectra while preserving the ability of the dye to bind to biomolecular hosts such as double-stranded DNA and a single-chain antibody fragment originally selected for binding to the parent unsubstituted dye, thiazole orange (TO). The observed spectral shifts are consistent with calculated HOMO-LUMO energy gaps and reflect electron density localization on the quinoline half of TO in the LUMO. A dye bearing donating methoxy and withdrawing trifluoromethyl groups on the benzothiazole and quinoline rings, respectively, shifts the absorption spectrum to sufficiently longer wavelengths to allow excitation at green wavelengths as opposed to the parent dye, which is optimally excited in the blue. PMID:26171668

  10. Dibenzothiophene-Substituted Fullerene Derivative as Electron Acceptor for Polymer Solar Cells.

    PubMed

    Kim, Hee Un; Park, Jong Baek; Hwang, Do-Hoon

    2016-05-01

    A new fullerene derivative, [6,6]-dibenzo[b,d]thiophene-C61-butyric acid methyl ester (DBTC61BM) was synthesized from C60 using tosylhydrazone, and used as an electron-acceptor material for poly(3-hexylthiophene) (P3HT)-based organic photovoltaic cells. The synthesized DBTC61BM was used to modify the basic structure of [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) by replacing the aromatic part with dibenzo[b,d]thiophene. The solubilities of DBTC61BM and PC61BM are similar; they have good solubilities in common organic solvents such as dichloromethane, chloroform, toluene, and 1,2-dichlorobenzene. The Stern-Volmer quenching constant (K(sv)) of DBTC61BM was 7.14 x 10(3) M(-1), and was correlated with the binding affinity between the fluorophore and a quencher. The lowest unoccupied molecular orbital energy level of DBTC61BM was -3.71 eV. The charge-carrier mobility of a P3HT:DBTC61BM blend film was determined using the space-charge-limited current method; the electron mobility value obtained for the P3HT:DBTC61BM blend film was 2.13 x 10(-4) cm2 V(-1) s(-1). Photovoltaic devices were fabricated using P3HT as the electron donor and DBTC61BM as the electron acceptor. Among the fabricated devices, photovoltaic cells with the structure ITO/PEDOT:PSS/P3HT:DBTC61BM/LiF/Al showed the highest power conversion efficiency, namely 3.23%, with an open-circuit voltage of 0.64 V, short-circuit-current density of 8.14 mA cm(-2), and fill factor of 0.59, under AM 1.5 G (100 mW cm(-2)) illumination. PMID:27483863

  11. Polymer Acceptor Based on B←N Units with Enhanced Electron Mobility for Efficient All-Polymer Solar Cells.

    PubMed

    Zhao, Ruyan; Dou, Chuandong; Xie, Zhiyuan; Liu, Jun; Wang, Lixiang

    2016-04-18

    We demonstrate that polymer electron acceptors with excellent all-polymer solar-cell (all-PSC) device performance can be developed from polymer electron donors by using B←N units. By alleviating the steric hindrance effect of the bulky pendant moieties on the conjugated polymers that contain B←N units, the π-π stacking distance of polymer backbones is decreased and the electron mobility is consequently enhanced by nearly two orders of magnitude. As a result, the power conversion efficiency of all-PSCs with the polymer acting as the electron acceptor is greatly improved from 0.12 % to 5.04 %. This PCE value is comparable to that of the best all-PSCs with state-of-the-art polymer acceptors. PMID:26990376

  12. Understanding the charge-transfer phenomena between prototypical electron-donors and acceptors: TTF-TCNQ as an example

    NASA Astrophysics Data System (ADS)

    Park, Changwon; Atalla, Viktor; Smith, Sean; Yoon, Mina

    2014-03-01

    It is widely accepted that the charge transfer between the conventional electron donor and acceptor molecules is independent of their relative configurations and electrons are always transferred from the molecule with the lower ionization potential, the electron-donor, to the high electron affinity molecule, the electron-acceptor. Conventional first-principles density functional theory (DFT) supports this conclusion. However, the computational results are dominated by a term in the DFT exchange-correlation functional, which often results in qualitatively and quantitatively wrong conclusion due to an artifact. In our study of prototypical electron donor-acceptor molecules, TTF-TCNQ, we show that the conventional electronic picture is not valid and the relative orientation between TTF and TCNQ is equally important as the electronic structure of the individual molecules. Our results show that the current understanding of the donor-acceptor interaction and charge transfer mechanism has to be modified. This research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Office of Basic Energy Sciences, U.S. Department of Energy.

  13. Microbial Diversity in Coastal Subsurface Sediments: a Cultivation Approach Using Various Electron Acceptors and Substrate Gradients

    PubMed Central

    Köpke, Beate; Wilms, Reinhard; Engelen, Bert; Cypionka, Heribert; Sass, Henrik

    2005-01-01

    Microbial communities in coastal subsurface sediments are scarcely investigated and have escaped attention so far. But since they are likely to play an important role in biogeochemical cycles, knowledge of their composition and ecological adaptations is important. Microbial communities in tidal sediments were investigated along the geochemical gradients from the surface down to a depth of 5.5 m. Most-probable-number (MPN) series were prepared with a variety of different carbon substrates, each at a low concentration, in combination with different electron acceptors such as iron and manganese oxides. These achieved remarkably high cultivation efficiencies (up to 23% of the total cell counts) along the upper 200 cm. In the deeper sediment layers, MPN counts dropped significantly. Parallel to the liquid enrichment cultures in the MPN series, gradient cultures with embedded sediment subcores were prepared as an additional enrichment approach. In total, 112 pure cultures were isolated; they could be grouped into 53 different operational taxonomic units (OTU). The isolates belonged to the Proteobacteria, “Bacteroidetes,” “Fusobacteria,” Actinobacteria, and “Firmicutes.” Each cultivation approach yielded a specific set of isolates that in general were restricted to this single isolation procedure. Analysis of the enrichment cultures by PCR and denaturing gradient gel electrophoresis revealed an even higher diversity in the primary enrichments that was only partially reflected by the culture collection. The majority of the isolates grew well under anoxic conditions, by fermentation, or by anaerobic respiration with nitrate, sulfate, ferrihydrite, or manganese oxides as electron acceptors. PMID:16332756

  14. Humic substances as fully regenerable electron acceptors in recurrently anoxic environments

    NASA Astrophysics Data System (ADS)

    Klüpfel, Laura; Piepenbrock, Annette; Kappler, Andreas; Sander, Michael

    2014-03-01

    Humic substances form through the degradation of microbial and plant precursors, and make up a significant fraction of natural organic matter in terrestrial and aquatic environments. Humic substances are redox-active and can act as terminal electron acceptors in anaerobic microbial respiration. Reduced humic substances may become re-oxidized during aeration of temporarily anoxic systems, such as wetlands, sediments and many soils. If the transfer of electrons from anaerobic respiration through humic substances to oxygen is sustained over many redox cycles, it may competitively suppress electron transfer to carbon dioxide, and thereby lower the formation of methane in temporarily anoxic systems. Here, we monitor changes in the redox states of four chemically distinct dissolved humic substances over successive cycles of reduction by the bacterium Shewanella oneidensis MR-1 and oxidation by oxygen, in a series of laboratory experiments. We show that electron transfer to and from these substances is fully reversible and sustainable over successive redox cycles. We suggest that redox cycling of humic substances may largely suppress methane production in temporarily anoxic systems.

  15. 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. PMID:26663513

  16. Bioavailability of Fe(III) in Loess Sediments: An Important Source of Electron Acceptors

    SciTech Connect

    Bishop, Michael E.; Jaisi, Deb P.; Dong, Hailiang; Kukkadapu, Ravi K.; Ji, Junfeng

    2010-08-01

    A quantitative study was conducted to understand if Fe (III) in loess sediments is available for microbial respiration by using a common metal reducing bacterium, Shewanella putrefaciens, CN32. The loess samples were collected from three different sites: St. Louis (Peoria), Missouri, USA; Huanxia (HX) and Yanchang (YCH), Shanxi Province of China. Wet chemical analyses indicated that the total Fe concentration for the three samples was 1.69%, 2.76%, and 3.29%, respectively, of which 0.48%, 0.67%, and 1.27% was Fe(III). All unreduced loess sediments contained iron oxides and phyllosilicates (smectite, illite, chlorite, vermiculite), in addition to common minerals such as quartz, feldspar, plagioclase, calcite, and dolomite. Bioreduction experiments were performed at a loess concentration of 20 mg/mL using lactate as the sole electron donor, Fe(III) in loess as the sole electron acceptor in the presence and absence of anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle. Experiments were performed in non-growth (bicarbonate buffer) and growth (M1) media with a cell concentration of ~2.8 x 107 and 2.1 x 107 cells/mL, respectively. The unreduced and bioreduced solids were analyzed by X-ray diffraction (XRD), Mössbauer spectroscopy, diffuse reflection spectroscopy (DRS), and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) methods. Despite many similarities among the three loess samples, the extent and rate of Fe (III) reduction varied significantly. For example, in presence of AQDS the extent of reduction in the non-growth experiment was 25% in HX, 34% in Peoria, and 38% in YCH. The extent of reduction in the growth experiment was 72% in HX, 94% in Peoria, and 56% in YCH. The extent of bioreduction was lower in absence of AQDS. Overall, AQDS and the M1 growth medium significantly enhanced the rate and extent of bioreduction. Fe(III) in iron oxides and Fe(III)-containing phyllosilicates was bioreduced. Biogenic illite, siderite, and

  17. 2010 Electron Donor-Acceptor Interactions Gordon Research Conference, August 8 - 13, 2010.

    SciTech Connect

    Gerald Meyer

    2010-08-18

    The Gordon Research Conference on Electron Donor Acceptor Interactions (GRC EDAI) presents and advances the current frontiers in experimental and theoretical studies of Electron Transfer Processes and Energy Conversion. The fundamental concepts underpinning the field of electron transfer and charge transport phenomena are understood, but fascinating experimental discoveries and novel applications based on charge transfer processes are expanding the discipline. Simultaneously, global challenges for development of viable and economical alternative energy resources, on which many researchers in the field focus their efforts, are now the subject of daily news headlines. Enduring themes of this conference relate to photosynthesis, both natural and artificial, and solar energy conversion. More recent developments include molecular electronics, optical switches, and nanoscale charge transport structures of both natural (biological) and man-made origin. The GRC EDAI is one of the major international meetings advancing this field, and is one of the few scientific meetings where fundamental research in solar energy conversion has a leading voice. The program includes sessions on coupled electron transfers, molecular solar energy conversion, biological and biomimetic systems, spin effects, ultrafast reactions and technical frontiers as well as electron transport in single molecules and devices. In addition to disseminating the latest advances in the field of electron transfer processes, the conference is an excellent forum for scientists from different disciplines to meet and initiate new directions; for scientists from different countries to make contacts; for young scientists to network and establish personal contacts with other young scientists and with established scientists who, otherwise, might not have the time to meet young people. The EDAI GRC also features an interactive atmosphere with lively poster sessions, a few of which are selected for oral presentations.

  18. Theory and computational modeling: Medium reorganization and donor/acceptor coupling in electron transfer processes

    SciTech Connect

    Newton, M.D.; Feldberg, S.W.; Smalley, J.F.

    1998-03-01

    The continuing goal is to convert the rapidly accumulating mechanistic information about electron transfer (et) kinetics (often representable in terms of simple rate constants) into precise tools for fine-tuned control of the kinetics and for design of molecular-based systems which meet specified et characteristics. The present treatment will be limited to the kinetic framework defined by the assumption of transition state theory (TST). The primary objective of this paper is to report recent advances in the theoretical formulation, calculation, and analysis of energetics and electronic coupling pertinent to et in complex molecular aggregates. The control of et kinetics (i.e., enhancing desired processes, while inhibiting others) involves, of course, both system energetics (especially reorganization energies (E{sub r}) and free energy changes ({Delta}G{sup 0})) and electronic coupling of local D and A sites, which for thermal processes is most directly relevant only after the system has reached the appropriate point (or region) along the reaction coordinate (i.e., the transition state). The authors first discuss TST rate constant models, emphasizing genetic features, but also noting some special features arising when metal electrodes are involved. They then turn to a consideration of detailed aspects of medium reorganization and donor/acceptor coupling. With these theoretical tools in hand, they examine the results of recent applications to complex molecular systems using the techniques of computational quantum chemistry and electrostatics, together with detailed analysis of the numerical results and comparison with recent electrochemical kinetic data.

  19. Electronic spectrum of non-tetrahedral acceptors in CdTe:Cl and CdTe:Bi,Cl single crystals

    NASA Astrophysics Data System (ADS)

    Krivobok, V. S.; Nikolaev, S. N.; Bagaev, V. S.; Pruchkina, A. A.; Onishchenko, E. E.; Kolosov, S. A.; Klevkov, Yu. V.; Skorikov, M. L.

    2016-02-01

    The electronic spectra of complex acceptors in compensated CdTe:Cl, CdTe:Ag,Cl, and CdTe:Bi,Cl single crystals are studied using low-temperature photoluminescence (PL) measurements under both nonresonant and resonant excitation of distant donor-acceptor pairs (DAP). The wavelength modulation of the excitation source combined with the analysis of the differential PL signal is used to enhance narrow spectral features obscured because of inhomogeneous line broadening and/or excitation transfer for selectively excited DAPs. For the well-known tetrahedral (TD) AgCd acceptor, the energies of four excited states are measured, and the values obtained are shown to be in perfect agreement with the previous data. Moreover, splitting between the 2P3/2 (D8) and 2S3/2 (D8) states is clearly observed for AgCd centers located at a short distance (5-7 nm) from a hydrogen-like donor (ClTe). This splitting results from the reduction of the TD symmetry taking place when the acceptor is a member of a donor-acceptor pair. For the Cl-related complex acceptor with an activation energy of ˜121 meV (A-center), the energies of eight excited states are measured. It is shown that this defect produces low-symmetry central-cell correction responsible for the strong splitting of S-like TD shells. The energy spectrum of the Bi-related shallow acceptor with an activation energy of ˜36 meV is measured as well. The spectrum obtained differs drastically from the hydrogen-like set of levels, which indicates the existence of repulsive low-symmetry perturbation of the hydrogen-like Coulomb potential. It is also shown that the spectra of selectively excited PL recorded for a macroscopic ensemble of distant donor-acceptor pairs allow one to detect the low symmetry of acceptors of a given type caused by their complex nature or by the Jahn-Teller distortion. This method does not require any additional (external) field and is applicable to acceptors in diverse zinc-blende compound semiconductors.

  20. Charge-transfer complexes formed in the reaction of 1,4,7,10-tetraazacyclododecane with π-electron acceptors

    NASA Astrophysics Data System (ADS)

    AlQaradawi, Siham Y.; Mostafa, Adel; Bazzi, Hassan S.

    2013-04-01

    The reactions of the electron donor 1,4,7,10-tetraazacyclododecane (TACDD) with the π-electron acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge-transfer (CT) complexes were recorded. The obtained results showed that the stoichiometries of the reactions are fixed and depend on the nature of both the donor and the acceptor. Based on the obtained data, the formed charge-transfer complexes were formulated as [(Donor)(Acceptor)2] for the donor (TACDD) and the acceptors TCNQ, TCNE, DDQ, CHL and TBCHD. These CT-complexes were isolated as solids and have been characterized through electronic and infrared spectra as well as elemental and thermal analysis measurements. The formation constants (KCT), charge transfer energy (ECT), molar extinction coefficients (ɛCT), free energy change ΔG0, ionization potential Ip and oscillator strength ƒ of the formed CT-complexes were obtained.

  1. Tuning the electronic coupling in a low-bandgap donor-acceptor copolymer via the placement of side-chains

    SciTech Connect

    Oberhumer, Philipp M.; Huang, Ya-Shih; Massip, Sylvain; Albert-Seifried, Sebastian; Greenham, Neil C.; Hodgkiss, Justin M.; Friend, Richard H.; James, David T.; Kim, Ji-Seon; Tu Guoli; Huck, Wilhelm T. S.; Beljonne, David; Cornil, Jerome

    2011-03-21

    We present a spectroscopic and theoretical investigation of the effect of the presence and position of hexyl side-chains in the novel low-bandgap alternating donor-acceptor copolymer poly[bis-N,N-(4-octylphenyl)-bis-N,N-phenyl-1, 4-phenylenediamine-alt-5,5'-4',7',-di-2-thienyl-2',1',3'-benzothiadiazole] (T8TBT). We use electronic absorption and Raman spectroscopic measurements supported by calculations of chain conformation, electronic transitions, and Raman modes. Using these tools, we find that sterically demanding side-chain configurations induce twisting in the electronic acceptor unit and reduce the electronic interaction with the donor. This leads to a blue-shifted and weakened (partial) charge-transfer absorption band together with a higher photoluminescence efficiency. On the other hand, sterically relaxed side-chain configurations promote coupling between donor and acceptor units and exhibit enhanced absorption at the expense of luminescence efficiency. The possibility of tuning the donor-acceptor character of conjugated polymers by varying the placement of side-chains has very important ramifications for light emitting diode, Laser, display, and photovoltaic device optimization.

  2. Listeria monocytogenes Scott A: Cell Surface Charge, Hydrophobicity, and Electron Donor and Acceptor Characteristics under Different Environmental Growth Conditions

    PubMed Central

    Briandet, Romain; Meylheuc, Thierry; Maher, Catherine; Bellon-Fontaine, Marie Noëlle

    1999-01-01

    We determined the variations in the surface physicochemical properties of Listeria monocytogenes Scott A cells that occurred under various environmental conditions. The surface charges, the hydrophobicities, and the electron donor and acceptor characteristics of L. monocytogenes Scott A cells were compared after the organism was grown in different growth media and at different temperatures; to do this, we used microelectrophoresis and the microbial adhesion to solvents method. Supplementing the growth media with glucose or lactic acid affected the electrical, hydrophobic, and electron donor and acceptor properties of the cells, whereas the growth temperature (37, 20, 15, or 8°C) primarily affected the electrical and electron donor and acceptor properties. The nonlinear effects of the growth temperature on the physicochemical properties of the cells were similar for cells cultivated in two different growth media, but bacteria cultivated in Trypticase soy broth supplemented with 6 g of yeast extract per liter (TSYE) were slightly more hydrophobic than cells cultivated in brain heart infusion medium (P < 0.05). Adhesion experiments conducted with L. monocytogenes Scott A cells cultivated in TSYE at 37, 20, 15, and 8°C and then suspended in a sodium chloride solution (1.5 × 10−1 or 1.5 × 10−3 M NaCl) confirmed that the cell surface charge and the electron donor and acceptor properties of the cells had an influence on their attachment to stainless steel. PMID:10583984

  3. 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

  4. Theoretical study of the interaction of electron donor and acceptor molecules with monolayer WS2

    NASA Astrophysics Data System (ADS)

    Zhou, C. J.; Yang, W. H.; Wu, Y. P.; Lin, W.; Zhu, H. L.

    2015-07-01

    With the aim of understanding recent experimental data concerning molecular doping in WS2-based FET gas sensors, we have investigated the interaction of NH3 and H2O molecules with monolayer WS2, by means of first-principles calculations. The structural relaxations and total energy calculations are performed to determine the preferential binding configurations and it is found that both NH3 and H2O molecules are physisorbed on monolayer WS2. The Bader analysis combined with the plane-averaged differential charge density results indicate that NH3 acts as the electron donor, while H2O acts as the electron acceptor, leading to n- and p-type doping of WS2, respectively. The charge transfer mechanism is discussed in light of the mixing of the molecular highest occupied molecular orbital and lowest unoccupied molecular orbital with the underlying WS2 orbitals. In addition, the modification of the work function is found to be almost linearly dependent on the total charge transfer. The modification of the work function and the carrier concentration can be obtained by tuning the molecule coverages, without destroying the band structure of monolayer WS2. The electrical sensitivities to the gas adsorption make WS2 a gas sensor that promises wide-ranging applications.

  5. Utilization of toxic and vapors as alternate electron acceptors in biofilters

    SciTech Connect

    Lee, B.D.; Apel, W.A.; Walton, M.R.

    1997-08-01

    Conceptually, biofilters are vapor phase bioreactors that rely on microorganisms in the bed medium to oxidize contaminants in off-gases flowing through the bed to less hazardous compounds. In the most studied and utilized systems reduced compounds such as fuel hydrocarbons are enzymatically oxidized to compounds such as carbon dioxide and water. In these types of reactions the microorganisms in the bed oxidize the contaminant and transfer the electrons to oxygen which is the terminal electron acceptor in the process. In essence the contaminant is the carbon and energy source for the microorganisms in the bed medium and through this catabolic process oxygen is reduced to water. An example of this oxidation process can be seen during the degradation of benzene and similar aromatic compounds. Aromatics are initially attacked by a dioxygenase enzyme which oxidizes the compounds to a labile dihydrodiole which is spontaneously converted to a catechol. The dihydroxylated aromatic rings is then opened by oxidative {open_quotes}ortho{close_quotes} or {open_quotes}meta{close_quotes} cleavage yielding cis, cis-muconic acid or 2-hydroxy-cis, cis-muconic semialdehyde, respectively. These organic compounds are further oxidized to carbon dioxide or are assimilated for cellular material. This paper describes the conversion of carbon tetrachloride using methanol as the primary carbon and energy source.

  6. Single-molecule interfacial electron transfer in donor-bridge-nanoparticle acceptor complexes.

    PubMed

    Jin, Shengye; Snoeberger, Robert C; Issac, Abey; Stockwell, David; Batista, Victor S; Lian, Tianquan

    2010-11-18

    Photoinduced interfacial electron transfer (IET) in sulforhodamine B (SRhB)-aminosilane-Tin oxide (SnO(2)) nanoparticle donor-bridge-acceptor complexes has been studied on a single molecule and ensemble average level. On both SnO(2) and ZrO(2), the sum of single molecule fluorescence decays agree with the ensemble average results, suggesting complete sampling of molecules under single molecule conditions. Shorter fluorescence lifetime on SnO(2) than on ZrO(2) is observed and attributed to IET from SRhB to SnO(2). Single molecule lifetimes fluctuate with time and vary among different molecules, suggesting both static and dynamic IET heterogeneity in this system. Computational modeling of the complexes shows a distribution of molecular conformation, leading to a distribution of electronic coupling strengths and ET rates. It is likely that the conversion between these conformations led to the fluctuation of ET rate and fluorescence lifetime on the single molecule level. PMID:20225886

  7. ENDOR studies of the intermediate electron acceptor radical anion I-. in Photosystem II reaction centers.

    PubMed

    Lubitz, W; Isaacson, R A; Okamura, M Y; Abresch, E C; Plato, M; Feher, G

    1989-11-23

    The EPR and ENDOR characteristics of the intermediate electron acceptor radical anion I-. in Photosystem II (PS II) are shown to be identical in membrane particles and in the D1D2 cytochrome b-559 complex (Nanba, O. and Satoh, K. (1987) Proc. Natl. Acad. Sci. USA 84, 109-112). These findings provide further evidence that the D1D2 complex is the reaction center of PS II and show that the pheophytin binding site is intact. A hydrogen bond between I-. and the protein (GLU D1-130) is postulated on the basis of D2O exchange experiments. The ENDOR data of I-. and of the pheophytin a radical anion in different organic solvents are compared and the observed differences are related to structural changes of the molecule on the basis of molecular orbital calculations (RHF-INDO/SP). The importance of the orientation of the vinyl group (attached to ring I) on electron transfer is discussed. PMID:2553112

  8. Remarkable Dependence of the Final Charge Separation Efficiency on the Donor-Acceptor Interaction in Photoinduced Electron Transfer.

    PubMed

    Higashino, Tomohiro; Yamada, Tomoki; Yamamoto, Masanori; Furube, Akihiro; Tkachenko, Nikolai V; Miura, Taku; Kobori, Yasuhiro; Jono, Ryota; Yamashita, Koichi; Imahori, Hiroshi

    2016-01-11

    The unprecedented dependence of final charge separation efficiency as a function of donor-acceptor interaction in covalently-linked molecules with a rectilinear rigid oligo-p-xylene bridge has been observed. Optimization of the donor-acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100% efficiency. This finding is extremely useful for the rational design of artificial photosynthesis and organic photovoltaic cells toward efficient solar energy conversion. PMID:26610285

  9. Tailorable acceptor C(60-n)B(n) and donor C(60-m)N(m) pairs for molecular electronics.

    PubMed

    Xie, Rui-Hua; Bryant, Garnett W; Zhao, Jijun; Smith, Vedene H; Di Carlo, Aldo; Pecchia, Alessandro

    2003-05-23

    Our first-principles calculations demonstrate that C(60-n)B(n) and C(60-m)N(m) can be engineered as the acceptors and donors, respectively, needed for molecular electronics by properly controlling the dopant number n and m in C60. We show that acceptor C48B12 and donor C48N12 are promising components for molecular rectifiers, carbon nanotube-based n-p-n (p-n-p) transistors, and p-n junctions. PMID:12785911

  10. Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex.

    PubMed

    Rosokha, Sergiy V; Kochi, Jay K

    2008-05-01

    Seminal insights provided by the iconic R. S. Mulliken and his "charge-transfer" theory, H. Taube and his "outer/inner-sphere" mechanisms, R. A. Marcus and his "two-state non-adiabatic" theory, and N. S. Hush and his "intervalence" theory are each separately woven into the rich panoramic tapestry constituting chemical research into electron-transfer dynamics, and its mechanistic dominance for the past half century and more. In this Account, we illustrate how the simultaneous melding of all four key concepts allows sharp focus on the charge-transfer character of the critical encounter complex to evoke the latent facet of traditional electron-transfer mechanisms. To this end, we exploit the intervalence (electronic) transition that invariably accompanies the diffusive encounter of electron-rich organic donors (D) with electron-poor acceptors (A) as the experimental harbinger of the collision complex, which is then actually isolated and X-ray crystallographically established as loosely bound pi-stacked pairs of various aromatic and olefinic donor/acceptor dyads with uniform interplanar separations of r(DA) = 3.1 +/- 0.2 A. These X-ray structures, together with the spectral measurements of their intervalence transitions, lead to the pair of important electron-transfer parameters, H(DA) (electronic coupling element) versus lambdaT (reorganization energy), the ratio of which generally defines the odd-electron mobility within such an encounter complex in terms of the resonance stabilization of the donor/acceptor assembly [D, A] as opposed to the reorganization-energy penalty required for its interconversion to the electron-transfer state [D(+*), A(-*)]. We recognize the resonance-stabilization energy relative to the intrinsic activation barrier as the mechanistic binding factor, Q = 2H(DA)/lambdaT, to represent the quantitative measure of the highly variable continuum of inner-sphere/outer-sphere interactions that are possible within various types of precursor complexes

  11. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods.

    PubMed

    Knight, Joseph W; Wang, Xiaopeng; Gallandi, Lukas; Dolgounitcheva, Olga; Ren, Xinguo; Ortiz, J Vincent; Rinke, Patrick; Körzdörfer, Thomas; Marom, Noa

    2016-02-01

    The performance of different GW methods is assessed for a set of 24 organic acceptors. Errors are evaluated with respect to coupled cluster singles, doubles, and perturbative triples [CCSD(T)] reference data for the vertical ionization potentials (IPs) and electron affinities (EAs), extrapolated to the complete basis set limit. Additional comparisons are made to experimental data, where available. We consider fully self-consistent GW (scGW), partial self-consistency in the Green's function (scGW0), non-self-consistent G0W0 based on several mean-field starting points, and a "beyond GW" second-order screened exchange (SOSEX) correction to G0W0. We also describe the implementation of the self-consistent Coulomb hole with screened exchange method (COHSEX), which serves as one of the mean-field starting points. The best performers overall are G0W0+SOSEX and G0W0 based on an IP-tuned long-range corrected hybrid functional with the former being more accurate for EAs and the latter for IPs. Both provide a balanced treatment of localized vs delocalized states and valence spectra in good agreement with photoemission spectroscopy (PES) experiments. PMID:26731609

  12. Decolorization of kraft bleaching effluent by advanced oxidation processes using copper (II) as electron acceptor.

    PubMed

    Yeber, María C; Oñate, Katherine P; Vidal, Gladys

    2007-04-01

    Two advanced oxidation processes (AOPs), TiO2/UV/O2 and TiO2/UV/Cu (II), were used to remove color from a Kraft bleaching effluent. The optimal decoloration rate was determined by multivariate analysis, obtaining a mathematical model to evaluate the effect among variables. TiO2 and Cu (II) concentrations and the reaction times were optimized. The experimental design resulted in a quadratic matrix of 30 experiments. Additionally, the pH influence on the color removal was determined by multivariate analysis. Results indicate that color removal was 94% at acidic pH (3.0) in the presence of Cu (11) as an electron acceptor. Under this condition, the biodegradation of the effluent increased from 0.3 to 0.6. Moreover, 70% of COD (chemical oxygen demand) was removed, and the ecotoxicity, measured by Daphnia magna, was reduced. Photocatalytic oxidation to remove the color contained in the Kraft mill bleaching effluent was effective under the following conditions: short reaction time, acidic pH values, and without the addition of oxygen due to the presence of Cu (II) in the effluent. Moreover, residual Cu (II) was a minimum (0.05.mg L(-1)) and was not toxic to the next biological stage. The experimental design methodology indicated that a quadratic polynomial model may be used to representthe efficiencyfor degradation of the Kraft bleach pulp effluent by a photocatalytic process. PMID:17438808

  13. NOx in the Atmosphere of Early Earth as Electron Acceptors for Life

    NASA Astrophysics Data System (ADS)

    Wong, M. L.; Charnay, B.; Gao, P.; Yung, Y. L.; Russell, M. J.

    2015-12-01

    We quantify the amount of NOx produced in the Hadean atmosphere and available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO3-) and nitrite (NO2-) are the most attractive high-potential electron acceptors for driving the highly endergonic reactions at the entry points to autotrophic metabolic pathways at submarine alkaline hydrothermal vents (Ducluzeau, 2008; Russell, 2014). The Hadean atmosphere, dominated by CO2 and N2, will produce nitric oxide (NO) when shocked by lightning and impacts (Ducluzeau, 2008; Nna Mvondo, 2001). Photochemical reactions involving NO and H2O vapor will then produce acids such as HNO3 and HNO2 that rain into the ocean and dissociate into NO3- and NO2-. Previous work suggests that 1018 g of NOx can be produced in a million years or so, satisfying the need for micromolar concentrations of NO3- and NO2- in the ocean (Ducluzeau, 2008). But because this number is controversial, we present new calculations based on a novel combination of early-Earth GCM and photochemical modeling, calculating the sources and sinks for fixed nitrogen. Finally, it is notable that lightning has been detected on Venus and Mars along with evidence of atmospheric NO; in the distant past, could NOx have been created and available for the emergence of life on numerous wet, rocky worlds?

  14. Magnetite nanoparticles facilitate methane production from ethanol via acting as electron acceptors

    NASA Astrophysics Data System (ADS)

    Yang, Zhiman; Shi, Xiaoshuang; Wang, Chuanshui; Wang, Lin; Guo, Rongbo

    2015-11-01

    Potential for interspecies hydrogen transfer within paddy soil enrichments obtained via addition of magnetite nanoparticles and ethanol (named as PEM) was investigated. To do this, PEM derived from rice field of Hangzhou (named as PEM-HZ) was employed, because it offered the best methane production performance. Methane production and Fe (III) reduction proceeded in parallel in the presence of magnetite. Inhibition experiments with 2-bromoethane sulfonate (BES) or phosphate showed that interspecies hydrogen transfer and Fe (III) reduction also occurred in methane production from ethanol. 16S rRNA-based Illumina sequencing results showed that Dechloromonas, Thauera, Desulfovibrio and Clostridium were the dominant putative Fe (III) -reducers, and that hydrogenotrophic Methanobacterium accounted for about 88% of the total archaeal community. These results indicated that magnetite nanoparticles that acted as electron acceptor could facilitate rapid oxidation of ethanol by members of the Fe (III) -reducers in PEM-HZ and establishment of the syntrophic relationship of Fe (III) -reducers with Methanobacterium via interspecies hydrogen transfer. Our results could offer a model to understand the microbial interaction with magnetite from a novel angle during methanogenesis.

  15. Magnetite nanoparticles facilitate methane production from ethanol via acting as electron acceptors.

    PubMed

    Yang, Zhiman; Shi, Xiaoshuang; Wang, Chuanshui; Wang, Lin; Guo, Rongbo

    2015-01-01

    Potential for interspecies hydrogen transfer within paddy soil enrichments obtained via addition of magnetite nanoparticles and ethanol (named as PEM) was investigated. To do this, PEM derived from rice field of Hangzhou (named as PEM-HZ) was employed, because it offered the best methane production performance. Methane production and Fe (III) reduction proceeded in parallel in the presence of magnetite. Inhibition experiments with 2-bromoethane sulfonate (BES) or phosphate showed that interspecies hydrogen transfer and Fe (III) reduction also occurred in methane production from ethanol. 16S rRNA-based Illumina sequencing results showed that Dechloromonas, Thauera, Desulfovibrio and Clostridium were the dominant putative Fe (III) -reducers, and that hydrogenotrophic Methanobacterium accounted for about 88% of the total archaeal community. These results indicated that magnetite nanoparticles that acted as electron acceptor could facilitate rapid oxidation of ethanol by members of the Fe (III) -reducers in PEM-HZ and establishment of the syntrophic relationship of Fe (III) -reducers with Methanobacterium via interspecies hydrogen transfer. Our results could offer a model to understand the microbial interaction with magnetite from a novel angle during methanogenesis. PMID:26559132

  16. Effects of auxiliary carbon sources and electron acceptors on methanogenic degradation of chlorinated phenols

    SciTech Connect

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y. )

    1993-08-01

    The authors studied the degradation of chlorinated phenols under methanogenic conditions by establishing enrichment cultures on 4-chlorophenol and 2,4-dichlorophenol with or without a supplementary substrate. p-Cresol was chosen as a nonchlorinated aromatic compound structurally similar to the chlorophenols, and propionate was chosen as a readily utilizable carbon source. 2,4-Dichlorophenol was dechlorinated to 4-chlorophenol, which was degraded without further detection of metabolites. The rates of chlorophenols and supplementary substrates. The addition of p-cresol or propionate as an auxiliary carbon source enhanced the rate of 4-chlorophenol degradation. Methanogenic cultures capable of ortho dechlorination were repeatedly subcultured by dilution into fresh media and refeeding of 2,6-dichlorophenol and either p-cresol or propionate as auxiliary substrates. 2,6-Dichlorophenol was sequentially dechlorinated to 2-chlorophenol and phenol and ultimately mineralized to methane and carbon dioxide. Cultures adapted to 2,4- or 2,6-dichlorophenol also readily dechlorinated other dichlorophenols containing an ortho chlorine. The alternative electron acceptors nitrate, sulfite, and thiosulfate completely inhibited dechlorination of 2,6-dichlorophenol, whereas sulfate slowed the dechlorination rate.

  17. Magnetite nanoparticles facilitate methane production from ethanol via acting as electron acceptors

    PubMed Central

    Yang, Zhiman; Shi, Xiaoshuang; Wang, Chuanshui; Wang, Lin; Guo, Rongbo

    2015-01-01

    Potential for interspecies hydrogen transfer within paddy soil enrichments obtained via addition of magnetite nanoparticles and ethanol (named as PEM) was investigated. To do this, PEM derived from rice field of Hangzhou (named as PEM-HZ) was employed, because it offered the best methane production performance. Methane production and Fe (III) reduction proceeded in parallel in the presence of magnetite. Inhibition experiments with 2-bromoethane sulfonate (BES) or phosphate showed that interspecies hydrogen transfer and Fe (III) reduction also occurred in methane production from ethanol. 16S rRNA-based Illumina sequencing results showed that Dechloromonas, Thauera, Desulfovibrio and Clostridium were the dominant putative Fe (III) -reducers, and that hydrogenotrophic Methanobacterium accounted for about 88% of the total archaeal community. These results indicated that magnetite nanoparticles that acted as electron acceptor could facilitate rapid oxidation of ethanol by members of the Fe (III) -reducers in PEM-HZ and establishment of the syntrophic relationship of Fe (III) -reducers with Methanobacterium via interspecies hydrogen transfer. Our results could offer a model to understand the microbial interaction with magnetite from a novel angle during methanogenesis. PMID:26559132

  18. NOx in the atmospheres of aquaplanets as electron acceptors for life

    NASA Astrophysics Data System (ADS)

    Wong, M. L.; Yung, Y. L.; Russell, M. J.

    2014-12-01

    A high potential electron acceptor is required to drive the highly endergonic reactions at the entry points to the autotrophic metabolic pathways that would lead to life on any wet rocky world. Nitrate and nitrite in the earliest oceans are the most attractive candidates (Ducluzeau et al., 2009, 2014). It has been estimated that, given a CO2 and N2 atmosphere, lightning (a proportion of it volcanic), meteorite impacts and volcanic gases would have produced enough NOx in a million years or so (>1018 g) to generate micromolar amounts of NO3- and NO2- in the ocean (Yung and McElroy, 1979; Kasting, 1990; Navarro-González et al., 1998; Martin et al., 2007). It is notable that lightning has been detected on Venus and Mars along with evidence of atmospheric NO. Because a figure 1018 g of nitrate/nitrite is controversial, we will present new calculations based on 10 atmospheres of CO2, two atmospheres of N2 and stepped concentrations of water vapor dependent on surface temperatures.

  19. Tuning the Electronic Coupling and Electron Transfer in Mo2 Donor-Acceptor Systems by Variation of the Bridge Conformation.

    PubMed

    Kang, Mei Ting; Meng, Miao; Tan, Ying Ning; Cheng, Tao; Liu, Chun Y

    2016-02-24

    Assembling two quadruply bonded dimolybdenum units [Mo2 (DAniF)3 ](+) (DAniF=N,N'-di(p-anisyl)formamidinate) with 1,4-naphthalenedicarboxylate and its thiolated derivatives produced three complexes [{Mo2 (DAniF)3 }2 (μ-1,4-O2 CC10 H6 CO2 )], [{Mo2 (DAniF)3 }2 (μ-1,4-OSCC10 H6 COS)], and [{Mo2 (DAniF)3 }2 (μ-1,4-S2 CC10 H6 CS2 )]. In the X-ray structures, the naphthalene bridge deviates from the plane defined by the two Mo-Mo bond vectors with the torsion angle increasing as the chelating atoms of the bridging ligand vary from O to S. The mixed-valent species exhibit intervalence transition absorption bands with high energy and very low intensity. In comparison with the data for the phenylene analogues, the optically determined electronic coupling matrix elements (Hab =258-345 cm(-1) ) are lowered by a factor of two or more, and the electron-transfer rate constants (ket ≈10(11)  s(-1) ) are reduced by about one order of magnitude. These results show that, when the electron-transporting ability of the bridge and electron-donating (electron-accepting) ability of the donor (acceptor) are both variable, the former plays a dominant role in controlling the intramolecular electron transfer. DFT calculations revealed that increasing the torsion angle enlarges the HOMO-LUMO energy gap by elevating the (bridging) ligand-based LUMO energy. Therefore, our experimental results and theoretical analyses verify the superexchange mechanism for electronic coupling and electron transfer. PMID:26807909

  20. Gallium vacancies and gallium antisites as acceptors in electron-irradiated semi-insulating GaAs

    SciTech Connect

    Corbel, C.; Pierre, F. ); Saarinen, K.; Hautojaervi, P. ); Moser, P. )

    1992-02-15

    Positron-lifetime measurements show that acceptors are produced in semi-insulating GaAs by 1.5-MeV electron irradiation at 20 K. Two types of acceptors can be separated. The first ones are negative vacancy-type defects which anneal out over a very broad range of temperature between 77 and 500 K. The second ones are negative ion-type defects which are stable still at 450 K. The data show that these two types of defects are independent and do not form close pairs. We attribute both to gallium-related defects. We identify the ion-type acceptors as isolated gallium antisites. The vacancy-type acceptors are identified as gallium vacancies which are isolated or involved in negatively charged complexes. The introduction rate of the gallium antisite is estimated to be 1.8{plus minus}0.3 cm{sup {minus}1} in the fluence range 10{sup 17}--10{sup 18} cm{sup {minus}2} for 1.5-MeV electron irradiation at 20 K.

  1. 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.

  2. Effects of the addition of alcohols, cryoprotective agents, and salts on the photoionization yield of chlorophyll a in frozen vesicle solutions with and without electron acceptors

    SciTech Connect

    Hiff, T.; Kevan, L. )

    1989-04-20

    The photoionization yield of chlorophyll a (Chla) in rapidly frozen vesicles with and without potassium ferricyanide (FC) or tetrachloro-p-benzoquinone (TCBQ) has been studied versus several structural variations of phospholipid vesicles, including the addition of medium chain length alcohols, the effect of added salts (metal chlorides), the presence of a double bond in the alkyl tail of the surfactant, and the addition of dimethyl sulfoxide or glycerol which tend to enhance vesicular structure retention upon freezing. Variations in the photoionization yield versus these structural parameters are discussed in terms of distance variations between Chla and electron acceptors, loss of integrity of the vesicle structure, and differences in the degree of hydration of the headgroups of the surfactant molecules. Electron spin echo (ESE) deuterium modulation associated with a 5-doxylstearic acid spin probe interacting with deuterated water probes the degree of water interaction at the vesicle interface. The ESE data support a correlation between the degree of interface hydration and the photoionization yield for vesicles containing Chla and FC as an electron acceptor. Parallel ESE studies of 5-doxylstearic acid spin probes in anionic and cationic surfactant vesicles reveal changes in the interface hydration if the surfactant counterion is changed; this can be roughly correlated to the Chla photoionization yields.

  3. Microbial Anaerobic Ammonium Oxidation Under Iron Reducing Conditions, Alternative Electron Acceptors

    NASA Astrophysics Data System (ADS)

    Ruiz-Urigüen, M.; Jaffe, P. R.

    2015-12-01

    Autotrophic Acidimicrobiaceae-bacterium named A6 (A6), part of the Actinobacteria phylum have been linked to anaerobic ammonium (NH4+) oxidation under iron reducing conditions. These organisms obtain their energy by oxidizing NH4+ and transferring the electrons to a terminal electron acceptor (TEA). Under environmental conditions, the TEAs are iron oxides [Fe(III)], which are reduced to Fe(II), this process is known as Feammox. Our studies indicate that alternative forms of TEAs can be used by A6, e.g. iron rich clays (i.e. nontronite) and electrodes in bioelectrochemical systems such as Microbial Electrolysis Cells (MECs), which can sustain NH4+removal and A6 biomass production. Our results show that nontronite can support Feammox and promote bacterial cell production. A6 biomass increased from 4.7 x 104 to 3.9 x 105 cells/ml in 10 days. Incubations of A6 in nontronite resulted in up to 10 times more NH4+ removal and 3 times more biomass production than when ferrihydrite is used as the Fe(III) source. Additionally, Fe in nontronite can be reoxidized by aeration and A6 can reutilize it; however, Fe is still finite in the clay. In contrast, in MECs, A6 harvest electrons from NH4+ and use an anode as an unlimited TEA, as a result current is produced. We operated multiple MECs in parallel using a single external power source, as described by Call & Logan (2011). MECs were run with an applied voltage of 0.7V and different growing mediums always containing initial 5mM NH4+. Results show that current production is favored when anthraquinone-2,6-disulfonate (AQDS), an electron shuttled, is present in the medium as it facilitates the transfer of electrons from the bacterial cell to the anode. Additionally, A6 biomass increased from 1 x 104 to 9.77 x 105cells/ml in 14 days of operation. Due to Acidimicrobiaceae-bacterium A6's ability to use various TEAs, MECs represent an alternative, iron-free form, for optimized biomass production of A6 and its application in NH4

  4. A Systematic Study on the Influence of Electron-Acceptors in Phenanthrocarbazole Dye-Sensitized Solar Cells.

    PubMed

    Yang, Lin; Yao, Zhaoyang; Liu, Jiao; Wang, Junting; Wang, Peng

    2016-04-20

    In this work, by conjugating 2-cyanoacrylic acid (CA), 4-(benzo[c][1,2,5]thiadiazol-7-yl)benzoic acid (BTBA), 4-(7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoic acid (EBTBA), and 4-((7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)ethynyl)benzoic acid (EBTEBA) to a binary electron-donor diphenylamine-phenanthrocarbazole (DPA-PC), we systematically investigate the impacts of electron-acceptors upon energy level, energy gap, light-harvesting ability, photovoltaic parameter, and cell stability of donor-acceptor dyes in photoelectrochemical cells. In conjunction with an ionic liquid composite electrolyte, the DPA-PC dye with EBTEBA as electron-acceptor yields a high power conversion efficiency of 8% and an outstanding stability after a 1000 h aging test under the soaking of full sunlight at 60 °C in a dye-sensitized solar cell. Femtosecond fluorescence up-conversion measurements have suggested that energy relaxation and electron injection both occur to dye molecules in the nonequilibrium excited states. Moreover, the time constants of injecting electrons from dye molecules in the excited states to titania are very dispersive for over 1 order of magnitude, mainly owing to the broad energy distribution of excited states. PMID:27045539

  5. The reduction of artificial electron acceptors at sub-zero temperatures by chloroplasts suspended in fluid media.

    PubMed

    Cox, R P

    1975-06-17

    1. Chloroplasts can be suspended in aqueous/organic mixtures which are liquid at sub-zero temperatures with a good retention of the ability to reduce artificial electron acceptors. The reduction of ferricyanide and 2,6-dichlorophenolindophenol at temperatures above 0 degrees C is about 50% inhibited by 50% (v/v) ethylene glycol. Higher concentrations cause more extensive inhibition. 2. Different solvents were compared on the basis of their ability to cause a given depression of the freezing point of an aqueous solution. Ethylene glycol caused less inhibition of electron transport than glycerol, which in turn was found to be superior to methanol. 3. The reduction of oxidised 2,3,5,6-tetramethyl-p-phenylenediamine could be measured at -25 degrees C in 40% (v/v) ethylene glycol. Using an acceptor with a high extinction coefficient, methyl purple (a derivative of 2,6-dichlorophenolindophenol) it was possible to observe electron flow at temperatures as low as -40 degrees C in 50% (v/v) ethylene glycol. 4. From studies of the effects of the inhibitors 3(3,4-dichlorophenyl)-1,1-dimethylurea and 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone it is suggested that electron flow from the donor side of Photosystem II to the acceptor side of Photosystem I can occur at temperatures at least as low as -25 degrees C. The ultimate electron donor is presumably water but it was not possible to demonstrate this directly. PMID:1138892

  6. Anaerobic α-Amylase Production and Secretion with Fumarate as the Final Electron Acceptor in Saccharomyces cerevisiae

    PubMed Central

    Liu, Zihe; Österlund, Tobias; Hou, Jin; Petranovic, Dina

    2013-01-01

    In this study, we focus on production of heterologous α-amylase in the yeast Saccharomyces cerevisiae under anaerobic conditions. We compare the metabolic fluxes and transcriptional regulation under aerobic and anaerobic conditions, with the objective of identifying the final electron acceptor for protein folding under anaerobic conditions. We find that yeast produces more amylase under anaerobic conditions than under aerobic conditions, and we propose a model for electron transfer under anaerobic conditions. According to our model, during protein folding the electrons from the endoplasmic reticulum are transferred to fumarate as the final electron acceptor. This model is supported by findings that the addition of fumarate under anaerobic (but not aerobic) conditions improves cell growth, specifically in the α-amylase-producing strain, in which it is not used as a carbon source. Our results provide a model for the molecular mechanism of anaerobic protein secretion using fumarate as the final electron acceptor, which may allow for further engineering of yeast for improved protein secretion under anaerobic growth conditions. PMID:23435897

  7. Measurement of Acceptor-TΨC Helix Length of tRNA for Terminal A76-Addition by A-Adding Enzyme.

    PubMed

    Yamashita, Seisuke; Martinez, Anna; Tomita, Kozo

    2015-05-01

    The 3'-terminal CCA (C74C75A76-3') of tRNA is required for protein synthesis. In Aquifex aeolicus, the CCA-3' is synthesized by CC-adding and A-adding enzymes, although in most organisms, CCA is synthesized by a single CCA-adding enzyme. The mechanisms by which the A-adding enzyme adds only A76, but not C74C75, onto tRNA remained elusive. The complex structures of the enzyme with various tRNAs revealed the presence of a single tRNA binding site on the enzyme, with the enzyme measuring the acceptor-TΨC helix length of tRNA. The 3'-C75 of tRNA lacking A76 can reach the active site and the size and shape of the nucleotide binding pocket at the insertion stage are suitable for ATP. The 3'-C74 of tRNA lacking C75A76 cannot reach the active site, although CTP or ATP can bind the active pocket. Thus, the A-adding enzyme adds only A76, but not C74C75, onto tRNA. PMID:25914059

  8. Monitoring electron donor metabolism under variable electron acceptor conditions using 13C-labeled lactate

    NASA Astrophysics Data System (ADS)

    Bill, M.; Conrad, M. E.; Yang, L.; Beller, H. R.; Brodie, E. L.

    2010-12-01

    Three sets of flow-through columns constructed with aquifer sediment from Hanford (WA) were used to study reduction of Cr(VI) to poorly soluble Cr(III) under denitrifying, sulfate-reducing/fermentative, and iron-reducing conditions with lactate as the electron donor. In order to understand the relationship between electron donors and biomarkers, and to determine the differences in carbon isotope fractionation resulting from different microbial metabolic processes, we monitored the variation in carbon isotopes in dissolved inorganic carbon (DIC), in total organic carbon (TOC), and in lactate, acetate and propionate. The greatest enrichment in 13C in columns was observed under denitrifying conditions. The δ13C of DIC increased by ~1750 to ~2000‰ fifteen days after supplementation of natural abundance lactate with a 13C-labeled lactate tracer (for an influent δ13C of ~2250‰ for the lactate) indicating almost complete oxidation of the electron donor. The denitrifying columns were among the most active columns and had the highest cell counts and the denitrification rate was highly correlated with Cr(VI) reduction rate. δ13C values of DIC ranged from ~540 to ~1170‰ for iron-reducing conditions. The lower enrichment in iron columns was related to the lower biological activity observed with lower yields of RNA and cell numbers in the column effluents. The carbon isotope shift in the sulfate-reducing ~198 to ~1960‰ for sulfate-reducing conditions reflecting the lower levels of the lactate in these columns. Additionally, in two of the sulfate columns, almost complete fermentation of the lactate occurred, producing acetate and propionate with the labeled carbon signature, but relatively smaller amounts of inorganic carbon. For all electron-accepting conditions, TOC yielded similar δ13C values as lactate stock solutions. Differences in C use efficiency, metabolic rate or metabolic pathway contributed to the differing TOC δ13C to DIC δ13C ratios between treatments

  9. Decacyclene Trianhydride at Functional Interfaces: An Ideal Electron Acceptor Material for Organic Electronics.

    PubMed

    de Oteyza, Dimas G; Garcia-Lastra, Juan M; Toma, Francesca M; Borghetti, Patrizia; Floreano, Luca; Verdini, Alberto; Cossaro, Albano; Pho, Toan V; Wudl, Fred; Ortega, J Enrique

    2016-01-01

    We report the interface energetics of decacyclene trianhydride (DTA) monolayers on top of two distinct model surfaces, namely, Au(111) and Ag(111). On the latter, combined valence band photoemission and X-ray absorption measurements that access the occupied and unoccupied molecular orbitals, respectively, reveal that electron transfer from substrate to surface sets in. Density functional theory calculations confirm our experimental findings and provide an understanding not only of the photoemission and X-ray absorption spectral features of this promising organic semiconductor but also of the fingerprints associated with the interface charge transfer. PMID:26651535

  10. Selection of denitrifying phosphorous accumulating organisms in IFAS systems: comparison of nitrite with nitrate as an electron acceptor.

    PubMed

    Jabari, Pouria; Munz, Giulio; Oleszkiewicz, Jan A

    2014-08-01

    Nitrite and nitrate were compared as electron acceptors to select for denitrifying phosphorous accumulating organisms (DPAO) in two integrated fixed film activated sludge (IFAS 1 and IFAS 2) systems operated as sequencing batch reactors. The bench-scale experiment lasted one year and synthetic wastewater was used as feed. During anoxic conditions 20mgNO3(-)-NL(-1) were dosed into IFAS-1 and 20mgNO2(-)-NL(-1) were dosed into IFAS-2. Long term phosphorous and ammonia removal via nitritation were achieved in both systems and both attached and suspended biomass contributed to phosphorous and ammonia removal. DPAO showed no specific adaptation to the electron acceptor as evidenced by short term switch of feeding with nitrate or nitrite. Anoxic phosphorus uptake rate was significantly higher with nitrite than with nitrate. Results showed that DPAO activity with nitrite could be integrated into attached and suspended biomass of IFAS systems in long term operation. PMID:24873702

  11. Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps

    DOE PAGESBeta

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R.; Miller, John R.

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are asmore » large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.« less

  12. Modeling microbial degradation of propylene glycol: electron acceptors and their related redox conditions

    NASA Astrophysics Data System (ADS)

    Dathe, Annette; Fernandez, Perrine M.; Bloem, Esther; Meeussen, Johannes C. L.; French, Helen K.

    2014-05-01

    De-icing chemicals are applied in large amounts at airports during winter conditions to keep the runways and aircrafts ice-free. The commonly used propylene glycol (PG) is easily degradable by local microbial communities, but anoxic zones develop and soluble Fe+2 and Mn+2 ions can reach the groundwater. To enhance microbial induced remediation and reduce the release of iron and manganese, it was proposed to add NO3- together with PG. However, experiments conducted in the unsaturated zone at Gardermoen airport, Norway, revealed that manganese and iron were preferred over NO3- as electron acceptor [1]. The objectives of this study are to quantify mechanisms which control the order of reduction processes in an unsaturated sandy soil, and to test whether measured redox potentials can help to determine underlying biogeochemical reactions. We are modelling the microbial degradation of PG using Monod kinetics described for the chemical equilibrium tool ORCHESTRA [2], following an approach of [1]. The model is calibrated against gas measurements of CO2, NO2 and N2 released from batch experiments performed under controlled conditions. Fe+2 and Mn+2 were measured for the start and end of the experiment, as well as bulk resistivity, pH and electrical conductivity. With the calibrated model we are working towards a tool to quantify microbial induced redox reactions under different soil water saturations to account for seasonal water fluxes especially during snowmelt. [1] Schotanus, D., Meeussen, J.C.L., Lissner, H., van der Ploeg, M.J., Wehrer, M., Totsche, K.U., van der Zee, S.E.A.T.M., 2013. Transport and degradation of propylene glycol in the vadose zone: model development and sensitivity analysis. Environ Sci Pollut Res Int. [2] Meeussen, J.C.L., 2003. ORCHESTRA: An Object-Oriented Framework for Implementing Chemical Equilibrium Models. Environ. Sci. Technol. 37, 1175-1182.

  13. Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps

    SciTech Connect

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R.; Miller, John R.

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.

  14. Effects of electron acceptors on soluble reactive phosphorus in the overlying water during algal decomposition.

    PubMed

    Wang, Jinzhi; Jiang, Xia; Zheng, Binghui; Niu, Yuan; Wang, Kun; Wang, Wenwen; Kardol, Paul

    2015-12-01

    Endogenous phosphorus (P) release from sediments is an important factor to cause eutrophication and, hence, algal bloom in lakes in China. Algal decomposition depletes dissolved oxygen (DO) and causes anaerobic conditions and therefore increases P release from sediments. As sediment P release is dependent on the iron (Fe) cycle, electron acceptors (e.g., NO3 (-), SO4 (2-), and Mn(4+)) can be utilized to suppress the reduction of Fe(3+) under anaerobic conditions and, as such, have the potential to impair the release of sediment P. Here, we used a laboratory experiment to test the effects of FeCl3, MnO2, and KNO3 on soluble reactive phosphorus (SRP) concentration and related chemical variables in the overlying water column during algal decomposition at different algal densities. Results showed that algal decomposition significantly depleted DO and thereby increased sediment Fe-bound P release. Compared with the control, addition of FeCl3 significantly decreased water SRP concentration through inhibiting sediment P release. Compared with FeCl3, addition of MnO2 has less potential to suppress sediment P release during algal decomposition. Algal decomposition has the potential for NO3 (-) removal from aquatic ecosystem through denitrification and by that alleviates the suppressing role of NO3 (-) on sediment P release. Our results indicated that FeCl3 and MnO2 could be efficient in reducing sediment P release during algal decomposition, with the strongest effect found for FeCl3; large amounts of NO3 (-) were removed from the aquatic ecosystem through denitrification during algal decomposition. Moreover, the amounts of NO3 (-) removal increased with increasing algal density. PMID:26263882

  15. Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation.

    PubMed

    Ali, Muhammad Aslam; Lee, Chang Hoon; Kim, Sang Yoon; Kim, Pil Joo

    2009-10-01

    Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH(4)) emission resulting from rice cultivation. In laboratory incubations, CH(4) production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt(-1)), while observed CO(2) production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH(4) emission rates from the rice planted potted soils significantly decreased with the increasing levels (2-20 Mg ha(-1)) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha(-1) application level of the amendments, total seasonal CH(4) emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH(4) production rates as well as total seasonal CH(4) flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens' activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH(4) emissions as well as sustaining rice productivity. PMID:19560334

  16. Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation

    SciTech Connect

    Ali, Muhammad Aslam; Lee, Chang Hoon; Kim, Sang Yoon; Kim, Pil Joo

    2009-10-15

    Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH{sub 4}) emission resulting from rice cultivation. In laboratory incubations, CH{sub 4} production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt{sup -1}), while observed CO{sub 2} production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH{sub 4} emission rates from the rice planted potted soils significantly decreased with the increasing levels (2-20 Mg ha{sup -1}) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha{sup -1} application level of the amendments, total seasonal CH{sub 4} emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH{sub 4} production rates as well as total seasonal CH{sub 4} flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens' activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH{sub 4} emissions as well as sustaining rice productivity.

  17. Photon-gated persistent spectral hole burning by electron transfer from a doped donor to an acceptor branched to a host polymer matrix

    NASA Astrophysics Data System (ADS)

    Suzuki, H.; Nishi, T.; Shimada, T.; Hiratsuka, H.

