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Electron Donor (electron + donor)
Selected AbstractsThe Energy of Charge-Transfer States in Electron Donor,Acceptor Blends: Insight into the Energy Losses in Organic Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Dirk Veldman Abstract Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor,acceptor (D,A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D,A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D,A blends via eVoc,=,ECT,,,0.5,eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1,,,CT) occurs when Eg,,,ECT,>,0.1,eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT,,,T1) can occur when ECT,,,ET,>,0.1,eV. From these relations, it is concluded that in D,A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc,=,Eg,,,0.6,eV) and ii) the singlet,triplet energy gap should be ,EST,<,0.2,eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area. [source] Highly Efficient Reduction of Unactivated Aryl and Alkyl Iodides by a Ground-State Neutral Organic Electron Donor.CHEMINFORM, Issue 27 2005John A. Murphy Abstract For Abstract see ChemInform Abstract in Full Text. [source] Charge Transfer in the Electron Donor,Acceptor Complex BH3NH3CHEMINFORM, Issue 23 2004Yirong Mo Abstract For Abstract see ChemInform Abstract in Full Text. [source] Steady-State and Time-Resolved Studies on Photoinduced Disulfide Bond Cleavage Using Aniline as an Electron DonorCHEMPHYSCHEM, Issue 3 2004Changyuan Lu Dr. Crucial radicals: The aniline-mediated photochemical disulfide bond cleavage of linear or cyclic disulfide compounds (RSSR; see scheme) is shown to initiate by a photoinduced electron transfer from the excited state of aniline as well as by reduction with solvated electrons produced by the direct photoionization of aniline. The crucial intermediates in the disulfide cleavage are the disulfide radical anions. [source] ChemInform Abstract: Parallel (Face-to-Face) versus Perpendicular (Edge-to-Face) Alignment of Electron Donors and Acceptors in Fullerene Porphyrin Dyads: The Importance of Orientation in Electron Transfer.CHEMINFORM, Issue 3 2002Dirk M. Guldi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] The Interplay of Inverted Redox Potentials and Aromaticity in the Oxidized States of New ,-Electron Donors: 9-(1,3-Dithiol-2-ylidene)fluorene and 9-(1,3-Dithiol-2-ylidene)thioxanthene DerivativesCHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2006Samia Amriou Dr. Abstract Derivatives of 9-(1,3-dithiol-2-ylidene)fluorene (9) and 9-(1,3-dithiol-2-ylidene)thioxanthene (10) have been synthesised using Horner,Wadsworth,Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with fluorenone and thioxanthen-9-one. X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry and simultaneous electrochemistry and electron paramagnetic resonance (SEEPR), combined with theoretical calculations performed at the B3P86/6-31G** level, elucidate the interplay of the electronic and structural properties in these molecules. These compounds are strong two-electron donors, and the oxidation potentials depend on the electronic structure of the oxidised state. Two, single-electron oxidations (<) were observed for 9-(1,3-dithiol-2-ylidene)fluorene systems (9). In contrast, derivatives of 9-(1,3-dithiol-2-ylidene)thioxanthene (10) display the unusual phenomenon of inverted potentials (>) resulting in a single, two-electron oxidation process. The latter is due to the aromatic structure of the thioxanthenium cation (formed on the loss of a second electron), which stabilises the dication state (102+) compared with the radical cation. This contrasts with the nonaromatic structure of the fluorenium cation of system 9. The two-electron oxidation wave in the thioxanthene derivatives is split into two separate one-electron waves in the corresponding sulfoxide and sulfone derivatives 27,29 owing to destabilisation of the dication state. [source] Highly Conjugated p -Quinonoid ,-Extended Tetrathiafulvalene Derivatives: A Class of Highly Distorted Electron DonorsCHEMISTRY - A EUROPEAN JOURNAL, Issue 8 2004Marta C. Díaz Abstract A new class of ,-extended TTF-type electron donors (11,a,c) has been synthesized by Wittig,Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10,a,c). In cyclic voltammetry experiments, donors 11,a,c reveal a single, electrochemically irreversible oxidation,yielding the corresponding dicationic products,at relatively low oxidation potentials (,0.7,0.8 V). Theoretical calculations, performed at the DFT level (B3,P86/6-31,G*), predict a highly-folded C2h structure for 11,a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO,LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11,a.+ retains the folded C2h structure predicted for the neutral molecule as the most stable conformation, the dication 11,a2+ has a fully aromatic D2 structure, formed by an orthogonal 9,9,-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11,a,c was shown to lead to the radical cation species (11,a,c.