    1993-01-01

    Two-color photon-gated persistent spectral hole burning (PSHB) via donor-acceptor electron transfer is reported in systems where the acceptor, 10-chloroanthracene, was intentionally branched to a side chain of the poly(methylmethacrylate) (PMMA) host polymer while the donor, metal-free tetraphenylporphine, was dispersed in the polymer. The systems, which had an acceptor concentration of up to 10-1 M, were prepared without aggregation of the acceptor. Spectral holes were burnt in the Qx(0,0) absorption band of the donor when the systems were simultaneously irradiated with a frequency-selective excitation (duration: 500 ps; energy: 200 nJ/cm2) and a gating excitation (wavelength: 514.5 nm; duration: 33 ms; energy: 14 μJ/cm2). The difference absorption spectrum between the unburned absorption spectrum and one recorded after photon-gated PSHB has confirmed that the hole formation mechanism is donor-acceptor electron transfer from a photoexcited donor to a ground-state branched acceptor. The thermal stability of burnt holes measured with a temperature cycling experiment increased when the acceptor was branched into PMMA. The effect of acceptor branching on the PSHB characteristics is discussed with reference to those for an acceptor-doped system.

  18. Proteomic dataset of the organohalide-respiring bacterium Dehalococcoides mccartyi strain CBDB1 grown on hexachlorobenzene as electron acceptor

    PubMed Central

    Schiffmann, Christian L.; Otto, Wolfgang; Hansen, Rasmus; Nielsen, Per Halkjær; Adrian, Lorenz; Seifert, Jana; von Bergen, Martin; Jehmlich, Nico

    2016-01-01

    The proteome of the anaerobic organohalide-respiring bacterium Dehalococcoides mccartyi strain CBDB1 was analyzed by nano liquid chromatography coupled to mass spectrometry (LC-MS/MS). Two different preparation methods, (i) in-solution and (ii) in-gel proteolytic digestion were assessed to elucidate the core and the functional proteome of bacterial cultures grown in synthetic anaerobic medium with hexachlorobenzene as sole electron acceptor. A detailed analysis of the data presented is available (Schiffmann et al., 2014) [1]. PMID:26958645

  19. Proteomic dataset of the organohalide-respiring bacterium Dehalococcoides mccartyi strain CBDB1 grown on hexachlorobenzene as electron acceptor.

    PubMed

    Schiffmann, Christian L; Otto, Wolfgang; Hansen, Rasmus; Nielsen, Per Halkjær; Adrian, Lorenz; Seifert, Jana; von Bergen, Martin; Jehmlich, Nico

    2016-06-01

    The proteome of the anaerobic organohalide-respiring bacterium Dehalococcoides mccartyi strain CBDB1 was analyzed by nano liquid chromatography coupled to mass spectrometry (LC-MS/MS). Two different preparation methods, (i) in-solution and (ii) in-gel proteolytic digestion were assessed to elucidate the core and the functional proteome of bacterial cultures grown in synthetic anaerobic medium with hexachlorobenzene as sole electron acceptor. A detailed analysis of the data presented is available (Schiffmann et al., 2014) [1]. PMID:26958645

  20. Modeling the Effect of External Carbon Source Addition under Different Electron Acceptor Conditions in Biological Nutrient Removal Activated Sludge Systems.

    PubMed

    Hu, Xiang; Wisniewski, Kamil; Czerwionka, Krzysztof; Zhou, Qi; Xie, Li; Makinia, Jacek

    2016-02-16

    The aim of this study was to expand the International Water Association Activated Sludge Model No. 2d (ASM2d) to predict the aerobic/anoxic behavior of polyphosphate accumulating organisms (PAOs) and "ordinary" heterotrophs in the presence of different external carbon sources and electron acceptors. The following new aspects were considered: (1) a new type of the readily biodegradable substrate, not available for the anaerobic activity of PAOs, (2) nitrite as an electron acceptor, and (3) acclimation of "ordinary" heterotrophs to the new external substrate via enzyme synthesis. The expanded model incorporated 30 new or modified process rate equations. The model was evaluated against data from several, especially designed laboratory experiments which focused on the combined effects of different types of external carbon sources (acetate, ethanol and fusel oil) and electron acceptors (dissolved oxygen, nitrate and nitrite) on the behavior of PAOs and "ordinary" heterotrophs. With the proposed expansions, it was possible to improve some deficiencies of the ASM2d in predicting the behavior of biological nutrient removal (BNR) systems with the addition of external carbon sources, including the effect of acclimation to the new carbon source. PMID:26783836

  1. Existence of a new type of sulfite oxidase which utilizes ferric ions as an electron acceptor in Thiobacillus ferrooxidans

    SciTech Connect

    Sugio, T.; Katagiri, T.; Moriyama, M.; Zhen, Y.L.; Inagaki, K.; Tano, T.

    1988-01-01

    A new type of sulfite oxidase which utilizes ferric ion (Fe/sup 3 +/) as an electron acceptor was found in iron-grown Thiobacillus ferrooxidans. It was localized in the plasma membrane of the bacterium and had a pH optimum at 6.0. Under aerobic conditions, 1 mol of sulfite was oxidized by the enzyme to produce 1 mol of sulfate. Under anaerobic conditions in the presence of Fe/sup 3 +/, sulfite was oxidized by the enzyme as rapidly as it was under aerobic conditions. In the presence of o-phenanthroline or a chelator for Fe/sup 2 +/, the production of Fe/sup 2 +/ was observed during sulfite oxidation by this enzyme under not only anaerobic conditions but also aerobic conditions. No Fe/sup 2 +/ production was observed in the absence of o-phenanthroline, suggesting that the Fe/sup 2 +/ produced was rapidly reoxidized by molecular oxygen. Neither cytochrome c nor ferricyanide, both of which are electron acceptors for other sulfite oxidases, served as an electron acceptor for the sulfite oxidase of T. ferrooxidans. The enzyme was strongly inhibited by chelating agents for Fe/sup 3 +/. The physiological role of sulfite oxidase in sulfur oxidation of T. ferrooxidans is discussed.

  2. Effects of the acceptor unit in dyes with acceptor-bridge-donor architecture on the electron photo-injection mechanism and aggregation in DSSCs.

    PubMed

    Zarate, Ximena; Claveria-Cadiz, Francisca; Arias-Olivares, David; Rodriguez-Serrano, Angela; Inostroza, Natalia; Schott, Eduardo

    2016-09-21

    Dye-sensitized solar cells (DSSCs) are devices that convert light to electrical energy. Nowadays, researchers have focused on the understanding of the performance of dyes in solar cells. In this way, new efficient dyes have been obtained which can act as efficient light-harvesting compounds where the combination and the balance of acceptor(A)-bridge-donor(D) architectures confer suitable attributes and properties to the dye. Herein, we have carried out a DFT study on the optical and electronic properties of eight different A motifs and their influence on the electron photo-injection (PI) mechanisms through type I (indirect) or type II (direct) pathways in A-bridge-D dyes in DSSCs. The models consisted of thiophene as a bridge and triphenylamine as a D anchored to a TiO2 anatase cluster. All geometry optimizations were calculated using the B3LYP, CAM-B3LYP and BHandHLYP functionals combined with the 6-31G(d,p) basis set for C, H, N, O and S and the LANL2DZ pseudopotential for Ti atoms. Most of the A dyes display optoelectronic properties consistent with a type-I (indirect) mechanism except for the A5 dye where the results suggest a type-II (direct) PI pathway. In addition, molecular dynamics (MD) simulations have been carried out in order to describe the formation of dye dimers and analyze the stability of the aggregates due to intermolecular interactions. The observed trends indicate that dyes with A2 and A5 anchoring groups have less tendency to dimerize due to weaker intermolecular interactions resulting in less stable dimer complexes. Specifically, we found that the A motif influences the PI by a dye and the dimerization profiles. PMID:27530076

  3. Pristine reduced graphene oxide as an energy-matched auxiliary electron acceptor in nanoarchitectural metal oxide/poly(3-hexylthiophene) hybrid solar cell

    NASA Astrophysics Data System (ADS)

    Cho, Hsun-Wei; Liao, Wen-Pin; Lin, Wan-Hsien; Yoshimura, Masahiro; Wu, Jih-Jen

    2015-10-01

    In this work, pristine reduced graphene oxide (RGO) sheets are added in the nanoarchitectural TiO2 nanorod (NR)-ZnO nanoparticle (NP)/P3HT hybrid polymer solar cells. With the addition of RGOs, the enhancement of the charge separation and the decrease of the electron lifetime in the nanoarchitectural metal oxide/P3HT hybrid are determined by time-resolved photoluminescence (TRPL) and impedance spectroscopy, respectively. The photovoltaic performance of the hybrid solar cell is therefore optimized by an appropriate addition of RGOs in the active layer. Moreover, intensity modulation of photocurrent spectroscopy measurements indicate that the electron transport rates in the hybrid solar cells are improved as adding RGOs in the active layer. Energy matching among P3HT, RGOs, and ZnO NPs is demonstrated in the TiO2 NR-ZnO NP/RGO/P3HT hybrid solar cell. It is respectively confirmed by TRPL and Kelvin probe force microscopy measurements that electron transfers occur effectively from P3HT to RGOs and from RGOs to ZnO NPs in the active layer. The pristine RGOs are concluded to be an energy-matched auxiliary electron acceptor in the nanoarchitectural metal-oxide/P3HT hybrid solar cell. An efficiency of 3.79% is achieved in the RGO-incorporated nanoarchitectural metal oxide/P3HT hybrid solar cell fabricated free of interfacial modification using the 900 nm-thick TiO2 NR array.

  4. 2004 Electron Donor Acceptor Interactions Gordon Conference - August 8-13, 2004

    SciTech Connect

    GUILFORD JONES BOSTON UNIVERSITY PHOTONICS CENTER 8 ST. MARY'S ST BOSTON, MA 02215

    2005-09-14

    The 2004 Gordon Conference on Donor/Acceptor Interactions will take place at Salve Regina University in Newport, Rhode Island on August 8-13, 2004. The conference will be devoted to the consequences of charge interaction and charge motion in molecular and materials systems.

  5. Transcriptional analysis of Shewanella oneidensis MR-1 with an electrode compared to Fe(III)citrate or oxygen as terminal electron acceptor

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Background. Shewanella oneidensis is a target of extensive research efforts in the fields of bioelectrochemical systems and bioremediation because of its versatile metabolic capabilities, especially in regards to the respiration with extracellular electron acceptors. Here, we took a global approach ...

  6. Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis.

    PubMed

    Chen, Hung-Cheng; Hsu, Chao-Ping; Reek, Joost N H; Williams, René M; Brouwer, Albert M

    2015-11-01

    A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300-500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered =-0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2 O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2 =39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10(-2) ∼10(-1) cm(2) V(-1) s(-1)) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells. PMID:26395847

  7. Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis

    PubMed Central

    Chen, Hung-Cheng; Hsu, Chao-Ping; Reek, Joost N H; Williams, René M; Brouwer, Albert M

    2015-01-01

    A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300–500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered=−0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2=39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10−2∼10−1 cm2 V−1 s−1) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells. PMID:26395847

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

    PubMed

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

    2016-08-21

    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. PMID:27305145

  9. Covalently Bound Clusters of Alpha-Substituted PDI-Rival Electron Acceptors to Fullerene for Organic Solar Cells.

    PubMed

    Wu, Qinghe; Zhao, Donglin; Schneider, Alexander M; Chen, Wei; Yu, Luping

    2016-06-15

    A cluster type of electron acceptor, TPB, bearing four α-perylenediimides (PDIs), was developed, in which the four PDIs form a cross-like molecular conformation while still partially conjugated with the BDT-Th core. The blend TPB:PTB7-Th films show favorable morphology and efficient charge dissociation. The inverted solar cells exhibited the highest PCE of 8.47% with the extraordinarily high Jsc values (>18 mA/cm(2)), comparable with those of the corresponding PC71BM/PTB7-Th-based solar cells. PMID:27219665

  10. Photoinitiated Charge Transport through π-Stacked Electron Conduits in Supramolecular Ordered Assemblies of Donor−Acceptor Triads

    SciTech Connect

    Bullock, Joseph E.; Carmieli, Raanan; Mickley, Sarah M.; Vura-Weis, Josh; Wasielewski, Michael R.

    2009-09-25

    Photochemical electron donor-acceptor triads having an aminopyrene primary donor (APy) and a p-diaminobenzene secondary donor (DAB) attached to either one or both imide nitrogen atoms of a perylene-3,4:9,10-bis(dicarboximide) (PDI) electron acceptor were prepared to give DAB-APy-PDI and DAB-APy-PDI-APy-DAB. In toluene, both triads are monomeric, but in methylcyclohexane, they self-assemble into ordered helical heptamers and hexamers, respectively, in which the PDI molecules are {pi}-stacked in a columnar fashion, as evidenced by small- and wide-angle X-ray scattering. Photoexcitation of these supramolecular assemblies results in rapid formation of DAB{sup +}-PDI{sup -} spin-polarized radical ion pairs having spin-spin dipolar interactions, which show that the average distance between the two radical ions is much larger in the assemblies (31 {angstrom}) than it is in their monomeric building blocks (23 {angstrom}). This work demonstrates that electron hopping through the {pi}-stacked PDI molecules is fast enough to compete effectively with charge recombination (40 ns) in these systems, making these materials of interest as photoactive assemblies for artificial photosynthesis and organic photovoltaics.

  11. Charge-transfer complex versus σ-complex formed between TiO2 and bis(dicyanomethylene) electron acceptors.

    PubMed

    Fujisawa, Jun-ichi; Nagata, Morio; Hanaya, Minoru

    2015-11-01

    A novel group of organic-inorganic hybrid materials is created by the combination of titanium dioxide (TiO2) nanoparticles with bis(dicyanomethylene) (TCNX) electron acceptors. The TiO2-TCNX complex is produced by the nucleophilic addition reaction between a hydroxy group on the TiO2 surface and TCNX, with the formation of a σ-bond between them. The nucleophilic addition reaction generates a negatively-charged diamagnetic TCNX adsorbate that serves as an electron donor. The σ-bonded complex characteristically shows visible-light absorption due to interfacial charge-transfer (ICT) transitions. In this paper, we report on another kind of complex formation between TiO2 and TCNX. We have systematically studied the structures and visible-light absorption properties of the TiO2-TCNX complexes, with changing the electron affinity of TCNX. We found that TCNX acceptors with lower electron affinities form charge-transfer complexes with TiO2 without the σ-bond formation. The charge-transfer complexes show strong visible-light absorption due to interfacial electronic transitions with little charge-transfer nature, which are different from the ICT transitions in the σ-bond complexes. The charge-transfer complexes induce efficient light-to-current conversions due to the interfacial electronic transitions, revealing the high potential for applications to light-energy conversions. Furthermore, we demonstrate that the formation of the two kinds of complexes is selectively controlled by the electron affinity of TCNX. PMID:26418266

  12. Ultrafast Photoinduced Electron Transfer and Charge Stabilization in Donor-Acceptor Dyads Capable of Harvesting Near-Infrared Light.

    PubMed

    Bandi, Venugopal; Gobeze, Habtom B; D'Souza, Francis

    2015-08-01

    To harvest energy from the near-infrared (near-IR) and infrared (IR) regions of the electromagnetic spectrum, which constitutes nearly 70 % of the solar radiation, there is a great demand for near-IR and IR light-absorbing sensitizers that are capable of undergoing ultrafast photoinduced electron transfer when connected to a suitable electron acceptor. Towards achieving this goal, in the present study, we report multistep syntheses of dyads derived from structurally modified BF2-chelated azadipyrromethene (ADP; to extend absorption and emission into the near-IR region) and fullerene as electron-donor and electron-acceptor entities, respectively. The newly synthesized dyads were fully characterized based on optical absorbance, fluorescence, geometry optimization, and electrochemical studies. The established energy level diagram revealed the possibility of electron transfer either from the singlet excited near-IR sensitizer or singlet excited fullerene. Femtosecond and nanosecond transient absorption studies were performed to gather evidence of excited state electron transfer and to evaluate the kinetics of charge separation and charge recombination processes. These studies revealed the occurrence of ultrafast photoinduced electron transfer leading to charge stabilization in the dyads, and populating the triplet states of ADP, benzanulated-ADP and benzanulated thiophene-ADP in the respective dyads, and triplet state of C60 in the case of BF2 -chelated dipyrromethene derived dyad during charge recombination. The present findings reveal that these sensitizers are suitable for harvesting light energy from the near-IR region of the solar spectrum and for building fast-responding optoelectronic devices operating under near-IR radiation input. PMID:26130432

  13. Asymmetric electron transfer in cyanobacterial Photosystem I: charge separation and secondary electron transfer dynamics of mutations near the primary electron acceptor A0.

    PubMed

    Dashdorj, Naranbaatar; Xu, Wu; Cohen, Rachel O; Golbeck, John H; Savikhin, Sergei

    2005-02-01

    Point mutations were introduced near the primary electron acceptor sites assigned to A0 in both the PsaA and PsaB branches of Photosystem I in the cyanobacterium Synechocystis sp. PCC 6803. The residues Met688PsaA and Met668PsaB, which provide the axial ligands to the Mg2+ of the eC-A3 and eC-B3 chlorophylls, were changed to leucine and asparagine (chlorophyll notation follows Jordan et al., 2001). The removal of the ligand is expected to alter the midpoint potential of the A0/A0- redox pair and result in a change in the intrinsic charge separation rate and secondary electron transfer kinetics from A0- to A1. The dynamics of primary charge separation and secondary electron transfer were studied at 690 nm and 390 nm in these mutants by ultrafast optical pump-probe spectroscopy. The data reveal that mutations in the PsaB branch do not alter electron transfer dynamics, whereas mutations in the PsaA branch have a distinct effect on electron transfer, slowing down both the primary charge separation and the secondary electron transfer step (the latter by a factor of 3-10). These results suggest that electron transfer in cyanobacterial Photosystem I is asymmetric and occurs primarily along the PsaA branch of cofactors. PMID:15542554

  14. Thermally activated delayed fluorescence evidence in non-bonding transition electron donor-acceptor molecules

    NASA Astrophysics Data System (ADS)

    Marghad, Ikbal; Clochard, M. C.; Ollier, N.; Wade, Travis L.; Aymes-Chodur, C.; Renaud, C.; Zissis, G.

    2015-09-01

    The exhibition of thermally activated delayed fluorescence on triazine derivative by the introduction of a nonbonding part is demonstrated. Two molecules containing triazine core as acceptor and carbazole part as donor has been synthesized and characterized. One of these molecules bears an additional nonbonding part by the means of a phenoxy group. The results indicated that the molecule bearing the nonbonding molecular part (phenoxy) exhibit thermally activated delayed fluorescence while not on molecule free of non-bonding group. The results are supported by, photoluminescence, spectral analysis time-resolved fluorescence and time-dependent density functional estimation

  15. Electron Transfer within Self-Assembling Cyclic Tetramers Using Chlorophyll-Based Donor-Acceptor Building Blocks

    SciTech Connect

    Gunderson, Victoria L; Smeigh, Amanda L; Kim, Chul Hoon; Co, Dick T; Wasielewski, Michael R

    2012-05-09

    The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI2. The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from 1*Chl to PI to form Chl+.-PI-.-NDI and Chl+.-PI-.-NDI2. This initial charge separation is followed by a rapid charge shift from PI-. to NDI and subsequent charge recombination of Chl+.-PI-NDI-. and Chl+.-PI-(NDI)NDI-. on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI2 cyclic tetramer (τCR = 30 ± 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks (τCR = 10 ± 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems.

  16. Intramolecular electron transfer in fullerene/ferrocene based donor-bridge-acceptor dyads

    SciTech Connect

    Guldi, D.M.; Maggini, M.; Scorrano, G.; Prato, M.

    1997-02-05

    A systematic steady-state fluorescence and time-resolved flash photolytic investigation of a series of covalently linked fullerene/ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the spacer between the donor site (ferrocene) and acceptor site (fullerene) and the dielectric constant of the medium. The fluorescence of the investigated dyads 2, 3, 4, 5, and 6 in methylcyclohexane at 77 K were substantially quenched, relative to N-methylfulleropyrrolidine 1, indicating intramolecular quenching of the fullerene excited singlet state. Excitation of N-methylfulleropyrrolidine revealed the immediate formation of the excited singlet state, with {lambda}{sub max} around 886 nm. A rapid intersystem crossing ({tau}{sub 1/2} = 1.2 ps ) to the excited triplet state was observed with characteristic absorption around 705 nm. Picosecond resolved photolysis of dyads 2-6 in toluene showed light-induced formation of the excited singlet state which undergoes rapid intramolecular quenching. Nanosecond-resolved photolysis of dyads 3 and 4 in degassed benzonitrile revealed long-lived charge separated states with characteristic fullerene radical-anion bands at {lambda}{sub max} = 1055 nm. 30 refs., 5 figs., 3 tabs.

  17. Charge-transfer complexes formed in the reaction of 2-amino-4-ethylpyridine with π-electron acceptors

    NASA Astrophysics Data System (ADS)

    AlQaradawi, Siham Y.; Mostafa, Adel; Bengali, A. A.

    2016-02-01

    Molecular charge-transfer complexes (CT) of electron donor 2-amino-4-ethylpyridine (2A4EPy) with π-acceptors tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) have been studied spectrophotometrically in chloroform at 25 °C. These were investigated through electronic, infrared, mass spectra and thermal measurements as well as elemental analysis. All formed complexes exhibit well resolved charge-transfer bands in the regions where neither donor nor acceptors have any absorption. The obtained results show that the formed solid CT-complexes have the structures [(2A4EPy)(TCNE)2], [(2A4EPy)2(DDQ)] and [(2A4EPy)2(TBCHD)] for 2-amino-4-ethylpyridine in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements. The formation constant KCT, molar extinction coefficient εC.T, free energy change ΔG0, CT energy ECT, ionization potential Ip and oscillator strength ƒ have been calculated for these three CT-complexes.

  18. Synthesis of an A-D-A type of molecule used as electron acceptor for improving charge transfer in organic solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Chao-Zhi; Gu, Shu-Duo; Shen, Dan; Yuan, Yang; Zhang, Mingdao

    2016-08-01

    Electron-accepting molecules play an important role in developing organic solar cells. A new type of A-D-A molecule, 3,6-di([7-(5-bromothiophen-2-yl)-1,5,2,4,6,8-dithiotetrazocin-3-yl]thiophen-2-yl)-9-(2-ethylhexyl)carbazole, was synthesized. The lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels are -3.55 and -5.85 eV, respectively. Therefore, the A-D-A type of compound could be used as electron acceptor for fabricating organic solar cell with a high open circuit voltage. Gibbs free energy (-49.2 kJ/mol) reveals that the process of A-D-A acceptor accepting an electron from poly(3-hexylthiophene) at excited state is spontaneous. The value of entropy (118 J/mol) in the process of an electron transferring from P3HT to the A-D-A acceptor at organic interface suggests that electrons generated from separation of electron-hole pairs at donor/acceptor interface would be delocalized efficiently. Therefore, the A-D-A molecule would be a potential acceptor for efficient organic BHJ solar cells.

  19. Effects of electron acceptors on removal of antibiotic resistant Escherichia coli, resistance genes and class 1 integrons under anaerobic conditions.

    PubMed

    Yuan, Heyang; Miller, Jennifer H; Abu-Reesh, Ibrahim M; Pruden, Amy; He, Zhen

    2016-11-01

    Anaerobic biotechnologies can effectively remove antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs), but there is a need to better understand the mechanisms. Here we employ bioelectrochemical systems (BES) as a platform to investigate the fate of a native tetracycline and sulfonamide-resistant Escherichia coli strain and its ARGs. The E. coli strain carrying intI1, sulI and tet(E) was isolated from domestic wastewater and dosed into a tubular BES. The BES was first operated as a microbial fuel cell (MFC), with aeration in the cathode, which resulted in enhanced removal of E. coli and ARGs by ~2 log (i.e., order of magnitude) when switched from high current to open circuit operation mode. The BES was then operated as a microbial electrolysis cell (MEC) to exclude the effects of oxygen diffusion, and the removal of E. coli and ARGs during the open circuit configuration was again 1-2 log higher than that at high current mode. Significant correlations of E. coli vs. current (R(2)=0.73) and ARGs vs. E. coli (R(2) ranged from 0.54 to 0.87), and the fact that the BES substrate contained no electron acceptors, implied that the persistence of the E. coli and its ARGs was determined by the availability of indigenous electron acceptors in the BES, i.e., the anode electrode or the electron shuttles generated by the exoelectrogens. Subsequent experiments with pure-culture tetracycline and sulfonamide-resistant E. coli being incubated in a two-chamber MEC and serum bottles demonstrated that the E. coli could survive by respiring anode electrode and/or electron shuttles released by exoelectrogens, and ARGs persisted with their host E. coli. PMID:27450245

  20. Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors.

    PubMed

    Coe, Benjamin J; Harries, Josephine L; Helliwell, Madeleine; Brunschwig, Bruce S; Harris, James A; Asselberghs, Inge; Hung, Sheng-Ting; Clays, Koen; Horton, Peter N; Hursthouse, Michael B

    2006-02-01

    We have prepared a number of new dipolar complexes containing ethynyl or buta-1,3-diynyl units linking electron-rich {Ru(II)(NH3)5}2+, trans-{Ru(II)(NH3)4L}+ (L = pyridine or N-methylimidazole), or trans-{Ru(II)Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers to pyridinium electron acceptors. In acetonitrile solutions at 295 K, the new complexes display unusual blue-shifting of their metal-to-ligand charge-transfer (MLCT) bands as the conjugation is extended, in a fashion similar to that of the corresponding ethenyl systems. Hyper-Rayleigh scattering (HRS) and Stark spectroscopic measurements provide direct and indirect estimates of static first hyperpolarizabilities beta0, and both the linear and nonlinear optical (NLO) properties are temperature- and medium-dependent. Thus, at 77 K in butyronitrile glasses, the MLCT bands display more normal red shifts upon conjugation extension. While the Stark-derived beta0 values generally increase as n (the number of ethynyl units) increases from 0 to 2, the HRS data show maximization at n = 1 for two of the ammine series but an increase upon moving from n = 1 to 2 for the pdma complexes. Comparisons with the analogous ethenyl chromophores show that the latter generally display larger beta0 values, whether determined via HRS or Stark data, and the inferiority of the ethynyl systems in terms of NLO response is more pronounced when n = 2. This differing behavior is attributable primarily to larger increases in the transition dipole moment mu12 (and, hence, donor-acceptor pi-electronic coupling) on elongation in the ethenyl chromophores. PMID:16441133

  1. 2008 Electron Donor Acceptor Interactions Gordon Research Conference-August 3-8, 2009

    SciTech Connect

    Malcolm Forbes and Nancy Ryan Gray

    2009-09-19

    The conference presents and advances the current frontiers in experimental and theoretical studies of Electron Transfer and Transport in Molecular and Nano-scale Systems. The program includes sessions on coupled electron transfers, molecular solar energy conversion, biological and biomimetic systems, spin effects, ultrafast reactions and technical frontiers as well as electron transport in single molecules and devices.

  2. 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

  3. Temperature dependent electron spin echo studies of polarons in donor- and acceptor-doped poly(p-phenylene): Structural studies

    SciTech Connect

    Kispert, L.D.; Joseph, J.; Tang, J.; Bowman, M.K.; Van Brakel, G.H.; Norris, J.R.

    1986-06-06

    Electron spin echo (ESE) measurements of donor-doped (Li, Na, K and Cs) and acceptor-doped (AsF/sub 5/) poly(p-phenylene), PPP, and fully deuterated PPP samples predict a temperature independent EPR linewidth equal to less than 0.65 gauss that decreases with increasing conductivity. In contrast, EPR linewidths either decrease or increase with decreasing temperature, are dependent on dopant and always exhibit a linewidth either equal to or larger than that predicted from ESE measurements. Deuteration studies indicate that rapid spin exchange is present. Analysis of these results suggest that an exchange exists between isolated radicals in equilibrium with polarons and bipolarons with the equilibrium in favor of bipolarons at 4 K.

  4. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules II: Non-Empirically Tuned Long-Range Corrected Hybrid Functionals.

    PubMed

    Gallandi, Lukas; Marom, Noa; Rinke, Patrick; Körzdörfer, Thomas

    2016-02-01

    The performance of non-empirically tuned long-range corrected hybrid functionals for the prediction of vertical ionization potentials (IPs) and electron affinities (EAs) is assessed for a set of 24 organic acceptor molecules. Basis set-extrapolated coupled cluster singles, doubles, and perturbative triples [CCSD(T)] calculations serve as a reference for this study. Compared to standard exchange-correlation functionals, tuned long-range corrected hybrid functionals produce highly reliable results for vertical IPs and EAs, yielding mean absolute errors on par with computationally more demanding GW calculations. In particular, it is demonstrated that long-range corrected hybrid functionals serve as ideal starting points for non-self-consistent GW calculations. PMID:26731340

  5. Competition between Methane and Alkylbenzenes for Electron Acceptors during Natural Attenuation of Crude Oil in the Subsurface

    NASA Astrophysics Data System (ADS)

    Bekins, B. A.; Amos, R. T.; Cozzarelli, I.; Voytek, M. A.

    2009-12-01

    At a crude-oil spill site near the town of Bemidji, MN, entrapped oil is present at residual saturations exceeding 10% in the vadose zone and floating at the water table at saturations of 30-60%. The degradable fraction of the light crude oil includes n-alkanes, aromatics, and alkyl-cyclohexanes. Together these compounds constitute a reduced carbon concentration at least 500 times greater than is present in the dissolved hydrocarbon groundwater plume comprised mainly of aromatics. Methanogenic degradation of the stationary oil body has been occurring for at least 20 years providing a continuous supply of methane emanating from the oil. Transport of methane away from the oil body occurs in both the vapor phase through the vadose zone and in the dissolved phase with the groundwater flow. Within the vadose zone the supply of oxygen and other electron acceptors from the surface is completely consumed by the process of methane oxidation in a zone 2-3 meters above the water table. In the groundwater, the 1 ppm contour of the methane plume extends beyond the 0.5 ppb contour for benzene, which is located at the aerobic/anaerobic boundary in the plume approximately 120 m downgradient of the oil body. Between 75 m and 120 m downgradient, methane concentrations decrease steadily from >0.6 mmol/L to <0.06 mmol/L, accompanied by increases in the δ13C-CH4 indicating that methane attenuation occurs through microbially-mediated oxidation. Anaerobic methane oxidation under iron-reducing conditions has recently been demonstrated by Beal et al. (Science, 325, 184, 2009) and is indicated at this site by several lines of evidence. In the methane oxidation zone, values of bioavailable Fe(III) extracted from the sediments averaged 8 mmol/kg (n=16), or >8 times the amount required to degrade 0.5 mmol methane, while all other electron acceptors together can account for complete oxidation of only 0.07 mmol (sulfate <0.06 mmol/L, dissolved oxygen <3 µmol/L, and nitrate <0.02 mmol

  6. Comparison of approaches for simulating reactive solute transport involving organic degradation reactions by multiple terminal electron acceptors

    USGS Publications Warehouse

    Curtis, G.P.

    2003-01-01

    Reactive solute transport models are useful tools for analyzing complex geochemical behavior resulting from biodegradation of organic compounds by multiple terminal electron acceptors (TEAPs). The usual approach of simulating the reactions of multiple TEAPs by an irreversible Monod rate law was compared with simulations that assumed a partial local equilibrium or kinetically controlled reactions subject to the requirement that the Gibbs free energy of reaction (?? G) was either less than zero or less than a threshold value. Simulations were performed using a single organic substrate and O2, FeOOH, SO4-2 and CO2 as the terminal electron acceptors. It was assumed that the organic substrate was slowly and completely fermented to CO2 and H2 and the H2 was oxidized by the TEAPs. Simulations using the Monod approach showed that this irreversible rate law forced the reduction of both FeOOH and CO2 to proceed even when ?? G was positive. This resulted in an over prediction in amount of FeOOH reduced to Fe(II) in parts of the domain and it resulted in large errors in pH. Simulations using mass action kinetics agreed with equilibrium simulations for the case of large rate constants. The extent of reductive dissolution of FeOOH was strongly dependent on the thermodynamic stability of the FeOOH phase. Transport simulations performed assuming that the reactions of the TEAPs stopped when ?? G exceeded a threshold value showed that only simulated H2 concentrations were affected if the threshold value was the same for each TEAP. Simulated H2 concentrations were controlled by the fastest reaction of the TEAP, but it was common for reactions to occur concomitantly rather than sequentially. ?? 2003. Published by Elsevier Science Ltd.

  7. Microbial Community Succession during Lactate Amendment and Electron Acceptor Limitation Reveals a Predominance of Metal-Reducing Pelosinus spp.

    PubMed Central

    Mosher, Jennifer J.; Phelps, Tommy J.; Podar, Mircea; Hurt, Richard A.; Campbell, James H.; Drake, Meghan M.; Moberly, James G.; Schadt, Christopher W.; Brown, Steven D.; Hazen, Terry C.; Arkin, Adam P.; Palumbo, Anthony V.; Faybishenko, Boris A.

    2012-01-01

    The determination of the success of in situ bioremediation strategies is complex. By using controlled laboratory conditions, the influence of individual variables, such as U(VI), Cr(VI), and electron donors and acceptors on community structure, dynamics, and the metal-reducing potential can be studied. Triplicate anaerobic, continuous-flow reactors were inoculated with Cr(VI)-contaminated groundwater from the Hanford, WA, 100-H area, amended with lactate, and incubated for 95 days to obtain stable, enriched communities. The reactors were kept anaerobic with N2 gas (9 ml/min) flushing the headspace and were fed a defined medium amended with 30 mM lactate and 0.05 mM sulfate with a 48-h generation time. The resultant diversity decreased from 63 genera within 12 phyla to 11 bacterial genera (from 3 phyla) and 2 archaeal genera (from 1 phylum). Final communities were dominated by Pelosinus spp. and to a lesser degree, Acetobacterium spp., with low levels of other organisms, including methanogens. Four new strains of Pelosinus were isolated, with 3 strains being capable of Cr(VI) reduction while one also reduced U(VI). Under limited sulfate, it appeared that the sulfate reducers, including Desulfovibrio spp., were outcompeted. These results suggest that during times of electron acceptor limitation in situ, organisms such as Pelosinus spp. may outcompete the more-well-studied organisms while maintaining overall metal reduction rates and extents. Finally, lab-scale simulations can test new strategies on a smaller scale while facilitating community member isolation, so that a deeper understanding of community metabolism can be revealed. PMID:22267668

  8. Protein sequences and redox titrations indicate that the electron acceptors in reaction centers from heliobacteria are similar to Photosystem I

    NASA Technical Reports Server (NTRS)

    Trost, J. T.; Brune, D. C.; Blankenship, R. E.

    1992-01-01

    Photosynthetic reaction centers isolated from Heliobacillus mobilis exhibit a single major protein on SDS-PAGE of 47 000 Mr. Attempts to sequence the reaction center polypeptide indicated that the N-terminus is blocked. After enzymatic and chemical cleavage, four peptide fragments were sequenced from the Heliobacillus mobilis apoprotein. Only one of these sequences showed significant specific similarity to any of the protein and deduced protein sequences in the GenBank data base. This fragment is identical with 56% of the residues, including both cysteines, found in highly conserved region that is proposed to bind iron-sulfur center Fx in the Photosystem I reaction center peptide that is the psaB gene product. The similarity to the psaA gene product in this region is 48%. Redox titrations of laser-flash-induced photobleaching with millisecond decay kinetics on isolated reaction centers from Heliobacterium gestii indicate a midpoint potential of -414 mV with n = 2 titration behavior. In membranes, the behavior is intermediate between n = 1 and n = 2, and the apparent midpoint potential is -444 mV. This is compared to the behavior in Photosystem I, where the intermediate electron acceptor A1, thought to be a phylloquinone molecule, has been proposed to undergo a double reduction at low redox potentials in the presence of viologen redox mediators. These results strongly suggest that the acceptor side electron transfer system in reaction centers from heliobacteria is indeed analogous to that found in Photosystem I. The sequence similarities indicate that the divergence of the heliobacteria from the Photosystem I line occurred before the gene duplication and subsequent divergence that lead to the heterodimeric protein core of the Photosystem I reaction center.

  9. Quantum dynamics of charge carriers in donor-bridge-acceptor molecular segments with applications to molecular electronics

    NASA Astrophysics Data System (ADS)

    Gayen, Taposh Kumar

    1998-11-01

    The theory of electron transfer (ET) is important toward understanding the physics and process technology of electronic devices at the atomic and molecular scale. Computer simulation of ID model Hamiltonians has proven to be an effective method to study the ET processes in molecular electronic devices. In this thesis, we present our findings on electron transfer rate (ETR) in model molecular quantum wire (MQW) and donor-bridge-acceptor (DBA) molecular chain systems as our ID electron systems. In this thesis, we show that our trigonometric imaging method (TIM) is an excellent approach to calculating ETR both in MQW and DBA chain systems. First, we report the results on ETR using exact formulas for MQW and DBA chain systems without any nonlinear interactions and find that these results are the same as those obtained by TIM. We introduce a graphical approach to get time derivatives as necessary data for TIM to study the nonlinear effects, electron-phonon (e-p) and electron-electron (e-e) interactions, on ETR in a MQW. We show that time derivatives obtained by the graphical approach are the same as those obtained exactly in the case of e-p interactions. We conclusively report using both the exact and TIM results that e-p interactions enhance ETR in a MQW. Our research on nonlinear interactions also shows that temperature enhances ETR in a model MQW. Using TIM, we report that e-e interactions have virtually no effect on ETR in a MQW, where the data for TIM are obtained by the graphical approach.

  10. Electron and hole polaron accumulation in low-bandgap ambipolar donor-acceptor polymer transistors imaged by infrared microscopy

    NASA Astrophysics Data System (ADS)

    Khatib, O.; Mueller, A. S.; Stinson, H. T.; Yuen, J. D.; Heeger, A. J.; Basov, D. N.

    2014-12-01

    A resurgence in the use of the donor-acceptor approach in synthesizing conjugated polymers has resulted in a family of high-mobility ambipolar systems with exceptionally narrow energy bandgaps below 1 eV. The ability to transport both electrons and holes is critical for device applications such as organic light-emitting diodes and transistors. Infrared spectroscopy offers direct access to the low-energy excitations associated with injected charge carriers. Here we use a diffraction-limited IR microscope to probe the spectroscopic signatures of electron and hole injection in the conduction channel of an organic field-effect transistor based on an ambipolar DA polymer polydiketopyrrolopyrrole-benzobisthiadiazole. We observe distinct polaronic absorptions for both electrons and holes and spatially map the carrier distribution from the source to drain electrodes for both unipolar and ambipolar biasing regimes. For ambipolar device configurations, we observe the spatial evolution of hole-induced to electron-induced polaron absorptions throughout the transport path. Our work provides a platform for combined transport and infrared studies of organic semiconductors on micron length scales relevant to functional devices.

  11. Microscopic simulations of electronic excitations in donor-acceptor heterojunctions of small-molecule based solar cells

    NASA Astrophysics Data System (ADS)

    Baumeier, Bjoern

    2015-03-01

    Fundamental processes involving electronic excitations govern the functionality of molecular materials in which the dynamics of excitons and charges is determined by an interplay of molecular electronic structure and morphological order. To understand, e.g., charge separation and recombination at donor-acceptor heterojunctions in organic solar cells, knowledge about the microscopic details influencing these dynamics in the bulk and across the interface is required. For a set of prototypical heterojunctions of small-molecule donor materials with C60, we employ a hybrid QM/MM approach linking density-functional and many-body Green's functions theory and analyze the charged and neutral electronic excitations therein. We pay special attention the spatially-resolved electron/hole transport levels, as well as the relative energies of Frenkel and charge-transfer excitations at the interface. Finally, we link the molecular architecture of the donor material, its orientation on the fullerene substrate as well as mesoscale order to the solar cell performance.

  12. Ultrafast static and diffusion-controlled electron transfer at Ag29 nanocluster/molecular acceptor interfaces.

    PubMed

    Aly, Shawkat M; AbdulHalim, Lina G; Besong, Tabot M D; Soldan, Giada; Bakr, Osman M; Mohammed, Omar F

    2016-03-14

    Efficient absorption of visible light and a long-lived excited state lifetime of silver nanoclusters (Ag29 NCs) are integral properties for these new clusters to serve as light-harvesting materials. Upon optical excitation, electron injection at Ag29 NC/methyl viologen (MV(2+)) interfaces is very efficient and ultrafast. Interestingly, our femto- and nanosecond time-resolved results demonstrate clearly that both dynamic and static electron transfer mechanisms are involved in photoluminescence quenching of Ag29 NCs. PMID:26548942

  13. Single substitutional nitrogen defects revealed as electron acceptor states in diamond using ultrafast spectroscopy

    NASA Astrophysics Data System (ADS)

    Ulbricht, R.; van der Post, S. T.; Goss, J. P.; Briddon, P. R.; Jones, R.; Khan, R. U. A.; Bonn, M.

    2011-10-01

    We report on the carrier dynamics and recombination pathways of photogenerated electrons in type Ib synthetic diamond using ultrafast spectroscopic techniques. Samples with controlled amounts of nitrogen defects were grown using the high-pressure high-temperature (HPHT) method. Electrons were excited from single substitutional nitrogen defects into the conduction band via an ultrashort pulse from a frequency-doubled Ti-sapphire laser. Using time-resolved terahertz time-domain spectroscopy, we determined the mobility of the photoexcited electrons and monitored their recombination dynamics, at temperatures ranging from cryogenic temperatures to room temperature. The electron mobility was observed to be limited by scattering with neutral nitrogen impurity defects (Ns0). Electrons were observed to predominantly recombine into neutral nitrogen states rather than their original ionized nitrogen defects, thereby creating negatively charged nitrogen states (Ns-). The creation of Ns- states is confirmed experimentally by tracking the localized vibrational modes (LVM) of nitrogen defects during the electron recombination process using visible pump-infrared probe transient spectroscopy. We observe a transient infrared absorption feature at 1349 cm-1 that can be assigned to the LVM of Ns-. Density functional calculations are carried out to determine the LVMs of nitrogen in various charge states, and we find a ˜10 cm-1 upward shift of the mode on passing from Ns0 to Ns-, in agreement with experimental observations.

  14. Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

    SciTech Connect

    Mardis, Kristy L.; Webb, J.; Holloway, Tarita; Niklas, Jens; Poluektov, Oleg G.

    2015-11-16

    Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advanced electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.

  15. Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions: A Combined EPR and DFT Study.

    PubMed

    Mardis, Kristy L; Webb, Jeremy N; Holloway, Tarita; Niklas, Jens; Poluektov, Oleg G

    2015-12-01

    Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advanced electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM. PMID:26569578

  16. Electron transfer in photosystem I containing native and modified quinone acceptors.

    PubMed

    Semenov, A Yu; Petrova, A A; Mamedov, M D; Nadtochenko, V A

    2015-06-01

    The pigment-protein complex of photosystem I (PS I) catalyzes light-driven oxidation of plastocyanin or cytochrome c6 and reduction of ferredoxin or flavodoxin in oxygenic photosynthetic organisms. In this review, we describe the current state of knowledge of the processes of excitation energy transfer and formation of the primary and secondary ion-radical pairs within PS I. The electron transfer reaction involving quinone cofactor in the A1 site and its role in providing asymmetry of electron transport as well as interaction with oxygen and ascorbate in PS I are discussed. PMID:26531012

  17. Indan-1,3-dione electron-acceptor small molecules for solution-processable solar cells: a structure-property correlation.

    PubMed

    Winzenberg, Kevin N; Kemppinen, Peter; Scholes, Fiona H; Collis, Gavin E; Shu, Ying; Singh, Th Birendra; Bilic, Ante; Forsyth, Craig M; Watkins, Scott E

    2013-07-18

    A structure-device performance correlation in bulk heterojunction solar cells for new indandione-derived small molecule electron acceptors, FEHIDT and F8IDT, is presented. Devices based on the former exhibit higher power conversion efficiency (2.4%) and higher open circuit voltage, a finding consistent with reduced intermolecular interactions. PMID:23739171

  18. Photo-initiated multi-step electron transfer in donor-acceptor systems using a novel bi-functionalized perylene chromophore

    NASA Astrophysics Data System (ADS)

    Dyar, Scott M.; Smeigh, Amanda L.; Karlen, Steven D.; Young, Ryan M.; Wasielewski, Michael R.

    2015-06-01

    The excited state and redox properties of a new bi-functional perylene redox chromophore, 2,3-dihydro-1-azabenzo[cd]perylene (DABP), are described. Perylene has been widely used in electron donor-acceptor molecules in fields ranging from artificial photosynthesis to molecular spintronics. However, attaching multiple redox components to perylene to carry out multi-step electron transfer reactions often produces hard to separate regioisomers, which complicate data analysis. The use of DABP provides a strategy to retain the electronic properties of perylene, yet eliminate regioisomers. Ultrafast photo-initiated single- and two-step electron transfer reactions in three linear electron donor-acceptor systems incorporating DABP are described to illustrate its utility.

  19. Anaerobic respiration in engineered Escherichia coli with an internal electron acceptor to produce fuel ethanol.

    PubMed

    Peterson, Joy Doran; Ingram, Lonnie O

    2008-03-01

    Environmental concerns and unease with U.S. dependence on foreign oil have renewed interest in converting biomass into fuel ethanol. The volume of plant matter available makes lignocellulose conversion to ethanol desirable, although no one isolated organism has been shown to break bonds in lignocellulose and efficiently metabolize resulting sugars into one product. This work reviews directed engineering coupled with metabolic evolution resulting in microbial biocatalysts that produce up to 45 g L(-1) ethanol in 48 hours in a simple mineral salts medium and that convert various compounds of lignocellulosic materials to ethanol. Mutations contributing to ethanologenesis are discussed along with adding enzymatic capabilities to existing biocatalysts in order to decrease the commercial enzymes required to reduce plant matter into fermentable sugars. PMID:18378606

  20. Transition Metal Donor-Peptide-Acceptor Complexes: From Intramolecular Electron Transfer Reactions to the Study of Reactive Intermediates

    SciTech Connect

    Isied, Stephan S.

    2003-03-11

    The trans-polyproline (PII) oligomers (Figure 1) are unusually rigid peptide structures which have been extensively studied by our group for peptide mediated intramolecular electron transfer (ET) at long distances. We have previously studied ET across a series of metal ion donor (D) acceptor (A) oligoproline peptides with different distances, driving forces and reorganizational energies. The majority of these experiments involve generating the ET intermediate using pulse radiolysis methods, although more recently photochemical methods are also used. Results of these studies showed that ET across peptides can vary by more than twelve orders of magnitude. Using ruthenium bipyridine donors, ET reaction rate constants across several proline residues (n = 4 - 9) occurred in the millisecond (ms) to {micro}s timescale, thus limiting the proline peptide conformational motions to only minor changes (far smaller than the large changes that occur on the ms to sec timescale, such as trans to cis proline isomerization). The present report describes our large data base of experimental results for D-peptide-A complexes in terms of a model where the involvement of both superexchange and hopping (hole and electron) mechanisms account for the long range ET rate constants observed. Our data shows that the change from superexchange to hopping mechanisms occurs at different distances depending on the type of D and A and their interactions with the peptides. Our model is also consistent with generalized models for superexchange and hopping which have been put forward by a number of theoretical groups to account for long range ET phenomena.

  1. Magnetic field enhanced electroluminescence in organic light emitting diodes based on electron donor-acceptor exciplex blends

    NASA Astrophysics Data System (ADS)

    Baniya, Sangita; Basel, Tek; Sun, Dali; McLaughlin, Ryan; Vardeny, Zeev Valy

    2016-03-01

    A useful process for light harvesting from injected electron-hole pairs in organic light emitting diodes (OLED) is the transfer from triplet excitons (T) to singlet excitons (S) via reverse intersystem crossing (RISC). This process adds a delayed electro-luminescence (EL) emission component that is known as thermally activated delayed fluorescence (TADF). We have studied electron donor (D)/acceptor(A) blends that form an exciplex manifold in which the energy difference, ΔEST between the lowest singlet (S1) and triplet (T1) levels is relatively small (<100 meV), and thus allows RISC at ambient temperature. We found that the EL emission in OLED based on the exciplex blend is enhanced up to 40% by applying a relatively weak magnetic field of 50 mT at ambient. Moreover the MEL response is activated with activation energy similar that of the EL emission. This suggests that the large magneto-EL originates from an additional spin-mixing channel between singlet and triplet states of the generated exciplexes, which is due to TADF. We will report on the MEL dependencies on the temperature, bias voltage, and D-A materials for optimum OLED performance. Supported by SAMSUNG Global Research Outreach (GRO) program, and also by the NSF-Material Science & Engineering Center (MRSEC) program at the University of Utah (DMR-1121252).

  2. Charge transfer in the electron donor-acceptor complexes of a meso-phenol BODIPY dye with chloranils and fullerenes

    NASA Astrophysics Data System (ADS)

    Karmakar, Animesh; Chaudhuri, Tandrima; Mula, Soumyaditya; Chattopadhyay, Subrata

    2015-02-01

    UV-Vis spectral investigations of electron donor-acceptor complexes of laser dye 2,6-Diethyl-4,4-difluoro-1,3,5,7-tetramethyl-8-(4‧-hydroxyphenyl)-4-bora-3a,4a-diaza-s-indecene (1c) with chloranils and fullerenes are reported in toluene medium. Well defined charge transfer (CT) absorption bands have been located in the visible region. Oscillator strengths, transition dipole and resonance energies of the CT complexes have been estimated. Vertical ionization potential of 1c has been determined utilizing Mulliken's equation. A possible mechanism for the interaction between electronic subsystems of chloranils, [60]- and [70]fullerenes with three different BODIPY dyes (1a, 1b and 1c shown in Fig. 1) have been discussed in comparing the parameters like degree of charge transfer and binding constant in nonpolar toluene. Comparison of 1c complexes is done with DFT/B3LYP/6-31G optimized gas phase geometries.

  3. Modulating the Redox Potential of the Stable Electron Acceptor, QB, in Mutagenized Photosystem II Reaction Centers.

    SciTech Connect

    Perrine, Zoee; Sayre, Richard

    2011-02-10

    One of the unique features of electron transfer processes in photosystem II (PSII) reaction centers (RC) is the exclusive transfer of electrons down only one of the two parallel cofactor branches. In contrast to the RC core polypeptides (psaA and psaB) of photosystem I (PSI), where electron transfer occurs down both parallel redox-active cofactor branches, there is greater protein-cofactor asymmetry between the PSII RC core polypeptides (D1 and D2). We have focused on the identification of protein-cofactor relationships that determine the branch along which primary charge separation occurs (P680+/pheophytin-(Pheo)). We have previously shown that mutagenesis of the strong hydrogen-bonding residue, D1-E130, to less polar residues (D1-E130Q,H,L) shifted the midpoint potential of the PheoD1/PheoD1- couple to more negative values, reducing the quantum yield of primary charge separation. We did not observe, however, electron transfer down the inactive branch in D1-E130 mutants. The protein residue corresponding to D1-E130 on the inactive branch is D2-Q129 which presumably has a reduced hydrogen-bonding interaction with PheoD2 relative to the D1-E130 residue with PheoD1. Analysis of the recent 2.9 Å cyanobacterial PSII crystal structure indicated, however, that the D2-Q129 residue was too distant from the PheoD2 headgroup to serve as a possible hydrogen bond donor and directly impact its midpoint potential as well as potentially determine the directionality of electron transfer. Our objective was to characterize the function of this highly conserved inactive branch residue by replacing it with a nonconservative leucine or a conservative histidine residue. Measurements of Chl fluorescence decay kinetics and thermoluminescence studies indicate that the mutagenesis of D2-Q129 decreases the redox gap between QA and QB due to a lowering of the redox potential of QB. The

  4. 5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

    NASA Technical Reports Server (NTRS)

    Frank, Natia L.; Meade, Thomas J.

    2003-01-01

    Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

  5. 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.

  6. The electronic structure of Fe2+ in reaction centers from Rhodopseudomonas sphaeroides. III. EPR measurements of the reduced acceptor complex.

    PubMed Central

    Butler, W F; Calvo, R; Fredkin, D R; Isaacson, R A; Okamura, M Y; Feher, G

    1984-01-01

    Electron paramagnetic resonance (EPR) spectra of the reduced quinone-iron acceptor complex in reaction centers were measured in a variety of environments and compared with spectra calculated from a theoretical model. Spectra were obtained at microwave frequencies of 1, 9, and 35 GHz and at temperatures from 1.4 to 30 K. The spectra are characterized by a broad absorption peak centered at g = 1.8 with wings extending from g approximately equal to 5 to g less than 0.8. The peak is split with the low-field component increasing in amplitude with temperature. The theoretical model is based on a spin Hamiltonian, in which the reduced quinone, Q-, interacts magnetically with Fe2+. In this model the ground manifold of the interacting Q-Fe2+ system has two lowest doublets that are separated by approximately 3 K. Both perturbation analyses and exact numerical calculations were used to show how the observed spectrum arises from these two doublets. The following spin Hamiltonian parameters optimized the agreement between simulated and observed spectra: the electronic g tensor gFe, x = 2.16, gFe, y = 2.27, gFez = 2.04, the crystal field parameters D = 7.60 K and E/D = 0.25, and the antiferromagnetic magnetic interaction tensor, Jx = -0.13 K, Jy = -0.58 K, Jz = -0.58 K. The model accounts well for the g value (1.8) of the broad peak, the observed splitting of the peak, the high and low g value wings, and the observed temperature dependence of the shape of the spectra. The structural implications of the value of the magnetic interaction, J, and the influence of the environment on the spin Hamiltonian parameters are discussed. The similarity of spectra and relaxation times observed from the primary and secondary acceptor complexes Q-AFe2+ and Fe2+Q-B leads to the conclusion that the Fe2+ is approximately equidistant from QA and QB. PMID:6329347

  7. Description of electron transfer in the ground and excited states of organic donor–acceptor systems by single-reference and multi-reference density functional methods

    SciTech Connect

    Filatov, Michael

    2014-09-28

    Electron transfer in the ground and excited states of a model donor–acceptor (D–A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S{sub 0} state and a wave-like dependence of the S{sub 1} electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S{sub 0} and S{sub 1} electron transfer on the external electric field applied along the donor–acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S{sub 0} and S{sub 1} electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor–acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S{sub 0} and S{sub 1} states may interfere with the electron transfer in a weakly coupled donor–acceptor system. It is also suggested that the electronic excitation of a D{sup +}–A{sup −} system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths.

  8. Spectral probes of the holographic Fermi ground state: Dialing between the electron star and AdS Dirac hair

    SciTech Connect

    Cubrovic, Mihailo; Liu Yan; Schalm, Koenraad; Sun Yawen; Zaanen, Jan

    2011-10-15

    We argue that the electron star and the anti-de Sitter (AdS) Dirac hair solution are two limits of the free charged Fermi gas in AdS. Spectral functions of holographic duals to probe fermions in the background of electron stars have a free parameter that quantifies the number of constituent fermions that make up the charge and energy density characterizing the electron star solution. The strict electron star limit takes this number to be infinite. The Dirac hair solution is the limit where this number is unity. This is evident in the behavior of the distribution of holographically dual Fermi surfaces. As we decrease the number of constituents in a fixed electron star background the number of Fermi surfaces also decreases. An improved holographic Fermi ground state should be a configuration that shares the qualitative properties of both limits.

  9. Global transcriptional start site mapping in Geobacter sulfurreducens during growth with two different electron acceptors.

    PubMed

    González, Getzabeth; Labastida, Aurora; Jímenez-Jacinto, Verónica; Vega-Alvarado, Leticia; Olvera, Maricela; Morett, Enrique; Juárez, Katy

    2016-09-01

    Geobacter sulfurreducens is an anaerobic soil bacterium that is involved in biogeochemical cycles of elements such as Fe and Mn. Although significant progress has been made in the understanding of the electron transfer processes in G. sulfurreducens, little is known about the regulatory mechanisms involved in their control. To expand the study of gene regulation in G. sulfurreducens, we carried out a genome-wide identification of transcription start sites (TSS) by 5'RACE and by deep RNA sequencing of primary mRNAs in two growth conditions. TSSs were identified along G. sulfurreducens genome and over 50% of them were located in the upstream region of the associated gene, and in some cases we detected genes with more than one TSS. Our global mapping of TSSs contributes with valuable information, which is needed for the study of transcript structure and transcription regulation signals and can ultimately contribute to the understanding of transcription initiation phenomena in G. sulfurreducens. PMID:27488344

  10. Effect of acceptor strength on optical and electronic properties in conjugated polymers for solar applications.

    PubMed

    Adegoke, Oluwasegun O; Jung, In Hwan; Orr, Meghan; Yu, Luping; Goodson, Theodore

    2015-05-01

    Four new low-bandgap electron-accepting polymers-poly(4,10-bis(2-butyloctyl)-2-(2-(2-ethylhexyl)-1,1-dioxido-3-oxo-2,3-dihydrothieno[3,4-d]isothiazol-4-yl)thieno[2',3':5,6]pyrido[3,4-g]thieno[3,2-c]isoquinoline-5,11(4H,10H-dione) (PNSW); poly(4,10-bis(2-butyloctyl)-2-(5-(2-ethylhexyl)-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-c]pyrrol-1-yl)thieno[2',3':5,6]pyrido[3,4-g]thieno[3,2-c]isoquinoline-5,11(4H,10H)-dione) (PNTPD); poly(5-(4,10-bis(2-butyloctyl)-5,11-dioxo-4,5,10,11-tetrahydrothieno[2',3':5,6]pyrido[3,4-g]thieno[3,2-c]isoquinolin-2-yl)-2,9-bis(2-decyldodecyl)anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone) (PNPDI); and poly(9,9-bis(2-butyloctyl)-9H-fluorene-bis((1,10:5,6)2-(5,6-dihydro-4H-cyclopenta[b]thiophene-4-ylidene)malonitrile)-2-(2,3-dihydrothieno[3,4-b][1,4]dioxine)) (PECN)-containing thieno[2',3':5',6']pyrido[3,4-g]thieno[3,2-c]isoquinoline-5,11(4H,10H)-dione and fluorenedicyclopentathiophene dimalononitrile, were investigated to probe their structure-function relationships for solar cell applications. PTB7 was also investigated for comparison with the new low-bandgap polymers. The steady-state, ultrafast dynamics and nonlinear optical properties of all the organic polymers were probed. All the polymers showed broad absorption in the visible region, with the absorption of PNPDI and PECN extending into the near-IR region. The polymers had HOMO levels ranging from -5.73 to -5.15 eV and low bandgaps of 1.47-2.45 eV. Fluorescence upconversion studies on the polymers showed long lifetimes of 1.6 and 2.4 ns for PNSW and PNTPD, respectively, while PNPDI and PECN showed very fast decays within 353 and 110 fs. PECN exhibited a very high two-photon absorption cross section. The electronic structure calculations of the repeating units of the polymers indicated the localization of the molecular orbitals in different co-monomers. As the difference between the electron affinities of the co-monomers in the repeating units decreases, the highest

  11. The FX iron-sulfur cluster serves as the terminal bound electron acceptor in heliobacterial reaction centers.

    PubMed

    Romberger, Steven P; Golbeck, John H

    2012-03-01

    Phototrophs of the family Heliobacteriaceae contain the simplest known Type I reaction center (RC), consisting of a homodimeric (PshA)(2) core devoid of bound cytochromes and antenna proteins. Unlike plant and cyanobacterial Photosystem I in which the F(A)/F(B) protein, PsaC, is tightly bound to P(700)-F(X) cores, the RCs of Heliobacterium modesticaldum contain two F(A)/F(B) proteins, PshBI and PshBII, which are loosely bound to P(800)-F(X) cores. These two 2[4Fe-4S] ferredoxins have been proposed to function as mobile redox proteins, reducing downstream metabolic partners much in the same manner as does [2Fe-2S] ferredoxin or flavodoxin (Fld) in PS I. Using P(800)-F(X) cores devoid of PshBI and PshBII, we show that iron-sulfur cluster F(X) directly reduces Fld without the involvement of F(A) or F(B) (Fld is used as a proxy for soluble redox proteins even though a gene encoding Fld is not identified in the H. modesticaldum genome). The reduction of Fld is suppressed by the addition of PshBI or PshBII, an effect explained by competition for the electron on F(X). In contrast, P(700)-F(X) cores require the presence of the PsaC, and hence, the F(A)/F(B) clusters for Fld (or ferredoxin) reduction. Thus, in H. modesticaldum, the interpolypeptide F(X) cluster serves as the terminal bound electron acceptor. This finding implies that the homodimeric (PshA)(2) cores should be capable of donating electrons to a wide variety of yet-to-be characterized soluble redox partners. PMID:22297911

  12. The 6,6-dicyanopentafulvene core: a template for the design of electron-acceptor compounds.

    PubMed

    Finke, Aaron D; Jahn, Burkhard O; Saithalavi, Anas; Dahlstrand, Christian; Nauroozi, Djawed; Haberland, Sophie; Gisselbrecht, Jean-Paul; Boudon, Corinne; Mijangos, Edgar; Schweizer, W Bernd; Ott, Sascha; Ottosson, Henrik; Diederich, François

    2015-05-26

    The electron-accepting ability of 6,6-dicyanopentafulvenes (DCFs) can be varied extensively through substitution on the five-membered ring. The reduction potentials for a set of 2,3,4,5-tetraphenyl-substituted DCFs, with varying substituents at the para-position of the phenyl rings, strongly correlate with their Hammett σp-parameters. By combining cyclic voltammetry with DFT calculations ((U)B3LYP/6-311+G(d)), using the conductor-like polarizable continuum model (CPCM) for implicit solvation, the absolute reduction potentials of a set of twenty DCFs were reproduced with a mean absolute deviation of 0.10 eV and a maximum deviation of 0.19 eV. Our experimentally investigated DCFs have reduction potentials within 3.67-4.41 eV, however, the computations reveal that DCFs with experimental reduction potentials as high as 5.3 eV could be achieved, higher than that of F4-TCNQ (5.02 eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6 eV. PMID:25917111

  13. Assembly of coupled redox fuel cells using copper as electron acceptors to generate power and its in-situ retrieval

    NASA Astrophysics Data System (ADS)

    Zhang, Hui-Min; Xu, Wei; Li, Gang; Liu, Zhan-Meng; Wu, Zu-Cheng; Li, Bo-Geng

    2016-02-01

    Energy extraction from waste has attracted much interest nowadays. Herein, a coupled redox fuel cell (CRFC) device using heavy metals, such as copper, as an electron acceptor is assembled to testify the recoveries of both electricity and the precious metal without energy consumption. In this study, a NaBH4-Cu(II) CRFC was employed as an example to retrieve copper from a dilute solution with self-electricity production. The properties of the CRFC have been characterized, and the open circuit voltage was 1.65 V with a maximum power density of 7.2 W m-2 at an initial Cu2+ concentration of 1,600 mg L-1 in the catholyte. 99.9% of the 400 mg L-1 copper was harvested after operation for 24 h, and the product formed on the cathode was identified as elemental copper. The CRFC demonstrated that useful chemicals were recovered and the electricity contained in the chemicals was produced in a self-powered retrieval process.

  14. Fluorescent hybrid with electron acceptor methylene viologen units inside the pore walls of mesoporous MCM-48 silica.

    PubMed

    Liu, Aifeng; Han, Shuhua; Che, Hongwei; Hua, Lan

    2010-03-01

    A fluorescent material with methylene viologen units bonded into the pore walls of the mesoporous MCM-48 silica is synthesized using the method of periodic mesoporous organosilicas with bridging groups (PMOs), in which the methylene viologen units are located within the channel walls through the cohydrolysis and cocondensation of dichloride of N,N'-bis(triethoxysilylmethyl)-4,4'-bipyridinium (VP) and tetraethoxysilane (TEOS). It is found that the suspension of the hybrid emits fluorescence at ca. 380 and 420 nm, which is attributed to the S(1) state (pi* --> pi) of the viologen and the charge-transfer complex between the bipyridinium units as electron acceptor and accompanying halide (Br(-), Cl(-)) as donor components, respectively. The fluorescent emission intensity increases with increasing the amount of the VP covalently bonded to MCM-48 framework. The fluorescent intensity of VP adsorbed on the surface of the pore channel of MCM-48 was greatly weaker than that of the hybrid MCM-48-VP at the same molar ratio of TEOS to VP. No fluorescence was observed for pure VP. The different fluorescent intensity is ascribed to the fact that restricted degree of the rotation between two pyridine rings is different. It could be prospected that this material is potentially applied in drug delivery and fluorescence probing for medical diagnosis and synchronous therapy. PMID:20104919

  15. Assembly of coupled redox fuel cells using copper as electron acceptors to generate power and its in-situ retrieval

    PubMed Central

    Zhang, Hui-Min; Xu, Wei; Li, Gang; Liu, Zhan-Meng; Wu, Zu-Cheng; Li, Bo-Geng

    2016-01-01

    Energy extraction from waste has attracted much interest nowadays. Herein, a coupled redox fuel cell (CRFC) device using heavy metals, such as copper, as an electron acceptor is assembled to testify the recoveries of both electricity and the precious metal without energy consumption. In this study, a NaBH4-Cu(II) CRFC was employed as an example to retrieve copper from a dilute solution with self-electricity production. The properties of the CRFC have been characterized, and the open circuit voltage was 1.65 V with a maximum power density of 7.2 W m−2 at an initial Cu2+ concentration of 1,600 mg L−1 in the catholyte. 99.9% of the 400 mg L−1 copper was harvested after operation for 24 h, and the product formed on the cathode was identified as elemental copper. The CRFC demonstrated that useful chemicals were recovered and the electricity contained in the chemicals was produced in a self-powered retrieval process. PMID:26877144

  16. [Chromate reduction by Pseudomonas sp. str. 10 in the presence of some heavy metals and alternative electron acceptors].

    PubMed

    Smirnova, G F; Podgorskiĭ, V S

    2013-01-01

    Pseudomonas sp. str. 10 reduces chromate with a rate of 0.54 mg / L.h. The availability of Cd2+ and Zn2+ in the medium has no noticeable effect on the rate or slightly increases it. The presence of nickel and copper in the ionic form in the medium resulted in a decrease of chromate reduction rate 2.4 and 4.2 times, respectively. Change of these metals into hydroxide form significantly lowers their negative influence. Iron (III) both in ionic and hydroxide form inhibits the reduction of chromate by Pseudomonas sp. 10. Joint presence of all studied metals decreases their negative impact on chromate reduction, therefore these metals may be neutralized together without a significant lowering of the process efficacy on condition that copper-containing drain will be cleaned separately. The presence of alternative acceptors of electrons inhibited the reduction of chromate. Sulfate and oxyanions of chlorine - chlorate and perchlorate have the highest inhibitory effect on chromate reduction. PMID:24006778

  17. Influence of metronidazole and some electron acceptors on the chlorin e6 photosensitized killing of Ehrlich carcinoma cells

    NASA Astrophysics Data System (ADS)

    Chekulayev, V.; Shevchuk, Igor; Mihkelsoo, Virgo T.; Kallikorm, A. P.

    1992-06-01

    A decrease in the effectiveness of photosensitized killing of neoplasm cells was observed in the presence of chlorin-e6 at a reduced concentration of oxygen. But when metronidazole (MZ) was injected in vitro as well as in vivo, a significant increase in the photosensitized killing of Ehrlich carcinoma cells by chlorin-e6 was observed. Moreover, contrary to the hematoporphyrin derivative (HpD), MZ increases the effectiveness of photodynamic therapy (PDT) by using chlorin-e6 not only in the hypoxic but also in the aerobic conditions. The interaction between MZ and the excited photosensitizer may account for an increased phototoxicity of chlorin-e6. The formation of cytotoxic nitroimidazole radicals as a result of photochemical processes of type 1 is discussed. This property of the photosensitizer may be successfully used in working out a method of potentiating PDT in combination not only with nitroimidazoles, but also with other electron acceptor compounds (EACp), e.g., quinone antitumor antibiotics.

  18. Modulation of electronic and self-assembly properties of a donor-acceptor-donor-based molecular materials via atomistic approach.

    PubMed

    Dhar, Joydeep; Swathi, K; Karothu, Durga Prasad; Narayan, K S; Patil, Satish

    2015-01-14

    The performance of molecular materials in optoelectronic devices critically depends upon their electronic properties and solid-state structure. In this report, we have synthesized sulfur and selenium based (T4BT and T4BSe) donor-acceptor-donor (D-A-D) organic derivatives in order to understand the structure-property correlation in organic semiconductors by selectively tuning the chalcogen atom. The photophysical properties exhibit a significant alteration upon varying a single atom in the molecular structure. A joint theoretical and experimental investigation suggests that replacing sulfur with selenium significantly reduces the band gap and molar absorption coefficient because of lower electronegativity and ionization potential of selenium. Single-crystal X-ray diffraction analysis showed differences in their solid-state packing and intermolecular interactions. Subsequently, difference in the solid-state packing results variation in self-assembly. Micorstructural changes within these materials are correlated to their electrical resistance variation, investigated by conducting probe atomic force microscopy (CP-AFM) measurements. These results provide useful guidelines to understand the fundamental properties of D-A-D materials prepared by atomistic modulation. PMID:25532139

  19. Steady state protein levels in Geobacter metallireducens grown with Iron (III) citrate or nitrate as terminal electron acceptor.

    SciTech Connect

    Ahrendt, A. J.; Tollaksen, S. L.; Lindberg, C.; Zhu, W.; Yates, J. R., III; Nevin, K. P.; Lovley, D.; Giometti, C. S.; Biosciences Division; The Scripps Research Inst.; Univ. of Massachusetts

    2007-01-01

    Geobacter species predominate in aquatic sediments and submerged soils where organic carbon sources are oxidized with the reduction of Fe(III). The natural occurrence of Geobacter in some waste sites suggests this microorganism could be useful for bioremediation if growth and metabolic activity can be regulated. 2-DE was used to monitor the steady state protein levels of Geobacter metallireducens grown with either Fe(III) citrate or nitrate to elucidate metabolic differences in response to different terminal electron acceptors present in natural environments populated by Geobacter. Forty-six protein spots varied significantly in abundance (p<0.05) between the two growth conditions; proteins were identified by tryptic peptide mass and peptide sequence determined by MS/MS. Enzymes involved in pyruvate metabolism and the tricarboxylic acid (TCA) cycle were more abundant in cells grown with Fe(III) citrate, while proteins associated with nitrate metabolism and sensing cellular redox status along with several proteins of unknown function were more abundant in cells grown with nitrate. These results indicate a higher level of flux through the TCA cycle in the presence of Fe(III) compared to nitrate. The oxidative stress response observed in previous studies of Geobacter sulfurreducens grown with Fe(III) citrate was not seen in G. metallireducens.

  20. Assembly of coupled redox fuel cells using copper as electron acceptors to generate power and its in-situ retrieval.

    PubMed

    Zhang, Hui-Min; Xu, Wei; Li, Gang; Liu, Zhan-Meng; Wu, Zu-Cheng; Li, Bo-Geng

    2016-01-01

    Energy extraction from waste has attracted much interest nowadays. Herein, a coupled redox fuel cell (CRFC) device using heavy metals, such as copper, as an electron acceptor is assembled to testify the recoveries of both electricity and the precious metal without energy consumption. In this study, a NaBH4-Cu(II) CRFC was employed as an example to retrieve copper from a dilute solution with self-electricity production. The properties of the CRFC have been characterized, and the open circuit voltage was 1.65 V with a maximum power density of 7.2 W m(-2) at an initial Cu(2+) concentration of 1,600 mg L(-1) in the catholyte. 99.9% of the 400 mg L(-1) copper was harvested after operation for 24 h, and the product formed on the cathode was identified as elemental copper. The CRFC demonstrated that useful chemicals were recovered and the electricity contained in the chemicals was produced in a self-powered retrieval process. PMID:26877144

  1. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    NASA Astrophysics Data System (ADS)

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-07-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting.

  2. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    PubMed Central

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-01-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

  3. Electron donor-acceptor interaction of 3,4-dimethylaniline with 2,3-dicyano-1,4-naphthoquinone

    NASA Astrophysics Data System (ADS)

    Neelgund, Gururaj M.; Magadum, Subash R.; Budni, M. L.

    2011-01-01

    The electron donor-acceptor (EDA) interaction between 2,3-dicyano-1,4-naphthoquinone (DCNQ) and 3,4-dimethylaniline (3,4-DMA) is studied in chloroform, dichloromethane and 1:1 (v/v) mixture of chloroform and dichloromethane. The rate of formation of the product was measured as a function of time using UV-vis spectrophotometer. The formation constant ( K) and molar extinction coefficient ( ɛ) values for the formation of EDA complex were evaluated in the temperature range of 20-35 °C. The pseudo-first-order rate constant ( k1) and the second-order rate constant ( k2) for the disappearance of EDA complex and for the formation of product were evaluated. The activation parameters (Δ H#, Δ S# and Δ G#) of the reaction were determined by temperature dependence of rate constants using the Arrhenius plots. The effect of relative permittivity of the medium on the reaction is discussed. The observed results indicate that formation of final product proceeds through initial formation of EDA complex as an intermediate. The product of the reaction was purified by column chromatography method and identified as 3-( N-3,4-dimethyl-phenylamino)-2-cyano-1,4-naphthoquinone by elemental analysis, IR and NMR spectroscopy. On the basis of kinetic, analytical and spectroscopic results, a plausible mechanism for the formation of EDA complex and its transformation into product is proposed.

  4. Self-assembly properties of semiconducting donor-acceptor-donor bithienyl derivatives of tetrazine and thiadiazole-effect of the electron accepting central ring.

    PubMed

    Zapala, Joanna; Knor, Marek; Jaroch, Tomasz; Maranda-Niedbala, Agnieszka; Kurach, Ewa; Kotwica, Kamil; Nowakowski, Robert; Djurado, David; Pecaut, Jacques; Zagorska, Malgorzata; Pron, Adam

    2013-11-26

    Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates. PMID:24228736

  5. Thermodynamics of the Electron Acceptors in Heliobacterium modesticaldum: An Exemplar of an Early Homodimeric Type I Photosynthetic Reaction Center.

    PubMed

    Ferlez, Bryan; Cowgill, John; Dong, Weibing; Gisriel, Christopher; Lin, Su; Flores, Marco; Walters, Karim; Cetnar, Daniel; Redding, Kevin E; Golbeck, John H

    2016-04-26

    The homodimeric type I reaction center in heliobacteria is arguably the simplest known pigment-protein complex capable of conducting (bacterio)chlorophyll-based conversion of light into chemical energy. Despite its structural simplicity, the thermodynamics of the electron transfer cofactors on the acceptor side have not been fully investigated. In this work, we measured the midpoint potential of the terminal [4Fe-4S](2+/1+) cluster (FX) in reaction centers from Heliobacterium modesticaldum. The FX cluster was titrated chemically and monitored by (i) the decrease in the level of stable P800 photobleaching by optical spectroscopy, (ii) the loss of the light-induced g ≈ 2 radical from P800(+•) following a single-turnover flash, (iii) the increase in the low-field resonance at 140 mT attributed to the S = (3)/2 ground spin state of FX(-), and (iv) the loss of the spin-correlated P800(+) FX(-) radical pair following a single-turnover flash. These four techniques led to similar estimations of the midpoint potential for FX of -502 ± 3 mV (n = 0.99), -496 ± 2 mV (n = 0.99), -517 ± 10 mV (n = 0.65), and -501 ± 4 mV (n = 0.84), respectively, with a consensus value of -504 ± 10 mV (converging to n = 1). Under conditions in which FX is reduced, the long-lived (∼15 ms) P800(+) FX(-) state is replaced by a rapidly recombining (∼15 ns) P800(+)A0(-) state, as shown by ultrafast optical experiments. There was no evidence of the presence of a P800(+) A1(-) spin-correlated radical pair by electron paramagnetic resonance (EPR) under these conditions. The midpoint potentials of the two [4Fe-4S](2+/1+) clusters in the low-molecular mass ferredoxins were found to be -480 ± 11 mV/-524 ± 13 mV for PshBI, -453 ± 6 mV/-527 ± 6 mV for PshBII, and -452 ± 5 mV/-533 ± 8 mV for HM1_2505 as determined by EPR spectroscopy. FX is therefore suitably poised to reduce one [4Fe-4S](2+/1+) cluster in these mobile electron carriers. Using the measured midpoint potential of FX and a

  6. Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors.

    PubMed

    Baesman, Shaun M; Bullen, Thomas D; Dewald, James; Zhang, Donghui; Curran, Seamus; Islam, Farhana S; Beveridge, Terry J; Oremland, Ronald S

    2007-04-01

    Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [epsilon] = -0.4 to -1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods ( approximately 10-nm diameter by 200-nm length), which cluster together, forming larger ( approximately 1,000-nm) rosettes composed of numerous individual shards ( approximately 100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. PMID:17277198

  7. Hydroxycinnamic acids used as external acceptors of electrons: an energetic advantage for strictly heterofermentative lactic acid bacteria.

    PubMed

    Filannino, Pasquale; Gobbetti, Marco; De Angelis, Maria; Di Cagno, Raffaella

    2014-12-01

    The metabolism of hydroxycinnamic acids by strictly heterofermentative lactic acid bacteria (19 strains) was investigated as a potential alternative energy route. Lactobacillus curvatus PE5 was the most tolerant to hydroxycinnamic acids, followed by strains of Weissella spp., Lactobacillus brevis, Lactobacillus fermentum, and Leuconostoc mesenteroides, for which the MIC values were the same. The highest sensitivity was found for Lactobacillus rossiae strains. During growth in MRS broth, lactic acid bacteria reduced caffeic, p-coumaric, and ferulic acids into dihydrocaffeic, phloretic, and dihydroferulic acids, respectively, or decarboxylated hydroxycinnamic acids into the corresponding vinyl derivatives and then reduced the latter compounds to ethyl compounds. Reductase activities mainly emerged, and the activities of selected strains were further investigated in chemically defined basal medium (CDM) under anaerobic conditions. The end products of carbon metabolism were quantified, as were the levels of intracellular ATP and the NAD(+)/NADH ratio. Electron and carbon balances and theoretical ATP/glucose yields were also estimated. When CDM was supplemented with hydroxycinnamic acids, the synthesis of ethanol decreased and the concentration of acetic acid increased. The levels of these metabolites reflected on the alcohol dehydrogenase and acetate kinase activities. Overall, some biochemical traits distinguished the common metabolism of strictly heterofermentative strains: main reductase activity toward hydroxycinnamic acids, a shift from alcohol dehydrogenase to acetate kinase activities, an increase in the NAD(+)/NADH ratio, and the accumulation of supplementary intracellular ATP. Taken together, the above-described metabolic responses suggest that strictly heterofermentative lactic acid bacteria mainly use hydroxycinnamic acids as external acceptors of electrons. PMID:25261518

  8. Hydroxycinnamic Acids Used as External Acceptors of Electrons: an Energetic Advantage for Strictly Heterofermentative Lactic Acid Bacteria

    PubMed Central

    Filannino, Pasquale; Gobbetti, Marco; De Angelis, Maria

    2014-01-01

    The metabolism of hydroxycinnamic acids by strictly heterofermentative lactic acid bacteria (19 strains) was investigated as a potential alternative energy route. Lactobacillus curvatus PE5 was the most tolerant to hydroxycinnamic acids, followed by strains of Weissella spp., Lactobacillus brevis, Lactobacillus fermentum, and Leuconostoc mesenteroides, for which the MIC values were the same. The highest sensitivity was found for Lactobacillus rossiae strains. During growth in MRS broth, lactic acid bacteria reduced caffeic, p-coumaric, and ferulic acids into dihydrocaffeic, phloretic, and dihydroferulic acids, respectively, or decarboxylated hydroxycinnamic acids into the corresponding vinyl derivatives and then reduced the latter compounds to ethyl compounds. Reductase activities mainly emerged, and the activities of selected strains were further investigated in chemically defined basal medium (CDM) under anaerobic conditions. The end products of carbon metabolism were quantified, as were the levels of intracellular ATP and the NAD+/NADH ratio. Electron and carbon balances and theoretical ATP/glucose yields were also estimated. When CDM was supplemented with hydroxycinnamic acids, the synthesis of ethanol decreased and the concentration of acetic acid increased. The levels of these metabolites reflected on the alcohol dehydrogenase and acetate kinase activities. Overall, some biochemical traits distinguished the common metabolism of strictly heterofermentative strains: main reductase activity toward hydroxycinnamic acids, a shift from alcohol dehydrogenase to acetate kinase activities, an increase in the NAD+/NADH ratio, and the accumulation of supplementary intracellular ATP. Taken together, the above-described metabolic responses suggest that strictly heterofermentative lactic acid bacteria mainly use hydroxycinnamic acids as external acceptors of electrons. PMID:25261518

  9. Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

    USGS Publications Warehouse

    Baesman, S.M.; Bullen, T.D.; Dewald, J.; Zhang, Dongxiao; Curran, S.; Islam, F.S.; Beveridge, T.J.; Oremland, R.S.

    2007-01-01

    Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [??] = -0.4 to -1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (???10-nm diameter by 200-nm length), which cluster together, forming larger (???1,000-nm) rosettes composed of numerous individual shards (???100-nm width by 1,000-nm length). In contrast, Sulfurospirillium barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. Copyright ?? 2007, American Society for Microbiology. All Rights Reserved.

  10. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules I. Reference Data at the CCSD(T) Complete Basis Set Limit.

    PubMed

    Richard, Ryan M; Marshall, Michael S; Dolgounitcheva, O; Ortiz, J V; Brédas, Jean-Luc; Marom, Noa; Sherrill, C David

    2016-02-01

    In designing organic materials for electronics applications, particularly for organic photovoltaics (OPV), the ionization potential (IP) of the donor and the electron affinity (EA) of the acceptor play key roles. This makes OPV design an appealing application for computational chemistry since IPs and EAs are readily calculable from most electronic structure methods. Unfortunately reliable, high-accuracy wave function methods, such as coupled cluster theory with single, double, and perturbative triples [CCSD(T)] in the complete basis set (CBS) limit are too expensive for routine applications to this problem for any but the smallest of systems. One solution is to calibrate approximate, less computationally expensive methods against a database of high-accuracy IP/EA values; however, to our knowledge, no such database exists for systems related to OPV design. The present work is the first of a multipart study whose overarching goal is to determine which computational methods can be used to reliably compute IPs and EAs of electron acceptors. This part introduces a database of 24 known organic electron acceptors and provides high-accuracy vertical IP and EA values expected to be within ±0.03 eV of the true non-relativistic, vertical CCSD(T)/CBS limit. Convergence of IP and EA values toward the CBS limit is studied systematically for the Hartree-Fock, MP2 correlation, and beyond-MP2 coupled cluster contributions to the focal point estimates. PMID:26731487

  11. Electrochemical response of a biofilm community to changes in electron-acceptor redox potential elucidated using microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Arbour, T.; Wrighton, K. C.; Mullin, S. W.; Luef, B.; Gilbert, B.; Banfield, J. F.

    2012-12-01

    Currently, we have limited insight into how mineral properties affect dissimilatory metal-reducing bacteria (DMRB) or the microbial communities that contain them. Advances in our understanding of DMRB metabolism have been achieved using microbial fuel cells (MFCs), which exploit the ability of these organisms to transfer electrons extracellularly. By replacing the mineral electron acceptor with a conductive electrode under potentiostat control, the activity of microorganisms capable of interfacial electron transfer can be quantified by the current flowing through the electrode and related to the thermodynamics of respiration. We seek to understand how communities and their individual members respond to changes in mineralogy, and expect mineral redox potential to be a primary control. The ability to precisely control the redox potential of the electron-accepting anodic electrode is our primary motivation for using MFCs. We inoculated duplicate MFCs containing 10 mM acetate in phosphate buffered media with a slurry of subsurface sediment and groundwater obtained from the Integrated Field-Scale Research Challenge Site at Rifle, CO. Electroactive biofilms were established on graphite anodes poised at a favorable potential (0.0 V vs. SHE) before poising at -0.2 V—a potential representative of natural iron reduction. The current was stable across both anodes over more than 100 days of operation, and the percentage of the electrons in acetate recovered as current ("Coulombic efficiency") was typically 70 to >90%. Current density reached 0.4 A/m2 at -0.2 V, to a max of over 1.0 A/m2 at or above ~0.0 V (based on geometric electrode surface area). Media exchanges and biofilm cyclic voltammetry (CV) experiments indicate that electrode-attached microbial communities were responsible for primary electron transfer. Cryo-electron and confocal fluorescence microscopies of the biofilm reveal numerous morphologies of viable microorganisms that are currently being characterized

  12. Characterization of Shewanella oneidensis MtrC: a cell-surface decaheme cytochrome involved in respiratory electron transport to extracellular electron acceptors

    SciTech Connect

    Hartshorne, Robert S.; Jepson, Brian N.; Clarke, Thomas A.; Field, Sarah J.; Fredrickson, Jim K.; Zachara, John M.; Shi, Liang; Butt, Julea N.; Richardson, David

    2007-09-04

    Abstract MtrC is a decaheme c-type cytochrome associated with the outer cell membrane of Fe(III)-respiring species of the Shewanella genus. It is proposed to play a role in anaerobic respiration by mediating electron transfer to extracellular mineral oxides that can serve as terminal electron acceptors. The present work presents the first spectropotentiometric and voltammetric characterization of MtrC, using protein purified from Shewanella oneidensis MR-1. Potentiometric titrations, monitored by UV–vis absorption and electron paramagnetic resonance (EPR) spectroscopy, reveal that the hemes within MtrC titrate over a broad potential range spanning between approximately +100 and approximately *500 mV (vs. the standard hydrogen electrode). Across this potential window the UV– vis absorption spectra are characteristic of low-spin c-type hemes and the EPR spectra reveal broad, complex features that suggest the presence of magnetically spin-coupled lowspin c-hemes. Non-catalytic protein film voltammetry of MtrC demonstrates reversible electrochemistry over a potential window similar to that disclosed spectroscopically. The voltammetry also allows definition of kinetic properties of MtrC in direct electron exchange with a solid electrode surface and during reduction of a model Fe(III) substrate. Taken together, the data provide quantitative information on the potential domain in which MtrC can operate.

  13. Electronic Alteration on Oligothiophenes by o-Carborane: Electron Acceptor Character of o-Carborane in Oligothiophene Frameworks with Dicyano-Vinyl End-On Group.

    PubMed

    Kim, So-Yoen; Lee, Ah-Rang; Jin, Guo Fan; Cho, Yang-Jin; Son, Ho-Jin; Han, Won-Sik; Kang, Sang Ook

    2015-05-01

    We studied electronic change in oligothiophenes by employing o-carborane into a molecular array in which one or both end(s) were substituted by electron-withdrawing dicyano-vinyl group(s). Depending on mono- or bis-substitution at the o-carborane, a series of linear A1-D-A2 (1a-1c) or V-shaped A1-D-A2-D-A1 (2a-2c) oligothiophene chain structures of variable length were prepared; A1, D, and A2, represent dicyano-vinyl, oligothiophenyl, and o-carboranyl groups, respectively. Among this series, 2a shows strong electron-acceptor capability of o-carborane comparable to that of the dicyano-vinyl substituent, which can be elaborated by a conformational effect driven by cage σ*-π* interaction. As a result, electronic communications between o-carborane and dicyano-vinyl groups are successfully achieved in 2a. PMID:25844983

  14. Self-Assembly of Electron Donor-Acceptor-Based Carbazole Derivatives: Novel Fluorescent Organic Nanoprobes for Both One- and Two-Photon Cellular Imaging.

    PubMed

    Zhang, Jinfeng; Chen, Wencheng; Kalytchuk, Sergii; Li, King Fai; Chen, Rui; Adachi, Chihaya; Chen, Zhan; Rogach, Andrey L; Zhu, Guangyu; Yu, Peter K N; Zhang, Wenjun; Cheah, Kok Wai; Zhang, Xiaohong; Lee, Chun-Sing

    2016-05-11

    In this study, we report fluorescent organic nanoprobes with intense blue, green, and orange-red emissions prepared by self-assembling three carbazole derivatives into nanorods/nanoparticles. The three compounds consist of two or four electron-donating carbazole groups linked to a central dicyanobenzene electron acceptor. Steric hindrance from the carbazole groups leads to noncoplanar 3D molecular structures favorable to fluorescence in the solid state, while the donor-acceptor structures endow the molecules with good two-photon excited emission properties. The fluorescent organic nanoprobes exhibit good water dispersibility, low cytotoxicity, superior resistance against photodegradation and photobleaching. Both one- and two-photon fluorescent imaging were shown in the A549 cell line. Two-photon fluorescence imaging with the fluorescent probes was demonstrated to be more effective in visualizing and distinguishing cellular details compared to conventional one-photon fluorescence imaging. PMID:27097920

  15. Preparation, spectroscopic and thermal characterization of charge-transfer molecular complexes formed in the reaction of 4-dimethylaminopyridine with π-electron acceptors

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; Benjamin Cieslinski, G.; Bazzi, Hassan S.

    2015-02-01

    The interactions of the electron donor 4-dimethylaminopyridine (4DMAP) with the π-acceptors tetracyanoethylene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge-transfer (CT) complexes were recorded. Photometric titration showed that the stoichiometries of the reactions were not fixed and depended on the nature of both the donor and the acceptor. The molecular structures of the CT-complexes were, however, affected by the amino group in 4-dimethylaminopyridine and the two methyl groups and were formulated as [(4DMAP)(TCNE)2], [(4DMAP)(TCNQ)2] and [(4DMAP)(TBCHD)]. The formation constant (KCT), charge transfer energy (ECT), molar extinction coefficients (εCT) and free energy change of the formed CT-complexes were obtained.

  16. Synthesis, spectrophotometric, structural and thermal studies of the charge transfer complex of p-phenylenediamine, as an electron donor with π acceptor 3,5-dinitrobenzoic acid

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq

    2010-08-01

    The interaction between p-phenylenediamine (PPD) as a donor with the π acceptor 3,5-dinitrobenzoic acid (DNB) has been investigated spectrophotometrically in methanol at room temperature. CT complex formed as a result of transfer of lone pair of electrons and exhibits well resolved charge transfer bands in the regions where neither donor nor acceptor have any absorption. The stoichiometry of the charge transfer complex (CTC) was found to be 1:1. The solid state CTC has also been synthesized, and has been characterized by elemental analysis, FTIR spectra, 1H NMR spectroscopy and electronic absorption. The thermal stability of CT complex was studies using TGA and DTA analyses techniques. On the basis of the studies, the structure of CT complex is [(PPD)(DNB)], and a general mechanism for its formation is proposed. The formation constant and other physical parameters of the CT complex were determined by the Benesi-Hildebrand equation.

  17. Isolation and characterization of Alicycliphilus denitrificans strain BC, which grows on benzene with chlorate as the electron acceptor.

    PubMed

    Weelink, Sander A B; Tan, Nico C G; ten Broeke, Harm; van den Kieboom, Corné; van Doesburg, Wim; Langenhoff, Alette A M; Gerritse, Jan; Junca, Howard; Stams, Alfons J M

    2008-11-01

    A bacterium, strain BC, was isolated from a benzene-degrading chlorate-reducing enrichment culture. Strain BC degrades benzene in conjunction with chlorate reduction. Cells of strain BC are short rods that are 0.6 microm wide and 1 to 2 microm long, are motile, and stain gram negative. Strain BC grows on benzene and some other aromatic compounds with oxygen or in the absence of oxygen with chlorate as the electron acceptor. Strain BC is a denitrifying bacterium, but it is not able to grow on benzene with nitrate. The closest cultured relative is Alicycliphilus denitrificans type strain K601, a cyclohexanol-degrading nitrate-reducing betaproteobacterium. Chlorate reductase (0.4 U/mg protein) and chlorite dismutase (5.7 U/mg protein) activities in cell extracts of strain BC were determined. Gene sequences encoding a known chlorite dismutase (cld) were not detected in strain BC by using the PCR primers described in previous studies. As physiological and biochemical data indicated that there was oxygenation of benzene during growth with chlorate, a strategy was developed to detect genes encoding monooxygenase and dioxygenase enzymes potentially involved in benzene degradation in strain BC. Using primer sets designed to amplify members of distinct evolutionary branches in the catabolic families involved in benzene biodegradation, two oxygenase genes putatively encoding the enzymes performing the initial successive monooxygenations (BC-BMOa) and the cleavage of catechol (BC-C23O) were detected. Our findings suggest that oxygen formed by dismutation of chlorite can be used to attack organic molecules by means of oxygenases, as exemplified with benzene. Thus, aerobic pathways can be employed under conditions in which no external oxygen is supplied. PMID:18791031

  18. UV-Vis, IR spectra and thermal studies of charge transfer complexes formed in the reaction of 4-benzylpiperidine with σ- and π-electron acceptors

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; El-Ghossein, Nada; Cieslinski, G. Benjamin; Bazzi, Hassan S.

    2013-12-01

    The reactions of the electron donor 4-benzylpiperidine (4BP) with the σ-acceptor iodine and π-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge-transfer (CT) complexes were recorded. Based on the obtained data, the charge-transfer complexes were formulated as [I3-, [(4BP)(DDQ)2], and [(4BP)(TBCHD)] for the donor (4BP) and the acceptors I2, DDQ and TBCHD. In the 4BP-TCNQ reaction, a short-lived CT complex is formed followed by rapid N-substitution by TCNQ forming the final reaction product 7,7,8-tricyano-8-benzylpiperidinylquinodimethane [TCBPQDM]. These products were isolated as solids and have been characterized through electronic and infrared spectra as well as elemental and thermal analysis measurements. The formation constants (KCT), charge transfer energy (ECT), molar extinction coefficients (ɛCT), free energy change ΔG∘ and ionization potential IP of the formed CT-complexes [I3-, [(4BP)(DDQ)2] and [(4BP)(TBCHD)] were obtained.

  19. Factoring the contribution of through-space and through-bond interactions to rates of photoinduced electron transfer in donor- spacer-acceptor molecules using ultrafast transient absorption spectroscopy

    SciTech Connect

    Gosztola, D.; Wang, Bing; Wasielewski, M.R. |

    1996-06-01

    Contributions from through-space and through-bond interactions to the electronic coupling matrix elements for photoinduced charge separation and recombination in linked donor-spacer-acceptor molecules were studied. The molecules consisted of a 4-piperidinyl-naphthalene-1,8-dicarboximide electron donor and a N-(n-octyl)pyromellitimide electron acceptor attached to the 1,5- and 1,8-positions of either anthracene or dibenzobicyclo(2.2.2)octatriene spacers.

  20. A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage.

    PubMed

    Patil, Hemlata; Zu, Wang Xi; Gupta, Akhil; Chellappan, Vijila; Bilic, Ante; Sonar, Prashant; Rananaware, Anushri; Bhosale, Sidhanath V; Bhosale, Sheshanath V

    2014-11-21

    A novel solution-processable non-fullerene electron acceptor 6,6'-(5,5'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor. PMID:25274538

  1. EPR studies of the vitamin K 1 semiquinone radical anion. Comparison to the electron acceptor A 1 in green plant photosystem I

    NASA Astrophysics Data System (ADS)

    Thurnauer, Marion C.; Brown, James W.; Gast, P.; Feezel, Laura L.

    Suggestions that the electron acceptor, A 1, in Photosystem I is a quinone have come from both optical and epr experiments. Vitamin K 1 (phylloquinone) is present in the PSI complex with a stoichiometry of two molecules per reaction center. In order to determine if A 1 can be identified with vitamin K 1, X-band and Q-band epr properties of the vitamin K 1 radical anion in frozen alcohol solutions are examined. The results are compared to the epr properties that have been observed for the reduced A 1 acceptor in vivo. The g-values obtained for the vitamin K 1 radical anion are consistent with identifying A 1 with vitamin K 1.

  2. Electronic, infrared, mass, 1H NMR spectral studies of the charge-transfer complexes of sulphonamide drugs with π-acceptors in acetonitrile

    NASA Astrophysics Data System (ADS)

    Frag, Eman Y.; Mohamed, Gehad G.

    2010-08-01

    The rapid interaction between sulphonamides (sulphamethoxazole (SMZ), sulphaguanidine (SGD), sulphaquinoxaline sodium (SQX) and sulphadimidine sodium (SDD)) as n-electron donors with the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, p-CLA) as π-acceptors resulted in the formation of 1:1 charge-transfer complexes as the final products with the formula [(drug) (acceptor)]. The final products of the reactions have been isolated and characterized using FT-IR, 1H NMR, mass spectroscopy and elemental analyses as well as photometric measurements and thermogravimetric analysis (TG). The stoichiometry and apparent formation constants of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

  3. Bimolecular electron transfer reactions in coumarin amine systems: Donor acceptor orientational effect on diffusion-controlled reaction rates

    NASA Astrophysics Data System (ADS)

    Satpati, A. K.; Nath, S.; Kumbhakar, M.; Maity, D. K.; Senthilkumar, S.; Pal, H.

    2008-04-01

    Electron transfer (ET) reactions between excited coumarin dyes and different aliphatic amine (AlA) and aromatic amine (ArA) donors have been investigated in acetonitrile solution using steady-state (SS) and time-resolved (TR) fluorescence quenching measurements. No ground state complex or emissive exciplex formation has been indicated in these systems. SS and TR measurements give similar quenching constants ( kq) for each of the coumarin-amine pairs, suggesting dynamic nature of interaction in these systems. On correlating kq values with the free energy changes (Δ G0) of the ET reactions show the typical Rehm-Weller type of behavior as expected for bimolecular ET reactions under diffusive condition, where kq increases with -Δ G0 at the lower exergonicity (-Δ G0) region but ultimately saturate to a diffusion-limited value (kqDC) at the higher exergonicity region. It is, however, interestingly observed that the kqDC values vary largely depending on the type of the amines used. Thus, kqDC is much higher with ArAs than AlAs. Similarly, the kqDC for cyclic monoamine 1-azabicyclo-[2,2,2]-octane (ABCO) is distinctly lower and that for cyclic diamine 1,4-diazabicyclo-[2,2,2]-octane (DABCO) is distinctly higher than the kqDC value obtained for other noncyclic AlAs. These differences in the kqDC values have been rationalized on the basis of the differences in the orientational restrictions involved in the ET reactions with different types of amines. As understood, n-type donors (AlAs) introduce large orientational restriction and thus significantly reduces the ET efficiency in comparison to the π-type donors (ArAs). Structural constrains are inferred to be the reason for the differences in the kqDC values involving ABCO, DABCO donors in comparison to other noncyclic AlAs. Supportive evidence for the orientational restrictions involving different types of amines donors has also been obtained from DFT based quantum chemical calculations on the molecular orbitals of

  4. Achieving high performance non-fullerene organic solar cells through tuning the numbers of electron deficient building blocks of molecular acceptors

    NASA Astrophysics Data System (ADS)

    Yang, Lei; Chen, Yusheng; Chen, Shangshang; Dong, Tao; Deng, Wei; Lv, Lei; Yang, Saina; Yan, He; Huang, Hui

    2016-08-01

    Two analogous dimer and tetramer compounds, SF-PDI2 and SF-PDI4, were designed, theoretically calculated, synthesized, and developed as electron acceptors for organic solar cells. The effects of the number of the electron deficient building blocks on the optical absorption, energy levels, charge transport, morphology, crystallinity, and photovoltaic performance of the molecules were investigated. In combination with two different donors, PTB7-Th and PffBT4T-2OD, the results showed that increasing the numbers of PDI building blocks is beneficial to photovoltaic performance and leads to efficiency over 5%.

  5. Oxygen as Acceptor.

    PubMed

    Borisov, Vitaliy B; Verkhovsky, Michael I

    2015-01-01

    Like most bacteria, Escherichia coli has a flexible and branched respiratory chain that enables the prokaryote to live under a variety of environmental conditions, from highly aerobic to completely anaerobic. In general, the bacterial respiratory chain is composed of dehydrogenases, a quinone pool, and reductases. Substrate-specific dehydrogenases transfer reducing equivalents from various donor substrates (NADH, succinate, glycerophosphate, formate, hydrogen, pyruvate, and lactate) to a quinone pool (menaquinone, ubiquinone, and dimethylmenoquinone). Then electrons from reduced quinones (quinols) are transferred by terminal reductases to different electron acceptors. Under aerobic growth conditions, the terminal electron acceptor is molecular oxygen. A transfer of electrons from quinol to O₂ is served by two major oxidoreductases (oxidases), cytochrome bo₃ encoded by cyoABCDE and cytochrome bd encoded by cydABX. Terminal oxidases of aerobic respiratory chains of bacteria, which use O₂ as the final electron acceptor, can oxidize one of two alternative electron donors, either cytochrome c or quinol. This review compares the effects of different inhibitors on the respiratory activities of cytochrome bo₃ and cytochrome bd in E. coli. It also presents a discussion on the genetics and the prosthetic groups of cytochrome bo₃ and cytochrome bd. The E. coli membrane contains three types of quinones that all have an octaprenyl side chain (C₄₀). It has been proposed that the bo₃ oxidase can have two ubiquinone-binding sites with different affinities. "WHAT'S NEW" IN THE REVISED ARTICLE: The revised article comprises additional information about subunit composition of cytochrome bd and its role in bacterial resistance to nitrosative and oxidative stresses. Also, we present the novel data on the electrogenic function of appBCX-encoded cytochrome bd-II, a second bd-type oxidase that had been thought not to contribute to generation of a proton motive force in E

  6. The role of O2 as an electron acceptor alternative to CO2 in photosynthesis of the common marine angiosperm Zostera marina L.

    PubMed

    Buapet, Pimchanok; Björk, Mats

    2016-07-01

    This study investigates the role of O2 as an electron acceptor alternative to CO2 in photosynthesis of the common marine angiosperm Zostera marina L. Electron transport rates (ETRs) and non-photochemical quenching (NPQ) of Z. marina were measured under saturating irradiance in synthetic seawater containing 2.2 mM DIC and no DIC with different O2 levels (air-equilibrated levels, 3 % of air equilibrium and restored air-equilibrated levels). Lowering O2 did not affect ETR when DIC was provided, while it caused a decrease in ETR and an increase in NPQ in DIC-free media, indicating that O2 acted as an alternative electron acceptor under low DIC. The ETR and NPQ as a function of irradiance were subsequently assessed in synthetic seawater containing (1) 2.2 mM DIC, air-equilibrated O2; (2) saturating CO2, no O2; and (3) no DIC, air-equilibrated O2. These treatments were combined with glycolaldehyde pre-incubation. Glycolaldehyde caused a marked decrease in ETR in DIC-free medium, indicating significant electron flow supported by photorespiration. Combining glycolaldehyde with O2 depletion completely suppressed ETR suggesting the operation of the Mehler reaction, a possibility supported by the photosynthesis-dependent superoxide production. However, no notable effect of suppressing the Mehler reaction on NPQ was observed. It is concluded that during DIC-limiting conditions, such as those frequently occurring in the habitats of Z. marina, captured light energy exceeds what is utilised for the assimilation of available carbon, and photorespiration is a major alternative electron acceptor, while the contribution of the Mehler reaction is minor. PMID:27125819

  7. Tuning Optical and Electron Donor Properties by Peripheral Thio-Aryl Substitution of Subphthalocyanine: A New Series of Donor-Acceptor Hybrids for Photoinduced Charge Separation.

    PubMed

    Kc, Chandra B; Lim, Gary N; D'Souza, Francis

    2016-09-01

    Subphthalocyanine (SubPc), a unique ring-reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light-energy-harvesting applications. In the present study, by peripheral thio-aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near-IR region. Additionally, for α-ring-substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor-acceptor dyads containing the well-known electron acceptor C60 connected to the central boron atom of SubPc was accomplished by making use of the 1,3-dipolar cycloaddition reaction. Control experiments and free-energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light-to-electricity or light-to-fuel production devices. PMID:27515576

  8. (Per)Chlorate-Reducing Bacteria Can Utilize Aerobic and Anaerobic Pathways of Aromatic Degradation with (Per)Chlorate as an Electron Acceptor

    PubMed Central

    Carlström, Charlotte I.; Loutey, Dana; Bauer, Stefan; Clark, Iain C.; Rohde, Robert A.; Iavarone, Anthony T.; Lucas, Lauren

    2015-01-01

    ABSTRACT The pathways involved in aromatic compound oxidation under perchlorate and chlorate [collectively known as (per)chlorate]-reducing conditions are poorly understood. Previous studies suggest that these are oxygenase-dependent pathways involving O2 biogenically produced during (per)chlorate respiration. Recently, we described Sedimenticola selenatireducens CUZ and Dechloromarinus chlorophilus NSS, which oxidized phenylacetate and benzoate, two key intermediates in aromatic compound catabolism, coupled to the reduction of perchlorate or chlorate, respectively, and nitrate. While strain CUZ also oxidized benzoate and phenylacetate with oxygen as an electron acceptor, strain NSS oxidized only the latter, even at a very low oxygen concentration (1%, vol/vol). Strains CUZ and NSS contain similar genes for both the anaerobic and aerobic-hybrid pathways of benzoate and phenylacetate degradation; however, the key genes (paaABCD) encoding the epoxidase of the aerobic-hybrid phenylacetate pathway were not found in either genome. By using transcriptomics and proteomics, as well as by monitoring metabolic intermediates, we investigated the utilization of the anaerobic and aerobic-hybrid pathways on different electron acceptors. For strain CUZ, the results indicated utilization of the anaerobic pathways with perchlorate and nitrate as electron acceptors and of the aerobic-hybrid pathways in the presence of oxygen. In contrast, proteomic results suggest that strain NSS may use a combination of the anaerobic and aerobic-hybrid pathways when growing on phenylacetate with chlorate. Though microbial (per)chlorate reduction produces molecular oxygen through the dismutation of chlorite (ClO2−), this study demonstrates that anaerobic pathways for the degradation of aromatics can still be utilized by these novel organisms. PMID:25805732

  9. Probing the effect of electron acceptor structure and morphology on charge separation in ZnO/P3HT hybrid photovoltaics using steady-state transient photoinduced absorption.

    SciTech Connect

    Davis, Robert Jackson; Lloyd, Matthew T.; Ferreira, Summer Rhodes; Lee, Yun-Ju; Hsu, Julia W. P.

    2010-04-01

    Hybrid cells based on ZnO/P3HT heterojunctions have the advantage of better device stability, but suffer poor photovoltaic performance compared to all-organic cells which use PCBM as the electron acceptor. The photovoltaic effect in these hybrid systems is accomplished via photoinduced charge separation at the interface between the absorbing polymer (P3HT) and the electron acceptor (ZnO). Efforts to improve device performance in these hybrid systems have centered on reducing the required diffusion length for P3HT excitons by creating bulk heterojunctions from either ZnO nanoparticles and P3HT or using ZnO precursors which convert in situ to form ZnO networks inside a polymer matrix. In this study, we use transient photoinduced absorption to access the lifetimes of P3HT polarons and excitons in bulk heterojunctions constructed using P3HT and ZnO nanoparticles or ZnO precursors and compare to those in planar ZnO/P3HT devices. Steady-state photoinduced absorption spectra of ZnO/P3HT show characteristic of sub-bandgap transitions associated with the formation of long-lived (msec lifetimes) radical cations (polarons) in P3HT. Similar short-lived polarons (psec lifetimes) are observed by picosecond transient photoinduced absorption in addition to infrared absorption due to excitons. Here we examine the lifetimes of both the excitons and polarons in ZnO:P3HT bulk heterojunctions using both picosecond and millisecond techniques in an effort to understand the effect of the structure and morphology of the electron acceptor on charge separation. We will also compare the relative photoexitation lifetimes, hence charge separation efficiency, for the planar and bulk heterojunction hybrid system to an all-organic P3HT:PCBM system.

  10. Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

    SciTech Connect

    Eisenhardt, A.; Reiß, S.; Krischok, S. Himmerlich, M.

    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 disappearance of surface states, which initially pin the Fermi level and induce downward band bending.

  11. Systematic Investigations on the Roles of the Electron Acceptor and Neighboring Ethynylene Moiety in Porphyrins for Dye-Sensitized Solar Cells.

    PubMed

    Wei, Tiantian; Sun, Xi; Li, Xin; Ågren, Hans; Xie, Yongshu

    2015-10-01

    Cyanoacrylic and carboxyl groups have been developed as the most extensively used electron acceptor and anchoring group for the design of sensitizers for dye-sensitized solar cells. In terms of the photoelectric conversion efficiency, each of them has been demonstrated to be superior to the other one in certain cases. Herein, to further understand the effect of these two groups on cell efficiencies, a series of porphyrin sensitizers were designed and synthesized, with the acceptors systematically varied, and the effect of the neighboring ethynylene unit was also investigated. Compared with the sensitizer XW5 which contains a carboxyphenyl anchoring moiety directly linked to the meso-position of the porphyrin framework, the separate introduction of a strongly electron-withdrawing cyanoacrylic acid as the anchoring group or the insertion of an ethynylene unit can achieve broadened light absorption and IPCE response, resulting in higher Jsc and higher efficiency. Thus, compared with the efficiency of 4.77% for XW5, dyes XW1 and XW6 exhibit higher efficiencies of 7.09% and 5.92%, respectively. Simultaneous introduction of the cyanoacrylic acid and the ethynylene units into XW7 can further broaden light absorption and thus further improve the Jsc. However, XW7 exhibits the lowest Voc value, which is not only related to the floppy structure of the cyanoacrylic group but also related to the aggravated dye aggregation effect due to the extended framework. As a result, XW7 exhibits a relatively low efficiency of 5.75%. These results indicate that the combination of the ethynylene and cyanoacrylic groups is an unsuccessful approach. To address this problem, a cyano substituent was introduced to XW8 at the ortho position of the carboxyl group in the carboxyphenyl acceptor. Thus, XW8 exhibits the highest efficiency of 7.59% among these dyes. Further cosensitization of XW8 with XS3 dramatically improved the efficiency to 9.31%. PMID:26355437

  12. Bi-induced acceptor level responsible for partial compensation of native free electron density in InP1-x Bi x dilute bismide alloys

    NASA Astrophysics Data System (ADS)

    Gelczuk, Łukasz; Stokowski, Hubert; Kopaczek, Jan; Zhang, Liyao; Li, Yaoyao; Wang, Kai; Wang, Peng; Wang, Shumin; Kudrawiec, Robert

    2016-03-01

    Deep level transient spectroscopy (DLTS) has been applied to study electron and hole traps in InPBi alloys with 2.2 and 2.4% Bi grown by molecular beam epitaxy. One donor-like trap with the activation energy of 0.45-0.47 eV and one acceptor-like trap with activation energy of 0.08 eV have been identified in DLTS measurements. For the reference sample (InP grown at the same temperature), the deep donor trap has also been observed, while the acceptor trap was not detected. According to the literature, the deep donor level found in InP(Bi) at 0.45-0.47 eV below the conduction band has been attributed to the isolated PIn defect, while the second trap, which is observed only for Bi containing samples at 0.08 eV above the valence band can be attributed to Bi clusters in InPBi. This acceptor level was proposed to be responsible for the observed partial compensation of native free electron density in InPBi layers. It is also shown that the deep donor traps are active in photoluminescence (PL). A strong radiative recombination between donor traps and the valence band are observed in PL spectra at energy 0.6-0.8 eV, i.e. ~0.47 eV below the energy gap of InPBi, which is determined by contactless electroreflectance.

  13. Spectral investigations of multiple charge transfer complex of p-nitrophenol as an electron acceptor with donor p-dimethylaminobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Naeem, A.; Khan, I. M.; Ahmad, A.

    2011-10-01

    The convincing evidence have been given that both the interactions π-π and π-π* (between p-nitrophenol ( p-NTP) and p-dimethylaminobenzaldehyde ( p-DAB)) are simultaneously involved. This has been established by using IR spectrometry. Association constant K evaluated by the method of Foster under the condition [A]0 = [D]0 with apply in this equation, [A]0/ A = 1/ Kɛλ[D]0 + 2/ɛλ, where [A]0 is the initial concentration of acceptor equal to [D]0, A is the absorbance of the complex at λ, K is the association constant, and ɛλ is the molar absorptivity of the complex at λ. In the IR spectral studies of several related organic compounds, one comes to the conclusion that p-NTP shows a broad band centred at 1600 cm-1 and to nitro asymmetric stretching vibrations. In the complex while the 1500 cm-1 band remains without shift, the broad band localized at 1600 cm-1 shift to 1610 cm-1. A shift of 10 cm-1 shows weak interactions. Studies on molecular complexes of organ metallic donors and acceptors are of very recent origin. Though alkyl donors have been extensively studied, very few studies have appeared on aryl donors.

  14. Spectrophotometric and thermal studies on the charge - Transfer complexes of 4-(aminomethyl) piperidine as donor with σ- and π-electron acceptors

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; El-Ghossein, Nada; AlQaradawi, Siham Y.

    2014-01-01

    The spectroscopic characteristics of the solid charge-transfer molecular complexes (CT) formed in the reaction of the electron donor 4-(aminomethyl) piperidine (4AMP) with the σ-acceptor iodine and the π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been studied in chloroform at 25 °C. These were investigated through electronic, infrared spectra and thermal analysis as well as elemental analysis. The results show that the formed solid CT-complexes have the formulas [I3-, [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] while in the case of 4AMP-TCNQ reaction, a short-lived CT complex is formed followed by rapid N-substitution by TCNQ forming the final reaction product 7,7,8-tricyano-8-aminomethylpiperidinylquinodimethane [TCAMPQDM] in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements and the thermal analysis confirmed the structure of the obtained compounds. The formation constant kCT, molar extinction coefficient εCT, free energy change ΔG0 and CT energy ECT have been calculated for the CT-complexes [I3-, [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)].

  15. Electronic Structure, Donor and Acceptor Transitions, and Magnetism of 3d Impurities in In2O3 and ZnO

    SciTech Connect

    Raebiger, H.; Lany, S,; Zunger, A.

    2009-01-01

    3d transition impurities in wide-gap oxides may function as donor/acceptor defects to modify carrier concentrations, and as magnetic elements to induce collective magnetism. Previous first-principles calculations have been crippled by the LDA error, where the occupation of the 3d-induced levels is incorrect due to spurious charge spilling into the misrepresented host conduction band, and have only considered magnetism and carrier doping separately. We employ a band-structure-corrected theory, and present simultaneously the chemical trends for electronic properties, carrier doping, and magnetism along the series of 3d{sup 1}-3d{sup 8} transition-metal impurities in the representative wide-gap oxide hosts In{sub 2}O{sub 3} and ZnO. We find that most 3d impurities in In{sub 2}O{sub 3} are amphoteric, whereas in ZnO, the early 3d's (Sc, Ti, and V) are shallow donors, and only the late 3d's (Co and Ni) have acceptor transitions. Long-range ferromagnetic interactions emerge due to partial filling of 3d resonances inside the conduction band and, in general, require electron doping from additional sources.

  16. Ligand structure, conformational dynamics, and excited-state electron delocalization for control of photoinduced electron transfer rates in synthetic donor-bridge-acceptor systems.

    PubMed

    Meylemans, Heather A; Lei, Chi-Fong; Damrauer, Niels H

    2008-05-19

    Synthesis, ground-, and excited-state properties are reported for two new electron donor-bridge-acceptor (D-B-A) molecules and two new photophysical model complexes. The D-B-A molecules are [Ru(bpy)2(bpy-phi-MV)](PF6)4 (3) and [Ru(tmb)2(bpy-phi-MV)](PF6)4 (4), where bpy is 2,2'-bipyridine, tmb is 4,4',5,5'-tetramethyl-2,2'-bipyridine, MV is methyl viologen, and phi is a phenylene spacer. Their model complexes are [Ru(bpy)2(p-tol-bpy)](PF6)2 (1) and [Ru(tmb)2(p-tol-bpy)](PF6)2 (2), where p-tolyl-bpy is 4-(p-tolyl)-2,2'-bipyridine. Photophysical characterization of 1 and 2 indicates that 2.17 eV and 2.12 eV are stored in their respective (3)MLCT (metal-to-ligand charge transfer) excited state. These values along with electrochemical measurements show that photoinduced electron transfer (D*-B-A-->D (+)-B-A(-)) is favorable in 3 and 4 with DeltaG degrees(ET)=-0.52 eV and -0.62 eV, respectively. The driving force for the reverse process (D(+)-B-A(-) --> D-B-A) is also reported: DeltaG degrees(BET)=-1.7 eV for 3 and -1.5 eV for 4. Transient absorption (TA) spectra for 3 and 4 in 298 K acetonitrile provide evidence that reduced methyl viologen is observable at 50 ps following excitation. Detailed TA kinetics confirm this, and the data are fit to a model to determine both forward (k(ET)) and back (k(BET)) electron transfer rate constants: k(ET)=2.6 x 10(10) s(-1) for 3 and 2.8 x 10(10) s(-1) for 4; k(BET)=0.62 x 10(10) s(-1) for 3 and 1.37 x 10(10) s(-1) for 4. The similar rate constants k ET for 3 and 4 despite a 100 meV driving force (DeltaG degrees(ET)) increase suggests that forward electron transfer in these molecules in room temperature acetonitrile is nearly barrierless as predicted by the Marcus theory. The reduction in electron transfer reorganization energy necessary for this barrierless reactivity is attributed to excited-state electron delocalization in the (3)MLCT excited states of 3 and 4, an effect that is made possible by excited-state conformational

  17. C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60

    SciTech Connect

    Kuvychko, Igor V.; Dubceac, Cristina; Deng, Shihu; Wang, Xue B.; Granovsky, Alexander A.; Popov, Alexey A.; Petrukhina, Marina A.; Strauss, Steven H.; Boltalina, Olga V.