+), which were found to disproportionate with generation of the respective dication species (11,a,c2+) and the neutral molecules (11,a,c). Una nueva familia de moléculas dadoras de electrones de tipo TTF , -extendido, altamente conjugadas, (11,a,c) se han sintetizado mediante la reacción de olefinación de Wittig,Horner de la biantrona (9) con fosfonatos de 1,3-ditiol (10,a,c). En los experimentos de voltamperometría cíclica, los dadores 11,a,c muestran una única onda de oxidación electroquímicamente irreversible,dando lugar a los productos dicatiónicos,a potenciales relativamente bajos (,0.7,0.8 V). Cálculos teóricos, llevados a cabo a nivel DFT (B3,P86/6-31,G*), predicen una estructuraC2haltamente distorsionada para 11,a. La molécula adopta una conformación en forma de doble mariposa para aliviar el impedimento estérico. Los cálculos sugieren que la transferencia de carga intramolecular asociada a la transición HOMO,LUMO es responsable de la banda de absorción observada por encima de 400 nm en el espectro electrónico. El catión radical 11,a.+retiene la estructura C2hplegada predicha para la molécula neutra como la conformación más estable. Por el contrario, el dicatión 11,a2+muestra una estructuraD2totalmente aromática,formada por una unidad central de 9,9,-biantrilo ortogonal, unida a los anillos cargados de ditiol. Los profundos cambios conformacionales que experimentan los compuestos 11 tras la oxidación explican sus propiedades electroquímicas. Medidas de radiólisis de pulso, esto es, la oxidación monoelectrónica de 11,a,c inducida por radicales, conduce a las especies catión radical (11,a,c.+), las cuales dismutan para generar las respectivas especies dicatiónicas (11,a,c2+) y la molécula neutra (11,a,c). [source] Mycothiol-dependent proteins in actinomycetesFEMS MICROBIOLOGY REVIEWS, Issue 3 2007Mamta Rawat Abstract The pseudodisaccharide mycothiol is present in millimolar levels as the dominant thiol in most species of Actinomycetales. The primary role of mycothiol is to maintain the intracellular redox homeostasis. As such, it acts as an electron acceptor/donor and serves as a cofactor in detoxification reactions for alkylating agents, free radicals and xenobiotics. In addition, like glutathione, mycothiol may be involved in catabolic processes with an essential role for growth on recalcitrant chemicals such as aromatic compounds. Following a little over a decade of research since the discovery of mycothiol in 1994, we summarize the current knowledge about the role of mycothiol as an enzyme cofactor and consider possible mycothiol-dependent enzymes. [source] Amperometric Sensor for Heparin: Sensing Mechanism and Application in Human Blood Plasma AnalysisELECTROANALYSIS, Issue 13-14 2006Jan Langmaier Abstract Voltammetric measurements of heparin at a rotating glassy carbon (GC) electrode coated with a polyvinylchloride membrane are reported. A spin-coating technique is used to prepare thin membranes (20,40,,m) with a composition of 25% (w/w) PVC, 1,1,-dimethylferrocene as a reference electron donor for the GC|membrane interface, nitrophenyl octyl ether (o -NPOE) or bis(2-ethylhexyl) sebacate (DOS) as a plasticizer, and hexadecyltrimethylammonium tetrakis(4-chlorophenyl) borate (HTMATPBCl) or tridodecylmethylammonium tetrakis(4-chlorophenyl) borate (TDMATPBCl) as a background electrolyte. It is shown that the electrodes coated with either the HTMA+/o -NPOE (DOS) or TDMA+/o -NPOE (DOS) membrane provide a comparable amperometric response towards heparin (1,10,U mL,1) in the aqueous solution of 0.1,M LiCl. However, only the membranes formulated with TDMATPBCl can be used for an amperometric assay of heparin in human blood plasma with a detection limit of 0.2,U mL,1. Effects of membrane composition, heparin concentration, rotation speed and sweep rate on the voltammetric behavior of heparin provide some insight into the sensing mechanism. Theoretical analysis of the amperometric response is outlined, and the numeric simulation of the voltammetric behavior is presented. [source] The role of the nitrate respiration element of Thermus thermophilus in the control and activity of the denitrification apparatusENVIRONMENTAL MICROBIOLOGY, Issue 2 2008Felipe Cava Summary The nitrate conjugative element (NCE) encodes the ability to respire nitrate in the facultative Thermus thermophilus NAR1 strain. This process is carried out by two heterotetrameric enzymes that catalyse the oxidation of NADH (Nrc) and the reduction of nitrate (Nar), whose expression is activated by the NCE-encoded transcription factors DnrS and DnrT. We report the presence of NCE in other facultative strains of T. thermophilus and analyse its role in subsequent steps of the denitrification pathway. We encountered that nrc mutants of denitrifying strains show a decrease in anaerobic growth rates not only with nitrate, but also with nitrite, NO and N2O, which is concomitant to their lower NADH oxidation activities in vitro. We show that nitrate, nitrite and NO are activating signals for transcription