    2013-07-15

    There has been increased interest in the design and applications of small polyaromatic molecules for energy conversion and storage, organic transistors and OLEDs, and other emerging areas of modern technology.[1] In particular, functionalized polycyclic aromatic hydrocarbons (PAHs) were shown to demonstrate excellent electrical mobilities, in organic thin-film transistors, in some cases even under ambient conditions.[2] It has been suggested that air stability of such organic materials is correlated with their electronic properties, and more specifically, with a high electron affinity.[3] Until recently, geodesic PAHs, such as corannulene[4] or sumanene[5] and their numerous derivatives have not been seriously considered for optoelectronic applications because (i) they typically possess very low electron affinities (e.g., EA(C20H10) = 0.5(1) eV),[6] and (ii) laborious multistep syntheses with moderate-to-low yields made them practically unavailable for such studies.[7] Although the low availability of sumanene remains unchanged, significant progress has been made lately in the large-scale synthesis of corannulene.[8] Furthermore, our recent work demonstrated that functionalization of corannulene molecule with electron withdrawing groups (EWGs) results in drastic enhancement of its electron acceptor properties.[9] In particular, for trifluoromethylated derivative C20H5(CF3)5, a 950 mV positive shift in the reduction potential relative to the parent C20H10 was measured. We also predicted that other EWGs, including halogen atoms or cyanide group, could be used to enhance electron affinity of corannulene. Nearly linear correlation between the number of EWGs and the electron affinity (reduction potential) of the corresponding EWG-substituted corannulene molecules that was demonstrated by our DFT calculations, and, more recently, confirmed for C20H10-x(CF3)x=2,3,[10] provides a good tool for design of the molecules with desired electronic properties. Here, we report the

  18. Rational design of aggregation-induced emission luminogen with weak electron donor-acceptor interaction to achieve highly efficient undoped bilayer OLEDs.

    PubMed

    Chen, Long; Jiang, Yibin; Nie, Han; Hu, Rongrong; Kwok, Hoi Sing; Huang, Fei; Qin, Anjun; Zhao, Zujin; Tang, Ben Zhong

    2014-10-01

    In this work, two tailored luminogens (TPE-NB and TPE-PNPB) consisting of tetraphenylethene (TPE), diphenylamino, and dimesitylboryl as a π-conjugated linkage, electron donor, and electron acceptor, respectively, are synthesized and characterized. Their thermal stabilities, photophysical properties, solvachromism, fluorescence decays, electronic structures, electrochemical behaviors, and electroluminescence (EL) properties are investigated systematically, and the impacts of electron donor-acceptor (D-A) interaction on optoelectronic properties are discussed. Due to the presence of a TPE unit, both luminogens show aggregation-induced emission, but strong D-A interaction causes a decrease in emission efficiency and red-shifts in photoluminescence and EL emissions. The luminogen, TPE-PNPB, with a weak D-A interaction fluoresces strongly in solid film with a high fluorescence quantum yield of 94%. The trilayer OLED [ITO/NPB (60 nm)/TPE-PNPB (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)] utilizing TPE-PNPB as a light emitter shows a peak luminance of 49 993 cd m(-2) and high EL efficiencies up to 15.7 cd A(-1), 12.9 lm W(-1), and 5.12%. The bilayer OLED [ITO/TPE-PNPB (80 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)] adopting TPE-PNPB as a light emitter and hole transporter simultaneously affords even better EL efficiencies of 16.2 cd A(-1), 14.4 lm W(-1), and 5.35% in ambient air, revealing that TPE-PNPB is an eximious p-type light emitter. PMID:25254940

  19. Use of Fe(III) as an electron acceptor to recover previously uncultured hyperthermophiles: isolation and characterization of Geothermobacterium ferrireducens gen. nov., sp. nov.

    PubMed

    Kashefi, Kazem; Holmes, Dawn E; Reysenbach, Anna-Louise; Lovley, Derek R

    2002-04-01

    It has recently been recognized that the ability to use Fe(III) as a terminal electron acceptor is a highly conserved characteristic in hyperthermophilic microorganisms. This suggests that it may be possible to recover as-yet-uncultured hyperthermophiles in pure culture if Fe(III) is used as an electron acceptor. As part of a study of the microbial diversity of the Obsidian Pool area in Yellowstone National Park, Wyo., hot sediment samples were used as the inoculum for enrichment cultures in media containing hydrogen as the sole electron donor and poorly crystalline Fe(III) oxide as the electron acceptor. A pure culture was recovered on solidified, Fe(III) oxide medium. The isolate, designated FW-1a, is a hyperthermophilic anaerobe that grows exclusively by coupling hydrogen oxidation to the reduction of poorly crystalline Fe(III) oxide. Organic carbon is not required for growth. Magnetite is the end product of Fe(III) oxide reduction under the culture conditions evaluated. The cells are rod shaped, about 0.5 microm by 1.0 to 1.2 microm, and motile and have a single flagellum. Strain FW-1a grows at circumneutral pH, at freshwater salinities, and at temperatures of between 65 and 100 degrees C with an optimum of 85 to 90 degrees C. To our knowledge this is the highest temperature optimum of any organism in the Bacteria. Analysis of the 16S ribosomal DNA (rDNA) sequence of strain FW-1a places it within the Bacteria, most closely related to abundant but uncultured microorganisms whose 16S rDNA sequences have been previously recovered from Obsidian Pool and a terrestrial hot spring in Iceland. While previous studies inferred that the uncultured microorganisms with these 16S rDNA sequences were sulfate-reducing organisms, the physiology of the strain FW-1a, which does not reduce sulfate, indicates that these organisms are just as likely to be Fe(III) reducers. These results further demonstrate that Fe(III) may be helpful for recovering as-yet-uncultured microorganisms

  20. Use of Fe(III) as an Electron Acceptor To Recover Previously Uncultured Hyperthermophiles: Isolation and Characterization of Geothermobacterium ferrireducens gen. nov., sp. nov.

    PubMed Central

    Kashefi, Kazem; Holmes, Dawn E.; Reysenbach, Anna-Louise; Lovley, Derek R.

    2002-01-01

    It has recently been recognized that the ability to use Fe(III) as a terminal electron acceptor is a highly conserved characteristic in hyperthermophilic microorganisms. This suggests that it may be possible to recover as-yet-uncultured hyperthermophiles in pure culture if Fe(III) is used as an electron acceptor. As part of a study of the microbial diversity of the Obsidian Pool area in Yellowstone National Park, Wyo., hot sediment samples were used as the inoculum for enrichment cultures in media containing hydrogen as the sole electron donor and poorly crystalline Fe(III) oxide as the electron acceptor. A pure culture was recovered on solidified, Fe(III) oxide medium. The isolate, designated FW-1a, is a hyperthermophilic anaerobe that grows exclusively by coupling hydrogen oxidation to the reduction of poorly crystalline Fe(III) oxide. Organic carbon is not required for growth. Magnetite is the end product of Fe(III) oxide reduction under the culture conditions evaluated. The cells are rod shaped, about 0.5 μm by 1.0 to 1.2 μm, and motile and have a single flagellum. Strain FW-1a grows at circumneutral pH, at freshwater salinities, and at temperatures of between 65 and 100°C with an optimum of 85 to 90°C. To our knowledge this is the highest temperature optimum of any organism in the Bacteria. Analysis of the 16S ribosomal DNA (rDNA) sequence of strain FW-1a places it within the Bacteria, most closely related to abundant but uncultured microorganisms whose 16S rDNA sequences have been previously recovered from Obsidian Pool and a terrestrial hot spring in Iceland. While previous studies inferred that the uncultured microorganisms with these 16S rDNA sequences were sulfate-reducing organisms, the physiology of the strain FW-1a, which does not reduce sulfate, indicates that these organisms are just as likely to be Fe(III) reducers. These results further demonstrate that Fe(III) may be helpful for recovering as-yet-uncultured microorganisms from hydrothermal

  1. Electronic energy and electron transfer processes in photoexcited donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units.

    PubMed

    Lee, K J; Woo, J H; Kim, E; Xiao, Y; Su, X; Mazur, L M; Attias, A-J; Fages, F; Cregut, O; Barsella, A; Mathevet, F; Mager, L; Wu, J W; D'Aléo, A; Ribierre, J-C

    2016-03-01

    We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications. PMID:26911420

  2. Exploring the correlation between molecular conformation and optoelectronic properties of conjugated polymers : side-chain versus main-chain electron acceptors

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Chen; Huang, Ching-I.

    2013-03-01

    Polythiophene derivatives have been shown among the most promising materials for solar cell application because of their high charge mobility and light absorption. In the mostly studied, a recombination process often occurs, which is mainly due to the fact that the mobility of hole is much lower than that of electron. Hence, research about conjugated polymers containing donor-accepter pairs (such as PT-TPD) becomes quite popular because these materials have narrow band-gaps. Interestingly, these experimental studies have indicated a much more complex correlation between the optoelectronic properties and molecular conformation for polymers with acceptor units on either main or side chain. However, the effects associated with the molecular packing on the resultant chain conformation behavior and thereafter the optoelectronic properties have not been systematically discussed. In order to clarify the effects of the molecular conformation as well as the optoelectronic properties, we employ molecular dynamics and quantum mechanical methods to examine PBTTPD molecules with acceptor unit (TPD) on either main or side chain Computation resources from the National Center for High-Performance Computing of Taiwan and Computer and Information Networking Center of National Taiwan University.

  3. Mechanism of inner-sphere electron transfer via charge-transfer (precursor) complexes. Redox energetics of aromatic donors with the nitrosonium acceptor.

    PubMed

    Rosokha, S V; Kochi, J K

    2001-09-19

    Spontaneous formation of colored (1:1) complexes of various aromatic donors (ArH) with the nitrosonium acceptor (NO+) is accompanied by the appearance of two new (charge-transfer) absorption bands in the UV-vis spectrum. IR spectral and X-ray crystallographic analyses of the [ArH,NO+] complexes reveal their inner-sphere character by the ArH/NO+ separation that is substantially less than the van der Waals contact and by the significant enlargement of the aromatic chromophore. The reversible interchange between such an inner-sphere complex [ArH,NO+] and the redox product (ArH+.+ NO.) is quantitatively assessed for the first time to establish it as the critical intermediate in the overall electron-transfer process. Theoretical formulation of the NO+ binding to ArH is examined by LCAO-MO methodology sufficient to allow the unambiguous assignment of the pair of diagnostic (UV-vis) spectral bands. The MO treatment also provides quantitative insight into the high degree of charge-transfer extant in these inner-sphere complexes as a function of the HOMO-LUMO gap for the donor/acceptor pair. The relative stabilization of [ArH,NO+] is traced directly to the variation in the electronic coupling element H(AB), which is found to be substantially larger than the reorganization energy (lambda/2). In Sutin's development of Marcus-Hush theory, this inequality characterizes a completely delocalized Class III complex (which occupies a single potential well) according to the Robin-Day classification. The mechanistic relevance of such an unusual (precursor) complex to the inner-sphere mechanism for organic electron transfer is discussed. PMID:11552806

  4. Anaerobic growth of Escherichia coli K12 with fumarate as terminal electron acceptor. Genetic studies with menaquinone and fluoroacetate-resistant mutants.

    PubMed

    Guest, J R

    1979-12-01

    Fifteen independent menaquinone biosynthesis mutants (men) of Escherichia coli K12, selected for their inability to use fumarate as terminal electron acceptor, were investigated. Two nutritionally distinct groups were detected. The major group (13 mutants) responded to 1,4-dihydroxy-2-naphthoate (DHN), 2-succinylbenzoate (SB) and its dilactone, whereas the minor group (2 mutants) only responded to DHN. DHN was at least five times more effective than SB but it inhibited growth at concentrations greater than 10 microM. For anaerobic growth on glucose minimal medium the auxotrophs responded to much lower concentrations of DHN and SB and these intermediates could be replaced by uracil. Anaerobic growth tests showed that glycerol, formate and H2 are good substrates for E. coli when fumarate is the ultimate electron acceptor but growth with lactate or with fumarate alone is poor. All 15 men mutations were located between glpT and purF at approximately 49 min in the E. coli linkage map. Cotransduction frequencies with relevant markers were: nalA (21%), glpT (35%) and purF (15%). The presence of at least three genetically distinct classes (menC and menD, SB-requirers; menB, DHN-requirers) was indicated using abortive transduction as a complementation test and three-factor genetic analysis. The relative orientation nalA...menC-(D,B)...purF was indicated. Fluoroacetate-resistant mutants were isolated and four different classes were identified: ack, lacking acetate kinase; pta, lacking phosphotransacetylase; facA, lacking both of these activities; and facB, which retained both of these enzyme activities. Some of the pta mutants and all of the facA mutants failed to grow on media containing fumarate as terminal electron acceptor or anaerobically on glucose minimal medium. All four types had genetic lesions clustered between the men and purF sites. Average cotransduction frequencies with relevant markers were: nalA (4%), men (27 to 35%) and purF (71 to 80%). PMID:393800

  5. DONOR-ACCEPTOR INTERACTIONS OF NITROGEN*

    PubMed Central

    Kimura, J. E.; Szent-Györgyi, A.

    1969-01-01

    The nitrogen atoms of organic molecules readily enter into donor-acceptor interactions, giving off an electron from their lone pair. Under favorable conditions the acceptor can form free radicals. S and O atoms behave likewise but less intensely. PMID:4306047

  6. Increased Efficiency in Small Molecule Organic Solar Cells Through the Use of a 56-π Electron Acceptor - Methano Indene Fullerene

    NASA Astrophysics Data System (ADS)

    Ryan, James W.; Matsuo, Yutaka

    2015-02-01

    Organic solar cells (OSCs) offer the possibility of harnessing the sun's ubiquitous energy in a low-cost, environmentally friendly and renewable manner. OSCs based on small molecule semiconductors (SMOSCs) - have made a substantial improvement in recent years and are now achieving power conversion efficiencies (PCEs) that match those achieved for polymer:fullerene OSCs. To date, all efficient SMOSCs have relied on the same fullerene acceptor, PCBM, in order to achieve high performance. The use of PCBM however, is unfavourable due to its low lying LUMO level, which limits the open-circuit voltage (VOC). Alternative fullerene derivatives with higher lying LUMOs are thus required to improve the VOC. The challenge, however, is to prevent the typical concomitant decrease in the short circuit current density (JSC) when using a higher LUMO fullerene. In this communication, we address the issue by applying methano indene fullerene, MIF, a bis-functionalised C60 fullerene that has a LUMO level 140 mV higher than PCBM, in solution processed SMOSCs with a well known small molecule donor, DPP(TBFu)2. MIF-based devices show an improved VOC of 140 mV over PC61BM and only a small decrease in the JSC, with the PCE increasing to 5.1% (vs. 4.5% for PC61BM).

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

    PubMed

    Baruah, Tunna; Garnica, Amanda; Paggen, Marina; Basurto, Luis; Zope, Rajendra R

    2016-04-14

    We study the electronic structure of C60 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. Our results show that all functionalized fullerenes with an exception of the C60-pyrrolidine [6,6], where the pyrrolidine is attached at a [6,6] site, have larger electron affinities relative to the pristine C60 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-C61-butyric acid methyl ester (PCBM)-P3MT complex. PMID:27083718

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

    NASA Astrophysics Data System (ADS)

    Baruah, Tunna; Garnica, Amanda; Paggen, Marina; Basurto, Luis; Zope, Rajendra R.

    2016-04-01

    We study the electronic structure of C60 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. Our results show that all functionalized fullerenes with an exception of the C60-pyrrolidine [6,6], where the pyrrolidine is attached at a [6,6] site, have larger electron affinities relative to the pristine C60 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-C61-butyric acid methyl ester (PCBM)-P3MT complex.

  9. Digalactosyl-diacylglycerol deficiency impairs the capacity for photosynthetic intersystem electron transport and state transitions in Arabidopsis thaliana due to photosystem I acceptor-side limitations.

    PubMed

    Ivanov, Alexander G; Hendrickson, Luke; Krol, Marianna; Selstam, Eva; Oquist, Gunnar; Hurry, Vaughan; Huner, Norman P A

    2006-08-01

    Compared with wild type, the dgd1 mutant of Arabidopsis thaliana exhibited a lower amount of PSI-related Chl-protein complexes and lower abundance of the PSI-associated polypeptides, PsaA, PsaB, PsaC, PsaL and PsaH, with no changes in the levels of Lhca1-4. Functionally, the dgd1 mutant exhibited a significantly lower light-dependent, steady-state oxidation level of P700 (P700(+)) in vivo, a higher intersystem electron pool size, restricted linear electron transport and a higher rate of reduction of P700(+) in the dark, indicating an increased capacity for PSI cyclic electron transfer compared with the wild type. Concomitantly, the dgd1 mutant exhibited a higher sensitivity to and incomplete recovery of photoinhibition of PSI. Furthermore, dgd1 exhibited a lower capacity to undergo state transitions compared with the wild type, which was associated with a higher reduction state of the plastoquinone (PQ) pool. We conclude that digalactosyl-diacylglycerol (DGDG) deficiency results in PSI acceptor-side limitations that alter the flux of electrons through the photosynthetic electron chain and impair the regulation of distribution of excitation energy between the photosystems. These results are discussed in terms of thylakoid membrane domain reorganization in response to DGDG deficiency in A. thaliana. PMID:16854937

  10. Origin of Enhanced Hole Injection in Organic Light-Emitting Diodes with an Electron-Acceptor Doping Layer: p-Type Doping or Interfacial Diffusion?

    PubMed

    Zhang, Lei; Zu, Feng-Shuo; Deng, Ya-Li; Igbari, Femi; Wang, Zhao-Kui; Liao, Liang-Sheng

    2015-06-10

    The electrical doping nature of a strong electron acceptor, 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HATCN), is investigated by doping it in a typical hole-transport material, N,N'-bis(naphthalen-1-yl)-N,N'-diphenylbenzidine (NPB). A better device performance of organic light-emitting diodes (OLEDs) was achieved by doping NPB with HATCN. The improved performance could, in principle, arise from a p-type doping effect in the codeposited thin films. However, physical characteristics evaluations including UV-vis absorption, Fourier transform infrared absorption, and X-ray photoelectron spectroscopy demonstrated that there was no obvious evidence of charge transfer in the NPB:HATCN composite. The performance improvement in NPB:HATCN-based OLEDs is mainly attributed to an interfacial modification effect owing to the diffusion of HATCN small molecules. The interfacial diffusion effect of the HATCN molecules was verified by the in situ ultraviolet photoelectron spectroscopy evaluations. PMID:25970499

  11. Syntheses and spectroscopic and quadratic nonlinear optical properties of extended dipolar complexes with ruthenium(II) ammine electron donor and N-methylpyridinium acceptor groups.

    PubMed

    Coe, Benjamin J; Jones, Lathe A; Harris, James A; Brunschwig, Bruce S; Asselberghs, Inge; Clays, Koen; Persoons, André; Garín, Javier; Orduna, Jesús

    2004-03-31

    In this paper, we describe the extremely unusual optical properties of Ru(II)-based electron donor-acceptor (D-A) polyene and some closely related chromophores. For three different polyene series, the intense, visible d-->pi* metal-to-ligand charge-transfer bands unexpectedly blue-shift as the number of E-ethylene units (n) increases from 1 to 3, and the static first hyperpolarizabilities beta(0) determined via hyper-Rayleigh scattering and Stark spectroscopy maximize at n = 2, in marked contrast to other known D-A polyenes in which beta(0) increases steadily with n. Time-dependent density-functional theory and finite field calculations verify these empirical trends, which arise from the orbital structures of the complexes. This study illustrates that transition metal-based nonlinear optical chromophores can show very different behavior when compared with their more thoroughly studied purely organic counterparts. PMID:15038742

  12. Ab initio MO based lattice energy for molecular crystals: packing structure of electron donor-acceptor (EDA) complex H 3N-BF 3

    NASA Astrophysics Data System (ADS)

    Ikeda, Tohru; Nagayoshi, Kanade; Kitaura, Kazuo

    2003-03-01

    A computational procedure is proposed for calculating the lattice energy of molecular crystals using the ab initio MO method. Our method does not require any adjustable parameters and provides a general description for various molecular crystals including electron donor-acceptor (EDA) complexes. Using the method, the packing structure of H 3N-BF 3 crystal was optimized at the HF/3-21 + G level and the lattice energy was calculated at the MP2/6-311 + G * level. The calculation reproduced the experimental lattice constants with reasonable accuracy. Moreover, the structural feature of the H 3N-BF 3 crystal was discussed based on the molecular interactions in the crystal.

  13. Effects of acceptor-donor complexes on electronic structure properties in co-doped TiO2: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Cai, L. L.; Yuan, X. B.; Hu, G. C.; Ren, J. F.

    2016-07-01

    We theoretically investigate the doping effects induced by impurity complexes on the electronic structures of anatase TiO2 based on the density functional theory. Mono-doping and co-doping effects are discussed separately. The results show that the impurity doping can make the band-edges shift. The induced defect levels in the band gaps by impurity doping reduce the band gap predominantly. The compensated acceptor-donor pairs in the co-doped TiO2 will improve the photoelectrochemical activity. From the calculations, it is also found that (S+Zr)-co-doped TiO2 has the ideal band gap and band edge, at the same time, the binding energy is higher than other systems, so (S+Zr)-co-doping in TiO2 is more promise in photoelectrochemical experiments.

  14. UV-B-induced inhibition of photosystem II electron transport studied by EPR and chlorophyll fluorescence. Impairment of donor and acceptor side components.

    PubMed

    Vass, I; Sass, L; Spetea, C; Bakou, A; Ghanotakis, D F; Petrouleas, V

    1996-07-01

    Inhibition of photosystem II electron transport by UV-B radiation has been studied in isolated spinach photosystem II membrane particles using low-temperature EPR spectroscopy and chlorophyll fluorescence measurements. UV-B irradiation results in the rapid inhibition of oxygen evolution and the decline of variable chlorophyll fluorescence. These effects are accompanied by the loss of the multiline EPR signal arising from the S2 state of the water-oxidizing complex and the induction of Signal IIfast originating from stabilized Try-Z+. The EPR signals from the QA-Fe2+ acceptor complex, Tyr-D+, and the oxidized non-heme iron (Fe3+) are also decreased during the course of UV-B irradiation, but at a significantly slower rate than oxygen evolution and the multiline signal. The decrease of the Fe3+ signal at high g values (g = 8.06, g = 5.6) is accompanied by the induction of another EPR signal at g = 4.26 that arises most likely from the same Fe3+ ion in a modified ligand environment. UV-B irradiation also affects cytochrome b-559. The g = 2.94 EPR signal that arises from the dark- oxidized form is enhanced, whereas the light inducible g = 3.04 signal that arises from the photo-oxidizable population of cytochrome b-559 is diminished. UV-B irradiation also induces the degradation of the D1 reaction center protein. The rate of the D1 protein loss is slower than the inhibition of oxygen evolution and of the multiline signal but follows closely the loss of Signal IIslow, the QA-Fe2+ and the Fe3+ EPR signals, as well as the release of protein-bound manganese. It is concluded from the results that UV-B radiation affects photosystem II redox components at both the donor and acceptor side. The primary damage occurs at the water-oxidizing complex. Modification and/or inactivation of tyrosine-D, cytochrome b-559, and the QAFe2+ acceptor complex are subsequent events that coincide more closely with the UV-B-induced damage to the protein structure of the photosystem II reaction

  15. Long-range coupling of electron-hole pairs in spatially separated organic donor-acceptor layers

    PubMed Central

    Nakanotani, Hajime; Furukawa, Taro; Morimoto, Kei; Adachi, Chihaya

    2016-01-01

    Understanding exciton behavior in organic semiconductor molecules is crucial for the development of organic semiconductor-based excitonic devices such as organic light-emitting diodes and organic solar cells, and the tightly bound electron-hole pair forming an exciton is normally assumed to be localized on an organic semiconducting molecule. We report the observation of long-range coupling of electron-hole pairs in spatially separated electron-donating and electron-accepting molecules across a 10-nanometers-thick spacer layer. We found that the exciton energy can be tuned over 100 megaelectron volts and the fraction of delayed fluorescence can be increased by adjusting the spacer-layer thickness. Furthermore, increasing the spacer-layer thickness produced an organic light-emitting diode with an electroluminescence efficiency nearly eight times higher than that of a device without a spacer layer. Our results demonstrate the first example of a long-range coupled charge-transfer state between electron-donating and electron-accepting molecules in a working device. PMID:26933691

  16. 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.

  17. Soluble Iron as an In Situ Indicator of the Redox State of Humic Substances in Arctic Soil: Implications for Seasonal Regeneration of Oxidized Terminal Electron Acceptors

    NASA Astrophysics Data System (ADS)

    Lipson, D.; Zlamal, J. E.; Srinivas, A. J.; Raab, T. K.

    2014-12-01

    Ferric iron (Fe(III)) and humic substances (HS) are important terminal electron acceptors for anaerobic respiration in wet tundra soils of the Arctic Coastal Plain near Barrow, Alaska. These soils are rich in both solid phase Fe minerals (including oxides such as ferrihydrite and goethite and other minerals with reduced or mixed valence such as siderite and magnetite) and soluble Fe, chelated by siderophores and other small organic molecules. This latter pool may also include nanocolloidal Fe: extremely fine-grained minerals that pass through a 0.2 micron filter. Both the solid phase and aqueous Fe pools undergo seasonal changes in redox state as a result of biological reduction by Fe-reducing microorganisms and oxidation by a variety of potential mechanisms, both abiotic and biotic. These redox cycles of solid and aqueous pools are not in phase: solid phase Fe became progressively more reduced from mid- to late summer, while aqueous phase Fe became reduced over the first half of the summer. It is well-known that HS interact with Fe, and that HS can act as electron shuttles in the reduction of Fe oxides. In other ecosystems chelated Fe(III) has been incubated with soil samples and the resulting Fe(II) produced is used as an indicator of the reducing power of HS. In these Fe-rich Arctic soils, HS are continuously in contact with chelated Fe, and therefore we interpret the redox state of this pool as an indicator of HS redox status. To verify this we conducted redox titrations of extracted HS with both reduced and oxidized Fe chelates and showed that chelated Fe could interact with HS both as electron acceptor and donator. In a field experiment, the addition of oxidized humic acids to soils resulted in an immediate oxidation of the aqueous Fe pool within 24 hours, which we attribute to abiotic oxidation of Fe by HS, followed by a slow reduction of this pool over the next week, presumably due to biological Fe reduction of the HS/aqueous Fe pool. At the end of summer

  18. Acceptors in ZnO

    SciTech Connect

    McCluskey, Matthew D. Corolewski, Caleb D.; Lv, Jinpeng; Tarun, Marianne C.; Teklemichael, Samuel T.; Walter, Eric D.; Norton, M. Grant; Harrison, Kale W.; Ha, Su

    2015-03-21

    Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence indicates these point defects have acceptor levels 3.2, 1.4, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO{sub 2} contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peak in ZnO nanocrystals is attributed to an acceptor, which may involve a Zn vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g{sub ⊥} = 2.0015 and g{sub //} = 2.0056, along with an isotropic center at g = 2.0035.

  19. Acceptors in ZnO

    SciTech Connect

    Mccluskey, Matthew D.; Corolewski, Caleb; Lv, Jinpeng; Tarun, Marianne C.; Teklemichael, Samuel T.; Walter, Eric D.; Norton, M. G.; Harrison, Kale W.; Ha, Su Y.

    2015-03-21

    Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence shows that these point defects have acceptor levels 3.2, 1.5, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO2 contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peak in ZnO nanocrystals has been attributed to an acceptor, which may involve a zinc vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g = 2.0033 and g = 2.0075, along with an isotropic center at g = 2.0053.

  20. Functional Inactivation of Putative Photosynthetic Electron Acceptor Ferredoxin C2 (FdC2) Induces Delayed Heading Date and Decreased Photosynthetic Rate in Rice

    PubMed Central

    Ruan, Banpu; Kang, Shujing; He, Lei; Zhang, Sen; Dong, Guojun; Hu, Jiang; Zeng, Dali; Zhang, Guangheng; Gao, Zhenyu; Ren, Deyong; Hu, Xingming; Chen, Guang; Guo, Longbiao; Qian, Qian; Zhu, Li

    2015-01-01

    Ferredoxin (Fd) protein as unique electron acceptor, involved in a variety of fundamental metabolic and signaling processes, which is indispensable for plant growth. The molecular mechanisms of Fd such as regulation of electron partitioning, impact of photosynthetic rate and involvement in the carbon fixing remain elusive in rice. Here we reported a heading date delay and yellowish leaf 1 (hdy1) mutant derived from Japonica rice cultivar “Nipponbare” subjected to EMS treatment. In the paddy field, the hdy1 mutant appeared at a significantly late heading date and had yellow-green leaves during the whole growth stage. Further investigation indicated that the abnormal phenotype of hdy1 was connected with depressed pigment content and photosynthetic rate. Genetic analysis results showed that the hdy1 mutant phenotype was caused by a single recessive nuclear gene mutation. Map-based cloning revealed that OsHDY1 is located on chromosome 3 and encodes an ortholog of the AtFdC2 gene. Complementation and overexpression, transgenic plants exhibited the mutant phenotype including head date, leaf color and the transcription levels of the FdC2 were completely rescued by transformation with OsHDY1. Real-time PCR revealed that the expression product of OsHDY1 was detected in almost all of the organs except root, whereas highest expression levels were observed in seeding new leaves. The lower expression levels of HDY1 and content of iron were detected in hdy1 than WT’s. The FdC2::GFP was detected in the chloroplasts of rice. Real-time PCR results showed that the expression of many photosynthetic electron transfer related genes in hdy1 were higher than WT. Our results suggest that OsFdC2 plays an important role in photosynthetic rate and development of heading date by regulating electron transfer and chlorophyll content in rice. PMID:26598971

  1. On the Potential of Using the Al7 Superatom as an Excess Electron Acceptor To Construct Materials with Excellent Nonlinear Optical Properties.

    PubMed

    Huang, Shaoyuan; Liao, Kuntian; Peng, Bin; Luo, Qiong

    2016-05-01

    With the aid of density functional theory (DFT) calculations, we found that, when alkali metal approaches the Al7 superatom, its outermost s-value electron can be trapped by Al7 to give the superatom compound MAl7 (M = Li, Na, K) with an excess electron. Different analyses including natural bond orbital (NBO), electron localization function (ELF), and energy decomposition analysis (EDA) show that the resulting M-Al bond is strong and has a polar covalent character. The optimizations of self-assemblies (MAl7)n (n = 2, 3) have been performed to explore the stability of MAl7 in the solid state. The results reveal that only NaAl7 can keep its structural integrity as a building block upon self-assembling, while serious aggregations between Al7 clusters occur in the dimers and trimers of LiAl7 and KAl7, despite the fact that the Li-Al7 and K-Al7 bond energies are comparable to that of Na-Al7. Born-Oppenheimer molecular dynamics (BOMD) simulations for (NaAl7)n (n = 2, 3) indicate that these species are stable toward fragmentation at 300 K. The β0 values of (NaAl7)n (n = 1, 2, and 3) predicted at the CAM-B3LYP/6-311+G(3df) level of theory are in the range of 1.6 × 10(4)a.u. to 7.5 × 10(4) a.u.. This theoretical study implies that NaAl7 is a promising candidate for nolinear optical (NLO) materials. We provide theoretical evidence for the possibility of using the Al7 superatom as an excess electron acceptor to construct materials with excellent NLO properties. Further experimental research is invited. PMID:27064431

  2. Functional Inactivation of Putative Photosynthetic Electron Acceptor Ferredoxin C2 (FdC2) Induces Delayed Heading Date and Decreased Photosynthetic Rate in Rice.

    PubMed

    Zhao, Juan; Qiu, Zhennan; Ruan, Banpu; Kang, Shujing; He, Lei; Zhang, Sen; Dong, Guojun; Hu, Jiang; Zeng, Dali; Zhang, Guangheng; Gao, Zhenyu; Ren, Deyong; Hu, Xingming; Chen, Guang; Guo, Longbiao; Qian, Qian; Zhu, Li

    2015-01-01

    Ferredoxin (Fd) protein as unique electron acceptor, involved in a variety of fundamental metabolic and signaling processes, which is indispensable for plant growth. The molecular mechanisms of Fd such as regulation of electron partitioning, impact of photosynthetic rate and involvement in the carbon fixing remain elusive in rice. Here we reported a heading date delay and yellowish leaf 1 (hdy1) mutant derived from Japonica rice cultivar "Nipponbare" subjected to EMS treatment. In the paddy field, the hdy1 mutant appeared at a significantly late heading date and had yellow-green leaves during the whole growth stage. Further investigation indicated that the abnormal phenotype of hdy1 was connected with depressed pigment content and photosynthetic rate. Genetic analysis results showed that the hdy1 mutant phenotype was caused by a single recessive nuclear gene mutation. Map-based cloning revealed that OsHDY1 is located on chromosome 3 and encodes an ortholog of the AtFdC2 gene. Complementation and overexpression, transgenic plants exhibited the mutant phenotype including head date, leaf color and the transcription levels of the FdC2 were completely rescued by transformation with OsHDY1. Real-time PCR revealed that the expression product of OsHDY1 was detected in almost all of the organs except root, whereas highest expression levels were observed in seeding new leaves. The lower expression levels of HDY1 and content of iron were detected in hdy1 than WT's. The FdC2::GFP was detected in the chloroplasts of rice. Real-time PCR results showed that the expression of many photosynthetic electron transfer related genes in hdy1 were higher than WT. Our results suggest that OsFdC2 plays an important role in photosynthetic rate and development of heading date by regulating electron transfer and chlorophyll content in rice. PMID:26598971

  3. Associative Memory Acceptors.

    ERIC Educational Resources Information Center

    Card, Roger

    The properties of an associative memory are examined in this paper from the viewpoint of automata theory. A device called an associative memory acceptor is studied under real-time operation. The family "L" of languages accepted by real-time associative memory acceptors is shown to properly contain the family of languages accepted by one-tape,…

  4. The surface properties of Shewanella putrefaciens 200 and S. oneidensis MR-1: the effect of pH and terminal electron acceptors

    PubMed Central

    2013-01-01

    Background We investigated the surface characteristics of two strains of Shewanella sp., S. oneidensis MR-1 and S. putrefaciens 200, that were grown under aerobic conditions as well as under anaerobic conditions with trimethylamine oxide (TMAO) as the electron acceptor. The investigation focused on the experimental determination of electrophoretic mobility (EPM) under a range of pH and ionic strength, as well as by subsequent modeling in which Shewanella cells were considered to be soft particles with water- and ion-permeable outermost layers. Results The soft layer of p200 is significantly more highly charged (i.e., more negative) than that of MR-1. The effect of electron acceptor on the soft particle characteristics of Shewanella sp. is complex. The fixed charge density, which is a measure of the deionized and deprotonated functional groups in the soft layer polymers, is slightly greater (i.e., more negative) for aerobically grown p200 than for p200 grown with TMAO. On the other hand, the fixed charge density of aerobically grown MR1 is slightly less than that of p200 grown with TMAO. The effect of pH on the soft particle characteristics is also complex, and does not exhibit a clear pH-dependent trend. Conclusions The Shewanella surface characteristics were attributed to the nature of the outermost soft layer, the extracellular polymeric substances (EPS) in case of p200 and lypopolysaccharides (LPS) in case of MR1 which generally lacks EPS. The growth conditions (i.e., aerobic vs. anaerobic TMAO) have an influence on the soft layer characteristics of Shewanella sp. cells. Meanwhile, the clear pH dependency of the mechanical and morphological characteristics of EPS and LPS layers, observed in previous studies through atomic force microscopy, adhesion tests and spectroscopies, cannot be corroborated by the electrohydrodynamics-based soft particle characteristics which does not exhibited a clear pH dependency in this study. While the electrohydrodynamics-based soft

  5. Evaluating microbial chemical choices: The ocean chemistry basis for the competition between use of O2 or NO3- as an electron acceptor

    NASA Astrophysics Data System (ADS)

    Brewer, Peter G.; Hofmann, Andreas F.; Peltzer, Edward T.; Ussler, William, III

    2014-05-01

    The traditional ocean chemical explanation for the emergence of suboxia is that once O2 levels decline to about 10 μmol kg-1 then onset of NO3- reduction occurs. This piece of ocean chemical lore is well founded in observations and is typically phrased as a microbial choice and not as an obligate requirement. The argument based on O2 levels alone could also be phrased as being dependent on an equivalent amount of NO3- that would yield the same energy gain. This description is based on the availability of the electron acceptor: but the oxidation reactions are usually written out as free energy yield per mole of organic matter, thus not addressing the oxidant availability constraint invoked by ocean scientists. Here we show that the argument can be phrased simply as competing rate processes dependent on the free energy yield ratio per amount of electron acceptor obtained, and thus the [NO3-]:[O2] molar ratio is the critical variable. The rate at which a microbe can acquire either O2 or NO3- to carry out the oxidation reactions is dependent on both the concentration in the bulk ocean, and on the diffusivity within the microbial external molecular boundary layer. From the free energy yield calculations combined with the ~25% greater diffusivity of the O2 molecule we find that the equivalent energy yield occurs at a ratio of about 3.8 NO3-:O2 for a typical Redfield ratio reaction, consistent with an ocean where NO3- reduction onset occurs at about 10 μmol O2:40 μmol NO3-, and the reactions then proceed in parallel along a line of this slope until the next energy barrier is approached. Within highly localized microbial consortia intensely reducing pockets may occur in a bulk ocean containing finite low O2 levels; and the local flux of reduced species from strongly reducing shelf sediments will perturb the large scale water column relationship. But all localized reactions drive towards maximal energy gain from their immediate diffusive surroundings, thus the ocean

  6. Evolution of the microbial community of the biofilm in a methane-based membrane biofilm reactor reducing multiple electron acceptors.

    PubMed

    Chen, Ran; Luo, Yi-Hao; Chen, Jia-Xian; Zhang, Yin; Wen, Li-Lian; Shi, Ling-Dong; Tang, Youneng; Rittmann, Bruce E; Zheng, Ping; Zhao, He-Ping

    2016-05-01

    Previous work documented complete perchlorate reduction in a membrane biofilm reactor (MBfR) using methane as the sole electron donor and carbon source. This work explores how the biofilm's microbial community evolved as the biofilm stage-wise reduced different combinations of perchlorate, nitrate, and nitrite. The initial inoculum, carrying out anaerobic methane oxidation coupled to denitrification (ANMO-D), was dominated by uncultured Anaerolineaceae and Ferruginibacter sp. The microbial community significantly changed after it was inoculated into the CH4-based MBfR and fed with a medium containing perchlorate and nitrite. Archaea were lost within the first 40 days, and the uncultured Anaerolineaceae and Ferruginibacter sp. also had significant losses. Replacing them were anoxic methanotrophs, especially Methylocystis, which accounted for more than 25 % of total bacteria. Once the methanotrophs became important, methanol-oxidizing denitrifying bacteria, namely, Methloversatilis and Methylophilus, became important in the biofilm, probably by utilizing organic matter generated by the metabolism of methanotrophs. When methane consumption was equal to the maximum-possible electron-donor supply, Methylomonas, also an anoxic methanotroph, accounted for >10 % of total bacteria and remained a major part of the community until the end of the experiments. We propose that aerobic methane oxidation coupled to denitrification and perchlorate reduction (AMO-D and AMO-PR) directly oxidized methane and reduced NO3 (-) to NO2 (-) or N2O under anoxic condition, producing organic matter for methanol-assimilating denitrification and perchlorate reduction (MA-D and MA-PR) to reduce NO3 (-). Simultaneously, bacteria capable of anaerobic methane oxidation coupled to denitrification and perchlorate reduction (ANMO-D and ANMO-PR) used methane as the electron donor to respire NO3 (-) or ClO4 (-) directly. Graphical Abstract ᅟ. PMID:26841777

  7. Photochemical Tyrosine Oxidation with a Hydrogen-Bonded Proton Acceptor by Bidirectional Proton-Coupled Electron Transfer

    PubMed Central

    Pizano, Arturo A.; Yang, Jay L.

    2012-01-01

    Amino acid radical generation and transport are fundamentally important to numerous essential biological processes to which small molecule models lend valuable mechanistic insights. Pyridyl-amino acid-methyl esters are appended to a rhenium(I) tricarbonyl 1,10-phenanthroline core to yield rhenium–amino acid complexes with tyrosine ([Re]–Y–OH) and phenylalanine ([Re]–F). The emission from the [Re] center is more significantly quenched for [Re]–Y–OH upon addition of base. Time-resolved studies establish that excited-state quenching occurs by a combination of static and dynamic mechanisms. The degree of quenching depends on the strength of the base, consistent with a proton-coupled electron transfer (PCET) quenching mechanism. Comparative studies of [Re]–Y–OH and [Re]–F enable a detailed mechanistic analysis of a bidirectional PCET process. PMID:23495362

  8. Electronic structure, molecular orientation, charge transfer dynamics and solar cells performance in donor/acceptor copolymers and fullerene: Experimental and theoretical approaches

    SciTech Connect

    Garcia-Basabe, Y.; Borges, B. G. A. L.; Rocco, M. L. M. E-mail: luiza@iq.ufrj.br; Marchiori, C. F. N.; Yamamoto, N. A. D.; Koehler, M.; Roman, L. S. E-mail: luiza@iq.ufrj.br; Macedo, A. G.

    2014-04-07

    By combining experimental and theoretical approaches, the electronic structure, molecular orientation, charge transfer dynamics and solar cell performance in donor/acceptor copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl) benzo-2,1,3-thiadiazole] (PSiF-DBT) films and blended with 6,6.-phenyl-C 61-butyric acid methyl ester (PSiF-DBT:PCBM) were investigated. Good agreement between experimental and theoretical PSiF-DBT UV-Vis absorption spectrum is observed and the main molecular orbitals contributing to the spectrum were determined using DFT single point calculations. Non-coplanar configuration was determined by geometric optimization calculation in isolated PSiF-DBT pentamer and corroborated by angular variation of the sulphur 1s near-edge X-ray absorption fine structure (NEXAFS) spectra. Edge-on and plane-on molecular orientations were obtained for thiophene and benzothiadiazole units, respectively. A power conversion efficiency up to 1.58%, open circuit voltage of 0.51 V, short circuit current of 8.71 mA/cm{sup 2} and a fill factor of 35% was obtained using blended PSiF-DBT:PCBM as active layer in a bulk heterojunction solar cell. Ultrafast electron dynamics in the low-femtosecond regime was evaluated by resonant Auger spectroscopy using the core-hole clock methodology around sulphur 1s absorption edge. Electron delocalization times for PSiF-DBT and PSiF-DBT:PCBM polymeric films were derived for selected excitation energies corresponding to the main transitions in the sulphur 1s NEXAFS spectra. The mixture of PSiF-DBT with PCBM improves the charge transfer process involving the π* molecular orbital of the thiophene units.

  9. Enhancement of p-Type Dye-Sensitized Solar Cell Performance by Supramolecular Assembly of Electron Donor and Acceptor

    PubMed Central

    Tian, Haining; Oscarsson, Johan; Gabrielsson, Erik; Eriksson, Susanna K.; Lindblad, Rebecka; Xu, Bo; Hao, Yan; Boschloo, Gerrit; Johansson, Erik M. J.; Gardner, James M.; Hagfeldt, Anders; Rensmo, Håkan; Sun, Licheng

    2014-01-01

    Supramolecular interactions based on porphyrin and fullerene derivatives were successfully adopted to improve the photovoltaic performance of p-type dye-sensitized solar cells (DSCs). Photoelectron spectroscopy (PES) measurements suggest a change in binding configuration of ZnTCPP after co-sensitization with C60PPy, which could be ascribed to supramolecular interaction between ZnTCPP and C60PPy. The performance of the ZnTCPP/C60PPy-based p-type DSC has been increased by a factor of 4 in comparison with the DSC with the ZnTCPP alone. At 560 nm, the IPCE value of DSCs based on ZnTCPP/C60PPy was a factor of 10 greater than that generated by ZnTCPP-based DSCs. The influence of different electrolytes on charge extraction and electron lifetime was investigated and showed that the enhanced Voc from the Co2+/3+(dtbp)3-based device is due to the positive EF shift of NiO. PMID:24603319

  10. Photobehavior of the geometrical isomers of two 1,4-distyrylbenzene analogues with side groups of different electron donor/acceptor character.

    PubMed

    Ciorba, S; Galiazzo, G; Mazzucato, U; Spalletti, A

    2010-10-14

    The photobehavior of two 1,4-distyrylbenzene analogues where the central benzene ring is asymmetrically substituted with a pyrid-4-ylethenyl group at one side and thien-2-ylethenyl or a p-nitrostyryl group at the other side, has been studied in two solvents at room temperature. The four geometrical isomers (EE, ZE, EZ, and ZZ) of each compound were separated by the combined use of HPLC and spectrophotometric techniques. The radiative/reactive competition in their excited state relaxation was particularly examined: the diabatic/adiabatic contributions were estimated and a reasonable interpretation of the photoisomerization mechanism was proposed. The role of the conformational isomers was also investigated by measured and computed spectral data. Since the different electron donor/acceptor character of the side groups of these molecules can induce charge transfer phenomena that can affect the relaxation pathways of their excited states, the photobehavior was compared in inert and polar solvents to clarify the role of the intramolecular charge transfer. The latter was found to affect markedly the relaxation properties and to induce interesting fluorosolvatochromic effects, particularly in the p-nitro derivative. The participation of the triplet state in the reaction mechanism of the latter was also investigated by flash photolysis and sensitized experiments. PMID:20857985

  11. Electronic and optical properties of novel carbazole-based donor-acceptor compounds for applications in blue-emitting organic light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Legaspi, Christian M.; Stubbs, Regan E.; Yaron, David J.; Peteanu, Linda A.; Sfeir, Matthew Y.; Kemboi, Abraham; Picker, Jesse; Fossum, Eric

    2015-08-01

    Organic light-emitting diodes (OLEDs) have received a significant attention over the past decade due to their energy-saving potential. We have recently synthesized two novel carbazole-based donor-acceptor compounds and analyzed their optical properties to determine their suitability for use as blue emitters in OLEDs. These compounds show remarkable photo-stability and high quantum yields in the blue region of the spectrum. In addition, they have highly solvatochromic emission. In non-polar solvents, bright, blue-shifted (λmax ≈ 398 nm), and highly structured emission is seen. With increasing solvent dielectric constant, the emission becomes weaker, red-shifted (λmax ≈ 507 nm), and broad. We aim to determine the underlying cause of these changes. Electronic structure calculations indicate the presence of multiple excited states with comparable oscillator strength. These states are of interest because there are several with charge-transfer (CT) character, and others centered on the donor moiety. We theorize that CT states play a role in the observed changes in emission lineshape and may promote charge mobility for electrofluorescence in OLEDs. In the future, we plan to use Stark spectroscopy to analyze the polarity of excited states and transient absorption spectroscopy to observe the dynamics in the excited state.

  12. Sulfonates as Terminal Electron Acceptors for Growth of Sulfite-Reducing Bacteria (Desulfitobacterium spp.) and Sulfate-Reducing Bacteria: Effects of Inhibitors of Sulfidogenesis

    PubMed Central

    Lie, Thomas J.; Godchaux, Walter; Leadbetter, Edward R.

    1999-01-01

    This study demonstrates the ability of Desulfitobacterium spp. to utilize aliphatic sulfonates as terminal electron acceptors (TEA) for growth. Isethionate (2-hydroxyethanesulfonate) reduction by Desulfitobacterium hafniense resulted in acetate as well as sulfide accumulation in accordance with the expectation that the carbon portion of isethionate was oxidized to acetate and the sulfur was reduced to sulfide. The presence of a polypeptide, approximately 97 kDa, was evident in isethionate-grown cells of Desulfitobacterium hafniense, Desulfitobacterium sp. strain PCE 1, and the two sulfate-reducing bacteria (SRB)—Desulfovibrio desulfuricans IC1 (T. J. Lie, J. R. Leadbetter, and E. R. Leadbetter, Geomicrobiol. J. 15:135–149, 1998) and Desulfomicrobium norvegicum; this polypeptide was not detected when these bacteria were grown on TEA other than isethionate, suggesting involvement in its metabolism. The sulfate analogs molybdate and tungstate, effective in inhibiting sulfate reduction by SRB, were examined for their effects on sulfonate reduction. Molybdate effectively inhibited sulfonate reduction by strain IC1 and selectively inhibited isethionate (but not cysteate) reduction by Desulfitobacterium dehalogenans and Desulfitobacterium sp. strain PCE 1. Desulfitobacterium hafniense, however, grew with both isethionate and cysteate in the presence of molybdate. In contrast, tungstate only partially inhibited sulfonate reduction by both SRB and Desulfitobacterium spp. Similarly, another inhibitor of sulfate reduction, 1,8-dihydroxyanthraquinone, effectively inhibited sulfate reduction by SRB but only partially inhibited sulfonate reduction by both SRB and Desulfitobacterium hafniense. PMID:10508097

  13. Formation of Unique Tellurium Nanocrystals with Anaerobic Growth of Bacillus selenitireducens and Sulfurospirillum barnesii using Te-oxyanions as Electron Acceptors.

    NASA Astrophysics Data System (ADS)

    Baesman, S. M.; Bullen, T. D.; Dewald, J.; Zhang, D. H.; Curran, S.; Islam, F. S.; Beveridge, T. J.; Oremland, R. S.

    2006-12-01

    A number of otherwise toxic elements are now known to support the metabolism of diverse prokaryotes by serving as electron acceptors for their anaerobic growth. Here we demonstrate that two microorganisms previously shown capable of respiring both As- and Se-oxyanions are also capable of achieving growth by the respiratory reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This dissimilatory reduction achieves a sizeable (epsilon = ~ 4 per mil) Te stable isotopic fractionation, and results in the formation of unique crystalline Te(0) endproducts. These Te(0) crystals occur externally from the cells and exhibit a diversity of forms. Structures formed by B. selenitireducens are nanorods (10 nm diameter x 200 nm length), and large (approx. 1,000 nm) rosettes composed of numerous individual shards (100 nm width x 1,000 nm length). In contrast, S. barnesii primarily forms large composite aggregates made up of many individual, irregularly-shaped nanospheres (diameter = less than 50 nm). These diverse, bacterially-formed Te(0) nanomaterials have unique spectral signatures (e.g., UV-VIS, Raman) that provide clues to their internal structure. We suggest that harnessing the ability of microorganisms to generate nanomaterials composed of rare elements may be an attractive alternative to the employment of harsh chemicals for bench-scaled syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods.

  14. (Dibenzoylmethanato)boron difluoride derivatives containing triphenylamine moieties: a new type of electron-donor/π-acceptor system for dye-sensitized solar cells.

    PubMed

    Mizuno, Yosuke; Yisilamu, Yilihamu; Yamaguchi, Tomoya; Tomura, Masaaki; Funaki, Takashi; Sugihara, Hideki; Ono, Katsuhiko

    2014-10-01

    (Dibenzoylmethanato)boron difluoride derivatives containing triphenylamine moieties were synthesized as a new type of electron-donor/π-acceptor system. These new compounds exhibited long-wavelength absorptions in the UV/Vis spectra, and reversible oxidation and reduction waves in cyclic voltammetry experiments. Their amphoteric redox properties are based on their resonance hybrid forms, in which a positive charge is delocalized on the triphenylamine moieties and a negative charge is localized on the boron atoms. Molecular orbital (MO) calculations indicate that their HOMO and LUMO energies vary with the number of phenylene rings connected to the difluoroboron-chelating ring. This is useful for optimizing the HOMO and LUMO levels to an iodine redox (I(-)/I3(-)) potential and a titanium dioxide conduction band, respectively. Dye-sensitized solar cells fabricated by using these compounds as dye sensitizers exhibited solar-to-electric power conversion efficiencies of 2.7-4.4 % under AM 1.5 solar light. PMID:25170797

  15. Mathematical modeling of autotrophic denitrification (AD) process with sulphide as electron donor.

    PubMed

    Xu, Guihua; Yin, Fengjun; Chen, Shaohua; Xu, Yuanjian; Yu, Han-Qing

    2016-03-15

    Autotrophic denitrification (AD) plays a critical role in nitrate removal from organic carbon-deficient wastewaters with a high level of nitrogen oxides. However, the AD process is not included in the current denitrification models, which limits the application of AD technology for wastewater treatment. In this work, a kinetic model for AD process involved 4 processes and 5 components with 9 parameters is established to describe the sulphide biooxidation and nitrite removal process. In this model, 4 oxidation-reduction reactions using sulphide as electronic donor in the AD process are taken into account. The model parameters are optimized by fitting data from the experiments with different combinations of sulphide, sulphur, sulphate, nitrate and nitrite at various concentrations. Model calibration and validation results demonstrate that the developed model is able to reasonably describe the removal rates of nitrate, nitrite, sulphide and sulphur in the AD process. The model simulation results also show that the sulphur term (η(S)) in the kinetic equations of nitrate, nitrite, sulphur and sulphate remains constant, rather than being controlled by its own concentration. Furthermore, with this model the products of sulphide biooxidation in the AD process, sulphur and sulphate, and their concentrations can be accurately predicted. Therefore, this model provides a strategy to control the sulphate concentration below the discharge limits or recover sulphur as the main end product from sulphide biooxidation. PMID:26799712

  16. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: Comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment

    SciTech Connect

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.

    2015-03-21

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical “gating” distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working

  17. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment.

    PubMed

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J Timothy; Champion, Paul M

    2015-03-21

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near

  18. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: Comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment

    NASA Astrophysics Data System (ADS)

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.

    2015-03-01

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near

  19. Proteome of Geobacter sulfurreducens grown with Fe(III) oxide or Fe(III) citrate as the electron acceptor.

    SciTech Connect

    Ding, Y-H R.; Hixson, Kim K.; Aklujkar, Ma; Lipton, Mary S.; Smith, Richard D.; Lovley, Derek R.; Mester, Tunde

    2008-12-01

    e(III) oxides are the most abundant source of reducible Fe(III) by microorganisms in most soils and sediments, yet few studies on the physiology of Fe(III)-reducing microorganisms during growth on Fe(III) oxide have been conducted because of the technical difficulties in working with cell growth and harvest in the presence of Fe(III) oxides. Geobacter sulfurreducens is a representative of the Geobacter species that predominate in a variety of subsurface environments in which Fe(III) oxide is important. In order to better understand the physiology of Geobacter species during growth on Fe(III) oxide, the proteome of G. sulfurreducens grown on Fe(III) oxide was compared with the proteome of cells grown with soluble Fe(III) citrate. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) revealed 19 proteins that were more abundant during growth on Fe(III) oxide than on soluble Fe(III). These included proteins related to protein synthesis, electron transfer and energy production, oxidative stress, protein folding, outer membrane proteins, nitrogen metabolism and hypothetical proteins. Further analysis of the proteome with the accurate mass and time (AMT) tag method revealed additional proteins associated with growth on Fe(III) oxide. These included the outer-membrane c-type cytochrome, OmcS and OmcG, which genetic studies have suggested are required for Fe(III) oxide reduction. Furthermore, several other cytochromes, as yet unstudied, were detected to be significantly up regulated during growth on Fe(III) oxide and other proteins of unknown function were more abundant during growth on Fe(III) oxide than on soluble Fe(III). PilA, the structural protein for pili, which is required for Fe(III) oxide reduction, and other pilin-associated proteins were also more abundant during growth on Fe(III) oxide. Confirmation of the differential expression of proteins known to be important in Fe(III) oxide reduction was observed, and an additional number of previously

  20. A putative multicopper protein secreted by an atypical type II secretion system involved in the reduction of insoluble electron acceptors in Geobacter sulfurreducens.

    PubMed

    Mehta, Teena; Childers, Susan E; Glaven, Richard; Lovley, Derek R; Mester, Tünde

    2006-08-01

    Extracellular electron transfer onto Fe(III) oxides in Geobacter sulfurreducens is considered to require proteins that must be exported to the outer surface of the cell. In order to investigate this, the putative gene for OxpG, the pseudopilin involved in a type II general secretion pathway of Gram-negative bacteria, was deleted. The mutant was unable to grow with insoluble Fe(III) oxide as the electron acceptor. Growth on soluble Fe(III) was not affected. An analysis of proteins that accumulated in the periplasm of the oxpG mutant, but not in the wild-type, led to the identification of a secreted protein, OmpB. OmpB is predicted to be a multicopper protein, with highest homology to the manganese oxidase, MofA, from Leptothrix discophora. OmpB contains a potential Fe(III)-binding site and a fibronectin type III domain, suggesting a possible role for this protein in accessing Fe(III) oxides. OmpB was localized to the membrane fraction of G. sulfurreducens and in the supernatant of growing cultures, consistent with the type II secretion system exporting OmpB. A mutant in which ompB was deleted had the same phenotype as the oxpG mutant, suggesting that the failure to export OmpB was responsible for the inability of the oxpG-deficient mutant to reduce Fe(III) oxide. This is the first report that proposes a role for a multicopper oxidase-like protein in an anaerobic organism. These results further emphasize the importance of outer-membrane proteins in Fe(III) oxide reduction and suggest that outer-membrane proteins other than c-type cytochromes are required for Fe(III) oxide reduction in Geobacter species. PMID:16849792

  1. Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells

    DOEpatents

    Jenekhe, Samson A; Subramaniyan, Selvam; Ahmed, Eilaf; Xin, Hao; Kim, Felix Sunjoo

    2014-10-28

    The inventions disclosed, described, and/or claimed herein relate to copolymers comprising copolymers comprising electron accepting A subunits that comprise thiazolothiazole, benzobisthiazole, or benzobisoxazoles rings, and electron donating subunits that comprise certain heterocyclic groups. The copolymers are useful for manufacturing organic electronic devices, including transistors and solar cells. The invention also relates to certain synthetic precursors of the copolymers. Methods for making the copolymers and the derivative electronic devices are also described.

  2. Developing an Accelerator Driven System (ADS) based on electron accelerators and heavy water

    NASA Astrophysics Data System (ADS)

    Feizi, H.; Ranjbar, A. H.

    2016-02-01

    An ADS based on electron accelerators has been developed specifically for energy generation and medical applications. Monte Carlo simulations have been performed using FLUKA code to design a hybrid electron target and the core components. The composition, geometry of conversion targets and the coolant system have been optimized for electron beam energies of 20 to 100 MeV . Furthermore, the photon and photoneutron energy spectra, distribution and energy deposition for various incoming electron beam powers have been studied. Light-heavy water of various mixtures have been used as heat removal for the targets, as γ-n converters and as neutron moderators. We have shown that an electron LINAC, as a neutron production driver for ADSs, is capable of producing a neutron output of > 3.5 × 1014 (n/s/mA). Accordingly, the feasibility of an electron-based ADS employing the designed features is promising for energy generation and high intense neutron production which have various applications such as medical therapies.

  3. The Nature of the Donor Motif in Acceptor-Bridge-Donor Dyes as an Influence in the Electron Photo-Injection Mechanism in DSSCs.

    PubMed

    Zarate, Ximena; Schott-Verdugo, Stephan; Rodriguez-Serrano, Angela; Schott, Eduardo

    2016-03-10

    The combination and balance of acceptor(A)-bridge-donor(D) architecture of molecules confer suitable attributes and/or properties to act as efficient light-harvesting and sensitizers in dye sensitized solar cells (DSSCs). An important process in a DSSC performance is the electron photoinjection (PI) mechanism which can take place either via type I (indirect), that consists in injecting from the excited state of the dye to the semiconductor, or type II (direct), where the PI is from the ground state of the dye to the semiconductor upon photoexcitation. Here, we present a computational study about the role of the donor motif in the PI mechanisms displayed from a family of 11 A-bridge-D structured dyes to a (TiO2)15 anatase cluster. To this end, different donor motifs (D1-D11) were evaluated while the A and bridge motifs remained the same. All the computations were carried out within the DFT framework, using the B3LYP, PW91, PBE, M06L and CAM-B3LYP functionals. The 6-31G(d) basis set was employed for nonmetallic atoms and the LANL2DZ pseudopotential for Ti atoms. The solvation effects were incorporated using the polarized continuum model (PCM) for acetonitrile. As benchmark systems, alizarin and naphthalenediol dyes were analyzed, as they are known to undergo Type I and Type II PI pathways in DSSCs, respectively. Donors in the studied family of dyes could influence to drive Type I or II PI since it was found that D2 could show some Type II PI route, showing a new absorption band, although with CAM-B3LYP this shows a very low oscillator strength, while the remaining dyes behave according to Type I photoinjectors. Finally, the photovoltaic parameters that govern the light absorption process were evaluated, as the use of these criteria could be applied to predict the efficiency of the studied dyes in DSSCs devices. PMID:26900717

  4. The strontium inorganic mutant of the water oxidizing center (CaMn4O5) of PSII improves WOC efficiency but slows electron flux through the terminal acceptors.

    PubMed

    Gates, Colin; Ananyev, Gennady; Dismukes, G Charles

    2016-09-01

    Herein we extend prior studies of biosynthetic strontium replacement of calcium in PSII-WOC core particles to characterize whole cells. Previous studies of Thermosynechococcus elongatus found a lower rate of light-saturated O2 from isolated PSII-WOC(Sr) cores and 5-8× slower rate of oxygen release. We find similar properties in whole cells, and show it is due to a 20% larger Arrhenius activation barrier for O2 evolution. Cellular adaptation to the sluggish PSII-WOC(Sr) cycle occurs in which flux through the QAQB acceptor gate becomes limiting for turnover rate in vivo. Benzoquinone derivatives that bind to QB site remove this kinetic chokepoint yielding 31% greater O2 quantum yield (QY) of PSII-WOC(Sr) vs. PSII-WOC(Ca). QY and efficiency of the WOC(Sr) catalytic cycle are greatly improved at low light flux, due to fewer misses and backward transitions and 3-fold longer lifetime of the unstable S3 state, attributed to greater thermodynamic stabilization of the WOC(Sr) relative to the photoactive tyrosine YZ. More linear and less cyclic electron flow through PSII occurs per PSII-WOC(Sr). The organismal response to the more active PSII centers in Sr-grown cells at 45°C is to lower the number of active PSII-WOC per Chl, producing comparable oxygen and energy per cell. We conclude that redox and protonic energy fluxes created by PSII are primary determinants for optimal growth rate of T. elongatus. We further conclude that the (Sr-favored) intermediate-spin S=5/2 form of the S2 state is the active form in the catalytic cycle relative to the low-spin S=1/2 form. PMID:27317268

  5. BPM ANALOG FRONT-END ELECTRONICS BASED ON THE AD8307 LOG AMPLIFIER

    SciTech Connect

    R. SHURTER; ET AL

    2000-06-01

    Beam position monitor (BPM) signal-processing electronics utilizing the Analog Devices AD8307 logarithmic amplifier has been developed for the Low Energy Demonstration Accelerator (LEDA), part of the Accelerator Production of Tritium (APT) project at Los Alamos. The low-pass filtered 350 MHz fundamental signal from each of the four microstrip electrodes in a BPM is ''detected'' by an AD8307 log amp, amplified and scaled to accommodate the 0 to +5V input of an analog-to-digital (A/D) converter. The resultant four digitized signals represent a linear power relationship to the electrode signals, which are in turn related to beam current and position. As the AD8307 has a potential dynamic range of approximately 92 dB, much attention must be given to noise reduction, sources of which can be digital signals on the same board, power supplies, inter-channel coupling, stray RF and others. This paper will describe the operational experience of this particular analog front-end electronic circuit design.

  6. PHOTOVOLTAIC PROPERTIES OF AU-MEROCYANINE-TiO2 SANDWICH CELLS. II. PROPERTIES OF ILLUMINATED CELLS AND EFFECTS OF DOPING WITH ELECTRON ACCEPTORS

    SciTech Connect

    Skotheim, T.; Yang, J.-M.; Otvos, J.; Klein, M.P.

    1980-07-01

    Photocurrent generation in thin films of a merocyanine photosensitizing dye sandwiched between a TiO{sub 2} single crystal doped n type and an Au overlayer has been studied using photovoltaic techniques. A theoretical model was developed to explain the observed photovoltaic properties. The model assumes that the principal route for the formation of charge carriers is via singlet excitons diffusing to the merocyanine - TiO{sub 2} interface followed by dissociation of the excitons into electron-hole pairs, the electrons being injected into the TiO{sub 2} conduction band and the holes into the merocyanine. The model also incorporates field dependence of the quantum efficiency for charge generation. An exciton diffusion length of 79 {angstrom} was determined by analyzing the short circuit action spectra using the theoretical model developed. The low fill factor of 0.35 for these cells was attributed to the field dependence of the quantum efficiency and the high series resistance of the undoped merocyanine films. Doping the merocyanine films with iodine was found to increase both the dark conductivity and the steady state photoconductivity, the latter by as much as a factor of 5. This resulted in a quantum yield of 12% for a 500 {angstrom} thick film and an increase in the fill factor to 0.44 giving a monochromatic power conversion efficiency of 0.4% at 520 nm. The carrier generation in iodine doped films is shown to result from a bulk process, possibly involving collisions between singlet excitons and acceptor-hole complexes resulting in activation out of the bound states formed by the charge-transfer complex. The quenching of excitons in the immediate vicinity of the metal surface was studied by monitoring the photoconductive response of a 200 {angstrom} merocyanine film with varying thickness of perylene sandwiched between the metal and the merocyanine. Perylene was shown to be able to transport the photoexcited holes from the merocyanine to the Au electrode. The

  7. Photovoltaic properties of Au-merocyanine-TiO2 sandwich cells. II. Properties of illuminated cells and effects of doping with electron acceptors

    NASA Astrophysics Data System (ADS)

    Skotheim, T.; Yang, J.-M.; Otvos, J.; Klein, M. P.

    1982-12-01

    Photocurrent generation in thin films of a merocyanine photosensitizing dye sandwiched between a TiO2 single crystal doped n type and an Au overlayer has been studied using photovoltaic techniques. A theoretical model was developed to explain the observed photovoltaic properties. The model assumes that the principal route for the formation of charge carriers is via singlet excitons diffusing to the merocyanine-TiO2 interface followed by dissociation of the excitons into electron-hole pairs, the electrons being injected into the TiO2 conduction band and the holes into the merocyanine. The model also incorporates field dependence of the quantum efficiency for charge generation. An exciton diffusion length of 79 Å was determined by analyzing the short circuit action spectra using the theoretical model developed. The low fill factor of 0.35 for these cells was attributed to the field dependence of the quantum efficiency and the high series resistance of the undoped merocyanine films. Doping the merocyanine films with iodine was found to increase both the dark conductivity and the steady state photoconductivity, the latter by as much as a factor of 5. This resulted in a quantum yield of 12% for a 500 Å thick film and an increase in the fill factor to 0.44 giving a monochromatic power conversion efficiency of 0.4% at 520 nm. The carrier generation in iodine doped films is shown to result from a bulk process, possibly involving collisions between singlet excitons and acceptor-hole complexes resulting in activation out of the bound states formed by the charge-transfer complex. The quenching of excitons in the immediate vicinity of the metal surface was studied by monitoring the photoconductive response of a 200 Å merocyanine film with varying thickness of perylene sandwiched between the metal and the merocyanine. Perylene was shown to be able to transport the photoexcited holes from the merocyanine to the Au electrode. The quantum efficiency for photocarrier production

  8. Comparison of the electronic structure of a thermoelectric skutterudite before and after adding rattlers: an electron energy loss study.

    PubMed

    Prytz, O; Saeterli, R; Løvvik, O M; Taftø, J

    2008-08-01

    Skutterudites, with rattler atoms introduced in voids in the crystal unit cell, are promising thermoelectric materials. We modify the binary skutterudite with atomic content Co(8)P(24) in the cubic crystal unit cell by adding La as rattlers in all available voids and replacing Co by Fe to maintain charge balance, resulting in La(2)Fe(8)P(24). The intention is to leave the electronic structure unaltered while decreasing the thermal conductivity due to the presence of the rattlers. We compare the electronic structure of these two compounds by studying the L-edges of P and of the transition elements Co and Fe using electron energy loss spectroscopy (EELS). Our studies of the transition metal white lines show that the 3d electron count is similar for Co and Fe in these compounds. As elemental Fe has one electron less than Co, this supports the notion that each La atom donates three electrons. The L-edges of P in these two skutterudites are quite similar, signalling only minor differences in electronic structure. This is in reasonable agreement with density functional theory (DFT) calculations, and with our multiple scattering FEFF calculations of the near edge structure. However, our experimental plasmon energies and dielectric functions deviate considerably from predictions based on DFT calculations. PMID:18042390

  9. Alternansucrase acceptor products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The regioselectivity of alternansucrase (EC 2.4.1.140) differs from dextransucrase (EC 2.4.1.5) in ways that can be useful for the synthesis of novel oligosaccharide structures. For example, it has been recently shown that the major oligosaccharides produced when maltose is the acceptor include one...

  10. The effect of permodified cyclodextrins encapsulation on the photophysical properties of a polyfluorene with randomly distributed electron-donor and rotaxane electron-acceptor units

    PubMed Central

    Resmerita, Ana-Maria; Aubert, Pierre-Henri; Farcas, Flavian; Stoica, Iuliana; Airinei, Anton

    2014-01-01

    Summary We report on the synthesis as well as the optical, electrochemical and morphological properties of two polyrotaxanes (4a and 4b), which consist of electron-accepting 9,9-dicyanomethylenefluorene 1 as an inclusion complex in persilylated β- or γ-cyclodextrin (TMS-β-CD, TMS-γ-CD) (1a, 1b) and methyltriphenylamine as an electron-donating molecule. They are statistically distributed into the conjugated chains of 9,9-dioctylfluorene 3 and compared with those of the corresponding non-rotaxane 4 counterpart. Rotaxane formation results in improvements of the solubility, the thermal stability, and the photophysical properties. Polyrotaxanes 4a and 4b exhibited slightly red-shifted absorption bands with respect to the non-rotaxane 4 counterpart. The fluorescence lifetimes of polyrotaxanes follow a mono-exponential decay with a value of τ = 1.14 ns compared with the non-rotaxane, where a bi-exponential decay composed of a main component with a relative short time of τ1 = 0.88 (57.08%) and a minor component with a longer lifetime of τ2 = 1.56 ns (42.92%) were determined. The optical and electrochemical band gaps (ΔE g) as well as the ionization potential and electronic affinity characterized by smaller values compared to the values of any of the constituents. AFM reveals that the film surface of 4a and 4b displays a granular morphology with a lower dispersity supported by a smaller roughness exponent compared with the non-rotaxane counterpart. PMID:25246973

  11. 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

    SciTech Connect

    Patarroyo, Manuel E.; Almonacid, Hannia; Moreno-Vranich, Armando

    2012-01-20

    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 their 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.

  12. Effects of inorganic electron acceptors on methanogenesis and methanotrophy and on the community structure of bacteria and archaea in sediments of a boreal lake

    NASA Astrophysics Data System (ADS)

    Rissanen, Antti J.; Karvinen, Anu; Nykänen, Hannu; Peura, Sari; Tiirola, Marja; Mäki, Anita; Kankaala, Paula

    2016-04-01

    Lake sediments are globally significant sources of CH4 to the atmosphere, but the factors controlling the production and consumption of CH4 in these systems are understudied. Increasing availability of electron acceptors (EA) (other than CO2) in sediments can decrease or even suppress CH4 production by diverting the electron flow (from H2 and organic substances) from methanogenic to other anaerobic respiration pathways. However, whether these changes in microbial function extend down to changes in the structure of microbial communities is not known. Also anaerobic oxidation of methane (AOM) could be enhanced by increased availability of EAs (SO42‑, NO3‑, Fe3+ and Mn4+), but information on the role of this process in lake sediments is scarce. We studied the effects of inorganic EAs on the potential for CH4 production and consumption and on the structure of microbial communities in sediments of a boreal lake. Anoxic slurries of sediment samples collected from two depths (0 - 10 cm; 10 - 30 cm) of the profundal zone of a boreal, mesotrophic Lake Ätäskö, were amended with 1) CH4 or with CH4 and either 2) 10 mM Mn4+, 3) 10 mM Fe3+, 4) O2 or 5) CH2F2 (inhibitor of aerobic methane oxidation) and incubated at +10° C for up to 4 months. Furthermore, slurries from the 10 - 30 cm layer were amended with CH4 and either 6) 2 mM NO3‑ or 7) 2 mM SO42‑ and incubated at +4 ° C for up to 14 months. The processes were measured using 13C-labelling and by concentration measurements of CH4 and CO2. Effects of treatments 1-3 on microbial communities were also analysed by next-generation sequencing of 16S rRNA, as well as methyl coenzyme-M reductase gene amplicons and mRNA transcripts. CH4 production (max. 83 nmol gdw‑1d‑1) took place in the anaerobic treatments but was generally decreased by the addition of NO3‑, SO42‑, Fe3+ and Mn4+. Although the structure of sediment archaeal community was resistant to Fe3+/Mn4+ - additions, slight changes in the structure of

  13. Electronic and vibronic states of the acceptor-bound-exciton complex (A0,X) in CdS. II. Determination of the fine structure of the (A0,XB) electronic states by high-resolution excitation spectroscopy

    NASA Astrophysics Data System (ADS)

    Gutowski, J.

    1985-03-01

    In a previous paper [R. Baumert, I. Broser, J. Gutowski, and A. Hoffman, Phys. Rev. B 27, 6263 (1983)] it has been shown that high-density, high-resolution excitation spectroscopy gives new information on the electronic and vibronic excited states of the acceptor-bound-exciton complex (A0,XA) with two holes from the A valence band in CdS. We now report on corresponding results for the (A0,XB) configuration which includes one hole from the second B valence band. This complex is unstable for a very fast B-->A hole conversion, and therefore gives rise to a set of excitation resonances of the I1 luminescence arising from the (A0,XA) recombination. A detailed theoretical analysis of the energetic structure of the (A0,XB) complex including the dependence on the excitation intensity and on an applied magnetic field allows the correct assignment of the excitation resonances to the (A0,XB) fine-structure levels originating from the interparticle-exchange interactions. It is shown that the magnetic field is a suitable means of distinguishing the different (A0,XB) ground-state levels. The magnetic field also creates allowed transitions which are dipole forbidden in the zero-field case. A self-contained model of the (A0,XB) complex thus can be developed, including all symmetry states and yielding adequate values for the exchange energies within the complex.

  14. Application of the Stopped Flow Technique to the TiO₂-Heterogeneous Photocatalysis of Hexavalent Chromium in Aqueous Suspensions: Comparison with O₂ and H₂O₂ as Electron Acceptors.

    PubMed

    Meichtry, Jorge M; Dillert, Ralf; Bahnemann, Detlef W; Litter, Marta I

    2015-06-01

    The dynamics of the transfer of electrons stored in TiO2 nanoparticles to Cr(VI) in aqueous solution have been investigated using the stopped flow technique. TiO2 nanoparticles were previously irradiated under UV light in the presence of formic acid, and trapped electrons (e(trap)(-)) were made to react with Cr(VI) as acceptor species; other common acceptor species such as O2 and H2O2 were also tested. The temporal evolution of the number of trapped electrons was followed by the decrease in the absorbance at 600 nm, and the kinetics of the electron-transfer reaction was modeled. Additionally, the rate of formation of the surface complex between Cr(VI) and TiO2 was determined with the stopped flow technique by following the evolution of the absorbance at 400 nm of suspensions of nonirradiated TiO2 nanoparticles and Cr(VI) at different concentrations. An approximately quadratic relationship was observed between the maximum absorbance of the surface complex and the concentration of Cr(VI), suggesting that Cr(VI) adsorbs onto the TiO2 surface as dichromate. The kinetic analyses indicate that the electron transfer from TiO2 to Cr(VI) does not require the previous formation of the Cr(VI)-TiO2 surface complex, at least the complex detected here through the stopped flow experiments. When previously irradiated TiO2 was used to follow the evolution of the Cr(VI)-TiO2 complex, an inhibition of the formation of the complex was observed, which can be related to the TiO2 deactivation caused by Cr(III) deposition. PMID:25974749

  15. Efficient Organic Light-Emitting Diode through Triplet Exciton Reharvesting by Employing Blended Electron Donor and Acceptor as the Emissive Layer.

    PubMed

    Zhang, Lu; Cai, Chao; Li, King Fai; Tam, Hoi Lam; Chan, Kin Long; Cheah, Kok Wai

    2015-11-18

    A blended bimolecular exciplex formation was demonstrated between two individual donor and acceptor molecules, which are tris(4-carbazoyl-9-ylphenyl)amine (TCTA) and 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine (Tm3PyBPZ). The photoluminescence spectrum of the exciplex in the solid state showed an emission with a peak around 514 nm (∼2.49 eV). By applying this exciplex as an emitting layer, a highly efficient all-fluorescent organic lighting emitting diode with maximum efficiencies of 13.1% and 53.4 lm/W can be realized under an extremely low turn-on voltage of only 2.4 V. The thermally activated delayed fluorescence (TADF) process is believed to be responsible for the excellent device performance. PMID:26529382

  16. Spermine and spermidine inhibition of photosystem II: Disassembly of the oxygen evolving complex and consequent perturbation in electron donation from TyrZ to P680+ and the quinone acceptors QA- to QB.

    PubMed

    Beauchemin, Rémy; Gauthier, Alain; Harnois, Johanne; Boisvert, Steve; Govindachary, Sridharan; Carpentier, Robert

    2007-07-01

    Polyamines are implicated in plant growth and stress response. However, the polyamines spermine and spermidine were shown to elicit strong inhibitory effects in photosystem II (PSII) submembrane fractions. We have studied the mechanism of this inhibitory action in detail. The inhibition of electron transport in PSII submembrane fractions treated with millimolar concentrations of spermine or spermidine led to the decline of plastoquinone reduction, which was reversed by the artificial electron donor diphenylcarbazide. The above inhibition was due to the loss of the extrinsic polypeptides associated with the oxygen evolving complex. Thermoluminescence measurements revealed that charge recombination between the quinone acceptors of PSII, QA and QB, and the S2 state of the Mn-cluster was abolished. Also, the dark decay of chlorophyll fluorescence after a single turn-over white flash was greatly retarded indicating a slower rate of QA- reoxidation. PMID:17511958

  17. Design and parameter optimization of a small-scale electron-based ADS for radioactive waste transmutation

    NASA Astrophysics Data System (ADS)

    Feizi, H.; Ranjbar, A. H.

    2015-05-01

    This paper presents the design and feasibility of an electron-LINAC-based small-scale system (ADS) for nuclear waste transmutation. FLUKA simulations have been performed to evaluate the photoneutron yield in high- Z metallic targets such as silver, tungsten, lead, tantalum and uranium irradiated by electron beams of 20-200MeV. The parameters involved in the photoneutron production mechanism including electron beam energy, target material and target shape have been investigated in order to obtain maximum photoneutron production. The neutron reflectors of the ADS, in particular, beryllium, lead and beryllium oxide (BeO) with various thicknesses have been studied. The results show that a combination of an internal reflector of Pb with a thickness of 3cm and an external reflector of BeO with a thickness of 10cm improves the fluence rate. The photoneutron energy spectrum, photoneutron fluence distribution and heat deposition in the electron target have also been presented. At incident electron beam energy of 155MeV, a neutron source of ˜ 4.6 × 1010 (n/cm2/s/mA) has been achieved, which is highly applicable for using in nuclear waste transmutation. The designed ADS has the ability to transmute ˜ 1.5 × 1022 (atoms/y/mA). The obtained results are promising and could lead to the development of a small-scale ADS based on electron LINAC for radioactive waste transmutation and for numerous applications when employed as a photoneutron source.

  18. Acceptor impurity activation in III-nitride light emitting diodes

    SciTech Connect

    Römer, Friedhard Witzigmann, Bernd

    2015-01-12

    In this work, the role of the acceptor doping and the acceptor activation and its impact on the internal quantum efficiency (IQE) of a Gallium Nitride (GaN) based multi-quantum well light emitting diode is studied by microscopic simulation. Acceptor impurities in GaN are subject to a high activation energy which depends on the presence of proximate dopant atoms and the electric field. A combined model for the dopant ionization and activation barrier reduction has been developed and implemented in a semiconductor carrier transport simulator. By model calculations, we demonstrate the impact of the acceptor activation mechanisms on the decay of the IQE at high current densities, which is known as the efficiency droop. A major contributor to the droop is the electron leakage which is largely affected by the acceptor doping.

  19. Decomposition of plant materials in marine sediment exposed to different electron acceptors (O 2, NO 3-, and SO 42-), with emphasis on substrate origin, degradation kinetics, and the role of bioturbation

    NASA Astrophysics Data System (ADS)

    Kristensen, Erik; Holmer, Marianne

    2001-02-01

    Carbon mineralization of fresh and aged diatoms ( Skeletonema costatum) and barley hay ( Hordeum vulgare) was followed for 23 to 35 d in sandy and silty sediment. By the use of a thin-layer flow-through technique, it was possible to expose the sediment selectively for oxygen, nitrate or sulfate as electron acceptors in the terminal oxidation of organic carbon. Decomposition took place in two basic stages. Mineralization of the rapidly leachable fraction of the fresh materials occurred rapidly and with the same constant rate regardless of the electron acceptor available, indicating that the dissolved organic carbon released initially was labile and readily available for all heterotrophic respirers. In the case of diatoms, decay of the remaining, more refractory, particulate fraction of fresh and aged diatoms were strikingly similar, although both were degraded 5 to 10 times faster under oxic than anoxic conditions. Most of the particulate remains of diatoms after leaching apparently belong to one fraction, which maintains the same degradability even after prolonged aging. With respect to hay, the late divergence in rates of aerobic and anaerobic decay (a factor of 4 to 5 for aged hay only after 20 d) indicated that the larger hay particles (<500 μm) became exhausted in labile organic matter much slower through time than fine-particulate diatoms (˜20 μm). Anaerobic carbon mineralization rates of diatoms and hay particulates with sulfate and nitrate as electron acceptors were similar or up to two times faster with sulfate. The generally low levels of dissolved organic carbon in all incubations after the initial leaching phase suggest that the limiting step of decomposition under both aerobic and anaerobic decay is the initial hydrolytic attack on the complex particulate remains. Based on a volumetric model, we show that the exposure of anoxic subsurface sediment containing partly degraded organic material to oxygen via irrigated worm burrows or by reworking may

  20. Halogen vs hydrogen bonding in thiazoline-2-thione stabilization with σ- and π-electron acceptors adducts: Theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    El-Sheshtawy, Hamdy S.; Salman, Hassan M. A.; El-Kemary, Maged

    2015-02-01

    Molecular charge-transfer complexes (CT) between thiazoline-2-thione (THZ) and different σ- (I2) and π-acceptors (Tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL)) were investigated. UV-Vis absorption spectroscopy and theoretical calculations using both MP2/aug-cc-pVDZ-PP and B3LYP/6-311++G(d,p) level of theory were corroborated to study the nature of the stabilizing forces for THZ-I2, THZ-DDQ, THZ-TCNE, and THZ-CHL. Halogen bonding (XB) was the stabilizing attractive force in THZ-I2 and THZ-CHL whereas; hydrogen bonding (HB) was dominated in both THZ-TCNE, and THZ-DDQ complexes. Formation constant (K), extinction coefficient (ɛ), thermodynamic parameters such as enthalpy change (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were measured in different solvents.

  1. Increased Efficiency in Small Molecule Organic Solar Cells Through the Use of a 56-π Electron Acceptor – Methano Indene Fullerene

    PubMed Central

    Ryan, James W.; Matsuo, Yutaka

    2015-01-01

    Organic solar cells (OSCs) offer the possibility of harnessing the sun's ubiquitous energy in a low-cost, environmentally friendly and renewable manner. OSCs based on small molecule semiconductors (SMOSCs) – have made a substantial improvement in recent years and are now achieving power conversion efficiencies (PCEs) that match those achieved for polymer:fullerene OSCs. To date, all efficient SMOSCs have relied on the same fullerene acceptor, PCBM, in order to achieve high performance. The use of PCBM however, is unfavourable due to its low lying LUMO level, which limits the open-circuit voltage (VOC). Alternative fullerene derivatives with higher lying LUMOs are thus required to improve the VOC. The challenge, however, is to prevent the typical concomitant decrease in the short circuit current density (JSC) when using a higher LUMO fullerene. In this communication, we address the issue by applying methano indene fullerene, MIF, a bis-functionalised C60 fullerene that has a LUMO level 140 mV higher than PCBM, in solution processed SMOSCs with a well known small molecule donor, DPP(TBFu)2. MIF-based devices show an improved VOC of 140 mV over PC61BM and only a small decrease in the JSC, with the PCE increasing to 5.1% (vs. 4.5% for PC61BM). PMID:25661976

  2. Recycling of mixed plastic waste from electrical and electronic equipment. Added value by compatibilization.

    PubMed

    Vazquez, Yamila V; Barbosa, Silvia E

    2016-07-01

    Plastic waste from electrical and electronic equipment (WEEE) grows up exponentially fast in the last two decades. Either consumption increase of technological products, like cellphones or computers, or the short lifetime of this products contributes to this rise generating an accumulation of specific plastic materials such ABS (Acrylonitrile-Butadiene-Styrene), HIPS (High impact Polystyrene), PC (Polycarbonate), among others. All of they can be recycled by themselves. However, to separate them by type is neither easy nor economically viable, then an alternative is recycling them together as a blend. Taking into account that could be a deterioration in final properties, to enhance phase adhesion and add value to a new plastic WEEE blend a compatibilization is needed. In this work, a systematical study of different compatibilizers for blends of HIPS and ABS from WEEE was performed. A screening analysis was carried out by adding two different compatibilizer concentration (2wt% and 20wt%) on a HIPS/ABS physical blend 80/20 proportion from plastic e-waste. Three copolymers were selected as possible compatibilizers by their possible affinity with initial plastic WEEE. A complete characterization of each WEEE was performed and compatibilization efficiency was evaluated by comparing either mechanical or morphological blends aspects. Considering blends analyzed in this work, the best performance was achieved by using 2% of styrene-acrylonitrile rubber, obtaining a compatibilized blend with double ultimate strength and modulus respect to the physical blend, and also improve mechanical properties of initial WEEE plastics. The proposed way is a promise route to improve benefit of e-scrap with sustainable, low costs and easy handling process. Consequently, social recycling interest will be encouraged by both ecological and economical points of view. PMID:27140655

  3. A Proposed Integration Environment for Enhanced User Interaction and Value-Adding of Electronic Documents: An Empirical Evaluation.

    ERIC Educational Resources Information Center

    Liew, Chern Li; Chennupati, K. R.; Foo, Schubert

    2001-01-01

    Explores the potential and impact of an innovative information environment in enhancing user activities in using electronic documents for various tasks, and to support the value-adding of these e-documents. Discusses the conceptual design and prototyping of a proposed environment, PROPIE. Presents an empirical and formative evaluation of the…

  4. A Value-Added Framework for Analyzing Electronic and Print Publishing.

    ERIC Educational Resources Information Center

    Perritt, Henry H., Jr.

    1991-01-01

    Discusses changes in the publishing industry resulting from digital electronic networks and optical storage technologies, and explains attributes of information products as types of value for both print and electronic contexts. Electronic products necessary for a shift from paper to electronic formats are identified, and legal issues are…

  5. Quantifying the Electron Donor and Acceptor Abilities of the Ketimide Ligands in M(N═C(t)Bu2)4 (M = V, Nb, Ta).

    PubMed

    Damon, Peter L; Liss, Cameron J; Lewis, Richard A; Morochnik, Simona; Szpunar, David E; Telser, Joshua; Hayton, Trevor W

    2015-10-19

    Addition of 4 equiv of Li(N═C(t)Bu2) to VCl3 in THF, followed by addition of 0.5 equiv of I2, generates the homoleptic V(IV) ketimide complex, V(N═C(t)Bu2)4 (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N═C(t)Bu2) with NbCl4(THF)2 in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N═C(t)Bu2)4 (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N═C(t)Bu2) in THF results in the isolation of a Ta(V) ketimide complex, Ta(Cl)(N═C(t)Bu2)4 (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf)(N═C(t)Bu2)4 (6) in 44% yield. Subsequent reduction of 6 with Cp*2Co in toluene generates the homoleptic Ta(IV) congener Ta(N═C(t)Bu2)4 (7), although the yields are poor. All three homoleptic group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a d(x(2)-y(2))(1) ((2)B1 in D(2d)) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Q-band frequencies (∼9 and 35 GHz, respectively), further supports the (2)B1 ground-state assignment, whereas comparison of 1, 2, and 7 with related group 5 tetra(aryl), tetra(amido), and tetra(alkoxo) complexes shows a higher M-L covalency in the ketimide-metal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong π-donor and strong π-acceptor, an unusual combination found in very few organometallic ligands. PMID:26419513

  6. Quantifying the electron donor and acceptor ability of the ketimide ligands in M(N=CtBu2)4 (M = V, Nb, Ta)

    PubMed Central

    Damon, Peter L.; Liss, Cameron J.; Lewis, Richard A.; Morochnik, Simona; Szpunar, David E.; Telser, Joshua; Hayton, Trevor W.

    2015-01-01

    Addition of 4 equiv of Li(N=CtBu2) to VCl3 in THF, followed by addition of 0.5 equiv I2, generates the homoleptic V(IV) ketimide complex, V(N=CtBu2)4 (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N=CtBu2) with NbCl4(THF)2 in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N=CtBu2)4 (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N=CtBu2) in THF results in a isolation of a Ta(V) ketimide complex, Ta(Cl)(N=CtBu2)4 (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf)(N=CtBu2)4 (6) in 44% yield. Subsequent reduction of 6 with Cp*2Co in toluene generates the homoleptic Ta(IV) congener Ta(N=CtBu2)4 (7), although the yields are poor. All three homoleptic Group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a dx2−y21 (2B1 in D2d) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Q-band frequencies (~9 and 35 GHz, respectively), further supports the 2B1 ground state assignment, while comparison of 1, 2, and 7 with related Group 5 tetra(aryl), tetra(amido) and tetra(alkoxo) complexes shows a higher M-L covalency in the ketimide-metal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong π-donor and strong π-acceptor, an unusual combination found in very few organometallic ligands. PMID:26419513

  7. Photoinduced intramolecular electron transfer in a bridged C{sub 60}. (Acceptor)-Aniline (donor) system. Photophysical properties of the first `active` fullerene diad

    SciTech Connect

    Williams, R.M.; Zwier, J.M.; Verhoeven, J.W.

    1995-04-12

    A covalently functionalized fullerene comprising an electron donating aniline group coupled to the fullerene unit by a saturated heterocyclic bridge is shown to undergo a photoinduced intramolecular electron transfer process that causes quenching of the fluorescence of the adduct and strong decrease triplet population in polar solvents. VIS-absorption, fluorescence and phosphorescence at 77 K, triplet-triplet absorption, time resolved fluorescence and redox potentials of the fullerene adduct are presented. Analysis of the solvent dependence of the energetics of the intramolecular electron transfer is given and is in good agreement with the experimental results. 17 refs., 6 figs., 3 tabs.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  9. Lithium related deep and shallow acceptors in Li-doped ZnO nanocrystals

    NASA Astrophysics Data System (ADS)

    Rauch, C.; Gehlhoff, W.; Wagner, M. R.; Malguth, E.; Callsen, G.; Kirste, R.; Salameh, B.; Hoffmann, A.; Polarz, S.; Aksu, Y.; Driess, M.

    2010-01-01

    We study the existence of Li-related shallow and deep acceptor levels in Li-doped ZnO nanocrystals using electron paramagnetic resonance (EPR) and photoluminescence (PL) spectroscopy. ZnO nanocrystals with adjustable Li concentrations between 0% and 12% have been prepared using organometallic precursors and show a significant lowering of the Fermi energy upon doping. The deep Li acceptor with an acceptor energy of 800 meV could be identified in both EPR and PL measurements and is responsible for the yellow luminescence at 2.2 eV. Additionally, a shallow acceptor state at 150 meV above the valence band maximum is made responsible for the observed donor-acceptor pair and free electron-acceptor transitions at 3.235 and 3.301 eV, possibly stemming from the formation of Li-related defect complexes acting as acceptors.

  10. Bi-anchoring organic sensitizers of type D-(π-A)2 comprising thiophene-2-acetonitrile as π-spacer and malonic acid as electron acceptor for dye sensitized solar cell applications

    NASA Astrophysics Data System (ADS)

    Reddy, Gachumale Saritha; Ramkumar, Sekar; Asiri, Abdullah M.; Anandan, Sambandam

    2015-06-01

    Two new bi-anchoring organic sensitizers of type D-(π-A)2 comprising the identical π-spacer (thiophene-2-acetonitrile) and electron acceptor (malonic acid) but different aryl amine as electron donors (diphenylamine and carbazole) were synthesized, characterized and fabricated metal free dye-sensitized solar cell devices. The intra molecular charge transfer property and electrochemical property of these dyes were investigated by molecular absorption, emission, cyclic voltammetric experiments and in addition, quantum chemical calculation studies were performed to provide sufficient driving force for the electron injection into the conduction band of TiO2 which leads to efficient charge collection. Among the fabricated devices, carbazole based device exhibits high current conversion efficiency (η = 4.7%) with a short circuit current density (JSC) 15.3 mA/cm2, an open circuit photo voltage (VOC) of 0.59 V and a fill factor of 0.44 under AM 1.5 illumination (85 mW/cm2) compared to diphenylamine based device.

  11. Bi-anchoring organic sensitizers of type D-(π-A)₂ comprising thiophene-2-acetonitrile as π-spacer and malonic acid as electron acceptor for dye sensitized solar cell applications.

    PubMed

    Reddy, Gachumale Saritha; Ramkumar, Sekar; Asiri, Abdullah M; Anandan, Sambandam

    2015-06-15

    Two new bi-anchoring organic sensitizers of type D-(π-A)2 comprising the identical π-spacer (thiophene-2-acetonitrile) and electron acceptor (malonic acid) but different aryl amine as electron donors (diphenylamine and carbazole) were synthesized, characterized and fabricated metal free dye-sensitized solar cell devices. The intra molecular charge transfer property and electrochemical property of these dyes were investigated by molecular absorption, emission, cyclic voltammetric experiments and in addition, quantum chemical calculation studies were performed to provide sufficient driving force for the electron injection into the conduction band of TiO2 which leads to efficient charge collection. Among the fabricated devices, carbazole based device exhibits high current conversion efficiency (η=4.7%) with a short circuit current density (JSC) 15.3 mA/cm(2), an open circuit photo voltage (VOC) of 0.59 V and a fill factor of 0.44 under AM 1.5 illumination (85 mW/cm(2)) compared to diphenylamine based device. PMID:25801442

  12. Dynamics of iron-acceptor-pair formation in co-doped silicon

    SciTech Connect

    Bartel, T.; Gibaja, F.; Graf, O.; Gross, D.; Kaes, M.; Heuer, M.; Kirscht, F.; Möller, C.; Lauer, K.

    2013-11-11

    The pairing dynamics of interstitial iron and dopants in silicon co-doped with phosphorous and several acceptor types are presented. The classical picture of iron-acceptor pairing dynamics is expanded to include the thermalization of iron between different dopants. The thermalization is quantitatively described using Boltzmann statistics and different iron-acceptor binding energies. The proper understanding of the pairing dynamics of iron in co-doped silicon will provide additional information on the electronic properties of iron-acceptor pairs and may become an analytical method to quantify and differentiate acceptors in co-doped silicon.

  13. Metal-enhanced luminescence of silicon quantum dots: effects of nanoparticles and molecular electron donors and acceptors on the photofading kinetics

    NASA Astrophysics Data System (ADS)

    Abualnaja, Khamael M.; Šiller, Lidija; Horrocks, Benjamin R.

    2015-04-01

    Alkyl-capped silicon quantum dots (SiQDs) show enhanced luminescence when drop cast as films on glass slides in mixtures with Ag or Au nanoparticles or the electron donor ferrocene (Fc). Metal enhancement of quantum dot photoluminescence (PL) is known to arise from a combination of the intense near-field associated with the surface plasmon of the metal on the rate of absorption and the decrease in the lifetime of the excited state. Here we present evidence that an additional factor is also involved: electron transfer from the metal to the quantum dot. Under CW irradiation with an argon ion laser at 488 nm, SiQDs undergo a reversible photofading of the PL as the particles photoionize. A steady-state condition is established by the competition between photoionization and electron-hole recombination. The fading of the initial PL I0 to the steady-state value {{I}∞ } can be modelled by a simple first order decay with a lognormal distribution of rates, which reflects the heterogeneity of the sample. In the presence of Ag and Au nanoparticles, the modal rate constants of photofading increase by factors of up to 4-fold and the ratio {{I}0}/{{I}∞ } decreases by factors up to 5-fold; this is consistent with an increase in the rate of electron-hole recombination facilitated by the metal nanoparticles acting as sources of electrons. Further support for this interpretation comes from the enhancement in PL observed in photofading experiments with films of SiQDs mixed with Fc; this compound is a well-known one-electron donor, but shows no plasmon band which complicates the estimation of PL enhancement with Ag NPs.

  14. No-carrier-added (NCA) aryl ([sup 18]F) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Yushin Ding; Fowler, J.S.; Wolf, A.P.

    1993-10-19

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  15. No-carrier-added (NCA) aryl (18E) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Ding, Yu-Shin; Fowler, Joanna S.; Wolf, Alfred P.

    1993-01-01

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  16. Electron and hole transfer dynamics of a triarylamine-based dye with peripheral hole acceptors on TiO2 in the absence and presence of solvent.

    PubMed

    Oum, Kawon; Flender, Oliver; Lohse, Peter W; Scholz, Mirko; Hagfeldt, Anders; Boschloo, Gerrit; Lenzer, Thomas

    2014-05-01

    We investigated photoinduced primary charge transfer processes of the sensitizer E6 on TiO2 without solvent and in contact with the organic solvent acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate [C2mim](+)[B(CN)4](-) using transient absorption spectroscopy, spectroelectrochemistry, and DFT/TDDFT calculations. E6, which belongs to a family of triarylamine dyes for solar cell applications, features two peripheral triarylamine units which are connected via diether spacer groups to the core chromophore and are designed to act as hole traps. This function was confirmed by spectroelectrochemistry, where the E6˙(+) radical cation shows a considerably blue-shifted absorption compared to dyes without these two substituents. This indicates that one of the terminal triarylamine units must carry the positive charge. After photoexcitation of E6 at 520 nm (S0 → S1 band), electrons are injected into TiO2 predominantly within the cross-correlation time (<80 fs), with some subsequent delayed electron injection (τ ca. 250 fs). Importantly, a transient Stark shift (electrochromism) is observed (time constants ca. 0.8 and 12 ps) which is related to a changing electric field generated by the E6˙(+) radical cations and injected electrons. This field induces absorption shifts of the dye species on the surface. Interestingly, these dynamics are largely unaffected by solvent molecules. However, pronounced differences are observed on longer timescales. In contact with solvent, one observes an increase in the E6˙(+) absorption band above 600 nm with a time constant of 75 ps. This is assigned to hole transfer from the core chromophore to one of the peripheral triarylamine substituents. Electron-cation recombination occurs on much longer timescales and is multiexponential, with time constants of ca. 100 μs, 1 ms and 15 ms. Because of hole trapping, it is slower than for similar dyes lacking the peripheral triarylamines. Additional experiments were

  17. Molecular dynamics study of the primary charge separation reactions in Photosystem I: effect of the replacement of the axial ligands to the electron acceptor A₀.

    PubMed

    Milanovsky, Georgy E; Ptushenko, Vasily V; Golbeck, John H; Semenov, Alexey Yu; Cherepanov, Dmitry A

    2014-09-01

    Molecular dynamics (MD) calculations, a semi-continuum (SC) approach, and quantum chemistry (QC) calculations were employed together to investigate the molecular mechanics of ultrafast charge separation reactions in Photosystem I (PS I) of Thermosynechococcus elongatus. A molecular model of PS I was developed with the aim to relate the atomic structure with electron transfer events in the two branches of cofactors. A structural flexibility map of PS I was constructed based on MD simulations, which demonstrated its rigid hydrophobic core and more flexible peripheral regions. The MD model permitted the study of atomic movements (dielectric polarization) in response to primary and secondary charge separations, while QC calculations were used to estimate the direct chemical effect of the A(0A)/A(0B) ligands (Met or Asn in the 688/668 position) on the redox potential of chlorophylls A(0A)/A(0B) and phylloquinones A(1A)/A(1B). A combination of MD and SC approaches was used to estimate reorganization energies λ of the primary (λ₁) and secondary (λ₂ ) charge separation reactions, which were found to be independent of the active branch of electron transfer; in PS I from the wild type, λ₁ was estimated to be 390 ± 20mV, while λ₂ was estimated to be higher at 445 ± 15mV. MD and QC approaches were used to describe the effect of substituting Met688(PsaA)/Met668(PsaB) by Asn688(PsaA)/Asn668(PsaB) on the energetics of electron transfer. Unlike Met, which has limited degrees of freedom in the site, Asn was found to switch between two relatively stable conformations depending on cofactor charge. The introduction of Asn and its conformation flexibility significantly affected the reorganization energy of charge separation and the redox potentials of chlorophylls A(0A)/A(0B) and phylloquinones A(1A)/A(1B), which may explain the experimentally observed slowdown of secondary electron transfer in the M688N(PsaA) variant. This article is part of a special issue entitled

  18. Metabolite-enabled mutualistic interaction between Shewanella oneidensis and Escherichia coli in a co-culture using an electrode as electron acceptor

    PubMed Central

    Wang, Victor Bochuan; Sivakumar, Krishnakumar; Yang, Liang; Zhang, Qichun; Kjelleberg, Staffan; Loo, Say Chye Joachim; Cao, Bin

    2015-01-01

    Mutualistic interactions in planktonic microbial communities have been extensively studied. However, our understanding on mutualistic communities consisting of co-existing planktonic cells and biofilms is limited. Here, we report a planktonic cells-biofilm mutualistic system established by the fermentative bacterium Escherichia coli and the dissimilatory metal-reducing bacterium Shewanella oneidensis in a bioelectrochemical device, where planktonic cells in the anode media interact with the biofilms on the electrode. Our results show that the transfer of formate is the key mechanism in this mutualistic system. More importantly, we demonstrate that the relative distribution of E. coli and S. oneidensis in the liquid media and biofilm is likely driven by their metabolic functions towards an optimum communal metabolism in the bioelectrochemical device. RNA sequencing-based transcriptomic analyses of the interacting organisms in the mutualistic system potentially reveal differential expression of genes involved in extracellular electron transfer pathways in both species in the planktonic cultures and biofilms. PMID:26061569

  19. Perfluorination of tetracene: effects on the optical gap and electron-acceptor properties. An electrochemical, theoretical DFT, and Raman spectroscopic study

    NASA Astrophysics Data System (ADS)

    Ponce Ortiz, Rocío; Malavé Osuna, Reyes; Ruiz Delgado, Mari Carmen; Casado, Juan; Hernández, Víctor; López Navarrete, Juan Teodomiro; Sakamoto, Youichi; Suzuki, Toshiyasu

    2006-04-01

    We report the synthesis and characterization of perfluorinated tetracene; a material with potential applications in organic electronics. The electrochemical behaviour of the compound is analyzed by differential pulse voltammetry, and compared with that of tetracene. The structure of perfluorotetracene is planar as observed for pentacene. We also report a comparative Raman spectroscopic study of tetracene and perfluorotetracene in relation to their π-conjugational properties. Density functional theory (DFT) calculations have been also performed, at the B3LYP/6-31G** level, to assess information regarding the topologies and energies of the frontier molecular orbitals (MOs) around the gap, and about the vibrational normal modes associated with the Raman features selectively enhanced by the π-conjugation.

  20. Electronic structure of p-type perylene monoimide-based donor-acceptor dyes on the nickel oxide (100) surface: a DFT approach.

    PubMed

    Kontkanen, O V; Niskanen, M; Hukka, T I; Rantala, T T

    2016-05-25

    A p-type dye-sensitized solar cell, where the dye injects a hole into the semiconductor, could be combined with a typical Grätzel cell to create an efficient tandem device. However, the current p-type devices suffer from low efficiency. Here, geometries and electronic structures of four perylenemonoimide-based dyes () both as free and adsorbed on the NiO(100) semiconductor surface have been investigated to gain a better understanding of the p-type devices. In particular, the electronic transitions relevant to charge transfer between the dye and the surface have been identified. Excitations have been evaluated using the time-dependent DFT calculations, and the roles of frontier orbitals and band edges in transitions have been assessed. The adsorbed dyes can adopt either upright or slightly tilted geometries depending on the structure of the anchoring group and the binding mode of the dye. The adsorption slightly lowers the NiO band gap, from 4.06 eV to 3.90-3.96 eV, depending on the surface-adsorbate system and the band gaps of the dye molecules by 0.1-0.2 eV. Additionally, the adsorption mode of dye moves the LUMO+1 level down by 0.5 eV. The effective mass of charge carrier holes is significantly smaller at the NiO surface than in the bulk indicating the importance of surface conductivity. We also found that the potential drop, i.e. the driving force for charge transfer from NiO to the dye molecule, depends on the adsorption mode of . PMID:27224900

  1. Electron-beam-induced current measurements with applied bias provide insight to locally resolved acceptor concentrations at p-n junctions

    SciTech Connect

    Abou-Ras, D. Schäfer, N.; Baldaz, N.; Brunken, S.; Boit, C.

    2015-07-15

    Electron-beam-induced current (EBIC) measurements have been employed for the investigation of the local electrical properties existing at various types of electrical junctions during the past decades. In the standard configuration, the device under investigation is analyzed under short-circuit conditions. Further insight into the function of the electrical junction can be obtained when applying a bias voltage. The present work gives insight into how EBIC measurements at applied bias can be conducted at the submicrometer level, at the example of CuInSe{sub 2} solar cells. From the EBIC profiles acquired across ZnO/CdS/CuInSe{sub 2}/Mo stacks exhibiting p-n junctions with different net doping densities in the CuInSe{sub 2} layers, values for the width of the space-charge region, w, were extracted. For all net doping densities, these values decreased with increasing applied voltage. Assuming a linear relationship between w{sup 2} and the applied voltage, the resulting net doping densities agreed well with the ones obtained by means of capacitance-voltage measurements.

  2. Electron-beam-induced current measurements with applied bias provide insight to locally resolved acceptor concentrations at p-n junctions

    NASA Astrophysics Data System (ADS)

    Abou-Ras, D.; Schäfer, N.; Baldaz, N.; Brunken, S.; Boit, C.

    2015-07-01

    Electron-beam-induced current (EBIC) measurements have been employed for the investigation of the local electrical properties existing at various types of electrical junctions during the past decades. In the standard configuration, the device under investigation is analyzed under short-circuit conditions. Further insight into the function of the electrical junction can be obtained when applying a bias voltage. The present work gives insight into how EBIC measurements at applied bias can be conducted at the submicrometer level, at the example of CuInSe2 solar cells. From the EBIC profiles acquired across ZnO/CdS/CuInSe2/Mo stacks exhibiting p-n junctions with different net doping densities in the CuInSe2 layers, values for the width of the space-charge region, w, were extracted. For all net doping densities, these values decreased with increasing applied voltage. Assuming a linear relationship between w2 and the applied voltage, the resulting net doping densities agreed well with the ones obtained by means of capacitance-voltage measurements.

  3. Dehalogenimonas lykanthroporepellens BL-DC-9T simultaneously transcribes many rdhA genes during organohalide respiration with 1,2-DCA, 1,2-DCP, and 1,2,3-TCP as electron acceptors.

    PubMed

    Mukherjee, Kalpataru; Bowman, Kimberly S; Rainey, Fred A; Siddaramappa, Shivakumara; Challacombe, Jean F; Moe, William M

    2014-05-01

    The genome sequence of the organohalide-respiring bacterium Dehalogenimonas lykanthroporepellensBL-DC-9(T) contains numerous loci annotated as reductive dehalogenase homologous (rdh) genes based on inferred protein sequence identity with functional dehalogenases of other bacterial species. Many of these genes are truncated, lack adjacent regulatory elements, or lack cognate genes coding for membrane-anchoring proteins typical of the functionally characterized active reductive dehalogenases of organohalide-respiring bacteria. To investigate the expression patterns of the rdh genes in D. lykanthroporepellensBL-DC-9(T), oligonucleotide primers were designed to uniquely target 25 rdh genes present in the genome as well as four putative regulatory genes. RNA extracts from cultures of strain BL-DC-9(T) actively dechlorinating three different electron acceptors, 1,2-dichloroethane, 1,2-dichloropropane, and 1,2,3-trichloropropane were reverse-transcribed and subjected to PCR amplification using rdh-specific primers. Nineteen rdh gene transcripts, including 13 full-length rdhA genes, six truncated rdhA genes, and five rdhA genes having cognate rdhB genes were consistently detected during the dechlorination of all three of the polychlorinated alkanes tested. Transcripts from all four of the putative regulatory genes were also consistently detected. Results reported here expand the diversity of bacteria known to simultaneously transcribe multiple rdh genes and provide insights into the transcription factors associated with rdh gene expression. PMID:24673292

  4. Synthesis, spectral investigations, antimicrobial activity and DNA-binding studies of novel charge transfer complex of 1,10-phenanthroline as an electron donor with π-acceptor p-Nitrophenol

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq

    2010-08-01

    Proton or charge transfer (CT) complex of donor, 1,10-phenanthroline (Phen) with π-acceptor, p-Nitrophenol (PNP) has been studied spectrophotometrically in methanol at room temperature. The binding of the CT complex with calf thymus (ct) DNA has been investigated by fluorescence spectrum, to establish the ability of the CT complex of its interaction with DNA. Stern-Volmer quenching constant ( Ksv) has also been calculated. The formation constant ( KCT), molar extinction coefficient ( ɛCT), free energy (Δ Go) and stoichiometric ratio of the CT complex have been determined by Benesi-Hildebrand equation. The stoichiometry was found to be 1:1. The CT complex was screened for its pharmacology as antibacterial and antifungal activity against various bacterial and fungal strains, showing excellent antibacterial and antifungal activity. The newly synthesized CT complex has been characterized by FTIR spectra, elemental analysis, 1H NMR, electronic absorption spectra. TGA-DTA studies were also carried out to check the stability of CT complex.

  5. Impact of electronic coupling, symmetry, and planarization on one- and two-photon properties of triarylamines with one, two, or three diarylboryl acceptors.

    PubMed

    Makarov, Nikolay S; Mukhopadhyay, Sukrit; Yesudas, Kada; Brédas, Jean-Luc; Perry, Joseph W; Pron, Agnieszka; Kivala, Milan; Müllen, Klaus

    2012-04-19

    We have performed a study of the one- and two-photon absorption properties of a systematically varied series of triarylamino-compounds with one, two, or three attached diarylborane arms arranged in linear dipolar, bent dipolar, and octupolar geometries. Two-photon fluorescence excitation spectra were measured over a wide spectral range with femtosecond laser pulses. We found that on going from the single-arm to the two- and three-arm systems, the peak in two-photon absorption (2PA) cross-section is suppressed by factors of 3-11 for the lowest excitonic level associated with the electronic coupling of the arms, whereas it is enhanced by factors of 4-8 for the higher excitonic level. These results show that the coupling of arms redistributes the 2PA cross-section between the excitonic levels in a manner that strongly favors the higher-energy excitonic level. The experimental data on one- and two-photon cross-sections, ground- and excited-state transition dipole moments, and permanent dipole moment differences between the ground and the lowest excited states were compared to the results obtained from a simple Frenkel exciton model and from highly correlated quantum-chemical calculations. It has been found that planarization of the structure around the triarylamine moiety leads to a sizable increase in peak 2PA cross-section for the lowest excitonic level of the two-arm system, whereas for the three-arm system, the corresponding peak was weakened and shifted to lower energy. Our studies show the importance of the interarm coupling, number of arms, and structural planarity on both the enhancement and the suppression of two-photon cross-sections in multiarm molecules. PMID:22429020

  6. Alkalilimnicola ehrlichii sp. nov., a novel, arsenite-oxidizing haloalkaliphilic gammaproteobacterium capable of chemoautotrophic or heterotrophic growth with nitrate or oxygen as the electron acceptor

    USGS Publications Warehouse

    Hoeft, S.E.; Blum, J.S.; Stolz, J.F.; Tabita, F.R.; Witte, B.; King, G.M.; Santini, J.M.; Oremland, R.S.

    2007-01-01

    A facultative chemoautotrophic bacterium, strain MLHE-1T, was isolated from Mono Lake, an alkaline hypersaline soda lake in California, USA. Cells of strain MLHE-1T were Gram-negative, short motile rods that grew with inorganic electron donors (arsenite, hydrogen, sulfide or thiosulfate) coupled with the reduction of nitrate to nitrite. No aerobic growth was attained with arsenite or sulfide, but hydrogen sustained both aerobic and anaerobic growth. No growth occurred when nitrite or nitrous oxide was substituted for nitrate. Heterotrophic growth was observed under aerobic and anaerobic (nitrate) conditions. Cells of strain MLHE-1T could oxidize but not grow on CO, while CH4 neither supported growth nor was it oxidized. When grown chemoautotrophically, strain MLHE-1T assimilated inorganic carbon via the Calvin-Benson-Bassham reductive pentose phosphate pathway, with the activity of ribulose 1,5-bisphosphate carboxylase (RuBisCO) functioning optimally at 0.1 M NaCl and at pH 7.3. Strain MLHE-1T grew over broad ranges of pH (7.3-10.0; optimum, 9.3), salinity (115-190 g l-1; optimum 30 g l-1) and temperature (113-40 ??C; optimum, 30 ??C). Phylogenetic analysis of 16S rRNA gene sequences placed strain MLHE-1T in the class Gammaproteobacteria (family Ectothiorhodospiraceae) and most closely related to Alkalispirillum mobile (98.5%) and Alkalilimnicola halodurans (98.6%), although none of these three haloalkaliphilic micro-organisms were capable of photoautotrophic growth and only strain MLHE-1T was able to oxidize As(III). On the basis of physiological characteristics and DNA-DNA hybridization data, it is suggested that strain MLHE-1T represents a novel species within the genus Alkalilimnicola for which the name Alkalilimnicola ehrlichii is proposed. The type strain is MLHE-1T (=DSM 17681T =ATCC BAA-1101T). Aspects of the annotated full genome of Alkalilimnicola ehrlichii are discussed in the light of its physiology. ?? 2007 IUMS.

  7. The structure and bonding of iron-acceptor pairs in silicon

    SciTech Connect

    Zhao, S.; Assali, L.V.C.; Kimerling, L.C.

    1995-08-01

    The highly mobile interstitial iron and Group III impurities (B, Al, Ga, In) form iron-acceptor pairs in silicon. Based on the migration kinetics and taking host silicon as a dielectric medium, we have simulated the pairing process in a static silicon lattice. Different from the conventional point charge ionic model, our phenomenological calculations include (1) a correction that takes into account valence electron cloud polarization which adds a short range, attractive interaction in the iron-acceptor pair bonding; and (2) silicon lattice relaxation due to the atomic size difference which causes a local strain field. Our model explains qualitatively (1) trends among the iron-acceptor pairs revealing an increase of the electronic state hole emission energy with increasing principal quantum number of acceptor and decreasing pair separation distance; and (2) the stable and metastable sites and configurational symmetries of the iron-acceptor pairs. The iron-acceptor pairing and bonding mechanism is also discussed.

  8. Comparative c-type cytochrome expression analysis in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C grown with soluble and insoluble oxidised metal electron acceptors

    SciTech Connect

    Nissen, Silke; Liu, Xiaoxin; Chourey, Karuna; Hettich, Robert {Bob} L; Wagner, Darlene D; Pffifner, Susan; Loeffler, Frank E

    2012-01-01

    The genomes of Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C encode 40 and 69 putative c-type cytochrome genes, respectively. Deletion mutant and biochemical studies have assigned specific functions to a few c-type cytochromes involved in electron transfer to oxidised metals in Shewanella oneidensis strain MR-1. Although promising, the genetic approach is limited to gene deletions that produce a distinct phenotype, and organism for which a genetic system is available. To more comprehensively investigate and compare c-type cytochrome expression in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C, proteomic measurements were used to characterise lysates of cells grown with soluble Fe(III) (as ferric citrate) and insoluble Mn(IV) (as MnO2) as electron acceptors. Strain MR-1 expressed 19 and 20, and strain 2CP-C expressed 27 and 25 c-type cytochromes when grown with Fe(III) and Mn(IV), respectively. The majority of c-type cytochromes (77% for strain MR-1 and 63% for strain 2CP-C) were expressed under both growth conditions; however, the analysis also revealed unique c-type cytochromes that were specifically expressed in cells grown with soluble Fe(III) or insoluble Mn(IV). Proteomic characterisation proved to be a promising approach for determining the c-type cytochrome complement expressed under different growth conditions, and will help elucidating the specific functions of more c-type cytochromes that are the basis for Shewanella and Anaeromyxobacter respiratory versatility.

  9. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

    NASA Astrophysics Data System (ADS)

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-01

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  10. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    PubMed

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally. PMID:26765027

  11. A User Study of the Design Issues of PROPIE: A Novel Environment for Enhanced Interaction and Value-Adding of Electronic Documents.

    ERIC Educational Resources Information Center

    Liew, Chern Li; Foo, Schubert; Chennupati, K. R.