of nrc in these strains. Finally, we demonstrate that DnrS and DnrT are required for anaerobic growth not only with nitrate, but also with nitrite, NO and N2O. These data allow us to conclude that: (i) Nrc constitutes the main electron donor for the four reductases of the denitrification pathway, and (ii) the NCE controls the expression of the whole denitrification pathway and the repression of the aerobic respiration through the transcription factors DnrS and DnrT. [source] Hydrogenase- and outer membrane c -type cytochrome-facilitated reduction of technetium(VII) by Shewanella oneidensis MR-1ENVIRONMENTAL MICROBIOLOGY, Issue 1 2008Matthew J. Marshall Summary Pertechnetate, 99Tc(VII)O4,, is a highly mobile radionuclide contaminant at US Department of Energy sites that can be enzymatically reduced by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble Tc(IV)O2(s). In other microorganisms, Tc(VII)O4, reduction is generally considered to be catalysed by hydrogenase. Here, we provide evidence that although the NiFe hydrogenase of MR-1 was involved in the H2 -driven reduction of Tc(VII)O4,[presumably through a direct coupling of H2 oxidation and Tc(VII) reduction], the deletion of both hydrogenase genes did not completely eliminate the ability of MR-1 to reduce Tc(VII). With lactate as the electron donor, mutants lacking the outer membrane c -type cytochromes MtrC and OmcA or the proteins required for the maturation of c -type cytochromes were defective in reducing Tc(VII) to nanoparticulate TcO2·nH2O(s) relative to MR-1 or a NiFe hydrogenase mutant. In addition, reduced MtrC and OmcA were oxidized by Tc(VII)O4,, confirming the capacity for direct electron transfer from these OMCs to TcO4,. c -Type cytochrome-catalysed Tc(VII) reduction could be a potentially important mechanism in environments where organic electron donor concentrations are sufficient to allow this reaction to dominate. [source] Anaerobic arsenite oxidation by novel denitrifying isolatesENVIRONMENTAL MICROBIOLOGY, Issue 5 2006E. Danielle Rhine Summary Autotrophic microorganisms have been isolated that are able to derive energy from the oxidation of arsenite [As(III)] to arsenate [As(V)] under aerobic conditions. Based on chemical energetics, microbial oxidation of As(III) can occur in the absence of oxygen, and may be relevant in some environments. Enrichment cultures were established from an arsenic contaminated industrial soil amended with As(III) as the electron donor, inorganic C as the carbon source and nitrate as the electron acceptor. In the active enrichment cultures, oxidation of As(III) was stoichiometrically coupled to the reduction of NO3,. Two autotrophic As(III)-oxidizing strains were isolated that completely oxidized 5 mM As(III) within 7 days under denitrifying conditions. Based on 16S rRNA gene sequencing results, strain DAO1 was 99% related to Azoarcus and strain DAO10 was most closely related to a Sinorhizobium. The nitrous oxide reductase (nosZ) and the RuBisCO Type II (cbbM) genes were successfully amplified from both isolates underscoring their ability to denitrify and fix CO2 while coupled to As(III) oxidation. Although limited work has been done to examine the diversity of anaerobic autotrophic oxidizers of As(III), this process may be an important component in the biological cycling of arsenic within the environment. [source] Exocellular electron transfer in anaerobic microbial communitiesENVIRONMENTAL MICROBIOLOGY, Issue 3 2006Alfons J. M. Stams Summary Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory syntrophic consortia of proton-reducing acetogenic bacteria and hydrogen-consuming methanogenic archaea. Anaerobic microorganisms that use insoluble electron acceptors for growth, such as iron- and manganese-oxide as well as inert graphite electrodes in microbial fuel cells, also transfer electrons exocellularly. Soluble compounds, like humic substances, quinones, phenazines and riboflavin, can function as exocellular electron mediators enhancing this type of anaerobic respiration. However, direct electron transfer by cell,cell contact is important as well. This review addresses the mechanisms of exocellular electron transfer in anaerobic microbial communities. There are fundamental differences but also similarities between electron transfer to another microorganism or to an insoluble electron acceptor. The physical separation of the electron donor and electron acceptor metabolism allows energy conservation in compounds as methane and hydrogen or as electricity. Furthermore, this separation is essential in the donation or acceptance of electrons in some environmental technological processes, e.g. soil remediation, wastewater purification and corrosion. [source] Perchlorate reduction by a novel chemolithoautotrophic, hydrogen-oxidizing bacteriumENVIRONMENTAL MICROBIOLOGY, Issue 10 2002Husen Zhang Summary Water treatment technologies are needed that can remove perchlorate from drinking water without introducing organic chemicals that stimulate bacterial growth in water distribution systems. Hydrogen is an ideal energy source for bacterial degradation of perchlorate as it leaves no organic residue and is sparingly soluble. We describe here the isolation of a perchlorate-respiring, hydrogen-oxidizing bacterium (Dechloromonas sp. strain HZ) that grows with carbon dioxide as sole carbon source. Strain HZ is a Gram-negative, rod-shaped facultative anaerobe that was isolated from a gas-phase anaerobic packed-bed biofilm reactor treating perchlorate-contaminated groundwater. The ability of strain HZ to grow autotrophically with carbon dioxide as the sole carbon source was confirmed by demonstrating that biomass carbon (100.9%) was derived from CO2. Chemolithotrophic growth with hydrogen was coupled with complete reduction of perchlorate (10 mM) to chloride with a maximum doubling time of 8.9 h. Strain HZ also grew using acetate as the electron donor and chlorate, nitrate, or oxygen (but not sulphate) as an electron acceptor. Phylogenetic analysis of the 16S rRNA sequence placed strain HZ in the genus Dechloromonas within the , subgroup of the Proteobacteria. The study of this and other novel perchlorate-reducing bacteria may lead to new, safe technologies for removing perchlorate and other chemical pollutants from drinking water. [source] Coexistence of a sulphate-reducing Desulfovibrio species and the dehalorespiring Desulfitobacterium frappieri TCE1 in defined chemostat cultures grown with various combinations of sulphate and tetrachloroetheneENVIRONMENTAL MICROBIOLOGY, Issue 2 2001Oliver Drzyzga A two-member co-culture consisting of the dehalorespiring Desulfitobacterium frappieri TCE1 and the sulphate-reducing Desulfovibrio sp. strain SULF1 was obtained via anaerobic enrichment from soil contaminated with tetrachloroethene (PCE). In this co-culture, PCE dechlorination to cis -dichloroethene was due to the activity of the dehalorespiring bacterium only. Chemostat experiments with lactate as the primary electron donor for both strains along with varying sulphate and PCE concentrations showed that the sulphate-reducing strain outnumbered the dehalogenating strain at relatively high ratios of sulphate/PCE. Stable co-cultures with both organisms present at similar cell densities were observed when both electron acceptors were supplied in the reservoir medium in nearly equimolar amounts. In the presence of low sulphate/PCE ratios, the Desulfitobacterium sp. became the numerically dominant strain within the chemostat co-culture. Surprisingly, in the absence of sulphate, strain SULF1 did not disappear completely from the co-culture despite the fact that there was no electron acceptor provided with the medium to be used by this sulphate reducer. Therefore, we propose a syntrophic association between the sulphate-reducing and the dehalorespiring bacteria via interspecies hydrogen transfer. The sulphate reducer was able to sustain growth in the chemostat co-culture by fermenting lactate and using the dehalogenating bacterium as a ,biological electron acceptor'. This is the first report describing growth of a sulphate-reducing bacterium in a defined two-member continuous culture by syntrophically coupling the electron and hydrogen transfer to a dehalorespiring bacterium. [source] Structure, Electrochemistry and Hydroformylation Catalytic Activity of the Bis(pyrazolylborato)rhodium(I) Complexes [RhBp(CO)P] [P = P(NC4H4)3, PPh3, PCy3, P(C6H4OMe-4)3]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2004Anna M. Trzeciak Abstract Rhodium complexes of formula [RhBp(CO)P] [Bp = bis(pyrazolylborate), P = P(NC4H4)31, PPh32, PCy33, P(C6H4OMe-4)34] have been prepared by exchange of the acetylacetonate (acac,) ligand in [Rh(acac)(CO)P] complexes. The spectroscopic and electrochemical properties as well as X-ray data of [Rh(acac)(CO)P] and [RhBp(CO)P] complexes have been compared with the aim to estimate the relative donor properties of both anionic ligands (acac, and Bp,). The cyclic voltammetric results indicate that the Bp, ligand behaves as a much stronger electron donor than acac, and a value of the Lever EL ligand parameter identical to that of the pyrazolate ligand (,0.24 V vs. NHE for each coordinating arm) is proposed for the bis- and tris(pyrazolyl)borate ligands, whereas P(C6H4OMe-4)3 is also shown to have an identical EL value (0.69 V) to that of P(NC4H4)3. An improved linear relationship between the oxidation potential and the sum of the ligand EL values for square-planar RhI complexes is also obtained and adjusted values for the Lever SM and IM parameters for the RhI/RhII redox couple are given. The trans influence of phosphanes was not observed in crystals of complexes 2 and 3, in contrast to analogous acetylacetonato complexes in which the Rh,O bonds differ by ca. 0.04,0.06 Å. Complexes 1,4 are very attractive precursors for hydroformylation catalysts and yields of aldehydes of 80,87% have been obtained with all complexes without extra phosphane as co-catalyst. During the hydroformylation