    2001-01-01

    Presents a proposed information environment (PROPIE) for enhanced interaction and value-adding of electronic documents that allows users multiple ways to query intuitively and navigate information in an electronic document. Highlights include user interface technologies; visualization and interactive techniques; query and browsing processes; and…

  12. Purification and characterization of a carbohydrate: acceptor oxidoreductase from Paraconiothyrium sp. that produces lactobionic acid efficiently.

    PubMed

    Kiryu, Takaaki; Nakano, Hirofumi; Kiso, Taro; Murakami, Hiromi

    2008-03-01

    A carbohydrate:acceptor oxidoreductase from Paraconiothyrium sp. was purified and characterized. The enzyme efficiently oxidized beta-(1-->4) linked sugars, such as lactose, xylobiose, and cellooligosaccharides. The enzyme also oxidized maltooligosaccharides, D-glucose, D-xylose, D-galactose, L-arabinose, and 6-deoxy-D-glucose. It specifically oxidized the beta-anomer of lactose. Molecular oxygen and 2,6-dichlorophenol indophenol were reduced by the enzyme as electron acceptors. The Paraconiothyrium enzyme was identified as a carbohydrate:acceptor oxidoreductase according to its specificity for electron donors and acceptors, and its molecular properties, as well as the N-terminal amino acid sequence. Further comparison of the amino acid sequences of lactose oxidizing enzymes indicated that carbohydrate:acceptor oxidoreductases belong to the same group as glucooligosaccharide oxidase, while they differ from cellobiose dehydrogenases and cellobiose:quinone oxidoreductases. PMID:18323642

  13. Covalent non-fused tetrathiafulvalene-acceptor systems.

    PubMed

    Pop, Flavia; Avarvari, Narcis

    2016-06-28

    Covalent donor-acceptor (D-A) systems have significantly contributed to the development of many organic materials and to molecular electronics. Tetrathiafulvalene (TTF) represents one of the most widely studied donor precursors and has been incorporated into the structure of many D-A derivatives with the objective of obtaining redox control and modulation of the intramolecular charge transfer (ICT), in order to address switchable emissive systems and to take advantage of its propensity to form regular stacks in the solid state. In this review, we focus on the main families of non-fused TTF-acceptors, which are classified according to the nature of the acceptor: nitrogen-containing heterocycles, BODIPY, perylenes and electron poor unsaturated hydrocarbons, as well as radical acceptors. We describe herein the most representative members of each family with a brief mention of their synthesis and a special focus on their D-A characteristics. Special attention is given to ICT and its modulation, fluorescence quenching and switching, photoconductivity, bistability and spin distribution by discussing and comparing spectroscopic and electrochemical features, photophysical properties, solid-state properties and theoretical calculations. PMID:27193500

  14. Fine structure of the Mn acceptor in GaAs

    NASA Astrophysics Data System (ADS)

    Krainov, I. V.; Debus, J.; Averkiev, N. S.; Dimitriev, G. S.; Sapega, V. F.; Lähderanta, E.

    2016-06-01

    We reveal the electronic level structure of the Mn acceptor, which consists of a valence-band hole bound to an Mn2 + ion, in presence of applied uniaxial stress and an external magnetic field in bulk GaAs. Resonant spin-flip Raman scattering is used to measure the g factor of the AMn0 center in the ground and excited states with the total angular momenta F =1 and F =2 and characterize the optical selection rules of the spin-flip transitions between these Mn-acceptor states. We determine the random stress fields near the Mn acceptor, the constant of the antiferromagnetic exchange interaction between the valence-band holes and the electrons of the inner Mn2 + shell as well as the deformation potential for the exchange energy. The p -d exchange energy, in particular, decreases significantly with increasing compressive stress. By combining the experimental Raman study with the developed theoretical model on the scattering efficiency, in which also the random local and external uniaxial stresses and magnetic field are considered, the fine structure of the Mn acceptor is determined in full detail.

  15. Acceptors in bulk and nanoscale ZnO

    NASA Astrophysics Data System (ADS)

    McCluskey, M. D.

    2012-02-01

    Zinc oxide (ZnO) is a semiconductor that emits bright UV light, with little wasted heat. This intrinsic feature makes it a promising material for energy-efficient white lighting, nano-lasers, and other optical applications. For devices to be competitive, however, it is necessary to develop reliable p-type doping. Although substitutional nitrogen has been considered as a potential p-type dopant for ZnO, theoretical and experimental work indicates that nitrogen is a deep acceptor and will not lead to p-type conductivity. This talk will highlight recent experiments on ZnO:N at low temperatures. A red/near-IR photoluminescence (PL) band is correlated with the presence of deep nitrogen acceptors. PL excitation (PLE) measurements show an absorption threshold of 2.26 eV, in good agreement with theory. Magnetic resonance experiments provide further evidence for this assignment. The results of these studies seem to rule out group-V elements as shallow acceptors in ZnO, contradicting numerous reports in the literature. If these acceptors do not work as advertised, is there a viable alternative? Optical studies on ZnO nanocrystals show some intriguing leads. At liquid-helium temperatures, a series of sharp IR absorption peaks arise from an unknown acceptor impurity. The data are consistent with a hydrogenic acceptor 0.46 eV above the valence band edge. While this binding energy is still too deep for many practical applications, it represents a significant improvement over the ˜ 1.3 eV binding energy for nitrogen acceptors. Nanocrystals present another twist. Due to their high surface-to-volume ratio, surface states are especially important. Specifically, electron-hole recombination at the surface give rises to a red luminescence band. From our PL and IR experiments, we have developed a ``unified'' model that attempts to explain acceptor and surface states in ZnO nanocrystals. This model could provide a useful framework for designing future nanoscale ZnO devices.

  16. Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model.

    PubMed

    Sosorev, Andrey Yu; Parashchuk, Olga D; Zapunidi, Sergey A; Kashtanov, Grigoriy S; Golovnin, Ilya V; Kommanaboyina, Srikanth; Perepichka, Igor F; Paraschuk, Dmitry Yu

    2016-02-14

    In some donor-acceptor blends based on conjugated polymers, a pronounced charge-transfer complex (CTC) forms in the electronic ground state. In contrast to small-molecule donor-acceptor blends, the CTC concentration in polymer:acceptor solution can increase with the acceptor content in a threshold-like way. This threshold-like behavior was earlier attributed to the neighbor effect (NE) in the polymer complexation, i.e., next CTCs are preferentially formed near the existing ones; however, the NE origin is unknown. To address the factors affecting the NE, we record the optical absorption data for blends of the most studied conjugated polymers, poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(3-hexylthiophene) (P3HT), with electron acceptors of fluorene series, 1,8-dinitro-9,10-antraquinone (), and 7,7,8,8-tetracyanoquinodimethane () in different solvents, and then analyze the data within the NE model. We have found that the NE depends on the polymer and acceptor molecular skeletons and solvent, while it does not depend on the acceptor electron affinity and polymer concentration. We conclude that the NE operates within a single macromolecule and stems from planarization of the polymer chain involved in the CTC with an acceptor molecule; as a result, the probability of further complexation with the next acceptor molecules at the adjacent repeat units increases. The steric and electronic microscopic mechanisms of NE are discussed. PMID:26799407

  17. Glucansucrase acceptor reactions with D-mannose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The main acceptor product of glucansucrases with D-mannose has not previously been identified. We used glucansucrases that form water-insoluble a-D-glucans to produce increased yields of acceptor products from D-mannose, and identified the major product as 6-O-a-D-glucopyranosyl-D-mannose. Glucansuc...

  18. Photoelectric covalent organic frameworks: converting open lattices into ordered donor-acceptor heterojunctions.

    PubMed

    Chen, Long; Furukawa, Ko; Gao, Jia; Nagai, Atsushi; Nakamura, Toshikazu; Dong, Yuping; Jiang, Donglin

    2014-07-16

    Ordered one-dimensional open channels represent the typical porous structure of two-dimensional covalent organic frameworks (COFs). Here we report a general synthetic strategy for converting these open lattice structures into ordered donor-acceptor heterojunctions. A three-component topological design scheme was explored to prepare electron-donating intermediate COFs, which upon click reaction were transformed to photoelectric COFs with segregated donor-acceptor alignments, whereas electron-accepting buckyballs were spatially confined within the nanochannels via covalent anchoring on the channel walls. The donor-acceptor heterojunctions trigger photoinduced electron transfer and allow charge separation with radical species delocalized in the π-arrays, whereas the charge separation efficiency was dependent on the buckyball content. This new donor-acceptor strategy explores both skeletons and pores of COFs for charge separation and photoenergy conversion. PMID:24963896

  19. Design directed self-assembly of donor-acceptor polymers.

    PubMed

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements. PMID:27440174

  20. Free Carrier Generation in Organic Photovoltaic Bulk Heterojunctions of Conjugated Polymers with Molecular Acceptors: Planar versus Spherical Acceptors

    SciTech Connect

    Nardes, Alexandre M.; Ferguson, Andrew J.; Wolfer, Pascal; Gui, Kurt; Burn, Paul L.; Meredith, Paul; Kopidakis, Nikos

    2014-03-05

    We present a comparative study of the photophysical performance of the prototypical fullerene derivative PC61BM with a planar small-molecule acceptor in an organic photovoltaic device. The small-molecule planar acceptor is 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c][1,2,5]thiadiazol-4-yl}methylene]malononitrile, termed K12. We discuss photoinduced free charge-carrier generation and transport in blends of PC61BM or K12 with poly(3-n-hexylthiophene) (P3HT), surveying literature results for P3HT:PC61BM and presenting new results on P3HT:K12. For both systems we also review previous work on film structure and correlate the structural and photophysical results. In both cases, a disordered mixed phase is formed between P3HT and the acceptor, although the photophysical properties of this mixed phase differ markedly for PC61BM and K12. In the case of PC61BM the mixed phase acts as a free carrier generation region that can efficiently shuttle carriers to the pure polymer and fullerene domains. As a result, the vast majority of excitons quenched in P3HT:PC61BM blends yield free carriers detected by the contactless time-resolved microwave conductivity (TRMC) method. In contrast, approximately 85 % of the excitons quenched in P3HT:K12 do not result in free carriers over the nanosecond timescale of the TRMC experiment. We attribute this to poor electron-transport properties in the mixed P3HT:K12 phase. Here, we propose that the observed differences can be traced to the respective shapes of PC61BM and K12: the three-dimensional nature of the fullerene cage facilitates coupling between PC61BM molecules irrespective of their relative orientation, whereas for K12 strong electronic coupling is only expected for molecules oriented with their π systems parallel to each other. Comparison between the eutectic compositions of the P3HT:PC61BM and P3HT:K12 shows that the former contains enough fullerene to form a percolation pathway for electrons, whereas the latter contains a sub

  1. Acceptor-donor-acceptor-based small molecules with varied crystallinity: processing additive-induced nanofibril in blend film for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Li, Chao; Chen, Yujin; Zhao, Yue; Wang, Huifang; Zhang, Wei; Li, Yaowen; Yang, Xiaoming; Ma, Changqi; Chen, Liwei; Zhu, Xiulin; Tu, Yingfeng

    2013-09-01

    A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance.A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance. Electronic supplementary information (ESI) available: Synthetic process and characterizations of SMs; TGA, electrochemical properties, molecular orbital surfaces of SMs; AFM images of SM:PC71BM blend films; EQE curves; optical, electrochemical properties and photovoltaic parameters. See DOI: 10.1039/c3nr03048b

  2. Bright Solid-State Emission of Disilane-Bridged Donor-Acceptor-Donor and Acceptor-Donor-Acceptor Chromophores.

    PubMed

    Shimada, Masaki; Tsuchiya, Mizuho; Sakamoto, Ryota; Yamanoi, Yoshinori; Nishibori, Eiji; Sugimoto, Kunihisa; Nishihara, Hiroshi

    2016-02-01

    The development of disilane-bridged donor-acceptor-donor (D-Si-Si-A-Si-Si-D) and acceptor-donor-acceptor (A-Si-Si-D-Si-Si-A) compounds is described. Both types of compound showed strong emission (λem =ca. 500 and ca. 400 nm, respectively) in the solid state with high quantum yields (Φ: up to 0.85). Compound 4 exhibited aggregation-induced emission enhancement in solution. X-ray diffraction revealed that the crystal structures of 2, 4, and 12 had no intermolecular π-π interactions to suppress the nonradiative transition in the solid state. PMID:26822564

  3. A new classification of the amino acid side chains based on doublet acceptor energy levels.

    PubMed Central

    Sneddon, S F; Morgan, R S; Brooks, C L

    1988-01-01

    We describe a new classification of the amino acid side chains based on the potential energy level at which each will accept an extra (doublet) electron. The doublet acceptor energy level, and the doublet acceptor orbital were calculated using semiempirical INDO/2-UHF molecular orbital theory. The results of these calculations show that the side chains fall into four groups. We have termed these groups repulsive, insulating, semiconducting, and attractive in accordance with where each lies on the relative energy scale. We use this classification to examine the role of residues between the donor and acceptor in modulating the rate and mechanism of electron transfer in proteins. With the calculated acceptor levels, we construct a potential barrier for those residues between the donor and acceptor. It is the area beneath this barrier that determines the decay of electronic coupling between donor and acceptor, and thus the transfer rate. We have used this schematic approach to characterize the four electron transfer pathways in myoglobin recently studied by Mayo et al. (Mayo, S.L., W.R. Ellis, R.J. Crutchley, and H.B. Gray. 1986. Science [Wash. DC]. 233:948-952). PMID:3342271

  4. New organic donor-acceptor-π-acceptor sensitizers for efficient dye-sensitized solar cells and photocatalytic hydrogen evolution under visible-light irradiation.

    PubMed

    Li, Xing; Cui, Shicong; Wang, Dan; Zhou, Ying; Zhou, Hao; Hu, Yue; Liu, Jin-Gang; Long, Yitao; Wu, Wenjun; Hua, Jianli; Tian, He

    2014-10-01

    Two organic donor-acceptor-π-acceptor (D-A-π-A) sensitizers (AQ and AP), containing quinoxaline/pyrido[3,4-b]pyrazine as the auxiliary acceptor, have been. Through fine-tuning of the auxiliary acceptor, a higher designed and synthesized photoelectric conversion efficiency of 6.02% for the AQ-based dye-sensitized solar cells under standard global AM1.5 solar conditions was achieved. Also, it was found that AQ-Pt/TiO2 photocatalysts displayed a better rate of H2 evolution under visible-light irradiation (420 nm<λ<780 nm) because of the stability of the oxidized states and the lower rates of electron recombination. Importantly, sensitizers AQ and AP-Pt/TiO2 showed strong photocatalytic activity during continuous light soaking for 10 h with methanol as the sacrificial electron donor. Additionally, the processes of their intermolecular electron transfer were further investigated theoretically by using time-dependent DFT. The calculated results indicate that the auxiliary acceptor plays the role of an electron trap and results in broad spectral responses. PMID:25154958

  5. Defect Donor and Acceptor in GaN

    SciTech Connect

    Look, D.C.; Reynolds, D.C.; Hemsky, J.W.; Sizelove, J.R.; Jones, R.L.

    1997-09-01

    High-energy (0.7{endash}1MeV) electron irradiation in GaN grown on sapphire produces shallow donors and deep or shallow acceptors at equal rates, 1{plus_minus}0.2 cm{sup {minus}1}. The data, in conjunction with theory, are consistent only with the shallow donor being the N vacancy, and the acceptor the N interstitial. The N-vacancy donor energy is 64{plus_minus}10 meV, much larger than the value of 18meV found for the residual donor (probably Si) in this material. The Hall-effect measurements also reveal a degenerate n -type layer at the GaN/sapphire interface which must be accounted for to get the proper donor activation energy. {copyright} {ital 1997} {ital The American Physical Society}

  6. Benzodipyrrole-based Donor-Acceptor-type Boron Complexes as Tunable Near-infrared-Absorbing Materials.

    PubMed

    Nakamura, Tomoya; Furukawa, Shunsuke; Nakamura, Eiichi

    2016-07-20

    Benzodipyrrole-based donor-acceptor boron complexes were designed and synthesized as near-infrared-absorbing materials. The electron-rich organic framework combined with the Lewis acidic boron co-ordination enabled us to tune the LUMO energy level and the HOMO-LUMO gap (i.e.,the absorption wavelength) by changing the organic acceptor units, the number of boron atoms, and the substituents on the boron atoms. PMID:27311060

  7. Acceptor Products of Alternansucrase with Gentiobiose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In the presence of suitable acceptor molecules, dextransucrase makes a homologous series of oligosaccharides in which the isomers differ by a single glucosyl unit, whereas alternansucrase synthesizes one trisaccharide, two tetrasaccharides, etc. Previously, we showed that alternansucrase only forms...

  8. Synthetic CO.sub.2 acceptor

    DOEpatents

    Lancet, Michael S.; Curran, George P.

    1981-08-18

    A synthetic CO.sub.2 acceptor consisting essentially of at least one compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix, the carrier having the general formula Ca.sub.5 (SiO.sub.4).sub.2 CO.sub.3. A method for producing the synthetic CO.sub.2 acceptor is also disclosed.

  9. Computational design of donor-bridge-acceptor systems exhibiting pronounced quantum interference effects.

    PubMed

    Gorczak, Natalie; Renaud, Nicolas; Galan, Elena; Eelkema, Rienk; Siebbeles, Laurens D A; Grozema, Ferdinand C

    2016-03-01

    Quantum interference is a well-known phenomenon that dictates charge transport properties of single molecule junctions. However, reports on quantum interference in donor-bridge-acceptor molecules are scarce. This might be due to the difficulties in meeting the conditions for the presence of quantum interference in a donor-bridge-acceptor system. The electronic coupling between the donor, bridge, and acceptor moieties must be weak in order to ensure localised initial and final states for charge transfer. Yet, it must be strong enough to allow all bridge orbitals to mediate charge transfer. We present the computational route to the design of a donor-bridge-acceptor molecule that features the right balance between these contradicting requirements and exhibits pronounced interference effects. PMID:26878200

  10. Azo compounds as electron acceptor or radical ligands in transition metal species: spectroelectrochemistry and high-field EPR studies of ruthenium, rhodium and copper complexes of 2,2‧-azobis(5-chloropyrimidine)

    NASA Astrophysics Data System (ADS)

    Kaim, Wolfgang; Doslik, Natasa; Frantz, Stephanie; Sixt, Torsten; Wanner, Matthias; Baumann, Frank; Denninger, Gert; Kümmerer, Hans-Jürgen; Duboc-Toia, Carole; Fiedler, Jan; Zališ, Stanislav

    2003-08-01

    Oxidative coupling of 2-aminopyrimidine with LiOCl produces 5-chloro-2,2‧-azobis(pyrimidine) and 2,2‧-azobis(5-chloropyrimidine) (abcp), both of which were structurally characterized. The symmetrical abcp was used as strongly π-accepting mono- and bis-chelate ligand in complexes with [(bpy)2Ru]2+, [(H6C6)ClRu]+, [(Ph3P)2Cu]+ and (OC)3ClRe. The π-acceptor capability of abcp results in low-energy MLCT transitions and facile reduction to isolable radical complexes of which the DFT-calculated and structurally characterized dicopper(I) species {(μ-abcp)[Cu(PPh3)2]2}(PF6) was studied by X- and W-band EPR and the complex {(μ-abcp)[Ru(bpy)2]2}(PF6)3 at 9.6, 230 and 285 GHz EPR frequency. The results indicate considerable metal-ligand orbital mixing in the singly occupied molecular orbitals.

  11. Stepwise charge transfer complexation of some pyrimidines with σ-acceptor iodine involving a new unconventional acceptor

    NASA Astrophysics Data System (ADS)

    Rabie, Usama. M.; Mohamed, Ramadan. A.; Abou-El-Wafa, Moustafa. H.

    2007-11-01

    Interactions of some pyrimidine derivatives, 4-amino-2,6-dimethylpyrimidine, kyanmethin, (4AP), 2-amino-4,6-dimethylpyrimidine (2AP), 2-aminopyrimidine (AP), 2-amino-4-methylpyrimidine (AMP), 2-amino-4-methoxy-6-methylpyrimidine (AMMP), and 4-amino-5-chloro-2,6-dimethylpyrimidine (ACDP) as electron donors, with iodine (I 2), as a typical σ-electron acceptor, have been studied. Electronic absorption spectra of these interactions in several organic solvents of different polarities have performed instant appearance of clear charge transfer (CT) bands. Formation constants ( KCT), molar absorption coefficients ( ɛCT) and thermodynamic properties, Δ H, Δ S, and Δ G, of these interactions have been determined and discussed. Electronic absorption spectra of the solutions of the synthesized pyrimidines-iodine, P-I 2, CT complexes have shown the characteristic bands of the triiodide ion, I 3-. UV/vis spectral tracking of these interactions have shown that by lapse of time the first formed CT complex, P-I 2, is transformed to the corresponding triiodide complex, P +I.I 3-, then, the later interacts as a new unconventional acceptor and it forms a CT complex of the form (P).(P +I.I 3-). Elemental analyses of these solid complexes have indicated the stoichiometric ratio 2:2, or formally 1:1, P:I 2.

  12. Stepwise charge transfer complexation of some pyrimidines with sigma-acceptor iodine involving a new unconventional acceptor.

    PubMed

    Rabie, Usama M; Mohamed, Ramadan A; Abou-El-Wafa, Moustafa H

    2007-11-01

    Interactions of some pyrimidine derivatives, 4-amino-2,6-dimethylpyrimidine, kyanmethin, (4AP), 2-amino-4,6-dimethylpyrimidine (2AP), 2-aminopyrimidine (AP), 2-amino-4-methylpyrimidine (AMP), 2-amino-4-methoxy-6-methylpyrimidine (AMMP), and 4-amino-5-chloro-2,6-dimethylpyrimidine (ACDP) as electron donors, with iodine (I(2)), as a typical sigma-electron acceptor, have been studied. Electronic absorption spectra of these interactions in several organic solvents of different polarities have performed instant appearance of clear charge transfer (CT) bands. Formation constants (KCT), molar absorption coefficients (epsilonCT) and thermodynamic properties, DeltaH, DeltaS, and DeltaG, of these interactions have been determined and discussed. Electronic absorption spectra of the solutions of the synthesized pyrimidines-iodine, P-I2, CT complexes have shown the characteristic bands of the triiodide ion, I3*. UV/vis spectral tracking of these interactions have shown that by lapse of time the first formed CT complex, P-I2, is transformed to the corresponding triiodide complex, P(+)I.I3*, then, the later interacts as a new unconventional acceptor and it forms a CT complex of the form (P).(P+I.I3*). Elemental analyses of these solid complexes have indicated the stoichiometric ratio 2:2, or formally 1:1, P:I2. PMID:17317281

  13. No-carrier-added (NCA) aryl [{sup 18}F]fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    SciTech Connect

    Ding, Yu-Shin; Fowler, J.S.; Wolf, A.P.

    1991-12-31

    A method for synthesizing no-carrier-added (NCA) aryl [{sup 18}F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substituent on an electron rich ring. The reaction is carried out by nucleophilic aromatic substitution with a no-carrier-added (NCA) [{sup 18}F]fluoride ion. The method can be used to synthesize various no-carrier-added aryl [{sup 18}F]fluoride compositions, including 6-[{sup 18}F]fluoro-L-DOPA, 2-[{sup 18}F]fluorotyrosine, 6-[{sup 18}F]fluoronorepinephrine, and 6-[{sup 18}F]fluorodopamine. In those instances when a racemic mixture of enantiomers is produced by the present invention, such as in the synthesis of 6-[{sup 18}F]fluoronorepinephrine, a preferred method also includes resolution of the racemic mixture on a chiral HPLC column. This procedure results in a high yield of enantiomerically pure [{sup 18}F] labeled isomers, for example [-]-6-[{sup 18}F]fluoronorepinephrine and [+]-6-[{sup 18}F]fluoronorepinephrine.

  14. Efficiency enhancement of planar perovskite solar cells by adding zwitterion/LiF double interlayers for electron collection

    NASA Astrophysics Data System (ADS)

    Sun, Kuan; Chang, Jingjing; Isikgor, Furkan Halis; Li, Pengcheng; Ouyang, Jianyong

    2014-12-01

    Double interlayers consisting of a zwitterionic small molecule layer and a LiF layer were introduced between the electron transport layer and the cathode of perovskite solar cells. The double interlayers improve the photovoltaic efficiency to 13.2%, which is higher than that of control devices without the double interlayer (9.2%) or with LiF (11.0%) or rhodamine 101 zwitterion (12.1%) alone.Double interlayers consisting of a zwitterionic small molecule layer and a LiF layer were introduced between the electron transport layer and the cathode of perovskite solar cells. The double interlayers improve the photovoltaic efficiency to 13.2%, which is higher than that of control devices without the double interlayer (9.2%) or with LiF (11.0%) or rhodamine 101 zwitterion (12.1%) alone. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05975a

  15. Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes and α,ω-diphenylpolyynes.

    PubMed

    Ma, Xiaonan; Yan, Linyin; Wang, Xuefei; Guo, Qianjin; Xia, Andong

    2011-10-14

    The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes (DPE) and α,ω-diphenylpolyynes (DPY) molecules with different conjugated bridge length and substitution modes were investigated by using quantum chemical calculations. We calculated the ground state structures and energy of two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of conjugation length and substitution modes of the electronic absorption spectra was obtained by TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected from several functionals by comparing the calculated electronic spectral data with experimental value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate coupling values H(AD) of the CT process. The calculation shows that both the HOMO-LUMO energy gaps and average bond length alternations between unsaturated multiple (C≡C and C=C) and saturated single bonds (C-C) decrease regularly with the extension of conjugation. The effective conjugated length (ECL) of DPE and DPY with the same order MM > MP/PM > PP is found together with the regular red shift of the electronic absorption spectra with the extension of conjugation, resulting from the different π-electron delocalization and conjugation efficiency. The GMH analysis further suggests that the CT process in both DPE and DPY is predominated by the through-bond mechanism. The remarkable difference of the conjugated length dependence of squared CT coupling between substituted DPE and DPY is the result of the energetic matching degree of the frontier molecular orbitals between donor/acceptor and the conjugated bridge. PMID:21879052

  16. Non-fullerene acceptors: exciton dissociation with PTCDA versus C60.

    PubMed

    Dutton, Gregory J; Robey, Steven W

    2015-06-28

    Extensive development of new polymer and small molecule donors has helped produce a steady increase in the efficiency of organic photovoltaic (OPV) devices. However, OPV technology would also benefit from the introduction of non-fullerene acceptors. Unfortunately, efforts to replace fullerenes have typically led to significantly reduced efficiencies. A number of possible explanations for reduced efficiencies with non-fullerene acceptors compared to fullerene acceptors have been suggested, including the formation of unfavorable morphologies in non-fullerene systems and/or favorable excitation/carrier delocalization in fullerenes. In addition, enhanced exciton dissociation associated with fundamental characteristics of the fullerene molecular electronic states has also been suggested. We used time-resolved two-photon photoemission (TR-2PPE) to directly compare exciton dissociation at interfaces between zinc phthalocyanine (ZnPc) interfaces and the non-fullerene acceptor, perylene tetracarboxylic dianhydride (PTCDA) versus dissociation measured at the analogous interface with C60, and thus help discriminate between these potential explanations. Exciton dissociation rates are comparable for phthalocyanine interfaces with both acceptors, allowing us to suggest a hierarchy for the importance of various effects producing higher efficiencies with fullerene acceptors. PMID:26027544

  17. 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

  18. Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices.

    PubMed

    Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

    2015-01-01

    We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm(2)·V(-1)·s(-1)), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution. PMID:26567845

  19. Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices

    PubMed Central

    Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

    2015-01-01

    We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm2·V−1·s−1), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution. PMID:26567845

  20. Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices

    NASA Astrophysics Data System (ADS)

    Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

    2015-11-01

    We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm2·V-1·s-1), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution.

  1. Adding the Third Dimension to Virus Life Cycles: Three-Dimensional Reconstruction of Icosahedral Viruses from Cryo-Electron Micrographs

    PubMed Central

    Baker, T. S.; Olson, N. H.; Fuller, S. D.

    1999-01-01

    Viruses are cellular parasites. The linkage between viral and host functions makes the study of a viral life cycle an important key to cellular functions. A deeper understanding of many aspects of viral life cycles has emerged from coordinated molecular and structural studies carried out with a wide range of viral pathogens. Structural studies of viruses by means of cryo-electron microscopy and three-dimensional image reconstruction methods have grown explosively in the last decade. Here we review the use of cryo-electron microscopy for the determination of the structures of a number of icosahedral viruses. These studies span more than 20 virus families. Representative examples illustrate the use of moderate- to low-resolution (7- to 35-Å) structural analyses to illuminate functional aspects of viral life cycles including host recognition, viral attachment, entry, genome release, viral transcription, translation, proassembly, maturation, release, and transmission, as well as mechanisms of host defense. The success of cryo-electron microscopy in combination with three-dimensional image reconstruction for icosahedral viruses provides a firm foundation for future explorations of more-complex viral pathogens, including the vast number that are nonspherical or nonsymmetrical. PMID:10585969

  2. Molecular Engineering of Pyrido[3,4-b]pyrazine-Based Donor-Acceptor-π-Acceptor Organic Sensitizers: Effect of Auxiliary Acceptor in Cobalt- and Iodine-Based Electrolytes.

    PubMed

    Liu, Bo; Giordano, Fabrizio; Pei, Kai; Decoppet, Jean-David; Zhu, Wei-Hong; Zakeeruddin, Shaik M; Grätzel, Michael

    2015-12-14

    Due to the ease of tuning its redox potential, the cobalt-based redox couple has been extensively applied for highly efficient dye-sensitized solar cells (DSSCs) with extraordinarily high photovoltages. However, a cobalt electrolyte needs particular structural changes in the organic dye components to obtain such high photovoltages. To achieve high device performance, specific requirements in the molecular tailoring of organic sensitizers still need to be met. Besides the need for large electron donors, studies of the auxiliary acceptor segment of donor-acceptor-π-acceptor (D-A-π-A) organic sensitizers are still rare in molecular optimization in the context of cobalt electrolytes. In this work, two novel organic D-A-π-A-type sensitizers (IQ13 and IQ17) have been developed and exploited in cobalt- and iodine-based redox electrolyte DSSCs, specifically to provide insight into the effect of π-bridge modification in different electrolytes. The investigation has been focused on the additional electron-withdrawing acceptor capability with grafted long alkoxy chains. Optoelectronic transient measurements have indicated that IQ17 containing a pyrido[3,4-b]pyrazine moiety bearing long alkoxyphenyl chains is more suitable for application in cobalt-based DSSCs. PMID:26548926

  3. Value Added?

    ERIC Educational Resources Information Center

    UCLA IDEA, 2012

    2012-01-01

    Value added measures (VAM) uses changes in student test scores to determine how much "value" an individual teacher has "added" to student growth during the school year. Some policymakers, school districts, and educational advocates have applauded VAM as a straightforward measure of teacher effectiveness: the better a teacher, the better students…

  4. Critical gaps in the world's largest electronic medical record: Ad Hoc nursing narratives and invisible adverse drug events.

    PubMed

    Hurdle, John F; Weir, Charlene R; Roth, Beverly; Hoffman, Jennifer; Nebeker, Jonathan R

    2003-01-01

    The Veterans Health Administration (VHA), of the U.S. Department of Veteran Affairs, operates one of the largest healthcare networks in the world. Its electronic medical record (EMR) is fully integrated into clinical practice, having evolved over several decades of design, testing, trial, and error. It is unarguably the world's largest EMR, and as such it makes an important case study for a host of timely informatics issues. The VHA consistently has been at the vanguard of patient safety, especially in its provider-oriented EMR. We describe here a study of a large set of adverse drug events (ADEs) that eluded a rigorous ADE survey based on prospective EMR chart review. These numerous ADEs were undetected (and hence invisible) in the EMR, missed by an otherwise sophisticated ADE detection scheme. We speculate how these invisible nursing ADE narratives persist and what they portend for safety re-engineering. PMID:14728184

  5. Carbon and group II acceptor coimplantation in GaAs

    SciTech Connect

    Morton, R.; Lau, S.S.; Poker, D.B.; Chu, P.K.; Fung, K.K.; Wang, N.

    1998-11-01

    Coimplantations of carbon and one of the group II acceptors, Mg, Zn, or Cd, were performed and compared to implantations involving only a single element (Mg, Zn, or Cd) or Ga and C coimplanted into GaAs substrates. The group II and C (II/C) coimplantations act to balance the crystal stoichiometry since group II atoms prefer to reside in the Ga sublattice and C prefers to reside in the As sublattice. The electrical characteristics of the various implantations were obtained from sheet and differential Hall measurements. Rutherford backscattering spectrometry was employed to determine the amount of implantation-induced damage which was then correlated to the amount of C activation in the group II/C coimplanted samples. It was found that coimplantation of the heavier group II acceptors, Zn and Cd, resulted in layers with larger peak hole concentrations. This is a result of the large amount of lattice damage created by these elements which is thought to provide the necessary abundance of As vacancies for C activation. Secondary ion mass spectroscopy measurements of the samples after implant activation indicate that C coimplantation significantly reduces the diffusivity of the group II acceptors. Cross-sectional transmission electron microscopy indicated a unique defect structure (extrinsic dislocation loops) for the cases of group II/C coimplantation. These dislocation loops are located at the diffusion front of the group II element in the samples and therefore have a rather profound influence on the diffusion of the group II elements. A rationalization of the defect structure and the effect it has on the diffusion of group II elements is given. {copyright} {ital 1998 American Institute of Physics.}

  6. Spectral, thermal, XRD and SEM studies of charge-transfer complexation of hexamethylenediamine and three types of acceptors: π-, σ- and vacant orbital acceptors that include quinol, picric acid, bromine, iodine, SnCl4 and ZnCl2 acceptors

    NASA Astrophysics Data System (ADS)

    Adam, Abdel Majid A.; Refat, Moamen S.; Saad, Hosam A.

    2013-11-01

    In this work, structural, thermal, morphological and pharmacological characterization was performed on the interactions between a hexamethylenediamine (HMDA) donor and three types of acceptors to understand the complexation behavior of diamines. The three types of acceptors include π-acceptors (i.e., quinol (QL) and picric acid (PA)), σ-acceptors (i.e., bromine and iodine) and vacant orbital acceptors (i.e., tin(IV) tetrachloride (SnCl4) and zinc chloride (ZnCl2)). The characterization of the obtained CT complexes was performed using elemental analysis, infrared (IR), Raman, 1H NMR and electronic absorption spectroscopy, powder X-ray diffraction (XRD) and thermogravimetric (TG) analysis. Their morphologies were studied using scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). The biological activities of the obtained CT complexes were tested for their antibacterial activities. The complex containing the QL acceptor exhibited a remarkable electronic spectrum with a strong, broad absorption band, which had an observed λmax that was at a much longer wavelength than those of the free reactants. In addition, this complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared to standard drugs. The complexes containing the PA, iodine, Sn(IV) and Zn(II) acceptors exhibited good thermal stability up to 240, 330, 275 and 295 °C, respectively. The complexes containing bromine, Sn(IV) and Zn(II) acceptors exhibited good crystallinity. In addition to its good crystallinity properties, the complex containing the bromine acceptor exhibits a remarkable morphology feature.

  7. Blinking fluorescence of single donor-acceptor pairs: Important role of ``dark'' states in resonance energy transfer via singlet levels

    NASA Astrophysics Data System (ADS)

    Osad'ko, I. S.; Shchukina, A. L.

    2012-06-01

    The influence of triplet levels on Förster resonance energy transfer via singlet levels in donor-acceptor (D-A) pairs is studied. Four types of D-A pair are considered: (i) two-level donor and two-level acceptor, (ii) three-level donor and two-level acceptor, (iii) two-level donor and three-level acceptor, and (iv) three-level donor and three-level acceptor. If singlet-triplet transitions in a three-level acceptor molecule are ineffective, the energy transfer efficiency E=IA/(IA+ID), where ID and IA are the average intensities of donor and acceptor fluorescence, can be described by the simple theoretical equation E(F)=FTD/(1+FTD). Here F is the rate of energy transfer, and TD is the donor fluorescence lifetime. In accordance with the last equation, 100% of the donor electronic energy can be transferred to an acceptor molecule at FTD≫1. However, if singlet-triplet transitions in a three-level acceptor molecule are effective, the energy transfer efficiency is described by another theoretical equation, E(F)=F¯(F)TD/[1+F¯(F)TD]. Here F¯(F) is a function of F depending on singlet-triplet transitions in both donor and acceptor molecules. Expressions for the functions F¯(F) are derived. In this case the energy transfer efficiency will be far from 100% even at FTD≫1. The character of the intensity fluctuations of donor and acceptor fluorescence indicates which of the two equations for E(F) should be used to find the value of the rate F. Therefore, random time instants of photon emission in both donor and acceptor fluorescence are calculated by the Monte Carlo method for all four types of D-A pair. Theoretical expressions for start-stop correlators (waiting time distributions) in donor and acceptor fluorescence are derived. The probabilities wND(t) and wNA(t) of finding N photons of donor and acceptor fluorescence in the time interval t are calculated for various values of the energy transfer rate F and for all four types of D-A pair. Comparison of the calculated D

  8. Role of functionalized acceptors in heteroleptic bipyridyl Cu(I) complexes for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Xiaoqing; Shao, Yang; Li, Ke; Zhao, Zigang; Wei, Shuxian; Guo, Wenyue

    2016-07-01

    The intrinsic optoelectronic properties of heteroleptic bipyridyl Cu(I) complexes bearing functionalized acceptor subunits have been investigated by density functional theory and time-dependent DFT. The Cu(I) complexes exhibit distorted trigonal-pyramidal geometries and typical metal-to-ligand electron transfer characteristics at the long wavelength region. Replacing carboxylic acid with cyanoacrylic acid in acceptor subunits stabilizes the LUMO levels, thus lowering the HOMOLUMO energy gaps and facilitating favorable donor-to-acceptor intramolecular electron transfer and charge separation. Introduction of heteroaromatic groups and cyanoacrylic acid significantly improves the light-harvesting capability of the complexes. Our results highlight the effect of functionalized acceptors on the optoelectronic properties of bipyridyl Cu(I) complexes and provide a fresh perspective on screening of efficient sensitizers for dye-sensitized solar cells.

  9. Tuning of Stepwise Neutral-Ionic Transitions by Acceptor Site Doping in Alternating Donor/Acceptor Chains.

    PubMed

    Nakabayashi, Keita; Nishio, Masaki; Miyasaka, Hitoshi

    2016-03-01

    The stepwise neutral-ionic (N-I) phase transition found in the alternating donor/acceptor (DA) chain [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)]·2(p-xylene) (0; 2,3,5,6-F4PhCO2(-) = 2,3,5,6-tetrafluorobenzoate; DMDCNQI = 2,5-dimethyl-N,N'-dicyanoquinonediimine) was tuned by partly substituting the acceptor DMDCNQI with 2,5-dimethoxy-N,N'-dicyanoquinonediimine (DMeODCNQI), which displays a poorer electron affinity in an isostructural series. The site-doped series comprised [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)1-x(DMeODCNQI)x]·2(p-xylene) for doping rates (x) = 0.05 (0.05-MeO), 0.10 (0.10-MeO), 0.15 (0.15-MeO), and 0.20 (0.20-MeO). The neutral chain [Ru2(2,3,5,6-F4PhCO2)4(DMeODCNQI)]·4(p-xylene) (1), which only contained DMeODCNQI, was also characterized. All site-doped compounds were isostructural to 0 except 1 despite their identical DA chain motif. Except at an x value of 0.20, they displayed a two-step N-I transition involving an intermediate phase. This transition occurred at high temperatures in 0 but shifted to lower temperatures in a parallel manner with increasing doping rate. Simultaneously, each transition broadened with increasing doping rate, leading to a convergence of two transitions at an x value approximating 0.2. Donor/acceptor-site-doping techniques present somewhat different impacts in terms of interchain Coulomb effects. PMID:26878151

  10. 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…

  11. Donor and acceptor concentrations in degenerate InN

    SciTech Connect

    Look, D.C.; Lu, H.; Schaff, W.J.; Jasinski, J.; Liliental-Weber, Z.

    2002-01-28

    A formalism is presented to determine donor (N{sub D}) and acceptor (N{sub A}) concentrations in wurtzitic InN characterized by degenerate carrier concentration (n) and mobility ({mu}). The theory includes scattering not only by charged point defects and impurities, but also by charged threading dislocations, of concentration N{sub dis}. For an 0.45-{micro}m-thick InN layer grown on Al{sub 2}O{sub 3} by molecular beam epitaxy, having N{sub dis} = 5 x 10{sup 10} cm{sup -2}, determined by transmission electron microscopy, n(20 K) = 3.5 x 10{sup 18} cm{sup -3}, and {mu}(20 K) = 1055 cm{sup 2}/V-s, determined by Hall-effect measurements, the fitted values are N{sub D} = 4.7 x 10{sup 18} cm{sup -3} and N{sub A} = 1.2 x 10{sup 18} cm{sup -3}. The identities of the donors and acceptors are not known, although a comparison of N{sub D} with analytical data, and also with calculations of defect formation energies, suggests that a potential candidate for the dominant donor is H.

  12. ADS pilot program Plan

    NASA Technical Reports Server (NTRS)

    Clauson, J.; Heuser, J.

    1981-01-01

    The Applications Data Service (ADS) is a system based on an electronic data communications network which will permit scientists to share the data stored in data bases at universities and at government and private installations. It is designed to allow users to readily locate and access high quality, timely data from multiple sources. The ADS Pilot program objectives and the current plans for accomplishing those objectives are described.

  13. First principle study of magnetic and electronic properties of single X (X = Al, Si) atom added to small carbon clusters (C n X, n = 2-10)

    NASA Astrophysics Data System (ADS)

    Afshar, M.; Hoseini, S. S.; Sargolzaei, M.

    2016-07-01

    In this paper, the magnetic and electronic properties of single aluminum and silicon atom added to small carbon clusters (C n X; X = Al, Si; n = 2-10) are studied in the framework of generalized-gradient approximation using density functional theory. The calculations were performed for linear, two dimensional and three dimensional clusters based on full-potential local-orbital (FPLO) method. The total energies, HOMO-LUMO energy gap and total magnetic moments of the most stable structures are presented in this work. The calculations show that C n Si clusters have more stability compared to C n Al clusters. In addition, our magnetic calculations were shown that the C n Al isomers are magnetic objects whereas C n Si clusters are nonmagnetic objects.

  14. Energy Level Tuning of Non-Fullerene Acceptors in Organic Solar Cells.

    PubMed

    Cnops, Kjell; Zango, German; Genoe, Jan; Heremans, Paul; Martinez-Diaz, M Victoria; Torres, Tomas; Cheyns, David

    2015-07-22

    The use of non-fullerene acceptors in organic photovoltaic (OPV) devices could lead to enhanced efficiencies due to increased open-circuit voltage (VOC) and improved absorption of solar light. Here we systematically investigate planar heterojunction devices comprising peripherally substituted subphthalocyanines as acceptors and correlate the device performance with the heterojunction energetics. As a result of a balance between VOC and the photocurrent, tuning of the interface energy gap is necessary to optimize the power conversion efficiency in these devices. In addition, we explore the role of the charge transport layers in the device architecture. It is found that non-fullerene acceptors require adjusted buffer layers with aligned electron transport levels to enable efficient charge extraction, while the insertion of an exciton-blocking layer at the anode interface further boosts photocurrent generation. These adjustments result in a planar-heterojunction OPV device with an efficiency of 6.9% and a VOC above 1 V. PMID:26104833

  15. Spectroscopic studies of charge transfer complexes between colchicine and some π acceptors

    NASA Astrophysics Data System (ADS)

    Arslan, Mustafa; Duymus, Hulya

    2007-07-01

    Charge transfer complexes between colchicine as donor and π acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL) have been studied spectrophotometrically in dichloromethane at 21 °C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.

  16. Theoretical calculation of the miniband-to-acceptor magnetoluminescence of semiconductor superlattices

    NASA Astrophysics Data System (ADS)

    Latgé, A.; Porras-Montenegro, N.; de Dios-Leyva, M.; Oliveira, L. E.

    1997-05-01

    The acceptor-related photoluminescence of a GaAs-(Ga,Al)As superlattice, under the influence of a magnetic field applied parallel to the interfaces, is theoretically studied following a variational procedure within the effective-mass approximation. Electron and hole magnetic Landau levels and envelope wave functions were obtained by an expansion in terms of sine functions, whereas for the impurity levels the envelope functions were taken as products of sine and hydrogenic-like variational functions. Impurity binding energies and wave functions are obtained for acceptors at a general position in the superlattice and for different in-plane magnetic fields. Theoretical results corresponding to transitions from the conduction subband to states of acceptors (miniband-to-acceptor e-A0 transitions) at the edge and center positions of the GaAs quantum well compare well with available experimental data by Skromme et al. [Phys. Rev. Lett. 65, 2050 (1990)] on the magnetic-field dependence of the photoluminescence peak position of conduction miniband-to-acceptor transitions for different temperatures and values of the superlattice period.

  17. Synthesis and characterization of a highly strained donor-acceptor nanohoop.

    PubMed

    Van Raden, J M; Darzi, E R; Zakharov, L N; Jasti, R

    2016-06-15

    A highly-strained, nitrogen-doped cycloparaphenylene (CPP), aza[6]CPP, was synthesized and then converted to a donor-acceptor nanohoop, N-methylaza[6]CPP, via alkylation of the nitrogen center. The energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) for both molecules were then probed by cyclic voltammetry (CV), which revealed that the donor-acceptor nanohoop had a significantly lower LUMO energy relative to [6]CPP and aza[6]CPP. Density functional theory (DFT) revealed that the donor-acceptor nanohoop underwent a redistribution of the frontier molecular orbital (FMO) density such that a significant portion of the LUMO density resided upon the electron-deficient nitrogen-containing ring. This localization of LUMO density caused a large lowering in the LUMO energy of nearly a full electron volt, while the HOMO energy was less affected due to a large centralization of the FMO on the electron-rich phenylene backbone. This ultimately resulted in a net lowering of the HOMO-LUMO energy gap which was observed both experimentally and computationally. In addition, N-methylaza[6]CPP has a significantly lower energy LUMO than N-methylaza[8]CPP, illustrating that the FMO levels of donor-acceptor nanohoops can be tuned by adjusting the hoop size. PMID:26881906

  18. Adding Value.

    ERIC Educational Resources Information Center

    Orsini, Larry L.; Hudack, Lawrence R.; Zekan, Donald L.

    1999-01-01

    The value-added statement (VAS), relatively unknown in the United States, is used in financial reports by many European companies. Saint Bonaventure University (New York) has adapted a VAS to make it appropriate for not-for-profit universities by identifying stakeholder groups (students, faculty, administrators/support personnel, creditors, the…

  19. Proficiency of acceptor-donor-acceptor organic dye with spiro-MeOTAD HTM on the photovoltaic performance of dye sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Ramavenkateswari, K.; Venkatachalam, P.

    2016-08-01

    This work investigates the proficiency of acceptor-donor-acceptor (A-D-A) organic dye Diisopropyl azodicarboxylate (DIAC) as photosensitizer on the photovoltaic parameters of silver (Ag) doped TiO2 photoanode dye-sensitized solar cells (DSSCs) with quasi-solid state electrolyte/hole transport material (HTM) spiro-MeOTAD. TNSs (TiO2 nanosticks) photoanodes are prepared through sol-gel method and hydrothermal technique. X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and BET measurement were used to characterize the structure and morphology of TiO2 nanostructures. The Diisopropyl azodicarboxylate organic dye with TNPs-Ag@TNSs composite photoanode structure and spiro-MeOTAD HTM exhibited better power conversion efficiency (PCE). [Figure not available: see fulltext.

  20. Dynamic combinatorial synthesis of a catenane based on donor–acceptor interactions in water

    PubMed Central

    Au-Yeung, Ho Yu; Pantoş, G. Dan; Sanders, Jeremy K. M.

    2009-01-01

    A new type of neutral donor–acceptor [2]-catenane, containing both complementary units in the same ring was synthesized from a dynamic combinatorial library in water. The yield of the water soluble [2]-catenane is enhanced by increasing either building-block concentrations or ionic strength, or by the addition of an electron-rich template. NMR spectroscopy demonstrates that the template is intercalated between the 2 electron-deficient naphthalenediimide units of the catenane. PMID:19171892

  1. Donor-acceptor conjugated polymers based on multifused ladder-type arenes for organic solar cells.

    PubMed

    Wu, Jhong-Sian; Cheng, Sheng-Wen; Cheng, Yen-Ju; Hsu, Chain-Shu

    2015-03-01

    Harvesting solar energy from sunlight to generate electricity is considered as one of the most important technologies to address the future sustainability of humans. Polymer solar cells (PSCs) have attracted tremendous interest and attention over the past two decades due to their potential advantage to be fabricated onto large area and light-weight flexible substrates by solution processing at a lower cost. PSCs based on the concept of bulk heterojunction (BHJ) configuration where an active layer comprises a composite of a p-type (donor) and an n-type (acceptor) material represents the most useful strategy to maximize the internal donor-acceptor interfacial area allowing for efficient charge separation. Fullerene derivatives such as [6,6]-phenyl-C61 or 71-butyric acid methyl ester (PCBM) are the ideal n-type materials ubiquitously used for BHJ solar cells. The major effort to develop photoactive materials is numerously focused on the p-type conjugated polymers which are generally synthesized by polymerization of electron-rich donor and electron-deficient acceptor monomers. Compared to the development of electron-deficient comonomers (acceptor segments), the development of electron-rich donor materials is considerably flourishing. Forced planarization by covalently fastening adjacent aromatic and heteroaromatic subunits leads to the formation of ladder-type conjugated structures which are capable of elongating effective conjugation, reducing the optical bandgap, promoting intermolecular π-π interactions and enhancing intrinsic charge mobility. In this review, we will summarize the recent progress on the development of various well-defined new ladder-type conjugated materials. These materials serve as the superb donor monomers to prepare a range of donor-acceptor semi-ladder copolymers with sufficient solution-processability for solar cell applications. PMID:25322211

  2. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  3. Decarboxylative 1,4-Addition of α-Oxocarboxylic Acids with Michael Acceptors Enabled by Photoredox Catalysis.

    PubMed

    Wang, Guang-Zu; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-10-01

    Enabled by iridium photoredox catalysis, 2-oxo-2-(hetero)arylacetic acids were decarboxylatively added to various Michael acceptors including α,β-unsaturated ester, ketone, amide, aldehyde, nitrile, and sulfone at room temperature. The reaction presents a new type of acyl Michael addition using stable and easily accessible carboxylic acid to formally generate acyl anion through photoredox-catalyzed radical decarboxylation. PMID:26366608

  4. DIS in AdS

    NASA Astrophysics Data System (ADS)

    Albacete, Javier L.; Kovchegov, Yuri V.; Taliotis, Anastasios

    2009-03-01

    We calculate the total cross section for the scattering of a quark-anti-quark dipole on a large nucleus at high energy for a strongly coupled N = 4 super Yang-Mills theory using AdS/CFT correspondence. We model the nucleus by a metric of a shock wave in AdS5. We then calculate the expectation value of the Wilson loop (the dipole) by finding the extrema of the Nambu-Goto action for an open string attached to the quark and antiquark lines of the loop in the background of an AdS5 shock wave. We find two physically meaningful extremal string configurations. For both solutions we obtain the forward scattering amplitude N for the quark dipole-nucleus scattering. We study the onset of unitarity with increasing center-of-mass energy and transverse size of the dipole: we observe that for both solutions the saturation scale Qs is independent of energy/Bjorken-x and depends on the atomic number of the nucleus as Qs˜A1/3. Finally we observe that while one of the solutions we found corresponds to the pomeron intercept of αP = 2 found earlier in the literature, when extended to higher energy or larger dipole sizes it violates the black disk limit. The other solution we found respects the black disk limit and yields the pomeron intercept of αP = 1.5. We thus conjecture that the right pomeron intercept in gauge theories at strong coupling may be αP = 1.5.

  5. Synthesis and Characterization of Ru(II) Tris(1,1O-phenanthroline)-Electron Acceptor Dyads Incorporating the 4-benzoyl-N-methylpyridinium Cation or N-Benzyl-N'-methyl-viologen. Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Optical Oxygen Sensors

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Rawashdeh, Abdel-Monen M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

    2004-01-01

    The title compounds (1 and 2, above) were synthesized by Sonogashira coupling reactions of appropriate Ru(1I) complexes with the electron a cceptors. Characterization was conducted in solution and in frozen ma trices. Finally, the title compounds were evaluated as dopants of sol-gel materials. It was found that the intramolecular quenching efficie ncy of 4-benzoyl-Nmethylpyridinium cation in solution depends on the solvent: photoluminescence is quenched completely in CH,CN, but not i n methanol or ethanol. On the other hand, intramolecular emission que nching by 4-benzyl-N-methyl viologen is complete in all solvents. The difference between the two quenchers is traced electrochemically to t he solvation of the 4-benzoyl-Nmethylpyridiniums by alcohol. In froze n matrices or adsorbed on the surfaces of silica aerogel, both Ru(I1) complex/electron acceptor dyads of this study are photoluminescent, and the absence of quenching has been traced to the environmental rigi dity. When doped aerogels are cooled at 77 K, the emission intensity increases by approximately 4x, and the spectra shift to the blue, analogous to what is observed with Ru(I1) complexes in solutions undergoi ng fluid-to-rigid transition. However, in contrast to frozen solution s, the luminescent moieties in the bulk of aerogels kept at low tempe ratures are still accessible to gas-phase quenchers diffusing through the mesopores, leading to more sensitive platforms for sensors than o ther room-temperature configurations. Thus the photoluminescence of o ur Ru(I1) complex dyads adsorbed on aerogel is quenchable by O2 both at room temperature and at 77 K. Furthermore, it was also found that O 2 modulates the photoluminescence of aerogels doped with 4-benzoyl -N -methylpyridinium-based dyads over a wider dynamic range compared wi th aerogels doped with either our vislogen-based dyads or with Ru(I1) tris(1,lO-phenanthroline) itself.

  6. Spectroscopic Structural Investigations of Charge-Transfer Complexes of n-DONORS and - and Pi-Acceptors

    NASA Astrophysics Data System (ADS)

    Nour, El-Metwally; Alqaradawi, Siham Y.

    2009-06-01

    Molecular charge - transfer complexes of n-electron donors such as amines, pyridines and polynitrogen cyclic bases with both sigma- and pi-acceptors have been studied spectrophotometrically in chloroform. The reaction stoichiometries were determined using photometric titration methods. The formed CT-complexes are characterized and formulated based on electronic and infrared spectra as well as elemental and thermal measurements.

  7. Acetylene-derived strong organic acceptors for planar and nonplanar push-pull chromophores.

    PubMed

    Kivala, Milan; Diederich, François

    2009-02-17

    Though investigated for decades, interest in push-pull chromophores (D-pi-A), strong electron donors (D) connected by pi-conjugating spacers to strong electron acceptors (A), continues to grow. Such chromophores are of substantial interest for optoelectronic devices such as waveguides. Also, strong donors and acceptors form bimolecular charge-transfer (CT) complexes and salts, some of which exhibit electrical conductivity and magnetic behavior. Furthermore, strong organic acceptors are increasingly explored as dopants in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. This Account describes systematic efforts pursued over the past decade in our laboratory to generate new families of organic electron acceptors (A) and conjugate them via pi-spacers to electron donors (D) under formation of push-pull systems with intense intramolecular CT interactions and high third-order optical nonlinearities. First, we describe donor-acceptor-substituted tetraethynylethenes (TEEs). In these chromophores, the peripherally attached p-nitrophenyl acceptors and N,N-dimethylanilino donors behave as nearly independent redox centers. Acetylenic scaffolding using TEE building blocks produces large all-carbon sheets, such as perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with potent electron-acceptor properties. Arylated TEEs act as molecular switches allowing two-way photochemical interconversion that is not perturbed by thermal isomerization pathways. Upon sequential substitution of the acetylene moieties in TEEs, we formed another family of potent acceptors, the cyanoethynylethenes (CEEs). Donor-substituted CEEs are planar CT chromophores with very high third-order optical nonlinearities. Their high environmental stability allows for the formation of thin films by vapor-phase deposition. Through careful analysis of the physicochemical properties of CEEs, we established useful guidelines for evaluating and tuning the optical gap in

  8. Thiadiazolo[3,4-c]pyridine as an Acceptor toward Fast-Switching Green Donor-Acceptor-Type Electrochromic Polymer with Low Bandgap.

    PubMed

    Ming, Shouli; Zhen, Shijie; Lin, Kaiwen; Zhao, Li; Xu, Jingkun; Lu, Baoyang

    2015-06-01

    Thiadiazolo[3,4-c]pyridine (PT), an important analog of benzothiadiazole (BT), has most recently been explored as a novel electron acceptor. It exhibits more electron-accepting ability and other unique properties and potential advantages over BT, thus inspiring us to investigate PT-based donor-acceptor-type (D-A) conjugated polymer in electrochromics. Herein, PT was employed for the rational design of novel donor-acceptor-type systems to yield a neutral green electrochromic polymer poly(4,7-di(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-[1,2,5] thiadiazolo[3,4-c]pyridine) (PEPTE). PEPTE revealed a lower bandgap (Eg,ele=0.85 eV, Eg,opt=1.12 eV) than its BT analog and also favorable redox activity and stability. Furthermore, electrochromic kinetic studies demonstrated that PEPTE displayed higher coloration efficiency than BT analog, good optical memory, and very fast switching time (0.3 s at all three wavelengths), indicating that PT would probably be a promising choice for developing novel neutral green electrochromic polymers by matching with various donor units. PMID:25955881

  9. Hole-transfer induced energy transfer in perylene diimide dyads with a donor-spacer-acceptor motif.

    PubMed

    Kölle, Patrick; Pugliesi, Igor; Langhals, Heinz; Wilcken, Roland; Esterbauer, Andreas J; de Vivie-Riedle, Regina; Riedle, Eberhard

    2015-10-14

    We investigate the photoinduced dynamics of perylene diimide dyads based on a donor-spacer-acceptor motif with polyyne spacers of varying length by pump-probe spectroscopy, time resolved fluorescence, chemical variation and quantum chemistry. While the dyads with pyridine based polyyne spacers undergo energy transfer with near-unity quantum efficiency, in the dyads with phenyl based polyyne spacers the energy transfer efficiency drops below 50%. This suggests the presence of a competing electron transfer process from the spacer to the energy donor as the excitation sink. Transient absorption spectra, however, reveal that the spacer actually mediates the energy transfer dynamics. The ground state bleach features of the polyyne spacers appear due to the electron transfer decay with the same time constant present in the rise of the ground state bleach and stimulated emission of the perylene energy acceptor. Although the electron transfer process initially quenches the fluorescence of the donor it does not inhibit energy transfer to the perylene energy acceptor. The transient signatures reveal that electron and energy transfer processes are sequential and indicate that the donor-spacer electron transfer state itself is responsible for the energy transfer. Through the introduction of a Dexter blocker unit into the spacer we can clearly exclude any through bond Dexter-type energy transfer. Ab initio calculations on the donor-spacer and the donor-spacer-acceptor systems reveal the existence of a bright charge transfer state that is close in energy to the locally excited state of the acceptor. Multipole-multipole interactions between the bright charge transfer state and the acceptor state enable the energy transfer. We term this mechanism coupled hole-transfer FRET. These dyads represent a first example that shows how electron transfer can be connected to energy transfer for use in novel photovoltaic and optoelectronic devices. PMID:26347443

  10. Quantum computing with acceptor spins in silicon

    NASA Astrophysics Data System (ADS)

    Salfi, Joe; Tong, Mengyang; Rogge, Sven; Culcer, Dimitrie

    2016-06-01

    The states of a boron acceptor near a Si/SiO2 interface, which bind two low-energy Kramers pairs, have exceptional properties for encoding quantum information and, with the aid of strain, both heavy hole and light hole-based spin qubits can be designed. Whereas a light-hole spin qubit was introduced recently (arXiv:1508.04259), here we present analytical and numerical results proving that a heavy-hole spin qubit can be reliably initialised, rotated and entangled by electrical means alone. This is due to strong Rashba-like spin–orbit interaction terms enabled by the interface inversion asymmetry. Single qubit rotations rely on electric-dipole spin resonance (EDSR), which is strongly enhanced by interface-induced spin–orbit terms. Entanglement can be accomplished by Coulomb exchange, coupling to a resonator, or spin–orbit induced dipole–dipole interactions. By analysing the qubit sensitivity to charge noise, we demonstrate that interface-induced spin–orbit terms are responsible for sweet spots in the dephasing time {T}2* as a function of the top gate electric field, which are close to maxima in the EDSR strength, where the EDSR gate has high fidelity. We show that both qubits can be described using the same starting Hamiltonian, and by comparing their properties we show that the complex interplay of bulk and interface-induced spin–orbit terms allows a high degree of electrical control and makes acceptors potential candidates for scalable quantum computation in Si.

  11. DIS in AdS

    SciTech Connect

    Albacete, Javier L.; Kovchegov, Yuri V.; Taliotis, Anastasios

    2009-03-23

    We calculate the total cross section for the scattering of a quark-anti-quark dipole on a large nucleus at high energy for a strongly coupled N = 4 super Yang-Mills theory using AdS/CFT correspondence. We model the nucleus by a metric of a shock wave in AdS{sub 5}. We then calculate the expectation value of the Wilson loop (the dipole) by finding the extrema of the Nambu-Goto action for an open string attached to the quark and antiquark lines of the loop in the background of an AdS{sub 5} shock wave. We find two physically meaningful extremal string configurations. For both solutions we obtain the forward scattering amplitude N for the quark dipole-nucleus scattering. We study the onset of unitarity with increasing center-of-mass energy and transverse size of the dipole: we observe that for both solutions the saturation scale Q{sub s} is independent of energy/Bjorken-x and depends on the atomic number of the nucleus as Q{sub s}{approx}A{sup 1/3}. Finally we observe that while one of the solutions we found corresponds to the pomeron intercept of {alpha}{sub P} = 2 found earlier in the literature, when extended to higher energy or larger dipole sizes it violates the black disk limit. The other solution we found respects the black disk limit and yields the pomeron intercept of {alpha}{sub P} = 1.5. We thus conjecture that the right pomeron intercept in gauge theories at strong coupling may be {alpha}{sub P} = 1.5.

  12. Seeded on-surface supramolecular growth for large area conductive donor-acceptor assembly.

    PubMed

    Goudappagouda; Chithiravel, Sundaresan; Krishnamoorthy, Kothandam; Gosavi, Suresh W; Babu, Sukumaran Santhosh

    2015-07-01

    Charge transport features of organic semiconductor assemblies are of paramount importance. However, large-area extended supramolecular structures of donor-acceptor combinations with controlled self-assembly pathways are hardly accessible. In this context, as a representative example, seeded on-surface supramolecular growth of tetrathiafulvalene and tetracyano-p-quinodimethane (TTF-TCNQ) using active termini of solution-formed sheaves has been introduced to form an extended assembly. We demonstrate for the first time, the creation of a large-area donor-acceptor assembly on the surface, which is practically very tedious, using a seeded, evaporation-assisted growth process. The excellent molecular ordering in this assembly is substantiated by its good electrical conductivity (~10⁻² S cm⁻¹). The on-surface assembly via both internally formed and externally added sheaf-like seeds open new pathways in supramolecular chemistry and device applications. PMID:26036616

  13. Charge separation and photovoltaic conversion in polymer composites with internal donor/acceptor heterojunctions

    SciTech Connect

    Yu, G.; Heeger, A.J.

    1995-10-01

    The photosensitivity of semiconducting polymers can be enhanced by blending donor and acceptor polymers to optimize photoinduced charge separation. We describe a novel phase-separated polymer blend (composite) made with poly[2-methoxy-5-(2{prime}-ethyl-hexyloxy)-1,4-phenylene vinylene], MEH-PPV, as donor and cyano-PPV, CN-PPV, as acceptor. The photoluminescence and electroluminescence of both component polymers are quenched in the blend, indicative of rapid and efficient separation of photogenerated electron-hole pairs with electrons on the acceptor and holes on the donor. Diodes made with such a composite semiconducting polymer as the photosensitive medium show promising photovoltaic characteristics with carrier collection efficiency of 5% electrons/photon and energy conversion efficiency of 0.9%, {similar_to}20 times larger than in diodes made with pure MEH-PPV and {similar_to}100 times larger than in diodes made with CN-PPV. The photosensitivity and the quantum yield increase with reverse bias voltage, to 0.3 A/W and 80% electrons/photon respectively at {minus}10 V, comparable to results obtained from photodiodes made with inorganic semiconductors. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  14. Bubbling AdS3

    NASA Astrophysics Data System (ADS)

    Martelli, Dario; Morales, Jose F.

    2005-02-01

    In the light of the recent Lin, Lunin, Maldacena (LLM) results, we investigate 1/2-BPS geometries in minimal (and next to minimal) supergravity in D = 6 dimensions. In the case of minimal supergravity, solutions are given by fibrations of a two-torus T2 specified by two harmonic functions. For a rectangular torus the two functions are related by a non-linear equation with rare solutions: AdS3 × S3, the pp-wave and the multi-center string. ``Bubbling'', i.e. superpositions of droplets, is accommodated by allowing the complex structure of the T2 to vary over the base. The analysis is repeated in the presence of a tensor multiplet and similar conclusions are reached, with generic solutions describing D1D5 (or their dual fundamental string-momentum) systems. In this framework, the profile of the dual fundamental string-momentum system is identified with the boundaries of the droplets in a two-dimensional plane.

  15. Spectroscopic and dynamical differences between exciplex and electronically excited EDA complex

    NASA Astrophysics Data System (ADS)

    Lim, B. T.; Okajima, S.; Lim, E. C.

    1986-02-01

    We demonstrate here that the electronically excited electron donor-acceptor (EDA) complex can be different from the corresponding exciplex even in the absence of viscosity constraints that prevent the attainment of preferred donor-acceptor orientation.

  16. Efficient Synthesis and Photosensitizer Performance of Nonplanar Organic Donor-Acceptor Molecules.

    PubMed

    Yuan, Yuping; Michinobu, Tsuyoshi; Satoh, Norifusa; Ashizawa, Minoru; Han, Liyuan

    2015-08-01

    Nonplanar organic donor-acceptor molecules bearing a carboxylic acid group were synthesized by the formal [2+2] cycloaddition-retroelectrocyclization reaction between aniline-substituted alkynes and tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). This reaction offers an atom-economic one-step approach to donor-acceptor chromophores in satisfactory high yields. The resulting donor-acceptor molecules were characterized by conventional analytical techniques. In addition, the nonplanarity and intermolecular interactions were investigated by X-ray crystallography. The energy levels and intramolecular charge-transfer (CT), evaluated by UV-Vis-near IR spectroscopy and electrochemistry, suggested that there is a linear correlation between the optical and electrochemical band gaps. Based on these structural and electronic analyses, the photosensitizer performances of the donor-acceptor molecules in dye-sensitized solar cells (DSSCs) were initially investigated using TiO2 or SnO2 electrodes. Although the power conversion efficiencies were limited, the incident-photon-to-current-conversion efficiency (IPCE) spectra indicated a better photocurrent generation for the devices on SnO2 as compared to those on TiO2. PMID:26369162

  17. How intermolecular geometrical disorder affects the molecular doping of donor-acceptor copolymers

    NASA Astrophysics Data System (ADS)

    di Nuzzo, Daniele; Fontanesi, Claudio; Jones, Rebecca; Allard, Sybille; Dumsch, Ines; Scherf, Ullrich; von Hauff, Elizabeth; Schumacher, Stefan; da Como, Enrico

    2015-03-01

    Molecular doping of conjugated polymers represents an important strategy for improving organic electronic devices. However, the widely reported low efficiency of doping remains a crucial limitation to obtain high performance. Here we investigate how charge transfer between dopant and donor-acceptor copolymers is affected by the spatial arrangement of the dopant molecule with respect to the copolymer repeat unit. We p-dope a donor-acceptor copolymer and probe its charge-sensitive molecular vibrations in films by infrared spectroscopy. We find that, compared with a related homopolymer, a four times higher dopant/polymer molar ratio is needed to observe signatures of charges. By DFT methods, we simulate the vibrational spectra, moving the dopant along the copolymer backbone and finding that efficient charge transfer occurs only when the dopant is close to the donor moiety. Our results show that the donor-acceptor structure poses an obstacle to efficient doping, with the acceptor moiety being inactive for p-type doping.

  18. Synthesis and optoelectronic properties of Janus-dendrimer-type multivalent donor-acceptor systems.

    PubMed

    Dengiz, Cagatay; Breiten, Benjamin; Gisselbrecht, Jean-Paul; Boudon, Corinne; Trapp, Nils; Schweizer, W Bernd; Diederich, François

    2015-01-16

    A convergent, multistep protocol was employed for the synthesis of a Janus-type multivalent donor-acceptor system. The synthetic approach is based on a Sonogashira cross-coupling of two differently ferrocene-(Fc) substituted dendrons and a final sixfold [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reaction with tetracyanoethene, which occurs regioselectively at only one of the rigidly linked dendrons. The structural and optoelectronic properties of the compounds were investigated by X-ray analysis, UV/vis spectroscopy, and electrochemistry. The target Janus-system displays redox-amphoteric behavior. The nonalkynylated Fc end groups in one dendron are readily and reversibly oxidized. The second dendron, in which the terminal Fc-activated alkynes underwent the CA-RE reaction to give tetracyanobuta-1,3-dienes in the final step of the synthesis, undergoes four reversible 3-e(-) reductions in the very narrow potential range of 1 V. A spontaneous intramolecular charge transfer from the donor into the acceptor hemisphere was not observed. Furthermore, the oxidation potential of the Fc donors in one hemisphere is hardly perturbed by the push-pull acceptors in the other, which suggests that electronic communication along the π-system, with several meta-connectivities, is not efficient. Therefore, the charge-transfer bands seen in the Janus-type system originate from the interaction of the Fc donors with the directly connected tetracyanobuta-1,3-diene acceptors in the same hemisphere. PMID:25489964

  19. Fermi Surface of Donor and Acceptor Graphite Intercalation Compounds.

    NASA Astrophysics Data System (ADS)

    Wang, Guonan

    The Fermi surfaces and the electronic properties of the donor-type stage-1 C_8K and stage-2 C_{24}K, as well as the acceptor-type stage-2 BiCl_3, stage-3 HgCl_2 and stage-3 SbF _5 graphite intercalation compounds were investigated by means of the de Haas-van Alphen effect. The dHvA spectra of the stage-1 C_8 K exhibit two dHvA frequencies, 3126 T and 4250 T. The corresponding effective masses were 0.86 m _0 and 0.92 m_0, respectively. The angular dependence of the dHvA frequencies for a direction within +/-18^circ of the c-axis showed that there are both three-dimensional and two dimensional parts of the Fermi surfaces in C _8K. The three-dimensional Fermi surface has a cross-sectional area corresponding to the dHvA frequency of 3126 T. The charge transfer per potassium atom measured from the dHvA effect is 0.97. This implies that the potassium is ionized completely. These dHvA experimental results support both the Tatar and Rabii model and the revised Ohno, Nakao and Kamimura model for C_8K. Two dominant dHvA frequencies were obtained in stage-2 C_{24}K. They are 286 T and 2570 T, respectively. The predictions of Blinowski's model are in agreement with the experimental data. The charge transfer per potassium is found to be 0.88. This suggests that the potassium s-band is above the Fermi level in C_{24}K. The dHvA measurements for the acceptor compounds show that the stage-2 BiCl_3 GIC had two dHvA frequencies, 327T and 1012T, and each stage -3 compound had three dominant frequencies. They are 121T, 523T and 664T for HgCl_2, and 172T, 656T and 852T for SbF_5. The cyclotron masses corresponding to the dHvA frequencies for these compounds were measured from the temperature dependence of the dHvA amplitudes. The theoretical predictions of the dHvA frequencies and the cyclotron masses from the Blinowski's band models for stage-2 and stage-3 compounds are in agreement with the experimental results. The angular dependence of the dHvA frequencies show that the Fermi

  20. Optoelectronic properties and charge transfer in donor-acceptor all-conjugated diblock copolymers.

    SciTech Connect

    Botiz, I.; Schaller, R. D.; Verduzco, R.; Darling, S. B.

    2011-05-12

    All-conjugated block copolymers, which can self-assemble into well-ordered morphologies, provide exciting opportunities to rationally design and control the nanoscale organization of electron-donor and electron-acceptor moieties in optoelectronic active layers. Here we report on the steady-state and time-resolved optical characterization of block copolymer films and solutions containing poly(3-hexylthiophene) as the donor block and poly(9,9-dioctylfluorene) with and without copolymerization with benzothiadiazole as the acceptor block. Transient absorption measurements suggest rapid charge transfer occurs in both systems, with higher efficiency observed in the latter composition. These results indicate that this class of materials has promise in preparing highly ordered bulk heterojunction all-polymer organic photovoltaic devices.

  1. Aromatic donor-acceptor interactions in non-polar environments.

    PubMed

    Prentice, Giles M; Pascu, Sofia I; Filip, Sorin V; West, Kevin R; Pantoş, G Dan

    2015-05-14

    We have evaluated the strength of aromatic donor-acceptor interactions between dialkyl naphthalenediimide and dialkoxynaphthalene in non-polar environments. (1)H NMR, UV-vis spectroscopy and isothermal titration calorimetry were used to characterise this interaction. We concluded that the strength of donor-acceptor interactions in heptane is sufficient to drive supramolecular assemblies in this and other aliphatic solvents. PMID:25875729

  2. Swift Electrofluorochromism of Donor-Acceptor Conjugated Polytriphenylamines.

    PubMed

    Sun, Jingwei; Liang, Ziqi

    2016-07-20

    Electrofluorochromic (EFC) materials, which exhibit electrochemically controllable fluorescence, hold great promise in optoelectronic devices and biological analysis. Here we design such donor-acceptor (D-A) conjugated polymers-P(TPACO) and P(TCEC)-that contain the same electron-rich and oxidizable polytriphenylamine (PTPA) as π-backbone, yet with different electron-deficient ketone and cyano units as pendant groups, respectively. They both exhibit solvatochromic effects due to intrinsic characteristics of intramolecular charge transfer (ICT). Compared to P(TPACO), P(TCEC) shows stronger ICT, which leads to higher electrochemical oxidation potential and lower ion diffusion coefficient. Moreover, both polymers present simultaneous electrochromic (EC) and EFC behaviors with multistate display and remarkably rapid fluorescence response. The response time of P(TPACO) is as short as 0.19 s, nearly 4-fold faster than that of P(TCEC) (0.92 s). Such rapid response is found to be determined by the ion diffusion coefficient which is associated with the ICT nature. Finally, the EFC display device based on P(TPACO) is successfully demonstrated, which shows green fluorescence ON/OFF switching upon applied potentials. This work has successfully demonstrated that swift EFCs can be achieved by rational modulation of the ICT effect in such D-A conjugated polymers. PMID:27347724

  3. Poly(trifluoromethyl)azulenes: structures and acceptor properties

    SciTech Connect

    Clikeman, Tyler T.; Bukovsky, Eric V.; Kuvychko, Igor V.; San, Long K.; Deng, Shihu; Wang, Xue B.; Chen, Yu-Sheng; Strauss, Steven H.; Boltalina, Olga V.

    2014-07-10

    Azulene is a non-alternant, non-benzenoid aromatic hydrocarbon with an intense blue colour, a dipole moment of 1.0 D,1 positive electron affinity, and an “anomalous” emission from the second excited state in violation of Kasha’s rule.2,3 Azulene’s unique properties have potential uses in molecular switches,4,5 molecular diodes,6 organic photovoltaics,7 and charge transfer complexes.8-12 Introduction of electron-withdrawing groups to the azulenic core, such as CN,8,13,14 halogens,15-19 and CF3,20,21 can enhance certain electrical and photophysical properties. In this work, we report six new trifluoromethyl derivatives of azulene (AZUL), three isomers of AZUL(CF3)3 and three isomers of AZUL(CF3)4, and the first X-ray structure of a π-stacked donor-acceptor complex of a trifluoromethyl azulene with donor pyrene.

  4. 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

  5. Inhibition of the water oxidizing complex of photosystem II and the reoxidation of the quinone acceptor QA- by Pb2+.

    PubMed

    Belatik, Ahmed; Hotchandani, Surat; Carpentier, Robert

    2013-01-01

    The action of the environmental toxic Pb(2+) on photosynthetic electron transport was studied in thylakoid membranes isolated from spinach leaves. Fluorescence and thermoluminescence techniques were performed in order to determine the mode of Pb(2+) action in photosystem II (PSII). The invariance of fluorescence characteristics of chlorophyll a (Chl a) and magnesium tetraphenylporphyrin (MgTPP), a molecule structurally analogous to Chl a, in the presence of Pb(2+) confirms that Pb cation does not interact directly with chlorophyll molecules in PSII. The results show that Pb interacts with the water oxidation complex thus perturbing charge recombination between the quinone acceptors of PSII and the S2 state of the Mn4Ca cluster. Electron transfer between the quinone acceptors QA and QB is also greatly retarded in the presence of Pb(2+). This is proposed to be owing to a transmembrane modification of the acceptor side of the photosystem. PMID:23861859

  6. Inhibition of the Water Oxidizing Complex of Photosystem II and the Reoxidation of the Quinone Acceptor QA− by Pb2+

    PubMed Central

    Belatik, Ahmed; Hotchandani, Surat; Carpentier, Robert

    2013-01-01

    The action of the environmental toxic Pb2+ on photosynthetic electron transport was studied in thylakoid membranes isolated from spinach leaves. Fluorescence and thermoluminescence techniques were performed in order to determine the mode of Pb2+ action in photosystem II (PSII). The invariance of fluorescence characteristics of chlorophyll a (Chl a) and magnesium tetraphenylporphyrin (MgTPP), a molecule structurally analogous to Chl a, in the presence of Pb2+ confirms that Pb cation does not interact directly with chlorophyll molecules in PSII. The results show that Pb interacts with the water oxidation complex thus perturbing charge recombination between the quinone acceptors of PSII and the S2 state of the Mn4Ca cluster. Electron transfer between the quinone acceptors QA and QB is also greatly retarded in the presence of Pb2+. This is proposed to be owing to a transmembrane modification of the acceptor side of the photosystem. PMID:23861859

  7. Creation of Superheterojunction Polymers via Direct Polycondensation: Segregated and Bicontinuous Donor-Acceptor π-Columnar Arrays in Covalent Organic Frameworks for Long-Lived Charge Separation.

    PubMed

    Jin, Shangbin; Supur, Mustafa; Addicoat, Matthew; Furukawa, Ko; Chen, Long; Nakamura, Toshikazu; Fukuzumi, Shunichi; Irle, Stephan; Jiang, Donglin

    2015-06-24

    By developing metallophthalocyanines and diimides as electron-donating and -accepting building blocks, herein, we report the construction of new electron donor-acceptor covalent organic frameworks (COFs) with periodically ordered electron donor and acceptor π-columnar arrays via direct polycondensation reactions. X-ray diffraction measurements in conjunction with structural simulations resolved that the resulting frameworks consist of metallophthalocyanine and diimide columns, which are ordered in a segregated yet bicontinuous manner to form built-in periodic π-arrays. In the frameworks, each metallophthalocyanine donor and diimide acceptor units are exactly linked and interfaced, leading to the generation of superheterojunctions-a new type of heterojunction machinery, for photoinduced electron transfer and charge separation. We show that this polycondensation method is widely applicable to various metallophthalocyanines and diimides as demonstrated by the combination of copper, nickel, and zinc phthalocyanine donors with pyrommellitic diimide, naphthalene diimide, and perylene diimide acceptors. By using time-resolved transient absorption spectroscopy and electron spin resonance, we demonstrated that the COFs enable long-lived charge separation, whereas the metal species, the class of acceptors, and the local geometry between donor and acceptor units play roles in determining the photochemical dynamics. The results provide insights into photoelectric COFs and demonstrate their enormous potential for charge separation and photoenergy conversions. PMID:26030399

  8. Efficient ambipolar transport properties in alternate stacking donor-acceptor complexes: from experiment to theory.

    PubMed

    Qin, Yunke; Cheng, Changli; Geng, Hua; Wang, Chao; Hu, Wenping; Xu, Wei; Shuai, Zhigang; Zhu, Daoben

    2016-05-18

    Comprehensive investigations of crystal structures, electrical transport properties and theoretical simulations have been performed over a series of sulfur-bridged annulene-based donor-acceptor complexes with an alternate stacking motif. A remarkably high mobility, up to 1.57 cm(2) V(-1) s(-1) for holes and 0.47 cm(2) V(-1) s(-1) for electrons, was obtained using organic single crystal field-effect transistor devices, demonstrating the efficient ambipolar transport properties. These ambipolar properties arise from the fact that the electronic couplings for both holes and electrons have the same super-exchange nature along the alternate stacking direction. The magnitude of super-exchange coupling depends not only on the intermolecular stacking distance and pattern, but also the energy level alignments between the adjacent donor-acceptor moieties. The concluded transport mechanism and structure-property relationship from this research will provide an important guideline for the future design of organic semiconductors based on donor-acceptor complexes. PMID:27157854

  9. Theoretical Study of Donor - Spacer - Acceptor Structure Molecule for Molecular Rectifier

    NASA Astrophysics Data System (ADS)

    Mizuseki, Hiroshi; Kenji, Niimura; Belosludov, Rodion; Farajian, Amir; Kawazoe, Yoshiyuki

    2003-03-01

    Recently, the molecular electronics has attracted strong attention as a ``post-silicone technology'' to establish a future nanoscale electronic devices. To realize this molecular device, unimolecular rectifiering function is one of the most important constituents in nanotechnology [C. Majumder, H. Mizuseki, and Y. Kawazoe, Molecular Scale Rectifier: Theoretical Study, J. Phys. Chem. A, 105 (2001) 9454-9459.]. In the present study, the geometric and electronic structure of alkyl derivative C37H50N4O4 (PNX) molecule, (donor - spacer - acceptor), a leading candidate of molecular rectifying device, has been investigated theoretically using ab initio quantum mechanical calculation. The results suggest that in such donor-acceptor molecular complexes, while the lowest unoccupied orbital concentrates on the acceptor subunit, the highest occupied molecular orbital is localized on the donor subunit. The approximate potential differences for optimized PNX molecule have been estimated at the B3PW91/6-311g++(d,p) level of theory, which achieves quite good agreement with experimentally reported results. This study was performed through Special Coordination Funds for Promoting Science and Technology of the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government.

  10. Light-Induced Charge Separation in Densely Packed Donor-Acceptor Coordination Cages.

    PubMed

    Frank, Marina; Ahrens, Jennifer; Bejenke, Isabel; Krick, Marcel; Schwarzer, Dirk; Clever, Guido H

    2016-07-01

    Photon-powered charge separation is achieved in a supramolecular architecture based on the dense packing of functional building blocks. Therefore, self-assembled dimers of interpenetrated coordination cages consisting of redoxactive chromophors were synthesized in a single assembly step starting from easily accessible ligands and Pd(II) cations. Two backbones consisting of electron rich phenothiazine (PTZ) and electron deficient anthraquinone (ANQ) were used to assemble either homo-octameric or mixed-ligand double cages. The electrochemical and spectroscopic properties of the pure cages, mixtures of donor and acceptor cages and the mixed-ligand cages were compared by steady-state UV-vis and transient absorption spectroscopy, supported by cyclic voltammetry and spectroelectrochemistry. Only the mixed-ligand cages, allowing close intra-assembly communication between the donors and acceptors, showed the evolution of characteristic PTZ radical cation and ANQ radical anion features upon excitation in the transient spectra. In contrast, excitation of the mixtures of the homo-octameric donor and acceptor cages in solution did not lead to any signs of electron transfer. Densely packed photo- and redox-functional self-assemblies promise molecular-level control over the morphology of the charge separation layer in future photovoltaic applications. PMID:27258549

  11. Electrochromism of a fused acceptor-donor-acceptor triad covering entire UV-vis and near-infrared regions.

    PubMed

    Yao, Bin; Ye, Xichong; Zhang, Jie; Wan, Xinhua

    2014-10-17

    A novel fused acceptor-donor-acceptor (A-D-A) type panchromatically electrochromic compound was synthesized. It exhibited intensive absorption bands covering entire UV-vis and near-infrared regions upon reduction to the radical anionic state, owing to the simultaneous presence of π*-π* transitions and intervalence charge transfer. PMID:25268224

  12. Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

    PubMed

    Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

    2016-07-21

    Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface. PMID:27355877

  13. Transition metal-free generation of the acceptor/acceptor-carbene viaα-elimination: synthesis of fluoroacetyl cyclopropanes.

    PubMed

    Wang, Yongdong; Han, Jing; Chen, Jie; Cao, Weiguo

    2016-05-21

    An efficient transition metal-free approach for the generation of acceptor/acceptor-carbene followed by trapping with alkenes to provide fluoroacetyl cyclopropanes has been described. The resulting cyclopropanes could be further converted into the fluoromethyl dihydrofurans or fluorodihydropyrroles through ring-expansion processes. PMID:27125517

  14. Identification of photoluminescence bands in AlGaAs/InGaAs/GaAs PHEMT heterostructures with donor-acceptor-doped barriers

    SciTech Connect

    Gulyaev, D. V. Zhuravlev, K. S.; Bakarov, A. K.; Toropov, A. I.

    2015-02-15

    The photoluminescence of AlGaAs/InGaAs/GaAs pseudomorphic high-electron mobility transistor heterostructures with donor-acceptor-doped AlGaAs barriers is studied. It is found that the introduction of additional p{sup +}-doped AlGaAs layers into the design brings about the appearance of new bands in the photoluminescence spectra. These bands are identified as resulting from transitions (i) in donor-acceptor pairs in doped AlGaAs layers and (ii) between the conduction subband and acceptor levels in the undoped InGaAs quantum well.

  15. Influence of coagulation factor x on in vitro and in vivo gene delivery by adenovirus (Ad) 5, Ad35, and chimeric Ad5/Ad35 vectors.

    PubMed

    Greig, Jenny A; Buckley, Suzanne Mk; Waddington, Simon N; Parker, Alan L; Bhella, David; Pink, Rebecca; Rahim, Ahad A; Morita, Takashi; Nicklin, Stuart A; McVey, John H; Baker, Andrew H

    2009-10-01

    The binding of coagulation factor X (FX) to the hexon of adenovirus (Ad) 5 is pivotal for hepatocyte transduction. However, vectors based on Ad35, a subspecies B Ad, are in development for cancer gene therapy, as Ad35 utilizes CD46 (which is upregulated in many cancers) for transduction. We investigated whether interaction of Ad35 with FX influenced vector tropism using Ad5, Ad35, and Ad5/Ad35 chimeras: Ad5/fiber(f)35, Ad5/penton(p)35/f35, and Ad35/f5. Surface plasmon resonance (SPR) revealed that Ad35 and Ad35/f5 bound FX with approximately tenfold lower affinities than Ad5 hexon-containing viruses, and electron cryomicroscopy (cryo-EM) demonstrated a direct Ad35 hexon:FX interaction. The presence of physiological levels of FX significantly inhibited transduction of vectors containing Ad35 fibers (Ad5/f35, Ad5/p35/f35, and Ad35) in CD46-positive cells. Vectors were intravenously administered to CD46 transgenic mice in the presence and absence of FX-binding protein (X-bp), resulting in reduced liver accumulation for all vectors. Moreover, Ad5/f35 and Ad5/p35/f35 efficiently accumulated in the lung, whereas Ad5 demonstrated poor lung targeting. Additionally, X-bp significantly reduced lung genome accumulation for Ad5/f35 and Ad5/p35/f35, whereas Ad35 was significantly enhanced. In summary, vectors based on the full Ad35 serotype will be useful vectors for selective gene transfer via CD46 due to a weaker FX interaction compared to Ad5. PMID:19603000

  16. Alternansucrase acceptor products and their applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alternansucrase is one of a family of enzymes known as glucansucrases. These enzymes are promising catalysts for the conversion of sugar to useful, value-added carbohydrates. The terms "alternan" and "alternansucrase" first entered the literature 25 years ago to refer to a unique glucan and its bi...

  17. Three holes bound to a double acceptor - Be(+) in germanium

    NASA Technical Reports Server (NTRS)

    Haller, E. E.; Mcmurray, R. E., Jr.; Falicov, L. M.; Haegel, N. M.; Hansen, W. L.

    1983-01-01

    A double acceptor binding three holes has been observed for the first time with photoconductive far-infrared spectroscopy in beryllium-doped germanium single crystals. This new center, Be(+), has a hole binding energy of about 5 meV and is only present when free holes are generated by ionization of either neutral shallow acceptors or neutral Be double acceptors. The Be(+) center thermally ionizes above 4 K. It disappears at a uniaxial stress higher than about a billion dyn/sq cm parallel to (111) as a result of the lifting of the valence-band degeneracy.

  18. Intramolecular charge transfer in donor-acceptor molecules

    SciTech Connect

    Slama-Schwok, A.; Blanchard-Desce, M.; Lehn, J.M. )

    1990-05-17

    The photophysical properties of donor-acceptor molecules, push-pull polyenes and carotenoids, have been studied by absorption and fluorescence spectroscopy. The compounds bear various acceptor and donor groups, linked together by chains of different length and structure. The position of the absorption and fluorescence maxima and their variation in solvents of increasing polarity are in agreement with long-distance intramolecular charge-transfer processes, the linker acting as a molecular wire. The effects of the linker length and structure and of the nature of acceptor and donor are presented.

  19. Ultrafast Energy Transfer in Ultrathin Organic Donor/Acceptor Blend

    PubMed Central

    Kandada, Ajay Ram Srimath; Grancini, Giulia; Petrozza, Annamaria; Perissinotto, Stefano; Fazzi, Daniele; Raavi, Sai Santosh Kumar; Lanzani, Guglielmo

    2013-01-01

    It is common knowledge that poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend, a prototype system for bulk heterojunction (BHJ) solar cells, consists of a network of tens of nanometers-large donor-rich and acceptor-rich phases separated by extended finely intermixed border regions where PCBM diffuse into P3HT. Here we specifically address the photo-induced dynamics in a 10 nm thin P3HT/PCBM blend that consists of the intermixed region only. Using the multi-pass transient absorption technique (TrAMP) that enables us to perform ultra high sensitive measurements, we find that the primary process upon photoexcitation is ultrafast energy transfer from P3HT to PCBM. The expected charge separation due to hole transfer from PCBM to P3HT occurs in the 100 ps timescale. The derived picture is much different from the accepted view of ultra-fast electron transfer at the polymer/PCBM interface and provides new directions for the development of efficient devices. PMID:23797845

  20. Ultrafast Energy Transfer in Ultrathin Organic Donor/Acceptor Blend

    NASA Astrophysics Data System (ADS)

    Kandada, Ajay Ram Srimath; Grancini, Giulia; Petrozza, Annamaria; Perissinotto, Stefano; Fazzi, Daniele; Raavi, Sai Santosh Kumar; Lanzani, Guglielmo

    2013-06-01

    It is common knowledge that poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend, a prototype system for bulk heterojunction (BHJ) solar cells, consists of a network of tens of nanometers-large donor-rich and acceptor-rich phases separated by extended finely intermixed border regions where PCBM diffuse into P3HT. Here we specifically address the photo-induced dynamics in a 10 nm thin P3HT/PCBM blend that consists of the intermixed region only. Using the multi-pass transient absorption technique (TrAMP) that enables us to perform ultra high sensitive measurements, we find that the primary process upon photoexcitation is ultrafast energy transfer from P3HT to PCBM. The expected charge separation due to hole transfer from PCBM to P3HT occurs in the 100 ps timescale. The derived picture is much different from the accepted view of ultra-fast electron transfer at the polymer/PCBM interface and provides new directions for the development of efficient devices.

  1. Variable temperature EPR studies of Illinois No. 6 coal treated with donor and acceptor molecules

    SciTech Connect

    Thompson, R.L.; Rothenberger, K.S.; Retcofsky, H.L.

    1996-10-01

    Variable, temperature EPR studies of Illinois No. 6 coal, its pyridine extract, and samples of each after treatment with known donor and acceptor molecules are reported. The purpose of the study was to explore the origin of the EPR signals near g = 2 and to assess the contribution of certain non-bonded interactions in coal. Curie Law behavior is exhibited for each sample indicating that the EPR signals are dominated by doublet state radicals. No evidence for thermally accessible, low-lying triplet states, such as those found in some charge-transfer complexes, was found. Infrared spectroscopy reveals, however, that some electron density is transferred from the coal after treatment with acceptors such as TCNQ and TCNE. EPR studies of chromat graphic fractions of the pyridine extract (approximately five percent of the whole coal), both untreated and treated with TTF and TCNE, indicated some minor contributions of low-lying triplet states.

  2. Tuning the Rainbow: Systematic Modulation of Donor-Acceptor Systems through Donor Substituents and Solvent.

    PubMed

    Larsen, Christopher B; van der Salm, Holly; Shillito, Georgina E; Lucas, Nigel T; Gordon, Keith C

    2016-09-01

    A series of donor-acceptor compounds is reported in which the energy of the triarylamine donor is systematically tuned through para substitution with electron-donating methoxy and electron-withdrawing cyano groups. The acceptor units investigated are benzothiadiazole (btd), dipyridophenazine (dppz), and its [ReCl(CO)3(dppz)] complex. The effect of modulating donor energy on the electronic and photophysical properties is investigated using (1)H NMR spectroscopy, DFT calculations, electrochemistry, electronic absorption and emission spectroscopies, ground state and resonance Raman spectroscopy, and transient absorption spectroscopy. Qualitative correlations between the donor energy and the properties of interest are obtained using Hammett σ(+) constants. Methoxy and cyano groups are shown to destabilize and stabilize, respectively, the frontier molecular orbitals, with the HOMO affected more significantly than the LUMO, narrowing the HOMO-LUMO band gap as the substituent becomes more electron-donating-observable as a bathochromic shift in low-energy charge-transfer absorption bands. Charge-transfer emission bands are also dependent on the electron-donating/withdrawing nature of the substituent, and in combination with the highly solvatochromic nature of charge-transfer states, emission can be tuned to span the entire visible region. PMID:27500590

  3. Free-Standing Undoped ZnO Microtubes with Rich and Stable Shallow Acceptors

    NASA Astrophysics Data System (ADS)

    Wang, Qiang; Yan, Yinzhou; Zeng, Yong; Lu, Yue; Chen, Liang; Jiang, Yijian

    2016-06-01

    Fabrication of reliable large-sized p-ZnO is a major challenge to realise ZnO-based electronic device applications. Here we report a novel technique to grow high-quality free-standing undoped acceptor-rich ZnO (A-ZnO) microtubes with dimensions of ~100 μm (in diameter) × 5 mm (in length) by optical vapour supersaturated precipitation. The A-ZnO exhibits long lifetimes (>1 year) against compensation/lattice-relaxation and the stable shallow acceptors with binding energy of ~127 meV are confirmed from Zn vacancies. The A-ZnO provides a possibility for a mimetic p-n homojunction diode with n+-ZnO:Sn. The high concentrations of holes in A-ZnO and electrons in n+-ZnO make the dual diffusion possible to form a depletion layer. The diode threshold voltage, turn-on voltage, reverse saturated current and reverse breakdown voltage are 0.72 V, 1.90 V, <10 μA and >15 V, respectively. The A-ZnO also demonstrates quenching-free donor-acceptor-pairs (DAP) emission located in 390–414 nm with temperature of 270–470 K. Combining the temperature-dependent DAP violet emission with native green emission, the visible luminescence of A-ZnO microtube can be modulated in a wide region of colour space across white light. The present work opens up new opportunities to achieve ZnO with rich and stable acceptors instead of p-ZnO for a variety of potential applications.

  4. Free-Standing Undoped ZnO Microtubes with Rich and Stable Shallow Acceptors.

    PubMed

    Wang, Qiang; Yan, Yinzhou; Zeng, Yong; Lu, Yue; Chen, Liang; Jiang, Yijian

    2016-01-01

    Fabrication of reliable large-sized p-ZnO is a major challenge to realise ZnO-based electronic device applications. Here we report a novel technique to grow high-quality free-standing undoped acceptor-rich ZnO (A-ZnO) microtubes with dimensions of ~100 μm (in diameter) × 5 mm (in length) by optical vapour supersaturated precipitation. The A-ZnO exhibits long lifetimes (>1 year) against compensation/lattice-relaxation and the stable shallow acceptors with binding energy of ~127 meV are confirmed from Zn vacancies. The A-ZnO provides a possibility for a mimetic p-n homojunction diode with n(+)-ZnO:Sn. The high concentrations of holes in A-ZnO and electrons in n(+)-ZnO make the dual diffusion possible to form a depletion layer. The diode threshold voltage, turn-on voltage, reverse saturated current and reverse breakdown voltage are 0.72 V, 1.90 V, <10 μA and >15 V, respectively. The A-ZnO also demonstrates quenching-free donor-acceptor-pairs (DAP) emission located in 390-414 nm with temperature of 270-470 K. Combining the temperature-dependent DAP violet emission with native green emission, the visible luminescence of A-ZnO microtube can be modulated in a wide region of colour space across white light. The present work opens up new opportunities to achieve ZnO with rich and stable acceptors instead of p-ZnO for a variety of potential applications. PMID:27263856

  5. Free-Standing Undoped ZnO Microtubes with Rich and Stable Shallow Acceptors

    PubMed Central

    Wang, Qiang; Yan, Yinzhou; Zeng, Yong; Lu, Yue; Chen, Liang; Jiang, Yijian

    2016-01-01

    Fabrication of reliable large-sized p-ZnO is a major challenge to realise ZnO-based electronic device applications. Here we report a novel technique to grow high-quality free-standing undoped acceptor-rich ZnO (A-ZnO) microtubes with dimensions of ~100 μm (in diameter) × 5 mm (in length) by optical vapour supersaturated precipitation. The A-ZnO exhibits long lifetimes (>1 year) against compensation/lattice-relaxation and the stable shallow acceptors with binding energy of ~127 meV are confirmed from Zn vacancies. The A-ZnO provides a possibility for a mimetic p-n homojunction diode with n+-ZnO:Sn. The high concentrations of holes in A-ZnO and electrons in n+-ZnO make the dual diffusion possible to form a depletion layer. The diode threshold voltage, turn-on voltage, reverse saturated current and reverse breakdown voltage are 0.72 V, 1.90 V, <10 μA and >15 V, respectively. The A-ZnO also demonstrates quenching-free donor-acceptor-pairs (DAP) emission located in 390–414 nm with temperature of 270–470 K. Combining the temperature-dependent DAP violet emission with native green emission, the visible luminescence of A-ZnO microtube can be modulated in a wide region of colour space across white light. The present work opens up new opportunities to achieve ZnO with rich and stable acceptors instead of p-ZnO for a variety of potential applications. PMID:27263856

  6. Nitrogen is a deep acceptor in ZnO

    DOE PAGESBeta

    Tarun, M. C.; Iqbal, M. Zafar; McCluskey, M. D.

    2011-04-14

    Zinc oxide is a promising material for blue and UV solid-state lighting devices, among other applications. Nitrogen has been regarded as a potential p-type dopant for ZnO. However, recent calculations indicate that nitrogen is a deep acceptor. This paper presents experimental evidence that nitrogen is, in fact, a deep acceptor and therefore cannot produce p-type ZnO. A broad photoluminescence (PL) emission band near 1.7 eV, with an excitation onset of ~2.2 eV, was observed, in agreement with the deep-acceptor model of the nitrogen defect. Thus the deep-acceptor behavior can be explained by the low energy of the ZnO valence bandmore » relative to the vacuum level.« less

  7. Nitrogen is a deep acceptor in ZnO

    SciTech Connect

    Tarun, M. C.; Iqbal, M. Zafar; McCluskey, M. D.

    2011-04-14

    Zinc oxide is a promising material for blue and UV solid-state lighting devices, among other applications. Nitrogen has been regarded as a potential p-type dopant for ZnO. However, recent calculations indicate that nitrogen is a deep acceptor. This paper presents experimental evidence that nitrogen is, in fact, a deep acceptor and therefore cannot produce p-type ZnO. A broad photoluminescence (PL) emission band near 1.7 eV, with an excitation onset of ~2.2 eV, was observed, in agreement with the deep-acceptor model of the nitrogen defect. Thus the deep-acceptor behavior can be explained by the low energy of the ZnO valence band relative to the vacuum level.

  8. Synthesis, Properties, and Design Principles of Donor–Acceptor Nanohoops

    PubMed Central

    2015-01-01

    We have synthesized a series of aza[8]cycloparaphenylenes containing one, two, and three nitrogens to probe the impact of nitrogen doping on optoelectronic properties and solid state packing. Alkylation of these azananohoops afforded the first donor–acceptor nanohoops where the phenylene backbone acts as the donor and the pyridinium units act as the acceptor. The impact on the optoelectronic properties was then studied experimentally and computationally to provide new insight into the effect of functionalization on nanohoops properties. PMID:27162989

  9. Fourier-transform photoluminescence spectroscopy of excitons bound to group-III acceptors in silicon: Uniaxial stress

    NASA Astrophysics Data System (ADS)

    Karasyuk, V. A.; Thewalt, M. L. W.; An, S.; Lightowlers, E. C.

    1997-12-01

    Photoluminescence of excitons bound to Al, Ga, In, and Tl acceptors in Si crystals subjected to <001>, <111>, or <110> uniaxial stress was studied at liquid-He temperatures with 0.0025-meV spectral resolution. The deformation-potential constants of the group-III acceptors in the ground state are (in eV) b=-1.01+/-0.02, d=-3.31+/-0.06 for Al, b=-1.03+/-0.02, d=-3.10+/-0.06 for Ga, b=-0.43+/-0.01, d=-2.41+/-0.05 for In, and b=-0.30+/-0.03, d=-1.95+/-0.2 for Tl. The shear deformation-potential constant for electrons in acceptor bound excitons Ξu=8.6 eV for all group-III acceptors within an experimental error of +/-0.15 eV for Al, Ga, and In, and +/-0.8 eV for Tl. The order of the valley-orbit states in Tl bound excitons is Γ1, Γ3, Γ5 with the Γ5 energy 1.21 meV above Γ1, and 0.10 meV above Γ3. All details of the spectra including positions, relative amplitudes, and polarizations of the components have been explained on the basis of a simple model of acceptor bound excitons with holes in the J=0 state taking into account the valley-orbit splitting and the spin-orbit coupling of the electron. Significant deviations from the theoretical predictions were observed only for very small strains producing acceptor splittings comparable with the intrinsic zero-stress splitting.

  10. Charge-transfer interactions of metoclopramide nausea drug against six kind of π-acceptors: spectral and thermal discussions.

    PubMed

    El-Habeeb, Abeer A; Al-Saif, Foziah A; Refat, Moamen S

    2014-04-01

    The target of this paper is aimed to discuss the fast and newly techniques in order to assessment the metoclopramide (Mcp) nausea drug in pure form in solid and solution shape with different kind of π-acceptors upon charge transfer interactions. Charge-transfer complexes (CTC) of metoclopramide with picric acid (PA), 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ), tetracyanoquinodimethane (TCNQ), m-dinitrobenzene (DNB), p-nitrobenzoic acid (p-NBA) and tetrachloro-p-quinon (p-CL) have been studied spectrophotometrically in absolute methanol at room temperature. The stoichiometries of the complexes were found to be 1:1 ratio by the spectrophotometric titration between metoclopramide and represented π-acceptors. The equilibrium constants, molar extinction coefficient (εCT) and spectroscopic-physical parameters (standard free energy (ΔG°), oscillator strength (ƒ), transition dipole moment (μ), resonance energy (RN) and ionization potential (ID)) of the complexes were determined upon the modified Benesi-Hildebrand equation. The results indicate that the formation constants for the complexes depend on the nature of electron acceptors and configuration of drug donor, and also the spectral studies of the complexes were determined by (infrared, Raman, and (1)H NMR) spectra and X-ray powder diffraction (XRD). The charge-transfer complexes are formed during the interaction of electron-acceptors and electron-donors as result of partial or complete transfer of a negative charge from (D(+)-A(-)). PMID:24434200

  11. Interplay between Mn-acceptor state and Dirac surface states in Mn-doped Bi2Se3 topological insulator

    NASA Astrophysics Data System (ADS)

    Mahani, M. R.; Pertsova, A.; Islam, M. Fhokrul; Canali, C. M.

    2014-11-01

    We investigate the properties of a single substitutional Mn impurity and its associated acceptor state on the (111) surface of Bi2Se3 topological insulator. Combining ab initio calculations with microscopic tight-binding modeling, we identify the effects of inversion symmetry and time-reversal-symmetry breaking on the electronic states in the vicinity of the Dirac point. In agreement with experiments, we find evidence that the Mn ion is in the +2 valence state and introduces an acceptor in the bulk band gap. The Mn acceptor has predominantly p character and is localized mainly around the Mn impurity and its nearest-neighbor Se atoms. Its electronic structure and spin-polarization are determined by the hybridization between the Mn d levels and the p levels of surrounding Se atoms, which is strongly affected by electronic correlations at the Mn site. The opening of the gap at the Dirac point depends crucially on the quasiresonant coupling and the strong real-space overlap between the spin-chiral surface states and the midgap spin-polarized Mn-acceptor states.

  12. Incremental Tuning Up of Fluorous Phenazine Acceptors.

    PubMed

    Castro, Karlee P; Clikeman, Tyler T; DeWeerd, Nicholas J; Bukovsky, Eric V; Rippy, Kerry C; Kuvychko, Igor V; Hou, Gao-Lei; Chen, Yu-Sheng; Wang, Xue-Bin; Strauss, Steven H; Boltalina, Olga V

    2016-03-14

    In a simple, one-step direct trifluoromethylation of phenazine with CF3 I we prepared and characterized nine (poly)trifluoromethyl derivatives with up to six CF3 groups. The electrochemical reduction potentials and gas-phase electron affinities show a direct, strict linear relation to the number of CF3 groups, with phenazine(CF3)6 reaching a record-high electron affinity of 3.24 eV among perfluoroalkylated polyaromatics. PMID:26617289

  13. Magnetic thaw-down and boil-off due to magneto acceptors in 2DEG

    SciTech Connect

    Chaubet, C.; Raymond, A.; Bisotto, I.; Harmand, J. C.; Kubisa, M.; Zawadzki, W.

    2013-12-04

    The Quantum Hall Effect (QHE) and Shubnikov-de Haas effect are investigated experimentally using n type modulation-doped GaAs/GaAlAs quantum wells (QWs) additionally doped in the well with beryllium acceptor atoms. It is presently shown that the localized magneto-acceptor (MA) states which possess discrete energies above the corresponding Landau levels (LLs) lead to two observable effects in magneto-transport: magnetic thaw-down and magnetic boil-off of 2D electrons. Both effects are related to the fact that electrons occupying the localized MA states cannot conduct. Thus in the thaw-down effect the electrons fall down from the MA states to the free Landau states. This leads to a shift of the Hall plateau towards higher magnetic fields as a consequence of an increase of the 2D electron density N{sub S}. In the boil-off effect the electrons are pushed from the free Landau states to the empty MA states under high enough Hall electric field. This process has an avalanche character leading to a dramatic increase of magneto-resistance, consequence of a decrease of N{sub S}.

  14. The Impact of Heterogeneity and Dark Acceptor States on FRET: Implications for Using Fluorescent Protein Donors and Acceptors

    PubMed Central

    Vogel, Steven S.; Nguyen, Tuan A.; van der Meer, B. Wieb; Blank, Paul S.

    2012-01-01

    Förster resonance energy transfer (FRET) microscopy is widely used to study protein interactions in living cells. Typically, spectral variants of the Green Fluorescent Protein (FPs) are incorporated into proteins expressed in cells, and FRET between donor and acceptor FPs is assayed. As appreciable FRET occurs only when donors and acceptors are within 10 nm of each other, the presence of FRET can be indicative of aggregation that may denote association of interacting species. By monitoring the excited-state (fluorescence) decay of the donor in the presence and absence of acceptors, dual-component decay analysis has been used to reveal the fraction of donors that are FRET positive (i.e., in aggregates)._However, control experiments using constructs containing both a donor and an acceptor FP on the same protein repeatedly indicate that a large fraction of these donors are FRET negative, thus rendering the interpretation of dual-component analysis for aggregates between separately donor-containing and acceptor-containing proteins problematic. Using Monte-Carlo simulations and analytical expressions, two possible sources for such anomalous behavior are explored: 1) conformational heterogeneity of the proteins, such that variations in the distance separating donor and acceptor FPs and/or their relative orientations persist on time-scales long in comparison with the excited-state lifetime, and 2) FP dark states. PMID:23152925

  15. Charge-transfer complexes of sulfamethoxazole drug with different classes of acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Korashy, Sabry A.; El-Deen, Ibrahim M.; El-Sayed, Shaima M.

    2010-09-01

    The charge-transfer complexes of the donor sulfamethoxazole (SZ) with iodine (I 2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), p-chloranil (CHL) and picric acid (PA) have been studied spectrophotometrically in chloroform or methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CT-complexes in case of four acceptors. The stoichiometry of the complexes was found to be 1:1 ratio by molar ratio method between donor and acceptor with maximum absorption bands (CT band). The data are discussed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G°), oscillator strength (ƒ), transition dipole moment ( μ), resonance energy ( RN) and ionization potential ( ID). The results indicate that the formation constant ( KCT) for the complexes were shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents which were used. IR, 1H NMR, mass spectra, UV-Vis techniques, elemental analyses (CHN) and TG-DTG investigation were used to characterize the four sulfamethoxazole charge-transfer complexes.

  16. Design of Reversible, Cysteine-Targeted Michael Acceptors Guided by Kinetic and Computational Analysis

    PubMed Central

    2015-01-01

    Electrophilic probes that covalently modify a cysteine thiol often show enhanced pharmacological potency and selectivity. Although reversible Michael acceptors have been reported, the structural requirements for reversibility are poorly understood. Here, we report a novel class of acrylonitrile-based Michael acceptors, activated by aryl or heteroaryl electron-withdrawing groups. We demonstrate that thiol adducts of these acrylonitriles undergo β-elimination at rates that span more than 3 orders of magnitude. These rates correlate inversely with the computed proton affinity of the corresponding carbanions, enabling the intrinsic reversibility of the thiol-Michael reaction to be tuned in a predictable manner. We apply these principles to the design of new reversible covalent kinase inhibitors with improved properties. A cocrystal structure of one such inhibitor reveals specific noncovalent interactions between the 1,2,4-triazole activating group and the kinase. Our experimental and computational study enables the design of new Michael acceptors, expanding the palette of reversible, cysteine-targeted electrophiles. PMID:25153195

  17. Design, synthesis and study of supramolecular donor-acceptor systems mimicking natural photosynthesis processes

    NASA Astrophysics Data System (ADS)

    Bikram, Chandra

    This dissertation investigates the chemical ingenuity into the development of various photoactive supramolecular donor -- acceptor systems to produce clean and carbon free energy for the next generation. The process is inspired by the principles learned from nature's approach where the solar energy is converted into the chemical energy through the natural photosynthesis process. Owing to the importance and complexity of natural photosynthesis process, we have designed ideal donor-acceptor systems to investigate their light energy harvesting properties. This process involves two major steps: the first step is the absorption of light energy by antenna or donor systems to promote them to an excited electronic state. The second step involves, the transfer of excitation energy to the reaction center, which triggers an electron transfer process within the system. Based on this principle, the research is focused into the development of artificial photosynthesis systems to investigate dynamics of photo induced energy and electron transfer events. The derivatives of Porphyrins, Phthalocyanines, BODIPY, and SubPhthalocyanines etc have been widely used as the primary building blocks for designing photoactive and electroactive ensembles in this area because of their excellent and unique photophysical and photochemical properties. Meanwhile, the fullerene, mainly its readily available version C60 is typically used as an electron acceptor component because of its unique redox potential, symmetrical shape and low reorganization energy appropriate for improved charge separation behavior. The primary research motivation of the study is to achieve fast charge separation and slow charge recombination of the system by stabilizing the radical ion pairs which are formed from photo excitation, for maximum utility of solar energy. Besides Fullerene C60, this dissertation has also investigated the potential application of carbon nanomaterials (Carbon nanotubes and graphene) as primary

  18. Neutral nitrogen acceptors in ZnO: The {sup 67}Zn hyperfine interactions

    SciTech Connect

    Golden, E. M.; Giles, N. C.; Evans, S. M.; Halliburton, L. E.

    2014-03-14

    Electron paramagnetic resonance (EPR) is used to characterize the {sup 67}Zn hyperfine interactions associated with neutral nitrogen acceptors in zinc oxide. Data are obtained from an n-type bulk crystal grown by the seeded chemical vapor transport method. Singly ionized nitrogen acceptors (N{sup −}) initially present in the crystal are converted to their paramagnetic neutral charge state (N{sup 0}) during exposure at low temperature to 442 or 633 nm laser light. The EPR signals from these N{sup 0} acceptors are best observed near 5 K. Nitrogen substitutes for oxygen ions and has four nearest-neighbor cations. The zinc ion along the [0001] direction is referred to as an axial neighbor and the three equivalent zinc ions in the basal plane are referred to as nonaxial neighbors. For axial neighbors, the {sup 67}Zn hyperfine parameters are A{sub ‖} = 37.0 MHz and A{sub ⊥} = 8.4 MHz with the unique direction being [0001]. For nonaxial neighbors, the {sup 67}Zn parameters are A{sub 1} = 14.5 MHz, A{sub 2} = 18.3 MHz, and A{sub 3} = 20.5 MHz with A{sub 3} along a [101{sup ¯}0] direction (i.e., in the basal plane toward the nitrogen) and A{sub 2} along the [0001] direction. These {sup 67}Zn results and the related {sup 14}N hyperfine parameters provide information about the distribution of unpaired spin density at substitutional neutral nitrogen acceptors in ZnO.

  19. Polarised black holes in AdS

    NASA Astrophysics Data System (ADS)

    Costa, Miguel S.; Greenspan, Lauren; Oliveira, Miguel; Penedones, João; Santos, Jorge E.

    2016-06-01

    We consider solutions in Einstein-Maxwell theory with a negative cosmological constant that asymptote to global AdS 4 with conformal boundary {S}2× {{{R}}}t. At the sphere at infinity we turn on a space-dependent electrostatic potential, which does not destroy the asymptotic AdS behaviour. For simplicity we focus on the case of a dipolar electrostatic potential. We find two new geometries: (i) an AdS soliton that includes the full backreaction of the electric field on the AdS geometry; (ii) a polarised neutral black hole that is deformed by the electric field, accumulating opposite charges in each hemisphere. For both geometries we study boundary data such as the charge density and the stress tensor. For the black hole we also study the horizon charge density and area, and further verify a Smarr formula. Then we consider this system at finite temperature and compute the Gibbs free energy for both AdS soliton and black hole phases. The corresponding phase diagram generalizes the Hawking-Page phase transition. The AdS soliton dominates the low temperature phase and the black hole the high temperature phase, with a critical temperature that decreases as the external electric field increases. Finally, we consider the simple case of a free charged scalar field on {S}2× {{{R}}}t with conformal coupling. For a field in the SU(N ) adjoint representation we compare the phase diagram with the above gravitational system.

  20. Exquisite 1D Assemblies Arising from Rationally Designed Asymmetric Donor-Acceptor Architectures Exhibiting Aggregation-Induced Emission as a Function of Auxiliary Acceptor Strength.

    PubMed

    Singh, Roop Shikha; Mukhopadhyay, Sujay; Biswas, Arnab; Pandey, Daya Shankar

    2016-01-11

    One-dimensional nanostructures with aggregation-induced emission (AIE) properties have been fabricated to keep the pace with growing demand from optoelectronics applications. The compounds 2-[4-(4-methylpiperazin-1-yl)benzylidene]malononitrile (PM1), 2-{4-[4-(pyridin-2-yl)piperazin-1-yl]-benzylidene}malononitrile (PM2), and 2-{4-[4-(pyrimidin-2-yl)piperazin-1-yl]benzylidene}malononitrile (PM3) have been designed and synthesized by melding piperazine and dicyanovinylene to investigate AIE in an asymmetric donor-acceptor (D-A) construct of A'-D-π-A- topology. The synthetic route has been simplified by using phenylpiperazine as a weak donor (D), dicyanovinylene as an acceptor (A), and pyridyl/pyrimidyl groups (PM2/PM3) as auxiliary acceptors (A'). It has been established that A' plays a vital role in triggering AIE in these compounds because the same D-A construct led to aggregation-caused quenching upon replacing A' with an electron-donating ethyl group (PM1). Moreover, the effect of restricted intramolecular rotation and twisted intramolecular charge transfer on the mechanism of AIE has also been investigated. Furthermore, it has been clearly shown that the optical disparities of these A'-D-π-A architectures are a direct consequence of comparative A' strength. Single-crystal X-ray analyses provided justification for role of intermolecular interactions in aggregate morphology. Electrochemical and theoretical studies affirmed the effect of the A' strength on the overall properties of the A'-D-π-A system. PMID:26615814

  1. Structural effects on the photoelectrochemical properties of new push-pull dyes based on vinazene acceptor triphenylamine donor

    NASA Astrophysics Data System (ADS)

    Arcos, Wilmmer A.; Guimarães, Robson R.; Insuasty, Braulio; Araki, Koiti; Ortiz, Alejandro

    2016-05-01

    The push-pull behavior of novel dyes, based on vinazene electron-acceptor groups linked to arrays of triphenylamine (TPA) electron-donor group, was studied by electronic absorption and emission spectroscopy, as well as by cyclic voltammetry. The most stable ground state structure and their electronic properties were modeled by density functional theory (DFT) calculations using the B3LYP functional and 6-31G++ basis set, whereas the electronic properties in the excited states were calculated by TD-DFT, under the same functional and basis set, using SCF and PCM methods. The theoretical calculations matched well with experimental data, showing that λmax of the lowest energy absorption band can be assigned to an intramolecular charge transfer transition. In fact, the HOMO and LUMO are respectively localized on the TPA donor and the dicyanomethylene acceptor moiety confirming a remarkable push-pull character. Photoelectrochemical cells parameters were correlated with dyes structural properties showing to be consistent with the anchoring through the nitrogen atoms of CN groups. The nature of the donor-acceptor groups, conformation and number of anchoring CN groups (2 seems to be the best) strongly influenced the overall efficiency of dye sensitized solar cells.