reaction, however, small amounts of a catalytically inactive [RhBp(CO)2] complex were formed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Volume Organization of Polymer and Hybrid Solar Cells as Revealed by Electron TomographyADVANCED FUNCTIONAL MATERIALS, Issue 19 2010Svetlana S. van Bavel Abstract Polymer and hybrid solar cells have the potential to become the leading technology of the 21st century in conversion of sun light to electrical energy because their ease processing from solution producing printable devices in a roll-to-roll fashion with high speed and low cost. The performance of such devices critically depends on the nanoscale organization of the photoactive layer, which is composed of at least two functional materials: the electron donor and the electron acceptor forming a so-called bulk heterojunction; however, control of its volume morphology still is a challenge. In this context, advanced analytical tools are required that are able to provide information on the local volume morphology of the photoactive layer with nanometer resolution. In this report electron tomography is introduced as the technique able to explore the 3D morphology of polymer and hybrid solar cells and the first results achieved are critically discussed. [source] Implication of the glutamine synthetase/glutamate synthase pathway in conditioning the amino acid metabolism in bundle sheath and mesophyll cells of maize leavesFEBS JOURNAL, Issue 12 2008Marie-Hélène Valadier We investigated the role of glutamine synthetases (cytosolic GS1 and chloroplast GS2) and glutamate synthases (ferredoxin-GOGAT and NADH-GOGAT) in the inorganic nitrogen assimilation and reassimilation into amino acids between bundle sheath cells and mesophyll cells for the remobilization of amino acids during the early phase of grain filling in Zea mays L. The plants responded to a light/dark cycle at the level of nitrate, ammonium and amino acids in the second leaf, upward from the primary ear, which acted as the source organ. The assimilation of ammonium issued from distinct pathways and amino acid synthesis were evaluated from the diurnal rhythms of the transcripts and the encoded enzyme activities of nitrate reductase, nitrite reductase, GS1, GS2, ferredoxin-GOGAT, NADH-GOGAT, NADH-glutamate dehydrogenase and asparagine synthetase. We discerned the specific role of the isoproteins of ferredoxin and ferredoxin:NADP+ oxidoreductase in providing ferredoxin-GOGAT with photoreduced or enzymatically reduced ferredoxin as the electron donor. The spatial distribution of ferredoxin-GOGAT supported its role in the nitrogen (re)assimilation and reallocation in bundle sheath cells and mesophyll cells of the source leaf. The diurnal nitrogen recycling within the plants took place via the specific amino acids in the phloem and xylem exudates. Taken together, we conclude that the GS1/ferredoxin-GOGAT cycle is the main pathway of inorganic nitrogen assimilation and recycling into glutamine and glutamate, and preconditions amino acid interconversion and remobilization. [source] Hydroperoxide reduction by thioredoxin-specific glutathione peroxidase isoenzymes of Arabidopsis thalianaFEBS JOURNAL, Issue 24 2006Aqib Iqbal Arabidopsis thaliana contains eight glutathione peroxidase (GPX) homologs (AtGPX1,8). Four mature GPX isoenzymes with different subcellular distributions, AtGPX1, -2, -5 and -6, were overexpressed in Escherichia coli and characterized. Interestingly, these recombinant proteins were able to reduce H2O2, cumene hydroperoxide, phosphatidylcholine and linoleic acid hydroperoxides using thioredoxin but not glutathione or NADPH as an electron donor. The reduction activities of the recombinant proteins with H2O2 were 2,7 times higher than those with cumene hydroperoxide. Km values for thioredoxin and H2O2 were 2.2,4.0 and 14.0,25.4 µm, respectively. These finding suggest that GPX isoenzymes may function to detoxify H2O2 and organic hydroperoxides using thioredoxin in vivo and may also be involved in regulation of the cellular redox homeostasis by maintaining the thiol/disulfide or NADPH/NADP balance. [source] Two W-containing formate dehydrogenases (CO2 -reductases) involved in syntrophic propionate oxidation by Syntrophobacter fumaroxidansFEBS JOURNAL, Issue 11 2003Frank A. M. De Bok Two formate dehydrogenases (CO2 -reductases) (FDH-1 and FDH-2) were isolated from the syntrophic propionate-oxidizing bacterium Syntrophobacter fumaroxidans. Both enzymes were produced in axenic fumarate-grown cells as well as in cells which were grown syntrophically on propionate with Methanospirillum hungatei as the H2 and formate scavenger. The purified enzymes exhibited extremely high formate-oxidation and CO2 -reduction rates, and low Km values for formate. For the enzyme designated FDH-1, a specific formate oxidation rate of 700 U·mg,1 and a Km for formate of 0.04 mm were measured when benzyl viologen was used as an artificial electron acceptor. The enzyme designated FDH-2 oxidized formate with a specific