  2. An overview of molecular acceptors for organic solar cells

    NASA Astrophysics Data System (ADS)

    Hudhomme, Piétrick

    2013-07-01

    Organic solar cells (OSCs) have gained serious attention during the last decade and are now considered as one of the future photovoltaic technologies for low-cost power production. The first dream of attaining 10% of power coefficient efficiency has now become a reality thanks to the development of new materials and an impressive work achieved to understand, control and optimize structure and morphology of the device. But most of the effort devoted to the development of new materials concerned the optimization of the donor material, with less attention for acceptors which to date remain dominated by fullerenes and their derivatives. This short review presents the progress in the use of non-fullerene small molecules and fullerene-based acceptors with the aim of evaluating the challenge for the next generation of acceptors in organic photovoltaics.

  3. Optical Properties of 1,3-Bisdicyanovinylindane, an Electro-Acceptor, Attached Bisthienylethene Molecule.

    PubMed

    Lil, Xiaochuan; Han, Yuzhen; Son, Young-A

    2016-02-01

    An electron acceptor, 1,3-bisdicyanovinylindane, was attached to the skeleton of bisthienylethene. Photochromic behavior was investigated in THF. Under exposure of UVNisible light cycles, the solution color can be toggled between colorless and yellow. Good fatigue resistance and photo-/thermal-stability were demonstrated with acceptable degradation. A full-photo mode switch was established. Optimized structure and molecular orbital of ring-open and ring-closed isomers were calculated on the platform of DmoP. The photochromic behavior was further supported by the required distance between photocyclizing atoms in antiparallel conformation. The absorption spectra change derived from calculation was in agreement with the experimental results. PMID:27433664

  4. Solvent-tuned intramolecular charge-recombination rates in a conjugated donor-acceptor molecule

    NASA Technical Reports Server (NTRS)

    Khundkar, Lutfur R.; Stiegman, A. E.; Perry, Joseph W.

    1990-01-01

    The nonradiative charge-recombination rates from the charge-transfer state of a new conjugated donor-acceptor molecule (p-cyano-p-prime-methylthiodiphenylacetylene) can be tuned over almost an order of magnitude by varying the polarity of the solvent. These measurements of intramolecular recombination show a turnover of rates as a function of emission energy, consistent with the 'normal' and 'inverted' behavior of Marcus theory. Steady-state spectra and time-resolved measurements make it possible to quantitatively compare thermal and optical electron-transfer rates as a function of driving force and demonstrate their correspondence.

  5. Donor-acceptor chemistry in the main group.

    PubMed

    Rivard, Eric

    2014-06-21

    This Perspective article summarizes recent progress from our laboratory in the isolation of reactive main group species using a general donor-acceptor protocol. A highlight of this program is the use of carbon-based donors in combination with suitable Lewis acidic acceptors to yield stable complexes of parent Group 14 element hydrides (e.g. GeH2 and H2SiGeH2). It is anticipated that this strategy could be extended to include new synthetic targets from throughout the Periodic Table with possible applications in bottom-up materials synthesis and main group element catalysis envisioned. PMID:24788390

  6. Sodium acceptor doping of ZnO crystals

    NASA Astrophysics Data System (ADS)

    Parmar, Narendra S.; Joni, I. Made; Lynn, Kelvin G.

    2016-02-01

    ZnO bulk single crystals were doped with sodium by thermal diffusion using sodium dispensers. Secondary-ion mass spectrometry measurement shows the diffusion of sodium with concentration ˜1×1018 cm-3 in near surface region. Photoluminescence (PL) measurements show donor acceptor pair (DAP) emission at 408 nm at room temperature which exhibits a blue-shift to 404 nm at 9 K. DC Hall measurements show the mixed conduction due to low Hall voltage in these samples. PL measurements and variable temperature resistivity measurements suggest that the sodium acceptor activation energy is ˜0.300 eV.

  7. Energy level realignment in weakly interacting donor-acceptor binary molecular networks.

    PubMed

    Zhong, Jian-Qiang; Qin, Xinming; Zhang, Jia-Lin; Kera, Satoshi; Ueno, Nobuo; Wee, Andrew Thye Shen; Yang, Jinlong; Chen, Wei

    2014-02-25

    Understanding the effect of intermolecular and molecule-substrate interactions on molecular electronic states is key to revealing the energy level alignment mechanism at organic-organic heterojunctions or organic-inorganic interfaces. In this paper, we investigate the energy level alignment mechanism in weakly interacting donor-acceptor binary molecular superstructures, comprising copper hexadecafluorophthalocyanine (F16CuPc) intermixed with copper phthalocyanine (CuPc), or manganese phthalocynine (MnPc) on graphite. The molecular electronic structures have been systematically studied by in situ ultraviolet photoelectron spectroscopy (UPS) and low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) experiments and corroborated by density functional theory (DFT) calculations. As demonstrated by the UPS and LT-STM/STS measurements, the observed unusual energy level realignment (i.e., a large downward shift in donor HOMO level and a corresponding small upward shift in acceptor HOMO level) in the CuPc-F16CuPc binary superstructures originates from the balance between intermolecular and molecule-substrate interactions. The enhanced intermolecular interactions through the hydrogen bonding between neighboring CuPc and F16CuPc can stabilize the binary superstructures and modify the local molecular electronic states. The obvious molecular energy level shift was explained by gap-state-mediated interfacial charge transfer. PMID:24433044

  8. Charge-transfer complexes of 4-methylpiperidine with σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    AlQaradawi, Siham Y.; Mostafa, Adel; Bazzi, Hassan S.

    2015-01-01

    The solid charge-transfer (CT) molecular complexes formed in the reaction of the electron donor 4-methylpiperidine (4MP) with the σ-electron acceptor iodine and π-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) have been investigated spectrophotometrically in chloroform at 25 °C. These were characterized through electronic and infrared spectra as well as elemental and thermal analysis. The obtained results showed that the formed solid CT-complexes have the formulas [(4MP) I]+I-3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)] and with TCNQ the adduct [TCMPQDM] is obtained through N-substitution reaction in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements. The formation constant KCT, molar extinction coefficient εCT, free energy change ΔG0, CT energy ECT and the ionization potential Ip have been calculated for the CT-complexes [(4MP) I]+I-3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)].

  9. Primary acceptor in bacterial photosynthesis: obligatory role of ubiquinone in photoactive reaction centers of Rhodopseudomonas spheroides.

    PubMed Central

    Okamura, M Y; Isaacson, R A; Feher, G

    1975-01-01

    Reaction centers were found to bind two ubiquinones, both of which could be removed by o-phenanthroline and the detergent lauryldimethylamine oxide. One ubiquinone was more easily removed than the other. The low-temperature light-induced optical and electron paramagnetic resonance (EPR) changes were eliminated and restored upon removal and readdition of ubiquinone and were quantitatively correlated with the amount of tightly bound ubiquinone. We, therefore, conclude that this ubiquinone plays an obligatory role in the primary photochemistry. The easily removed ubiquinone is thought to be the secondary electron acceptor. The low-temperature charge recombination kinetics, as well as the optical and EPR spectra, were the same for untreated reaction centers and for those reconstituted with ubiquinone. This indicates that extraction and reconstitution were accomplished without altering the conformation of the active site. Reaction centers reconstituted with other quinones also showed restored photochemical activity, although they exhibited changes in their low-temperature recombination kinetics and light-induced (g = 1.8) EPR signal is interpreted in terms of a magnetically coupled ubiquinone--Fe2+ acceptor complex. A possible role of iron is to facilitate electron transfer between the primary and secondary ubiquinones. PMID:1081231

  10. The Advantages of Using Electronic Processes for Commenting on and Exchanging the Written Work of Students with Learning Disabilities and/or AD/HD

    ERIC Educational Resources Information Center

    Carmichael, Stephen; Alden, Peg

    2006-01-01

    Researchers have explored the impact of computer-assisted feedback and electronic mail on students' writing, but most of the work to date seems to have focused on second language writers, peer response, or response as part of an online composition course. Although research has documented the importance of certain generic features of word…

  11. Interaction of /sup 125/I-labeled botulinum neurotoxins with nerve terminals. II. Autoradiographic evidence for its uptake into motor nerves by acceptor-mediated endocytosis

    SciTech Connect

    Black, J.D.; Dolly, J.O.

    1986-01-01

    Using pharmacological and autoradiographic techniques it has been shown that botulinum neurotoxin (BoNT) is translocated across the motor nerve terminal membrane to reach a postulated intraterminal target. In the present study, the nature of this uptake process was investigated using electron microscopic autoradiography. It was found that internalization is acceptor-mediated and that binding to specific cell surface acceptors involves the heavier chain of the toxin. In addition, uptake was shown to be energy and temperature-dependent and to be accelerated by nerve stimulation, a treatment which also shortens the time course of the toxin-induced neuroparalysis. These results, together with the observation that silver grains were often associated with endocytic structures within the nerve terminal, suggested that acceptor-mediated endocytosis is responsible for toxin uptake. Possible recycling of BoNT acceptors (an important aspect of acceptor-mediated endocytosis of toxins) at motor nerve terminals was indicated by comparing the extent of labeling in the presence and absence of metabolic inhibitors. On the basis of these collective results, it is concluded that BoNT is internalized by acceptor-mediated endocytosis and, hence, the data support the proposal that this toxin inhibits release of acetylcholine by interaction with an intracellular target.

  12. Fullerene-based materials for solar cell applications: design of novel acceptors for efficient polymer solar cells--a DFT study.

    PubMed

    Mohajeri, Afshan; Omidvar, Akbar

    2015-09-14

    Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Polymer solar cells (PSCs) hold promise for their potential to be used as low-cost and efficient solar energy converters. PSCs have been commonly made from bicontinuous polymer:fullerene composites or so-called bulk heterojunctions. The conjugated polymer donors and the fullerene derivative acceptors are the key materials for high performance PSCs. In the present study, we have performed density functional theory calculations to investigate the electronic structures and magnetic properties of several representative C60 fullerene derivatives, seeking ways to improve their efficiency as acceptors of photovoltaic devices. In our survey, we have successfully correlated the LUMO energy level as well as chemical hardness, hyper-hardness, nucleus-independent chemical shift, and static dipole polarizability of PC60BM-like fullerene derivative acceptors with the experimental open circuit voltage of the photovoltaic device based on the P3HT:fullerene blend. The obtained structure-property correlations allow finding the best fullerene acceptor match for the P3HT donor. For this purpose, four new fullerene derivatives are proposed and the output parameters for the corresponding P3HT-based devices are predicted. It is found that the proposed fullerene derivatives exhibit better photovoltaic properties than the traditional PC60BM acceptor. The present study opens the way for manipulating fullerene derivatives and developing promising acceptors for solar cell applications. PMID:26248255

  13. Single and double acceptor-levels of a carbon-hydrogen defect in n-type silicon

    NASA Astrophysics Data System (ADS)

    Stübner, R.; Scheffler, L.; Kolkovsky, Vl.; Weber, J.

    2016-05-01

    In the present study, we discuss the origin of two dominant deep levels (E42 and E262) observed in n-type Si, which is subjected to hydrogenation by wet chemical etching or a dc H-plasma treatment. Their activation enthalpies determined from Laplace deep level transient spectroscopy measurements are EC-0.06 eV (E42) and EC-0.51 eV (E262). The similar annealing behavior and identical depth profiles of E42 and E262 correlate them with two different charge states of the same defect. E262 is attributed to a single acceptor state due to the absence of the Poole-Frenkel effect and the lack of a capture barrier for electrons. The emission rate of E42 shows a characteristic enhancement with the electric field, which is consistent with the assignment to a double acceptor state. In samples with different carbon and hydrogen content, the depth profiles of E262 can be explained by a defect with one H-atom and one C-atom. From a comparison with earlier calculations [Andersen et al., Phys. Rev. B 66, 235205 (2002)], we attribute E42 to the double acceptor and E262 to the single acceptor state of the CH1AB configuration, where one H atom is directly bound to carbon in the anti-bonding position.

  14. Morphological study on small molecule acceptor-based organic solar cells with efficiencies beyond 7% (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Ma, Wei; Yan, He

    2015-10-01

    Despite the essential role of fullerenes in achieving best-performance organic solar cells (OSCs), fullerene acceptors have several drawbacks including poor light absorption, high-cost production and purification. For this reason, small molecule acceptor (SMA)-based OSCs have attracted much attention due to the easy tunability of electronic and optical properties of SMA materials. In this study, polymers with temperature dependent aggregation behaviors are combined with various small molecule acceptor materials, which lead to impressive power conversion efficiencies of up to 7.3%. The morphological and aggregation properties of the polymer:small molecule blends are studied in details. It is found that the temperature-dependent aggregation behavior of polymers allows for the processing of the polymer solutions at moderately elevated temperature, and more importantly, controlled aggregation and strong crystallization of the polymer during the film cooling and drying process. This results in a well-controlled and near-ideal polymer:small molecule morphology that is controlled by polymer aggregation during warm casting and thus insensitive to the choice of small molecules. As a result, several cases of highly efficient (PCE between 6-7.3%) SMA OSCs are achieved. The second part of this presentation will describe the morphology of a new small molecule acceptor with a unique 3D structure. The relationship between molecular structure and morphology is revealed.

  15. Spectrophotometric study of the charge-transfer and ion-pair complexation of methamphetamine with some acceptors

    NASA Astrophysics Data System (ADS)

    Shahdousti, Parvin; Aghamohammadi, Mohammad; Alizadeh, Naader

    2008-04-01

    The charge-transfer (CT) complexes of methamphetamine (MPA) as a n-donor with several acceptors including bromocresolgreen (BCG), bromocresolpurple (BCP), chlorophenolred (CPR), picric acid (PIC), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have been studied spectrophotometrically in chloroform solutions in order to obtain some information about their stoichiometry and stability of complexation. The oscillator strengths, transition dipole moments and resonance energy of the complex in the ground state for all complexes have been calculated. Vertical ionization potential of MPA and electron affinity of acceptors were determined by ab initio calculation. The acceptors were also used to utilize a simple and sensitive extraction-spectrophotometric method for the determination of MPA. The method is based on the formation of 1:1 ion-pair association complexes of MPA with BCG, BCP and PIC in chloroform medium. Beer's plots were obeyed in a general concentration range of 0.24-22 μg ml -1 for the investigated drug with different acceptors. The proposed methods were applied successfully for the determination of MAP in pure and abuse drug with good accuracy and precision.

  16. Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments

    PubMed Central

    Lissau, Henriette; Frisenda, Riccardo; Olsen, Stine T.; Jevric, Martyn; Parker, Christian R.; Kadziola, Anders; Hansen, Thorsten; van der Zant, Herre S. J.; Brøndsted Nielsen, Mogens; Mikkelsen, Kurt V.

    2015-01-01

    The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment. PMID:26667583

  17. High-resolution noncontact AFM and Kelvin probe force microscopy investigations of self-assembled photovoltaic donor-acceptor dyads.

    PubMed

    Grévin, Benjamin; Schwartz, Pierre-Olivier; Biniek, Laure; Brinkmann, Martin; Leclerc, Nicolas; Zaborova, Elena; Méry, Stéphane

    2016-01-01

    Self-assembled donor-acceptor dyads are used as model nanostructured heterojunctions for local investigations by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). With the aim to probe the photo-induced charge carrier generation, thin films deposited on transparent indium tin oxide substrates are investigated in dark conditions and upon illumination. The topographic and contact potential difference (CPD) images taken under dark conditions are analysed in view of the results of complementary transmission electron microscopy (TEM) experiments. After in situ annealing, it is shown that the dyads with longer donor blocks essentially lead to standing acceptor-donor lamellae, where the acceptor and donor groups are π-stacked in an edge-on configuration. The existence of strong CPD and surface photo-voltage (SPV) contrasts shows that structural variations occur within the bulk of the edge-on stacks. SPV images with a very high lateral resolution are achieved, which allows for the resolution of local photo-charging contrasts at the scale of single edge-on lamella. This work paves the way for local investigations of the optoelectronic properties of donor-acceptor supramolecular architectures down to the elementary building block level. PMID:27335768

  18. 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

  19. Smeared antibranes polarise in AdS

    NASA Astrophysics Data System (ADS)

    Gautason, Fridrik Freyr; Truijen, Brecht; Van Riet, Thomas

    2015-07-01

    In the recent literature it has been questioned whether the local backreaction of antibranes in flux throats can induce a perturbative brane-flux decay. Most evidence for this can be gathered for D6 branes and D p branes smeared over 6 - p compact directions, in line with the absence of finite temperature solutions for these cases. The solutions in the literature have flat worldvolume geometries and non-compact transversal spaces. In this paper we consider what happens when the worldvolume is AdS and the transversal space is compact. We show that in these circumstances brane polarisation smoothens out the flux singularity, which is an indication that brane-flux decay is prevented. This is consistent with the fact that the cosmological constant would be less negative after brane-flux decay. Our results extend recent results on AdS7 solutions from D6 branes to AdS p+1 solutions from D p branes. We show that supersymmetry of the AdS solutions depend on p non-trivially.

  20. AdS orbifolds and Penrose limits

    SciTech Connect

    Alishahiha, Mohsen; Sheikh-Jabbari, Mohammad M.; Tatar, Radu

    2002-12-09

    In this paper we study the Penrose limit of AdS{sub 5} orbifolds. The orbifold can be either in the pure spatial directions or space and time directions. For the AdS{sub 5}/{Lambda} x S{sup 5} spatial orbifold we observe that after the Penrose limit we obtain the same result as the Penrose limit of AdS{sub 5} x S{sup 5}/{Lambda}. We identify the corresponding BMN operators in terms of operators of the gauge theory on R x S{sup 3}/{Lambda}. The semi-classical description of rotating strings in these backgrounds have also been studied. For the spatial AdS orbifold we show that in the quadratic order the obtained action for the fluctuations is the same as that in S{sup 5} orbifold, however, the higher loop correction can distinguish between two cases.

  1. A donor-acceptor triptycene-coumarin hybrid dye featuring a charge separated excited state and AIE properties.

    PubMed

    Qian, Rui; Tong, Hongjuan; Huang, Cui; Li, Junhao; Tang, Yun; Wang, Rui; Lou, Kaiyan; Wang, Wei

    2016-06-14

    A triptycene-coumarin hybrid dye DCT-1 with a 1,4-dimethoxybenzene group as the electron donor and a coumarin fluorophore as the acceptor on the separated fins of a triptycene was synthesized. DCT-1 features a charge separated excited state with emissions sensitive to solvent polarities. Moreover, DCT-1 also exhibits aggregation-induced emission properties in water with excellent photostability and pH-stability for potential cell imaging applications. PMID:27186970

  2. Enhanced Charge Mobility in Polymer Nanocomposites Incorporating Donor-Acceptor Interfaces

    NASA Astrophysics Data System (ADS)

    Tameev, Alexey R.; Nikitenko, Vladimir R.; Vannikov, Anatoly V.

    2011-01-01

    Charge carrier transport in donor-acceptor (D-A) composites based on either poly(N-vinyl carbazole) or polyimide derivative incorporating either carbon single-walled nanotubes or nanocrystals of J-aggregated cyanine dyes is shown to exhibit a similar behavior. In the composite films, polymer/nanomaterial interface provides pathways of the high conductivity. Charge-transfer states (CTS) formed at the D-A interface are involved in the transport. The charge transport along the interface is suggested to arise due to the D-A integer charge transfer and strong interaction between adjacent opposite charges located on the donor and acceptor molecules. The approach based on the concept of sequence of charge carrier transfers through charge transfer states describes the increased electron and hole mobility in the composites. The approach predicts enhanced conductivity with reduced activation energy. Moreover, once the density of electron-hole pairs at the interface is rather high, significant part of the charge carriers can avoid hopping transport resulting in conductivity of metal type. The value of two-dimensional conductivity is estimated by numerical modeling.

  3. Photophysics and charge transfer in donor-acceptor triblock copolymer photovoltaic materials

    NASA Astrophysics Data System (ADS)

    Schwarz, Kyra N.; Jones, David J.; Smith, Trevor A.; Ghiggino, Kenneth P.

    2014-10-01

    Efficient conversion of solar energy to electricity in low-cost organic photovoltaic (OPV) devices requires the complex interplay between multiple processes and components over various length and time scales. Optimizing device morphology to ensure efficient exciton diffusion and charge transport as well as ensuring efficient charge photogeneration is necessary to achieve optimum performance in new materials. The conjugated polymer electron donor PFM (poly(9,9-diocetyluorene-co-bis-N,N-(4-methylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine)) and electron acceptor F8BT (poly[(9,9-di-n-octyluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)), comprise the novel triblock copolymer PFM-F8BT-PFM. This copolymer is designed to phase separate on the 20-30 nm scale, a domain size ideal for maximizing exciton collection at the donor-acceptor interface. Using steady-state and ultrafast spectroscopic characterization including high repetition rate transient absorption spectroscopy, the dynamics of charge and energy transfer of the component polymers and the triblock co-polymer have been investigated. The results demonstrate that for the homopolymers solvent dependent exciton transport processes dominate, while in the triblock copolymer solutions transient spectroscopy provides evidence for interfacial charge separation.

  4. Spectrophotometric and electrical studies of charge-transfer complexes of sodium flucloxacillin with π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Didamony, Akram M.

    2006-11-01

    The present study is interested to develop a simple, rapid and accurate spectrophotometric method for determination of sodium flucloxacillin (fluc) in pure form and pharmaceutical formulations. The charge-transfer (CT) interactions between sodium flucloxacillin as electron donor and chloranilic acid (CLA), dichloroquinone 4-chloroimide (DCQ), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) and 7,7,8,8 tetracyano- p-quinodimethane (TCNQ), as π-electron acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9979-0.9995) were found between the absorbance and the concentration of the drug in the range 16-880 μg ml -1. The proposed methods were applied successfully to the determination of the examined drug either in pure or pharmaceutical dosage forms with good accuracy and precision. The formation of the CT-complexes and the sites of interaction were confirmed by elemental analysis CHN, UV-vis, IR, 1H NMR and mass spectra techniques. Based on Job's method of continuous variation plots, the obtained results indicate the formation of 1:1 charge-transfer complexes with the general formula [(fluc)(acceptor)]. Statistical analysis of the obtained results showed no significant difference between the proposed method and official method.

  5. Spectrophotometric and electrical studies of charge-transfer complexes of sodium flucloxacillin with pi-acceptors.

    PubMed

    Refat, Moamen S; El-Didamony, Akram M

    2006-11-01

    The present study is interested to develop a simple, rapid and accurate spectrophotometric method for determination of sodium flucloxacillin (fluc) in pure form and pharmaceutical formulations. The charge-transfer (CT) interactions between sodium flucloxacillin as electron donor and chloranilic acid (CLA), dichloroquinone 4-chloroimide (DCQ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and 7,7,8,8 tetracyano-p-quinodimethane (TCNQ), as pi-electron acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9979-0.9995) were found between the absorbance and the concentration of the drug in the range 16-880 microg ml(-1). The proposed methods were applied successfully to the determination of the examined drug either in pure or pharmaceutical dosage forms with good accuracy and precision. The formation of the CT-complexes and the sites of interaction were confirmed by elemental analysis CHN, UV-vis, IR, (1)H NMR and mass spectra techniques. Based on Job's method of continuous variation plots, the obtained results indicate the formation of 1:1 charge-transfer complexes with the general formula [(fluc)(acceptor)]. Statistical analysis of the obtained results showed no significant difference between the proposed method and official method. PMID:16527531

  6. Optical spacing effect in organic photovoltaic cells incorporating a dilute acceptor layer

    SciTech Connect

    Menke, S. Matthew; Lindsay, Christopher D.; Holmes, Russell J.

    2014-06-16

    The addition of spacing layers in organic photovoltaic cells (OPVs) can enhance light absorption by optimizing the spatial distribution of the incident optical field in the multilayer structure. We explore the optical spacing effect in OPVs achieved using a diluted electron acceptor layer of C{sub 60}. While optical spacing is often realized by optimizing buffer layer thickness, we find that optical spacing via dilution leads to cells with similar or enhanced photocurrent. This is observed despite a smaller quantity of absorbing molecules, suggesting a more efficient use of absorbed photons. In fact, dilution is found to concentrate optical absorption near the electron donor-acceptor interface, resulting in a marked increase in the exciton diffusion efficiency. Contrasting the use of changes in thickness to engineer optical absorption, the use of dilution does not significantly alter the overall thickness of the OPV. Optical spacing via dilution is shown to be a viable alternative to more traditional optical spacing techniques and may be especially useful in the continued optimization of next-generation, tandem OPVs where it is important to minimize competition for optical absorption between individual sub-cells.

  7. Jahn-Teller splitting and Zeeman effect of acceptors in diamond.

    SciTech Connect

    Anthony, T. R.; Grimsditch, M.; Kim, H.; Ramdas, A. K.; Rodriguez, S.

    1999-09-11

    Employing the high resolution of a 5+4 tandem Fabry-Perot interferometer, we discovered that {Delta}{prime}, the Raman active electronic transition between the spin-orbit split 1s(p{sub 3/2}): {Lambda}{sub 8} and 1s(P{sub 1/2}) {Lambda}{sub 7} acceptor ground states, is a doublet for a boron impurity in diamond with a clearly resolved spacing of 0.81 {+-} 0.15 cm{sup {minus}1}. The direct observation of a Stokes/anti-Stokes pair with 0.80 {+-} 0.04 cm{sup {minus}1} shift provides a striking confirmation that the lower 1s(p{sub 3/2}): {Lambda}{sub 8} ground state has experienced a splitting due to a static Jahn-Teller distortion. The Zeeman effect of {Delta}{prime} has been investigated with a magnetic field along several crystallographic directions. Theory of the Zeeman effect, formulated in terms of the symmetry of the substitutional acceptor and the Luttinger parameters of the valence band, allows quantitative predictions of the relative intensities of the Zeeman components in full agreement with experiments. The observation of transitions within the {Lambda}{sub 8} Zeeman multiplet, i.e., the Raman-electron-paramagnetic-resonances, is yet another novel feature to emerge from the present study. The investigation has also yielded g-factors characterizing the Zeeman multiplets.

  8. Mobile hydrogen carbonate acts as proton acceptor in photosynthetic water oxidation

    PubMed Central

    Koroidov, Sergey; Shevela, Dmitriy; Shutova, Tatiana; Samuelsson, Göran; Messinger, Johannes

    2014-01-01

    Cyanobacteria, algae, and plants oxidize water to the O2 we breathe, and consume CO2 during the synthesis of biomass. Although these vital processes are functionally and structurally well separated in photosynthetic organisms, there is a long-debated role for CO2/ in water oxidation. Using membrane-inlet mass spectrometry we demonstrate that acts as a mobile proton acceptor that helps to transport the protons produced inside of photosystem II by water oxidation out into the chloroplast’s lumen, resulting in a light-driven production of O2 and CO2. Depletion of from the media leads, in the absence of added buffers, to a reversible down-regulation of O2 production by about 20%. These findings add a previously unidentified component to the regulatory network of oxygenic photosynthesis and conclude the more than 50-y-long quest for the function of CO2/ in photosynthetic water oxidation. PMID:24711433

  9. Mobile hydrogen carbonate acts as proton acceptor in photosynthetic water oxidation.

    PubMed

    Koroidov, Sergey; Shevela, Dmitriy; Shutova, Tatiana; Samuelsson, Göran; Messinger, Johannes

    2014-04-29

    Cyanobacteria, algae, and plants oxidize water to the O2 we breathe, and consume CO2 during the synthesis of biomass. Although these vital processes are functionally and structurally well separated in photosynthetic organisms, there is a long-debated role for CO2/ in water oxidation. Using membrane-inlet mass spectrometry we demonstrate that acts as a mobile proton acceptor that helps to transport the protons produced inside of photosystem II by water oxidation out into the chloroplast's lumen, resulting in a light-driven production of O2 and CO2. Depletion of from the media leads, in the absence of added buffers, to a reversible down-regulation of O2 production by about 20%. These findings add a previously unidentified component to the regulatory network of oxygenic photosynthesis and conclude the more than 50-y-long quest for the function of CO2/ in photosynthetic water oxidation. PMID:24711433

  10. Efficiency improvement of new Tetrathienoacene-based dyes by enhancing donor, acceptor and bridge units, a theoretical study.

    PubMed

    Tavangar, Zahra; Zareie, Nazanin

    2016-10-01

    A series of metal free Tetrathienoacene-based (TTA-based) organic dyes are designed and investigated as sensitizers for application in dye sensitized solar cells (DSSCs). Density function theory and time dependent density function theory calculations were performed on these dyes at vacuum and orthodichlorobenzene as the solvent. Effects of changing π-conjugation bridges and different functional groups in acceptor and donor units were investigated. UV-Vis absorption spectra were simulated to show the wavelength shifting and absorption properties. Inserting nitro and acyl chloride functional groups in acceptor and NH2 in donor units leads to the reduction of HOMO-LUMO gap by lowering the lowest unoccupied molecular orbital (LUMO) energy level and raising the highest occupied molecular orbital (HOMO) energy level and the increase in effective parameters in DSSC' efficiency. The results show that changing spacer units from thiophene to furan has a great effect on electronic structure and absorption spectra. Investigation of the electron distributions of frontier orbitals shows the HOMO and LUMO localization in donor and acceptor, respectively. Some key parameters that were studied here include light harvesting efficiency, free energy of electron injection and open circuit photo-voltage. PMID:27258685

  11. Red-shifted cyanide stretching frequencies in cyanide-bridged transition metal donor-acceptor complexes. Support for vibronic coupling

    SciTech Connect

    Watzky, M.A.; Endicott, J.F.; Song, X.

    1996-06-05

    Patterns in the cyanide stretching frequencies have been examined in several series of monometal- and CN{sup {minus}} bridged transition metal complexes. Metal-to-cyanide back-bonding can be identified as a major factor contributing to red shifts of v{sub CN} in monometal complexes. This effect is complicated in cyanide-bridged complexes in two ways: (a) when both metals can back-bond to cyanide, the net interaction is repulsive and results in a blue shift of v{sub CN}: and (b) when a donor and acceptor are bridged, V{sub CN} undergoes a substantial red shift (sometimes more than 60 cm{sup {minus}1} lower in energy than the parent monometal complex). These effects can be described by simple perturbational models for the electronic interactions. Monometal cyanide complexes and CN{sup {minus}}-bridged backbonding metals can be treated in terms of their perturbations of the CN{sup {minus}} {pi} and {pi}* orbitals by using a simple, Hueckel-like, three-center perturbational treatment of electronic interactions. However, bridged donor-acceptor pairs are best described by a vibronic model in which it is assumed that the extent of electronic delocalization is in equilibrium with variations of some nuclear coordinates. Consistent with this approach, it is found that (a) the oscillator strength of the donor-acceptor charge transfer (DACT) absorption is roughly proportional to the red shift of v{sub CN} and (b) there are strong symmetry constraints on the coupling.

  12. Donors contribute more than acceptors to increase the two-photon activity--a case study with cyclopenta[b]naphthalene based molecules.

    PubMed

    Alam, Md Mehboob

    2014-12-21

    In the present work, we address the question -"which among the electron donors and the electron acceptors contribute more to the two-photon (TP) activity of a donor-π-acceptor type of molecule?" For this purpose we have performed ab initio calculations to calculate the TP transition probability (δTP) of a recently synthesized (Benedetti et al., J. Am. Chem. Soc., 2012, 134(30), 12418-12421) cyclopenta[b]naphthalene based chemo-sensor and its derivatives containing different electron donor and acceptor groups. Our study revealed that both under vacuum and in solvent phases, an increase in electron donor strength (-OMe, -NH2, -NMe2) increases the δTP value up to five times, whereas, an increase in the acceptor group strength (-COCH3, -NO2, -CN) increases it by a factor of two only. The highest δTP value is obtained for the molecule having the strongest donor-acceptor pair (-CN, -NMe2) considered in this work. We have also noted that, the removal of the cyclopentane ring from the original system increases the δTP value by ∼20% and the replacement of the naphthyl group by the benzene ring decreases it by ∼70%. All these results are explained by inspecting different TP tensor elements and different transition moment vectors involved in a two-state model approach. A close scrutiny of different parameters in 2SM clearly reveals that upon increasing the strength of either the donor or the acceptor group the parameters change in favour of increasing the overall δTP values but in the case of donors this effect is much larger. PMID:25367708

  13. Equivalence of donor and acceptor fits of temperature dependent Hall carrier density and Hall mobility data: Case of ZnO

    SciTech Connect

    Brochen, Stéphane; Feuillet, Guy; Pernot, Julien

    2014-04-28

    In this work, statistical formulations of the temperature dependence of ionized and neutral impurity concentrations in a semiconductor, needed in the charge balance equation and for carrier scattering calculations, have been developed. These formulations have been used in order to elucidate a confusing situation, appearing when compensating acceptor (donor) levels are located sufficiently close to the conduction (valence) band to be thermally ionized and thereby to emit (capture) an electron to (from) the conduction (valence) band. In this work, the temperature dependent Hall carrier density and Hall mobility data adjustments are performed in an attempt to distinguish the presence of a deep acceptor or a deep donor level, coexisting with a shallower donor level and located near the conduction band. Unfortunately, the present statistical developments, applied to an n-type hydrothermal ZnO sample, lead in both cases to consistent descriptions of experimental Hall carrier density and mobility data and thus do not allow to determine the nature, donor or acceptor, of the deep level. This demonstration shows that the emission of an electron in the conduction band, generally assigned to a (0/+1) donor transition from a donor level cannot be applied systematically and could also be attributed to a (−1/0) donor transition from an acceptor level. More generally, this result can be extended for any semiconductor and also for deep donor levels located close to the valence band (acceptor transition)

  14. A theoretical study on tuning the electronic structures and photophysical properties of newly designed platinum(II) complexes by adding substituents on functionalized ligands as highly efficient OLED emitters.

    PubMed

    Zhang, Luqiong; Tian, Li; Li, Ming; He, Rongxing; Shen, Wei

    2014-05-01

    By imitating FIrpic, seven new platinum(II) complexes with pic (pic = picolinate) ligand have been designed to be guest materials by means of adding different substituents to functionalized ligands (ppy and fpy, ppy = phenylpyridyl-N,C and fpy = 2-(9',9'-diethyl-9H-fluorenyl)pyridyl-N,C). In order to reveal their molecular structures, photophysical properties and structure-property relationships with typical host materials, an in-depth theoretical investigation was performed via quantum chemical calculations. The electronic structures and photophysical properties of these complexes were investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) using the B3LYP functional with LANL2DZ and 6-31G* basis sets. It turns out that electronic structures and photophysical properties can be tuned by substituent modifications on functionalized ligands. This work highlights that the match between guest materials and host materials in typical OLED structures can be weighed by the energy levels of the HOMO and LUMO and the adiabatic triplet energy of each complex. Also, a combined analysis of electronic structures, host-guest match, reorganization energies (λ) and triplet exciton generation fraction (χ(T)) is helpful in exploring triplet emitters with high phosphorescence efficiency in OLEDs, which is an interesting and creative aspect of this work. Thereinto, λ reveals the capability of carrier transport and the balance between holes and electrons, whilst structural parameters and d-orbital splittings show that those complexes that have strong electron-withdrawing and electron-donating groups are nonemissive. Consequently, complexes 3-7 can be better triplet emitters than FIrpic. Moreover, the emission colors could be predicted by the 0-0 transition energy (E(0-0)) instead of the triplet vertical transition energy (E(vert)). Accordingly, complexes 3, 4 and 6 would be efficient phosphorescent materials with different predicted

  15. Exciton dissociation at organic small molecule donor-acceptor interfaces (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Robey, Steven W.

    2015-08-01

    Exciton dissociation at organic semiconductor donor-acceptor (D-A) heterojunctions is critical for the performance of organic photovoltaic (OPV) structures. Interfacial charge separation and recombination processes control device efficiency. We have investigated these fundamental interfacial issues using time-resolved two-photon photoemission (TR-2PPE), coupled with the formation of well-controlled D-A structures by organic molecular beam epitaxy. The interfacial electronic and molecular structure of these model interfaces was well-characterized using scanning tunneling microscopy and ultraviolet photoemission. Exciton dissociation dynamics were investigated by using a sub-picosecond pump pulse to create Pc π-->π* transitions, producing a population of singlet (S1) Pc excitons. The subsequent decay dynamics of this population was monitored via photoemission with a time-delayed UV pulse. For CuPcC60 interfaces, S1 exciton population decay in the interfacial CuPc layer was much faster than decay in the bulk due to interfacial charge separation. The rate constant for exciton dissociation was found to be ≍ 7 x 10 12 sec-1 (≍ 140 fs). Excitons that lose energy via intersystem crossing (ISC) to triplet levels dissociate approximately 500 to 1000 times slower. The dependence of exciton dissociation on separation was also studied. Exciton dissociation falls of rapidly with distance from the interface. Dissociation from the 2nd, and subsequent, layers of H2Pc is reduced by at least a factor of 10 from that in the interfacial layer. Finally, investigations of the relative efficiency for interfacial exciton dissociation by alternative acceptors based on perylene cores, (perylene tetracarboxylic dianhydride, or PTCDA) compared to fullerene-based acceptors such as C60 will also be discussed.

  16. Effects of strain on carbon donors and acceptors in hexagonal boron nitride monolayers

    NASA Astrophysics Data System (ADS)

    Fujimoto, Yoshitaka; Saito, Susumu

    2016-01-01

    We present first-principles density functional calculations that clarify the electronic properties of carbon defects in hexagonal boron nitride (h -BN) monolayers under biaxially applied strains. We find that strain can control the ionization energies of both donor and acceptor states. Furthermore, we also find that strain can lead to the dramatic change in conduction channel properties of donor states due to the interchange of the conduction-band-minimum state with the nearly-free-electron state. We also report the simulated scanning tunneling microscopy (STM) images of carbon defects in h -BN monolayers for experimental identification of those defects. We show that the STM images strongly reflect distinctive spatial distributions of local density of states around carbon defects depending on the substitution sites and thereby they could be identified by using STM experiments.

  17. Powering microbes with electricity: direct electron transfer from electrodes to microbes

    SciTech Connect

    Lovley, DR

    2010-09-16

    P>The discovery of electrotrophs, microorganisms that can directly accept electrons from electrodes for the reduction of terminal electron acceptors, has spurred the investigation of a wide range of potential applications. To date, only a handful of pure cultures have been shown to be capable of electrotrophy, but this process has also been inferred in many studies with undefined consortia. Potential electron acceptors include: carbon dioxide, nitrate, metals, chlorinated compounds, organic acids, protons and oxygen. Direct electron transfer from electrodes to cells has many advantages over indirect electrical stimulation of microbial metabolism via electron shuttles or hydrogen production. Supplying electrons with electrodes for the bioremediation of chlorinated compounds, nitrate or toxic metals may be preferable to adding organic electron donors or hydrogen to the subsurface or bioreactors. The most transformative application of electrotrophy may be microbial electrosynthesis in which carbon dioxide and water are converted to multi-carbon organic compounds that are released extracellularly. Coupling photovoltaic technology with microbial electrosynthesis represents a novel photosynthesis strategy that avoids many of the drawbacks of biomass-based strategies for the production of transportation fuels and other organic chemicals. The mechanisms for direct electron transfer from electrodes to microorganisms warrant further investigation in order to optimize envisioned applications.

  18. Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

    SciTech Connect

    Fonari, A.; Corbin, N. S.; Coropceanu, V. E-mail: coropceanu@gatech.edu; Vermeulen, D.; McNeil, L. E.; Goetz, K. P.; Jurchescu, O. D.; Bredas, J. L. E-mail: coropceanu@gatech.edu

    2015-12-14

    We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

  19. Probing the spin states of a single acceptor atom.

    PubMed

    van der Heijden, Joost; Salfi, Joe; Mol, Jan A; Verduijn, Jan; Tettamanzi, Giuseppe C; Hamilton, Alex R; Collaert, Nadine; Rogge, Sven

    2014-03-12

    We demonstrate a single-hole transistor using an individual acceptor dopant embedded in a silicon channel. Magneto-transport spectroscopy reveals that the ground state splits as a function of magnetic field into four states, which is unique for a single hole bound to an acceptor in a bulk semiconductor. The two lowest spin states are heavy (|m(j)| = 3/2) and light (|m(j)| = 1/2) hole-like, a two-level system that can be electrically driven and is characterized by a magnetic field dependent and long relaxation time, which are properties of interest for qubits. Although the bulklike spin splitting of a boron atom is preserved in our nanotransistor, the measured Landé g-factors, |g(hh)| = 0.81 ± 0.06 and |g(lh)| = 0.85 ± 0.21 for heavy and light holes respectively, are lower than the bulk value. PMID:24571637

  20. Interface effects on acceptor qubits in silicon and germanium.

    PubMed

    Abadillo-Uriel, J C; Calderón, M J

    2016-01-15

    Dopant-based quantum computing implementations often require the dopants to be situated close to an interface to facilitate qubit manipulation with local gates. Interfaces not only modify the energies of the bound states but also affect their symmetry. Making use of the successful effective mass theory we study the energy spectra of acceptors in Si or Ge taking into account the quantum confinement, the dielectric mismatch and the central cell effects. The presence of an interface puts constraints to the allowed symmetries and leads to the splitting of the ground state in two Kramers doublets (Mol et al 2015 Appl. Phys. Lett. 106 203110). Inversion symmetry breaking also implies parity mixing which affects the allowed optical transitions. Consequences for acceptor qubits are discussed. PMID:26618443

  1. Aluminum acceptor four particle bound exciton complex in 4H, 6H, and 3C SiC

    NASA Technical Reports Server (NTRS)

    Clemen, L. L.; Devaty, R. P.; Macmillan, M. F.; Yoganathan, M.; Choyke, W. J.; Larkin, D. J.; Powell, J. A.; Edmond, J. A.; Kong, H. S.

    1993-01-01

    Evidence is presented for a four particle acceptor complex in 3C, 6H, and 4H SiC, obtained in low-temperature photoluminescence and cathodoluminescence experiments. The new lines were observed in p-type films lightly doped with aluminum, of 6H, 4H, and 3C SiC grown on the silicon (0001) face of 6H SiC under special conditions. The lines increase in intensity as more aluminum is added during growth. The multiplicity of observed lines is consistent with symmetry-based models similar to those which have been proposed to describe 4A centers in p-type zincblende semiconductors.

  2. An extended Foerster-Dexter model for correlated donor-acceptor placement in solid state materials

    NASA Astrophysics Data System (ADS)

    Rotman, S. R.; Hartmann, F. X.

    1987-09-01

    The current theory of donor-acceptor interactions in solid-state materials is based on a random distribution of donors and acceptors through the crystal. In this paper, we present a model to calculate the observable transfer rates for the correlated positioning of donors and acceptors in laser materials. Chemical effects leading to such correlations are discussed.

  3. Quantum confined acceptors and donors in InSe nanosheets

    SciTech Connect

    Mudd, G. W.; Patanè, A. Makarovsky, O.; Eaves, L.; Kudrynskyi, Z. R.; Kovalyuk, Z. D.; Fay, M. W.; Zólyomi, V.; Falko, V.

    2014-12-01

    We report on the radiative recombination of photo-excited carriers bound at native donors and acceptors in exfoliated nanoflakes of nominally undoped rhombohedral γ-polytype InSe. The binding energies of these states are found to increase with the decrease in flake thickness, L. We model their dependence on L using a two-dimensional hydrogenic model for impurities and show that they are strongly sensitive to the position of the impurities within the nanolayer.

  4. Engineered oligosaccharyltransferases with greatly relaxed acceptor site specificity

    PubMed Central

    Ollis, Anne A.; Zhang, Sheng; Fisher, Adam C.; DeLisa, Matthew P.

    2015-01-01

    The Campylobacter jejuni protein glycosylation locus (pgl) encodes machinery for asparagine-linked (N-linked) glycosylation and serves as the archetype for bacterial N-glycosylation. This machinery has been functionally transferred into Escherichia coli, thereby enabling convenient mechanistic dissection of the N-glycosylation process in this genetically tractable host. Here, we sought to identify sequence determinants in the oligosaccharyltransferase PglB that restrict its specificity to only those glycan acceptor sites containing a negatively charged residue at the −2 position relative to asparagine. This involved creation of a genetic assay named glycoSNAP (glycosylation of secreted N-linked acceptor proteins) that facilitates high-throughput screening of glycophenotypes in E. coli. Using this assay, we isolated several C. jejuni PglB variants that were capable of glycosylating an array of noncanonical acceptor sequences including one in a eukaryotic N-glycoprotein. Collectively, these results underscore the utility of glycoSNAP for shedding light on poorly understood aspects of N-glycosylation and for engineering designer N-glycosylation biocatalysts. PMID:25129029

  5. Engineered oligosaccharyltransferases with greatly relaxed acceptor-site specificity.

    PubMed

    Ollis, Anne A; Zhang, Sheng; Fisher, Adam C; DeLisa, Matthew P

    2014-10-01

    The Campylobacter jejuni protein glycosylation locus (pgl) encodes machinery for asparagine-linked (N-linked) glycosylation and serves as the archetype for bacterial N-linked glycosylation. This machinery has been functionally transferred into Escherichia coli, enabling convenient mechanistic dissection of the N-linked glycosylation process in this genetically tractable host. Here we sought to identify sequence determinants in the oligosaccharyltransferase PglB that restrict its specificity to only those glycan acceptor sites containing a negatively charged residue at the -2 position relative to asparagine. This involved creation of a genetic assay, glycosylation of secreted N-linked acceptor proteins (glycoSNAP), that facilitates high-throughput screening of glycophenotypes in E. coli. Using this assay, we isolated several C. jejuni PglB variants that could glycosylate an array of noncanonical acceptor sequences, including one in a eukaryotic N-glycoprotein. These results underscore the utility of glycoSNAP for shedding light on poorly understood aspects of N-linked glycosylation and for engineering designer N-linked glycosylation biocatalysts. PMID:25129029

  6. News from the Periodic Table: An Introduction to "Periodicity Symbols, Tables, and Models for Higher-Order Valency and Donor-Acceptor Kinships"

    ERIC Educational Resources Information Center

    Bent, Henry A.; Weinhold, Frank

    2007-01-01

    The study presents and explains the various periodicity symbols, tables and models for the higher-order valency and donor-acceptor kinships used in chemistry. The described alternative tables are expected to improve the pedagogical consistency of the chemical periodicity patterns with better electronic behavior.

  7. Features of conduction mechanisms in n-HfNiSn semiconductor heavily doped with a Rh acceptor impurity

    SciTech Connect

    Romaka, V. A.; Rogl, P.; Stadnyk, Yu. V.; Romaka, V. V.; Hlil, E. K.; Krajovskii, V. Ya.; Horyn, A. M.

    2013-09-15

    The crystal structure and electron-density distribution, as well as the energy, kinetic, and magnetic characteristics of n-HfNiSn intermetallic semiconductor heavily doped with a Rh acceptor impurity in the temperature range T = 80-400 K, in the acceptor-concentration range N{sub A}{sup Rh} Almost-Equal-To 9.5 Multiplication-Sign 10{sup 19}-1.9 Multiplication-Sign 10{sup 21} cm{sup -3} (x = 0.005-0.10), and in magnetic fields H {<=} 10 kG are investigated. It is established that doping is accompanied by a simultaneous decrease in concentration, the elimination of donor-type structural defects (to x Almost-Equal-To 0.02), and an increase in the concentration of acceptor-type structural defects (0 < x {<=} 0.10). The dependence of the degree of semiconductor compensation on temperature is revealed. A model of the spatial arrangement of atoms in HfNi{sub 1-x}Rh{sub x}Sn is proposed, and the results of calculating the electron structure based on this model agree with the results of investigations of the kinetic and magnetic characteristics of the semiconductor. The results are discussed within the context of the Shklovskii-Efros model for a heavily doped and compensated semiconductor.

  8. Construction of an Artificial Ferrimagnetic Lattice by Lithium Ion Insertion into a Neutral Donor/Acceptor Metal-Organic Framework.

    PubMed

    Taniguchi, Kouji; Narushima, Keisuke; Mahin, Julien; Kosaka, Wataru; Miyasaka, Hitoshi

    2016-04-18

    Construction of a molecular system in which the magnetic lattice exhibits long-range order is one of the fundamental goals in materials science. In this study, we demonstrate the artificial construction of a ferrimagnetic lattice by doping electrons into acceptor sites of a neutral donor/acceptor metal-organic framework (D/A-MOF). This doping was achieved by the insertion of Li-ions into the D/A-MOF, which was used as the cathode of a Li-ion battery cell. The neutral D/A-MOF is a layered system composed of a carboxylate-bridged paddlewheel-type diruthenium(II,II) complex as the donor and a TCNQ derivative as the acceptor. The ground state of the neutral form was a magnetically disordered paramagnetic state. Upon discharge of the cell, spontaneous magnetization was induced; the transition temperature was variable. The stability of the magnetically ordered lattice depended on the equilibrium electric potential of the D/A-MOF cathode, which reflected the electron-filling level. PMID:26990927

  9. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors.

    PubMed

    Refat, Moamen S; Saad, Hosam A; Adam, Abdel Majid A

    2015-04-15

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, (1)H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor. PMID:25677533

  10. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2015-04-01

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, 1H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  11. Controlling the Conformational Changes in Donor–Acceptor [4]-Dendralenes through Intramolecular Charge-Transfer Processes

    PubMed Central

    Kanibolotsky, Alexander L; Forgie, John C; McEntee, Greg J; Talpur, M Munsif A; Skabara, Peter J; Westgate, Thomas DJ; McDouall, Joseph JW; Auinger, Michael; Coles, Simon J; Hursthouse, Michael B

    2009-01-01

    The synthesis of two [4]-dendralene compounds incorporating thiophene-(p-nitrophenyl) donor–acceptor units is presented. The dendralenes adopt two different conformers in solution and solid state and the transformation between the structures can be controlled by light and heat. The electron-donating components of the dendralenes are represented by bromothienyl (in 13) and ethylenedioxythiophene(EDOT)-thienyl (in 15) end-groups. The most facile transformation involves the isomerisation of donor–acceptor conjugated systems (a conformers) into structures in which only the thiophenes are conjugated (b conformers), and this process is driven by ambient light. The structures of the two conformers of compound 13 are confirmed by single-crystal X-ray diffraction studies and the structural changes in both compounds have been monitored by 1H NMR spectroscopy and absorption studies. The transformations were found to be first-order processes with rate constants of k = 0.0027 s−1 and k = 0.00022 s−1 for 13 and 15, respectively. Density functional theory calculations at the B3LYP/6-31G∗ level give credence to the proposed mechanism for the a→b conversion, which involves photoinduced intramolecular charge transfer (ICT) as the key step. The EDOT derivative (15) can be polymerised by electrochemical oxidation and a combination of cyclic voltammetry and UV/Vis spectroelectrochemical experiments indicate that the a conformer can be trapped and stabilised in the solid state. PMID:19760710

  12. A charge carrier transport model for donor-acceptor blend layers

    NASA Astrophysics Data System (ADS)

    Fischer, Janine; Widmer, Johannes; Kleemann, Hans; Tress, Wolfgang; Koerner, Christian; Riede, Moritz; Vandewal, Koen; Leo, Karl

    2015-01-01

    Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C60 in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (Et = 0.14 eV, Nt = 1.2 × 1018 cm-3) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

  13. A charge carrier transport model for donor-acceptor blend layers

    SciTech Connect

    Fischer, Janine Widmer, Johannes; Koerner, Christian; Vandewal, Koen; Leo, Karl; Kleemann, Hans; Tress, Wolfgang; Riede, Moritz

    2015-01-28

    Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C{sub 60} in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (E{sub t} = 0.14 eV, N{sub t} = 1.2 × 10{sup 18 }cm{sup −3}) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

  14. Optically tunable spin-exchange energy at donor:acceptor interfaces in organic solar cells

    SciTech Connect

    Li, Mingxing; Wang, Hongfeng; He, Lei; Zang, Huidong; Xu, Hengxing; Hu, Bin

    2014-07-14

    Spin-exchange energy is a critical parameter in controlling spin-dependent optic, electronic, and magnetic properties in organic materials. This article reports optically tunable spin-exchange energy by studying the line-shape characteristics in magnetic field effect of photocurrent developed from intermolecular charge-transfer states based on donor:acceptor (P3HT:PCBM) system. Specifically, we divide magnetic field effect of photocurrent into hyperfine (at low field < 10 mT) and spin-exchange (at high field > 10 mT) regimes. We observe that increasing photoexcitation intensity can lead to a significant line-shape narrowing in magnetic field effect of photocurrent occurring at the spin-exchange regime. We analyze that the line-shape characteristics is essentially determined by the changing rate of magnetic field-dependent singlet/triplet ratio when a magnetic field perturbs the singlet-triplet transition through spin mixing. Based on our analysis, the line-shape narrowing results indicate that the spin-exchange energy at D:A interfaces can be optically changed by changing photoexcitation intensity through the interactions between intermolecular charge-transfer states. Therefore, our experimental results demonstrate an optical approach to change the spin-exchange energy through the interactions between intermolecular charge-transfer states at donor:acceptor interface in organic materials.

  15. 1,8-Naphthalimide-Based Planar Small Molecular Acceptor for Organic Solar Cells.

    PubMed

    Zhang, Jicheng; Zhang, Xuejuan; Xiao, Hongmei; Li, Guangwu; Liu, Yahui; Li, Cuihong; Huang, Hui; Chen, Xuebo; Bo, Zhishan

    2016-03-01

    Four small molecular acceptors (SM1-4) comprising a central benzene core, two thiophene bridges and two 1,8-naphthalimide (NI) terminal groups were designed and synthesized by direct C-H activation. SM1 has a planar chemical structure and forms H-aggregation as films. By attachment of different substituents on the central benzene ring, the dihedral angles between the two NI end groups of SM1-4 gradually increased, leading to a gradual decrease of planarity. SM1-4 all possess a high-lying LUMO level, matching with wide band gap (WBG) polymer donors which usually have a high-lying LUMO level. When used in OSCs, devices based on SM1 and WBG donor PCDTBT-C12 gave higher electron mobility, superior film morphology and better photovoltaic performance. After optimization, a PCE of 2.78% with a V(oc) of 1.04 V was achieved for SM1 based devices, which is among the highest PCEs with a V(oc) higher than 1 V. Our results have demonstrated that NI based planar small molecules are potential acceptors for WBG polymer based OSCs. PMID:26845638

  16. Charge-transfer complexes of 1-(2-aminoethyl) piperazine with σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; Bazzi, Hassan S.

    2010-11-01

    The solid charge-transfer (CT) molecular complexes formed in the reaction of 1-(2-aminoethyl) piperazine (AEPIP) with the σ-acceptor iodine and π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 7,7,8,8-tetracyanoquinodi-methane (TCNQ), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) were studied in chloroform at 25 °C. The products were investigated through electronic and infrared spectra as well as elemental analysis. The obtained results showed that the formed solid CT-complexes have the formulas [(AEPIP) I] +I5-, [(AEPIP)(DDQ) 2], [(AEPIP)(TCNQ) 2], [(AEPIP) 2(TBCHD) 3] and [(AEPIP)(CHL)] which are in full agreement with the known reaction stoichiometries in solution as well as the elemental analysis measurements. The formation constant KCT, molar extinction coefficient ɛCT, free energy change Δ G0 and CT energy ECT have been calculated for the CT-complexes [(AEPIP)(DDQ) 2], [(AEPIP)(TCNQ) 2] and [(AEPIP)(CHL)] as well.

  17. Memory-switching phenomenon in acceptor-rich organic molecules: impedance spectroscopic studies.

    PubMed

    Bandyopadhyay, Anirban; Pal, Amlan J

    2005-04-01

    We have studied memory-switching phenomena in terms of impedance spectroscopy in a series of xanthene-class fluorescein molecules. Frequency response studies have revealed that the electronic conduction mechanism was largely tuned by increasing the number of acceptor groups attached to the molecular backbone. In molecules with weak intermolecular interactions, the transition between a low- and a high-conducting state has been associated with a change in bulk resistance and dielectric properties. The devices in the two states remained a parallel combination of a resistor and a capacitor (C(P)-R(P)) network. In devices based on Rose Bengal, which exhibits a strong dipole-dipole interaction due to its acceptor groups, the switching between the states has been modeled as a transition between a C(P)-R(P) network in the off-state and a distributed resistor-capacitor (R-C) line network in the on-state. Instead of isolated clusters, a highly coupled network of reduced Rose Bengal molecules with strong dipole-dipole interaction yielded the high-conducting state. Under a "write-read-erase-read" sequence, the device switched between the two networks reversibly for many cycles. PMID:16851669

  18. Acceptor Type Vacancy Complexes In As-Grown ZnO

    SciTech Connect

    Zubiaga, A.; Tuomisto, F.; Zuniga-Perez, J.

    2010-11-01

    One of the many technological areas that ZnO is interesting for is the construction of opto-electronic devices working in the blue-UV range as its large band gap ({approx}3.4 eV at 10 K) makes them suitable for that purpose. As-grown ZnO shows generally n-type conductivity partially due to the large concentration of unintentional shallow donors, like H, but impurities can also form complexes with acceptor type defects (Zn vacancy) leading to the creation of compensating defects. Recently, Li{sub Zn} and Na{sub Zn} acceptors have been measured and H could form similar type of defects. Doppler Broadening Positron Annihilation spectroscopy experimental results on the observation of Zn related vacancy complexes in ZnO thin films, as-grown, O implanted and Al doped will be presented. Results show that as-grown ZnO film show small Zn vacancy related complexed that could be related to presence of H as a unintentional doping element.