activity of 2700 U·mg,1 and a Km of 0.01 mm for formate with benzyl viologen as electron acceptor. The specific CO2 -reduction (to formate) rates measured for FDH-1 and FDH-2, using dithionite-reduced methyl viologen as the electron donor, were 900 U·mg,1 and 89 U·mg,1, respectively. From gel filtration and polyacrylamide gel electrophoresis it was concluded that FDH-1 is composed of three subunits (89 ± 3, 56 ± 2 and 19 ± 1 kDa) and has a native molecular mass of approximately 350 kDa. FDH-2 appeared to be a heterodimer composed of a 92 ± 3 kDa and a 33 ± 2 kDa subunit. Both enzymes contained tungsten and selenium, while molybdenum was not detected. EPR spectroscopy suggested that FDH-1 contains at least four [2Fe-2S] clusters per molecule and additionally paramagnetically coupled [4Fe-4S] clusters. FDH-2 contains at least two [4Fe-4S] clusters per molecule. As both enzymes are produced under all growth conditions tested, but with differences in levels, expression may depend on unknown parameters. [source] Characterization of a nif-regulated flavoprotein (FprA) from Rhodobacter capsulatusFEBS JOURNAL, Issue 3 20002S] ferredoxin, Redox properties, molecular interaction with a [2Fe A flavoprotein from Rhodobacter capsulatus was purified as a recombinant (His)6 -tag fusion from an Escherichia coli clone over-expressing the fprA structural gene. The FprA protein is a homodimer containing one molecule of FMN per 48-kDa monomer. Reduction of the flavoprotein by dithionite showed biphasic kinetics, starting with a fast step of semiquinone (SQ) formation, and followed by a slow reduction of the SQ. This SQ was in the anionic form as shown by EPR and optical spectroscopies. Spectrophotometric titration gave a midpoint redox potential for the oxidized/SQ couple of Em1 = +20 mV (pH 8.0), whereas the SQ/hydroquinone couple could not be titrated due to the thermodynamic instability of SQ associated with its slow reduction process. The inability to detect the intermediate form, SQ, upon oxidative titration confirmed this instability and led to an estimate of Em2 , Em1 of > 80 mV. The reduction of SQ by dithionite was significantly accelerated when the [2Fe,2S] ferredoxin FdIV was used as redox mediator. The midpoint redox potential of this ferredoxin was determined to be ,275 ± 2 mV at pH 7.5, consistent with FdIV serving as electron donor to FprA in vivo. FdIV and FprA were found to cross-react when incubated together with the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, giving a covalent complex with an Mr of , 60 000. Formation of this complex was unaffected by the redox states of the two proteins. Other [2Fe,2S] ferredoxins, including FdV and FdVI from R. capsulatus, were ineffective as electron carriers to FprA, and cross-reacted poorly with the flavoprotein. The possible function of FprA with regard to nitrogen fixation was investigated using an fprA -deleted mutant. Although nitrogenase activity was significantly reduced in the mutant compared with the wild-type strain, nitrogen fixation was apparently unaffected by the fprA deletion even under iron limitation or microaerobic conditions. [source] A novel NADPH-dependent oxidoreductase with a unique domain structure in the hyperthermophilic Archaeon, Thermococcus litoralisFEMS MICROBIOLOGY LETTERS, Issue 1 2008András Tóth Abstract Thermococcus litoralis, a hyperthermophilic Archaeon, is able to reduce elemental sulfur during fermentative growth. An unusual gene cluster (nsoABCD) was identified in this organism. In silico analysis suggested that three of the genes (nsoABC) probably originated from Eubacteria and one gene (nsoD) from Archaea. The putative NsoA and NsoB are similar to NuoE- and NuoF-type electron transfer proteins, respectively. NsoC has a unique domain structure and contains a GltD domain, characteristic of glutamate synthase small subunits, which seems to be integrated into a NuoG-type sequence. Flavin and NAD(P)H binding sites and conserved cysteines forming iron,sulfur clusters binding motifs were identified in the protein sequences deduced. The purified recombinant NsoC contains one FAD cofactor per protein molecule and catalyzes the reduction of polysulfide with NADPH as an electron donor and it also reduces oxygen. It was concluded that the Nso complex is a new type of NADPH-oxidizing enzyme using sulfur and/or oxygen as an electron acceptor. [source] Engineering NADH metabolism in Saccharomyces cerevisiae: formate as an electron donor for glycerol production by anaerobic, glucose-limited chemostat culturesFEMS YEAST RESEARCH, Issue 8 2006Jan-Maarten A. Geertman Abstract Anaerobic Saccharomyces cerevisiae cultures reoxidize the excess NADH formed in biosynthesis via glycerol production. This study investigates whether cometabolism of formate, a well-known NADH-generating substrate in aerobic cultures, can increase glycerol production in anaerobic S. cerevisiae cultures. In anaerobic, glucose-limited chemostat sultures (D=0.10 h,1) with molar formate-to-glucose ratios of 0 to 0.5, only a small fraction of the formate added to the cultures was consumed. To investigate whether incomplete formate consumption was by the unfavourable kinetics of yeast formate dehydrogenase (high kM for formate at low intracellular NAD+ concentrations) strains were constructed in which the FDH1 and/or GPD2 genes, encoding formate dehydrogenase and glycerol-3-phosphate dehydrogenase, respectively, were overexpressed. The engineered strains consumed up to 70% of the formate added to the feed, thereby increasing glycerol yields to 0.3 mol mol,1 glucose at a formate-to-glucose ratio of 0.34. In all strains tested, the molar ratio between formate consumption and additional glycerol production relative to a reference culture equalled one. While demonstrating that that format can be use to enhance glycerol yields in anaerobic S. cerevisiae cultures, This study also reveals kinetic constraints of yeast formate dehydrogenase as an NADH-generating system in yeast mediated reduction processes. [source] Improving the ON/OFF Ratio and Reversibility of Recording by Rational Structural Arrangement of Donor,Acceptor MoleculesADVANCED FUNCTIONAL MATERIALS, Issue 5 2010Ying Ma Abstract Organic molecules with donor,acceptor (D,A) structure are an important type of material for nanoelectronics and molecular electronics. The influence of the electron donor and acceptor units on the electrical function of materials is a worthy topic for the development of high-performance data storage. In this work, the effect of different D,A structures (namely D,,,A,,,D and A,,,D,,,A) on the electronic switching properties of triphenylamine-based molecules is investigated. Devices based on D,,,A,,,D molecules exhibit excellent write,read,erase characteristics with a high ON/OFF ratio of up to 106, while that based on A,,,D,,,A molecules exhibit irreversible switching behavior with an ON/OFF ratio of about (3.2,×,101),(1,×,103). Moreover, long retention time of the high conductance state and low threshold voltage are observed for the D,A switching materials. Accordingly, stable and reliable nanoscale data storage is achieved on the thin films of the D,A molecules by scanning tunneling microscopy. The influence of the arrangement of the D and A within the molecular backbone disclosed in this study will be of significance for improving the electronic switching properties (ON/OFF current ratio and reversibility) of new molecular systems, so as to achieve more efficient data storage through appropriate design strategies. [source] High-Resolution Spectroscopic Mapping of the Chemical Contrast from Nanometer Domains in P3HT:PCBM Organic Blend Films for Solar-Cell ApplicationsADVANCED FUNCTIONAL MATERIALS, Issue 3 2010Xiao Wang Abstract A high-resolution near-field spectroscopic mapping technique is successfully applied to investigate the influence of thermal annealing on the morphology of a poly(3-hexylthiophene) and [6,6]-penyl-C61 butyric acid methyl ester (P3HT:PCBM) blend film. Based on the simultaneously recorded morphological and spectroscopic information, the interplay among the blend film morphology, the local P3HT:PCBM molecular distribution, and the P3HT photoluminescence (PL) quenching efficiency are systematically discussed. The PL and Raman signals of the electron donor (P3HT) and acceptor (PCBM) are probed at an optical resolution of approximately 10,nm, which allows the chemical nature of the different domains to be identified directly. In addition, the local PL quenching efficiency, which is related to the electron transfer from P3HT to PCBM, is quantitatively revealed. From these experimental results, it is proposed that high-resolution near-field spectroscopic imaging is capable of mapping the local chemical composition and photophysics of the P3HT:PCBM blends on a scale of a few nanometers. [source] High-Performance Organic Photovoltaic Devices Using a New Amorphous Molecular Material with High Hole Drift Mobility, Tris[4-(5-phenylthiophen-2-yl)phenyl]amineADVANCED FUNCTIONAL MATERIALS, Issue 24 2009Hiroshi Kageyama Abstract A new amorphous molecular material, tris[4-(5-phenylthiophen-2-yl)phenyl]amine (TPTPA), is synthesized and characterized. TPTPA forms a stable amorphous glass with a glass-transition temperature of 83,°C when the melt sample is cooled. It also forms amorphous thin films by a thermal deposition technique. TPTPA exhibits a hole drift mobility of 1.0,×,10,2,cm2 V,1 s,1 at an electric field of 1.0,×,105,V cm,1 and at 293,K, as determined by the time-of-flight method, which is of the highest level among those of amorphous molecular materials. pn-Heterojunction organic photovoltaic devices (OPVs) using TPTPA as an electron donor and C60 or C70 as an electron acceptor exhibit high performance with fill factors of 0.66,0.71 and power conversion efficiencies of 1.7,2.2% under air-mass (AM) 1.5G illumination at an intensity of 100,mW cm,2, which are of the highest level ever reported for OPVs using amorphous molecular materials. [source] Self-Assembly of a Donor-Acceptor Dyad Across Multiple Length Scales: Functional Architectures for Organic ElectronicsADVANCED FUNCTIONAL MATERIALS, Issue 15 2009Jeffrey M. Mativetsky Abstract Molecular dyads based on polycyclic electron donor (D) and electron acceptor (A) units represent suitable building blocks for forming highly ordered, solution-processable, nanosegregated D-A domains for potential use in (opto)electronic applications. A new dyad, based on alkyl substituted hexa- peri -hexabenzocoronene (HBC) and perylene monoimide (PMI) separated by an ethinylene linker, is shown to have a high tendency to self-assemble into ordered supramolecular arrangements at multiple length scales: macroscopic extruded filaments display long-range crystalline order, nanofiber networks are produced by simple spin-coating, and monolayers with a lamellar packing are formed by physisorption at the solution-HOPG interface. Moreover, highly uniform mesoscopic ribbons bearing atomically flat facets and steps with single-molecule heights self-assemble upon solvent-vapor annealing. Electrical measurements of HBC-PMI films and mesoscopic ribbons in a transistor configuration exhibit ambipolar transport with well balanced p- and n-type mobilities. Owing to the increased level of order at the supramolecular level, devices based on ribbons show mobility increases of more than one order of magnitude. [source] The Energy of Charge-Transfer States in Electron Donor,Acceptor Blends: Insight into the Energy Losses in Organic Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Dirk Veldman Abstract Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor,acceptor (D,A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D,A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D,A blends via eVoc,=,ECT,,,0.5,eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1,,,CT) occurs when Eg,,,ECT,>,0.1,eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT,,,T1) can occur when ECT,,,ET,>,0.1,eV. From these relations, it is concluded that in D,A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc,=,Eg,,,0.6,eV) and ii) the singlet,triplet energy gap should be ,EST,<,0.2,eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area. [source] One-Dimensional Microwires Formed by the Co-Assembly of Complementary Aromatic Donors and AcceptorsADVANCED FUNCTIONAL MATERIALS, Issue 11 2009Jie-Yu Wang Abstract A truxene derivative (Tr3) with a C3 symmetric conjugated plane is synthesized; this derivative is a perfect match, in both size and structure, with its oxidized counterpart, the truxenone derivative (TrO3), a new electron acceptor that was recently reported. The complementary pair, Tr3 and TrO3, sets a good platform for the investigation of aromatic donor,acceptor interactions. Detailed 1H NMR experiments, photoluminescence spectroscopy, as well as differential scanning calorimetry are performed to investigate the interaction between Tr3 and TrO3, from solution to mesophase. One-dimensional microbelts readily formed from a 1:1 mixture of Tr3 and TrO3. Scanning electron microscopy, powder X-ray diffraction, as well as fluorescence microscopy are performed to elucidate their co-assembly structure in the solid state. Moreover, modulation of the co-assembly structure is easily realized by changing the concentration or mixing ratio. The present system opens the possibility of forming 1D heterostructures via electron donor,acceptor interaction, and its potential application as P,N junction and photowaveguide materials in optoelectronic devices. [source] Quantum-Chemical Characterization of the Origin of Dipole Formation at Molecular Organic/Organic InterfacesADVANCED FUNCTIONAL MATERIALS, Issue 4 2009Igor Avilov Abstract Recent experiments have reported a vacuum level shift at the interface between organic materials due to the formation of an interface dipole layer. On the basis of quantum-chemical calculations, this paper sheds light on the factors contributing to the formation of an interface dipole between an electron donor and an electron acceptor, considering as model system a complex made of tetrathiafulvalene (TTF) as a donor and tetracyanoquinodimethane (TCNQ) as an acceptor. The results indicate that the interface dipole is governed both by charge-transfer and polarization effects and allow for disentangling of their respective contributions. Two regimes of charge transfer can be distinguished depending on the strength of the electronic coupling: a fractional charge transfer occurs in the strong coupling regime while only integer charges are transferred when the coupling is weak. The polarization contribution can be significant, even in the presence of a pronounced charge transfer between the donor and acceptor molecules. The values of ionization potential and electron affinity of the donor and acceptor molecules may experience shifts as large as several tenths of an eV at the interface with respect to the isolated compounds. [source] | |||||||||||||||||||||||||||||||||||||||||||